New multicomponent catalysts for the selective aerobic oxidative condensation of benzylamine to N-benzylidenebenzylamine

Aerobic oxidative condensation of benzylamine to N-benzylidenebenzylamine was carried out on new gold-based catalysts using as support bimodal UVM-7-like mesoporous silica containing Ni and Ce (or Sn) as oxide nanodomains partially embedded inside the mesoporous UVM-7 silica walls. These nanodomains acted as effective and stable inorganic anchors favoring the nucleation, growth and stability of supported gold particles. Following the atrane method (a “one-pot” strategy able to harmonize the hydrolytic reactivity of different heteroelements through the use of complexes containing triethanolamine-derived ligands (atranes) as precursors) the stability of the oxide nanodomains during oxidation …

Amphetamine-type stimulants analysis in oral fluid based on molecularly imprinting extraction

Abstract A methamphetamine-based molecularly imprinted polymer (MIP) has been prepared by bulk polymerization to recognize new psychoactive substances (NPS) of the amphetamine, cathinones and 2C families in oral fluid samples, being the first precedent of a synthetized MIP for the extraction and preconcentration 32 NPS including amphetamine type substances and synthetic cathinones from oral fluids. Pre-polymerization complex and resulting materials were appropriately characterized by infrared spectroscopy, scanning electron microscopy, and nitrogen adsorption-desorption isotherms. Appropriateness of the material for the specific recognition of the target analytes was also evaluated through …

Glycosidase enzymes stabilization through immobilization onto nanoparticulated bimodal organosilicas

Expanding the atrane route: Generalized surfactant-free synthesis of mesoporous nanoparticulated xerogels

Abstract A diversity of silica-based and non-silica nanoparticulated mesoporous xerogels have been synthesized from aqueous solution using a surfactant-free strategy, and starting from molecular atrane complexes as precursors. This approach constitutes an extension of the “atrane route” previously described for the surfactant-assisted synthesis of mesoporous materials, and allows us to unify the multiplicity of protocols described for the preparation of conventional xerogels. In fact, we have used exactly the same preparative conditions for obtaining all the compositions reported here. The xerogels synthesized in this way include pure silica (UVM-11), aluminosilicates and titanosilicates (M…

Aggregation-induced heterogeneities in the emission of upconverting nanoparticles at the submicron scale unfolded by hyperspectral microscopy

Transparent upconverting hybrid nanocomposites are exciting materials for advanced applications such as 3D displays, nanosensors, solar energy converters, and fluorescence biomarkers. This work presents a simple strategy to disperse upconverting b-NaYF4:Yb3+/Er3+ or Tm3+ nanoparticles into low cost, widely used and easy-to-process polydimethylsiloxane (PDMS)-based organic–inorganic hybrids. The upconverting hybrids were shaped as monoliths, films or powders displaying in the whole volume Tm3+ or Er3+ emissions (in the violet/blue and green/red spectral regions, respectively). For the first time, hyperspectral microscopy allows the identification at the submicron scale of differences in the …

Selective, Sensitive, and Rapid Analysis with Lateral-Flow Assays Based on Antibody-Gated Dye-Delivery Systems: The Example of Triacetone Triperoxide

[EN] Antibodygated MSNs that are loaded with a rhodamine dye and that can be used for the determination of the presence of peroxide-based explosive TATP with a lateral-flow fluorescence reader have been designed and prepared, thereby allowing for detection limits in the lower ppb range. The mechanism of the detection relies on a displacement of the antibody from the surface of the hybrid material because of highly affine antibody-TATP interactions, which release a much larger number of entrapped dye molecules from the pores than antibodies are displaced. The high selectivity of the antibody is retained in the gated material, thus allowing for a remarkable discrimination against H2O2. System…

New trends in V–P–O solids

On the basis of the industrial interest of the oxovanadium phosphate catalysts, current research effort in this field is focused mainly on the development of synthetic strategies directed towards obtaining open-framework materials. There is a growing body of work describing preparations using hydrothermal procedures under a diversity of conditions. A great number of new solids, whose nets range from lamellar arrays to micro- and mesostructured organizations, has been prepared in last years. In this context, the applicability of concepts and procedures from the zeolites chemistry to systems involving transition elements is critically analyzed.

Peptide-Capped Mesoporous Nanoparticles: Toward a more Efficient Internalization of Alendronate

[EN] Osteoporosis is an illness which appears when the osteoblast/osteoclast activities are unbalanced taking place bone resorption (caused by osteoclasts) in higher extension than bone formation (induced by osteoblasts). Alendronate is one of the most used drugs for osteoporosis treatment despite its scarce bioavailability. Here we present the synthesis and characterization of mesoporous gated nanoparticles (two sets) for the controlled release of alendronate. The first set of nanoparticles (S1) were loaded with sulforhodamine B and capped with a peptide that could be selectively hydrolyzed by cathepsin K enzyme (overexpressed in osteoclasts). The second set (S2) was functionalized with am…

Mesoporous iron phosphate/phosphonate hybrid materials

Abstract Relatively high surface area pure mesoporous iron-phosphorus oxide-based derivatives have been synthesized through an S + I − surfactant-assisted cooperative mechanism by means of a one-pot preparative procedure from aqueous solution and starting from iron atrane complexes and phosphoric and phosphonic acids. A soft chemical extraction procedure allows opening the pore system of the parent as-prepared materials by exchanging the surfactant without mesostructure collapse. The nature of the pore wall can be modulated from iron phosphate up to hybrids involving approximately 30% of organophosphorus entities (phosphonates or diphosphonates). X-ray powder diffraction, transmission elect…

Selective, Highly Sensitive, and Rapid Detection of Genomic DNA by Using Gated Materials:MycoplasmaDetection

The coupling of gated-indicator delivery with highly specific biochemical recognition is an innovative strategy for the detection of DNA sequences, able to compete with classical methods which need PCR amplification, in important areas such as point-of-care diagnostics or detection of specific biological contaminations with pathogens. Such comparatively simple and cheap yet highly selective and sensitive assays hold promise for use in less-developed areas of the world.

2D and 3D mixed MII/CuIImetal–organic frameworks (M = Ca and Sr) withN,N′-2,6-pyridinebis(oxamate) and oxalate: preparation and magneto-structural study

Three heterobimetallic complexes of formula [Ca2Cu3(mpyba)2(2-apyma)(H2O)7]·8.3H2O (1), [Sr2Cu3(mpyba)2(2-apyma)(H2O)8]·11.6H2O (2) and [Sr4.5Cu4(mpyba)4(ox)(H2O)20]·8.5H2O (3) [H4mpyba = N,N'-2,6-pyridinebis(oxamic acid), 2-apyma = 2-(6-aminopyridinyl)oxamate and ox = oxalate] have been synthesized and structurally characterized. Complexes 1 and 2 are isostructural compounds, with tricopper(ii) units having mpyba and its hydrolytic product (2-apyma) as ligands. They are interlinked through strontium(ii) (1) and calcium(ii) (2) ions to afford neutral two-dimensional networks. Two of the copper(ii) ions are five-coordinate in distorted square pyramidal (Cu3) and trigonal bipyramidal (Cu1) su…

Molecular precursors of mesostructured silica materials in the atrane route: A DFT/GIAO/NBO theoretical study

Abstract Quantum chemical calculations using density functional theory have been carried out to investigate two assumed molecular precursors and identified as silatranes (N[OCH2CH2]3Si–OCH2CH2N–(CH2CH2OH)2 and N[OCH2CH2]3Si–OCH2CH2N–(CH2CH2OH)2Na+) which are present in the synthesis of mesoporous silica based material namely “the atrane route”. One of the ways in this synthesis leads to the well-known MCM-41. Additionally, in this work has been also investigated two others molecules such as triethanolamine (TEAH3) and sodatrane which are present in the medium. Gas phase and solution equilibrium geometries of the previous molecules were fully optimized at B3LYP level, modeling solvent effect…

Pore Length Effect on Drug Uptake and Delivery by Mesoporous Silicas

The capability of UVM-7 silicas to work as supports for drug storage and delivery is investigated using ibuprofen as a model. UVM-7 silicas are surfactant-assisted synthesised mesoporous materials displaying a characteristic bimodal pore architecture related to their nanoparticulate texture. Strict control of the drug-charge protocol allows the achievement of high ibuprofen loads, not only because of the availability of intra-nanoparticle mesopores and large textural voids, but also owing to the decrease in pore-blocking effects (with regard to related unimodal mesoporous materials such as MCM-41) achieved through the shortening of the mesopore length. The UVM-7/ibuprofen nanocomposites are…

Optical properties of exciton confinement in spherical ZnO quantum dots embedded in matrix

Abstract The optical characteristics of ZnO nanoparticles in SiO2 matrix have been determined by UV–visible and photoluminescence (PL) studies. The PL spectrum of the ZnO quantum dots shows two different bands: the first one is a broad green emission band related to deep level emission in the visible range and the second one is situated at 3.48 eV in the ultraviolet region, and is attributed to the recombination of electrons in the conduction band and holes in the valence band. The experimental result that we found was simulated numerically using different methods. Our calculations revealed a good agreement between the matrix element calculation method and the experimental result. We have a…

Modulation of folic acid bioaccessibility by encapsulation in pH-responsive gated mesoporous silica particles

[EN] A study on the controlled release of folic acid (FA) from pH-responsive gated mesoporous silica particles (MSP) is reported. The MCM-41 support was synthesized using tetraethyl orthosilicate (TEOS) as hydrolytic inorganic precursor and the surfactant hexadecyltrimethylammonium bromide (CTAB) as porogen species. Calcination of the mesostructured phase resulted in the starting solid. This solid was loaded with FA to obtain the initial support S0. Moreover, this FA-loaded material was further functionalized with 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (N3) in order to obtain the gated polyamine-functionalised material S1. Solids S0 and S1 were characterized using standar…

Enlarged pore size in nanoparticulated bimodal porous silicas: Improving accessibility

Abstract Mass-transfer kinetics seems to be highly favored in siliceous materials constructed from the aggregation of mesoporous nanoparticles. Besides intra-particle mesopores, over the course of the aggregation process an inter-particle (textural) large pore system is generated. Diffusion constrains through the resulting hierarchically structured pore systems mainly depend on the characteristics of the intra-particle mesopores. By using alkanes as swelling agents, we have been able to significantly increase the intra-particle mesopore size in previously well characterized UVM-7 materials. The Winsor-III-like behavior associated with the presence of alkanes in the hydro-alcoholic reaction …

Nanoscopic hybrid systems with a polarity-controlled gate-like scaffolding for the colorimetric signalling of long-chain carboxylates

Hybrid mesoporous systems containing a gate-like ensemble functionalised with imidazolium groups and a dye are used for the selective colorimetric sensing of long-chain carboxylates. Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Relationship between bulk phase, near surface and outermost atomic layer of VPO catalysts and their catalytic performance in the oxidative dehydrogenation of ethane

Abstract A set of vanadium phosphorous oxide (VPO) catalysts, mainly consisting of (VO) 2 P 2 O 7 , VO(PO 3 ) 2 or VOPO 4 ·2H 2 O bulk crystalline phases, has been investigated for the oxidative dehydrogenation (ODH) of ethane to ethylene, a key potential reaction for a sustainable industrial and socioeconomic development. The catalytic performance on these VPO catalysts has been explained on the basis of the main crystalline phases and the corresponding surface features found by XPS and LEISS at 400 °C, i.e. within the temperature range used for ODH reaction. The catalysts based on (VO) 2 P 2 O 7 phase presented the highest catalytic activity and productivity to ethylene. Nevertheless, the…

Enhanced manganese content in Mn-MCM-41 mesoporous silicas

The use of triethanolamine containing complexes of Si and Mn as hydrolytic precursors allows the synthesis of doped mesoporous silicas in which the Mn content can be modulated up to reach a minimum value of the Si/Mn molar ratio of 3. This limit value corresponds to a Mn relative content significantly higher than those reported to date for similar materials (Si/Mn = 6). According to XRD, TEM and porosity data, the mesoporous nature typical of the MCM-41 silicas is retained even for the samples having the highest Mn content.

Protective effect of mesoporous silica particles on encapsulated folates.

Mesoporous silica particles (MSPs) are considered suitable supports to design gated materials for the encapsulation of bioactive molecules. Folates are essential micronutrients which are sensitive to external agents that provoke nutritional deficiencies. Folates encapsulation in MSPs to prevent degradation and to allow their controlled delivery is a promising strategy. Nevertheless, no information exists about the protective effect of MSPs encapsulation to prevent their degradation. In this work, 5-formyltetrahydrofolate (FO) and folic acid (FA) were entrapped in MSPs functionalized with polyamines, which acted as pH-dependent molecular gates. The stability of free and entrapped vitamins af…

Hierarchical porous carbon with designed pore architecture and study of its adsorptive properties

Abstract Ordered mesoporous carbon nanoparticles have been synthesized by a nanocasting procedure from furfuryl alcohol impregnation into alumino–silica UVM-7 material. By a proper adjustment of the synthesis parameters, furfuryl alcohol volume vs . template pore volume, it was possible to obtain a carbonaceous templated material which keeps the hierarchical bimodal porosity of the silica together with its high surface area (>1000 m 2 /g), as it was confirmed by means of electron transmission microscopy and N 2 adsorption isotherms. This carbon material was evaluated by testing it as a sorbent for several pesticides in aqueous solutions. Its absorption efficiency was compared with typical c…

Hyaluronic Acid–Silica Nanohybrid Gels

Excessive water sorption and low mechanical properties are a severe drawback in some biomedical applications of hyaluronic acid (HA). A way to improve these properties is here explored through the novel concept of nanohybrid hydrogels consisting of a HA matrix including different amounts of silica-derived species. This inorganic filler phase controls the mechanical and swelling properties of HA cross-linked matrices. Below a 2 wt % of silica in the systems, nanoparticle aggregates of tens of nanometers and silica oligomers are distributed more or less homogeneously throughout the organic matrix, without percolating. This morphology of the silica phase is accompanied by an increased swelling…

Ceramic foam supported active materials for boron remediation in water

Due to the narrowrange between boron necessities and toxicity in the environment, there is a high interest in the design of effective boron remediation procedures. We have previously reported a promising boron adsorptionmaterial based on the affinity of boron aqueous species for cis-diol groups that were anchored on differentmesoporous silica matrices.However, the small particle size of these systemsmakes themdifficult to be applied on real remediation situations. In this context we report herein a novel systemfor boron adsorption fromaqueous solutions inwhich the high boron affinity for functionalized mesoporousmaterials is combined with themechanical properties of ceramic foams as macrosc…

Chromogenic Chemodosimeter Based on Capped Silica Particles to Detect Spermine and Spermidine

A new hybrid organic–inorganic material for sensing spermine (Spm) and spermidine (Spd) has been prepared and characterized. The material is based on MCM-41 particles functionalized with an N-hydroxysuccinimide derivative and loaded with Rhodamine 6G. The cargo is kept inside the porous material due to the formation of a double layer of organic matter. The inner layer is covalently bound to the silica particles, while the external layer is formed through hydrogen and hydrophobic interactions. The limits of detection determined by fluorimetric titration are 27 µM and 45 µM for Spm and Spd, respectively. The sensor remains silent in the presence of other biologically important amines and is a…

One‐Pot Synthesis of a New High‐Aluminium‐Content Super‐Microporous Aluminosilicate

A new super-microporous aluminosilicate having a high aluminium content (Si/Al ca. 1) has been prepared through a surfactant-assisted procedure with the use of a commercially available binary precursor (di-sec-butoxyaluminooxytriethoxysilane) as a single source of both Al and Si. The formation of super-micropores is a result of a significant network shrinkage associated with the thermal elimination of the surfactant. This solid has been studied by X-ray powder diffraction, electron microscopy, nuclear magnetic resonance spectroscopy and porosimetry. A preliminary analysis of the acidity and the catalytic activity of the super-microporous solid for the selective catalytic reduction of NOx is…

Precatalyst or dosing-device? The [Pd2{μ-(C6H4) PPh2}2{μ-O2C(C6H5)}2] complex anchored on a carboxypolystyrene polymer as an effective supplier of palladium catalytically active nanoparticles for the Suzuki-Miyaura reaction

Abstract A new catalyst has been synthesized from the precursor [Pd2{μ-(C6H4) PPh2}2 {μ-O2C(C6H5)}2] immobilized on a carboxypolystyrene polymer that exhibits an excellent dispersion of the Pd (II) centers, reusability, and catalytic activity in front of phenyl bromides. The activity of this new material was studied in detail for the Suzuki-Miyaura reaction and compared to that of Pd nanoparticles (NPs) supported on UVM-7 (a mesoporous silica), and Pd NPs stabilized with polyvinylpirrolydone. The homogeneous/heterogeneous character of the catalytic process was determined from the results of the hot-filtration, centrifugation, poisoning, three phases tests, and from differential sensitivity …

X-ray diffraction line broadening on vibrating dry-milled Two Crows sepiolite

A reference sample of sepiolite and products of its comminution by vibrating dry-milling have been studied using X-ray diffraction (XRD) line-broadening analysis, complementary field emission scanning electron microscopy (FESEM) images and surface area measurements. The apparent crystallite sizes determined via XRD are in agreement with observations on FESEM images. The sepiolite aggregates consist of lath-shaped agglutinations of prisms and pinacoids elongated along [001], each lath including several crystallites in that direction. The surface area magnitudes are in the range of previous experimental measurements of other sepiolites. The results obtained show the effectiveness of vibro-mil…

Bimodal porous silica nanomaterials as sorbents for an efficient and inexpensive determination of aflatoxin M1 in milk and dairy products

Abstract An extraction procedure was developed for the determination of aflatoxin M1 in milk and dairy products. A sorbent based on UVM-7 mesoporous silica was used as solid phase for the sample clean-up, and the analyte determination was carried out by HPLC coupled to a fluorescence detector. The material architecture was characterized by transmission electronic microscopy, X-ray diffraction, 29Si NMR and nitrogen adsorption-desorption. After the optimization of extraction parameters, the influence of the matrix has been evaluated, obtaining recoveries in the range 78–105% for whole and skimmed milk and yogurt matrix. The reusability of the material was also proved. The sensitivity of the …

Host Solids Containing Nanoscale Anion-Binding Pockets and Their Use in Selective Sensing Displacement Assays

Enzyme-Responsive Intracellular Controlled Release Using Nanometric Silica Mesoporous Supports Capped with "Saccharides"

The synthesis of new capped silica mesoporous nanoparticles for on-command delivery applications is described. The gate-like functional hybrid systems consisted of nanoscopic MCM-41-based materials functionalized on the pore outlets with different “saccharide” derivatives and a dye contained in the mesopores. A series of hydrolyzed starch products as saccharides were selected. The mesoporous silica nanoparticles S1, S2, and S3 containing the grafted starch derivatives Glucidex 47, Gludicex 39, and Glucidex 29 were synthesized. Additionally, for comparative purposes solid S4 containing lactose was prepared. Delivery studies in pure water in the presence of pancreatin or -D-galactosidase were…

ZnO nanoparticles embedded in UVM-7-like mesoporous silica materials: Synthesis and characterization

Abstract ZnO nanodomains embedded in bimodal mesoporous silica (UVM-7) materials with high Zn content (4≤Si/Zn≤30) have been synthesized by an one-pot surfactant-assisted procedure from a hydro alcoholic medium using a cationic surfactant (CTMABr=cetyltrimethylammonium bromide) as structural directing agent, and starting from molecular atrane complexes of Zn and Si as hydrolytic inorganic precursors. This chemical procedure allows optimizing the dispersion of the ZnO particles in the silica walls. The bimodal mesoporous nature of the final high surface area nano-sized materials is confirmed by XRD, TEM, and N2 adsorption–desorption isotherms. The small intra-particle mesopore system is due …

Large monolithic silica-based macrocellular foams with trimodal pore system.

Silica-based materials with hierarchical pore systems at three different length scales (small mesopores–large mesopores–macropores) have been prepared through a nanotectonic approach by using mesoporous nanoparticles as building blocks; the resulting materials present a highly accessible foam-like architecture and can be prepared as large monoliths. Huerta Morillo, Lenin Jose, Lenin.Huerta@uv.es ; Latorre Saborit, Julio, Julio.Latorre@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Azobenzene Polyesters Used as Gate-Like Scaffolds in Nanoscopic Hybrid Systems

The synthesis and characterisation of new capped silica mesoporous nanoparticles for on-command delivery applications is reported. Functional capped hybrid systems consist of MCM-41 nanoparticles functionalised on the external surface with polyesters bearing azobenzene derivatives and rhodamine¿B inside the mesopores. Two solid materials, Rh-PAzo8-S and Rh-PAzo6-S, containing two closely related polymers, PAzo8 and PAzo6, in the pore outlets have been prepared. Materials Rh-PAzo8-S and Rh-PAzo6-S showed an almost zero release in water due to steric hindrance imposed by the presence of anchored bulky polyesters, whereas a large delivery of the cargo was observed in the presence of an esteras…

11B-MAS NMR approach to the boron adsorption mechanism on a glucose-functionalised mesoporous silica matrix

[EN] Boron chemistry has raised much interest because, despite the difference between necessities and toxicity being very narrow, it is still widely used in industrial processes. In a previous work we reported an adsorbent for boron extraction from water by the functionalisation of a UVM-7 mesoporous silica matrix with gluconamide moieties. The ability of this material to adsorb boron is based on its well-known affinity for coordinating the cis-diols present in attached saccharide. Although much research on the formation of boron esters with sugars and sugar derivatives in solution has been done, very few reports have dealt with the adsorption mechanism of boron onto functionalised material…

ChemInform Abstract: Crystal Structure and Magnetic Properties of α-Mn(H2PO2)2× H2O.

Abstract The crystal structure of α-Mn(H2PO2)2·H2O has been refined from X-ray powder diffraction data. The cell is monoclinic (space group P21/c, Z − 4) with α = 7.8601(3) A , b = 7.4411(3) A , c = 10.7717(4) A and β = 102.859(2)°. The structure was refined with the Rietveld refinement principles, using as starting model the parameters of the presumably isostructural compound Zn(H2PO2)2·H2O. The structure can be described as being formed by dimeric entities Mn2O2 of edge-sharing manganese octahedra. Each group is linked through Mn-O-P-O-Mn bridges to four other groups, resulting in a three-dimensional network. The thermal variation in the susceptibility shows a sharp peak at T = 6.5 K and …

Crystalline microstructure of sepiolite influenced by grinding

The crystalline microstructure of ground sepiolite has been investigated. A reference sample of sepiolite and products of its comminution by dry grinding were studied through X-ray diffraction pattern analysis, specific surface measurements by nitrogen adsorption and complementary analysis of field emission scanning electron microscope images. A statistical model of polycrystals was applied to describe and determine the crystalline microstructure of the studied specimens. The model parameters characterizing the microstructure were prevalent crystallite shape, volume-weighted crystallite size distribution and second-order crystalline lattice strain distribution, and they were determined for …

Silica-based macrocellular foam monoliths with hierarchical trimodal pore systems

Abstract Silica-based large monoliths exhibiting a trimodal hierarchical pore system have been successfully prepared through a nanotectonic approach starting from sub-micro/nanometric mesoporous particles (as building blocks), and using a polyurethane foam as macrotemplate. Large trimodal pieces with macrocellular like interconnected macropores in the micrometer range are a mineralized replica of the polyurethane foam. Textural large-mesopores/macropores (in the 20–70 nm range) have their origin in the inter-particle voids. The small intra-particle mesopore system (with pore diameters around 2–3 nm) is due to the supramolecular templating effect of the surfactant.

Coordinating and hydrogen bonding ability of a bifunctional 2D paddle-wheel copper(II) coordination polymer

abstract A new copper(II) complex of formula {[Cu 2 (H 2 btc) 2 (dmf) 2 ] 4dmf} n (1)[H 4 btc = 1,2,4,5-benzenetetracarb-oxylic acid, dmf = dimethylformamide] has been synthesised and its structure determined by X-raydiffraction. The structure displays a new square grid of ‘‘paddle-wheel’’ tetracarboxylate-bridgeddicopper(II) units with an intradimer copper–copper separation of 2.619(2) A. The dmf molecules areretained through weak axial coordinative bonds and hydrogen bonding interactions with the carboxylicgroups of the porous neutral network of 4 4 net topology. The magnetic behaviour of 1 corresponds to astrong antiferromagnetic coupling within each dicopper(II) unit (J = 343 cm 1 with …

Oligonucleotide-capped mesoporous silica nanoparticles as DNA-responsive dye delivery systems for genomic DNA detection

[EN] New hybrid oligonucleotide-capped mesoporous silica nanoparticles able to detect genomic DNA were designed.

Energy of excitons and acceptor–exciton complexes to explain the origin of ultraviolet photoluminescence in ZnO quantum dots embedded in a SiO2 matrix

Abstract Assuming finite depth and within the effective mass approximation, the energies of exciton states and of the acceptor–exciton complexes confined in spherical ZnO quantum dots (QDs) embedded in a SiO2 matrix are calculated using a matrix procedure, including a three-dimensional confinement of carrier in the QDs. This theoretical model has been designed to illustrate the two emission bands in the UV region observed in our experimental Photoluminescence spectrum (PL), with the first emission band observed at 3.04 eV and attributed to the bound ionized acceptor–exciton complexes, and the second one located at 3.5 and assigned to the free exciton. Our calculations have revealed a good a…

Host-guest interactions for extracting antibiotics with a γ-cyclodextrin poly(glycidyl-co-ethylene dimethacrylate) hybrid sorbent

Abstract A procedure for the solid-phase extraction of antibiotics (enoxacin, ofloxacin, norfloxacin, ciprofloxacin, and sparfloxacin) in water has been developed. The sorbent used is based on a poly(glycidyl-co-ethylene dimethacrylate) network, whose previously modified surface has been functionalized with γ-cyclodextrin through a click-chemistry reaction. The architecture of the material has been characterized by thermogravimetric analysis, N2 adsorption-desorption, Raman spectroscopy, confocal microscopy, and scanning electron microscopy, showing good capability to be used as a filler for extraction cartridges. The optimization of the extraction methodology shows good intra-day and inter…

Understanding the role of Ti-rich domains in the stabilization of gold nanoparticles on mesoporous silica-based catalysts

3 Tablae, 14 Figures.-- Supplementary material.-- © 2018. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/

Selective hydrogenation of nitroderivatives over Au/TiO2/UVM-7 composite catalyst

Abstract Hydrogenation of nitroderivatives (4-nitrostyrene or 7-nitro-1-tetralone) was performed using as support a silica mesoporous material with high specific surface area (1091 m2/g) and a bimodal pore size distribution (UVM-7). Gold and/or TiO2 were deposited inside the pores of this support with the aim to achieve high activity and selectivity for this reaction. The morphology and structure of the powders have been characterized by adsorption-desorption isotherms, XRD, TEM, STEM-HAADF, XPS and ATR-FTIR. Structural characterizations shown differences between the catalysts with and without titania. The presence of TiO2 provides a better size distribution of the spherical gold nanopartic…

Highly Active Hydrogenation Catalysts Based on Pd Nanoparticles Dispersed along Hierarchical Porous Silica Covered with Polydopamine as Interfacial Glue

New catalysts based on Pd(0) nanoparticles (Pd NPs) on a bimodal porous silica of the UVM-7/polydopamine (PDA) support have been synthesized following two preparative strategies based on the sequential or joint incorporation of two components of the composite (Pd and PDA). We analyzed the role played by the PDA as &lsquo

Reversible solvatomagnetic switching in a single-ion magnet from an entatic state

We have developed a new strategy for the design and synthesis of multifunctional molecular materials showing reversible magnetic and optical switching.

New Chromogenic Probes into Nanoscopic Pockets in Enhanced Sensing Protocols for Amines in Aqueous Environments

A new sensory MCM-41-based material for the colorimetric sensing and discrimination of amines has been developed.

Enzyme-Mediated Controlled Release Systems by Anchoring Peptide Sequences on Mesoporous Silica Supports

[EN] Gated community: Peptides anchored to the surface of silica mesoporous supports by a valid procedure act as gatekeepers. In this way, "zero release" supports that selectively deliver the cargo in the presence of a suitable peptidase are obtained (see picture, red spheres: cargo, colored chains: peptides). © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cathepsin-B Induced Controlled Release from Peptide-Capped Mesoporous Silica Nanoparticles

New capped silica mesoporous nanoparticles for intracellular controlled cargo release within cathepsin B expressing cells are described. Nanometric mesoporous MCM-41 supports loaded with safranin O (S1-P) or doxorubicin (S2-P) containing a molecular gate based on a cathepsin B target peptidic sequence were synthesized. Solids were designed to show "zero delivery" and to display cargo release in the presence of cathepsin B enzyme, which selectively hydrolyzed in vitro the capping peptide sequence. Controlled delivery in HeLa, MEFs WT, and MEFs lacking cathepsin B cell lines were also tested. Release of safranin O and doxorubicin in these cells took place when cathepsin B was active or presen…

Low-cost materials for boron adsorption from water

[EN] Knowing the affinity of boron aqueous species for cis-diol organic groups, five different hybrid materials have been prepared by anchoring glucose groups onto the surface of silica matrices with a different surface topology: UVM-7 bimodal mesoporous silica, UVM-11 unimodal non-templated mesoporous silica, commercial silica fume and two silica xerogels with pores within the mesoporous range (13-50 nm). After optimizing the experimental conditions, a comparison was made of the boron adsorption capacities in water. The relationship of the structural and functionalization parameters is discussed and the importance of the surface topology in the final adsorption behaviour is revealed. Hence…

Targeted-lung delivery of dexamethasone using gated mesoporous silica nanoparticles. A new therapeutic approach for acute lung injury treatment

Acute lung injury (ALI) is a critical inflammatory syndrome, characterized by increased diffuse inflammation and severe lung damage, which represents a clinical concern due to the high morbidity and mortality in critical patients. In last years, there has been a need to develop more effective treatments for ALI, and targeted drug delivery to inflamed lungs has become an attractive research field. Here, we present a nanodevice based on mesoporous silica nanoparticles loaded with dexamethasone (a glucocorticoid extensively used for ALI treatment) and capped with a peptide that targets the TNFR1 receptor expressed in pro-inflammatory macrophages (TNFR-Dex-MSNs) and avoids cargo leakage. TNFR-D…

Chromogenic Discrimination of Primary Aliphatic Amines in Water with Functionalized Mesoporous Silica

Very high titanium content mesoporous silicas

Titanium content in mesoporous titanosilicate catalysts has been modulated up to a minimum Si/Ti value of 1.9 by using complexing agents able to coordinate both Si and Ti atoms and harmonize the reactivity of the resulting precursors avoiding subsequent phase segregation and leading to chemically very homogeneous materials. El Haskouri, Jamal, Jamal.Haskouri@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Towards chemical communication between gated nanoparticles.

The design of comparatively simple and modularly configurable artificial systems able to communicate through the exchange of chemical messengers is, to the best of our knowledge, an unexplored field. As a proof-of-concept, we present here a family of nanoparticles that have been designed to communicate with one another in a hierarchical manner. The concept involves the use of capped mesoporous silica supports in which the messenger delivered by a first type of gated nanoparticle is used to open a second type of nanoparticle, which delivers another messenger that opens a third group of gated nanoobjects.We believe that the conceptual idea that nanodevices can be designed to communicate with …

Borate-driven gatelike scaffolding using mesoporous materials functionalised with saccharides.

We report the development of an MCM-41 mesoporous support that is functionalised with saccharides at the pore outlets and contains the dye [Ru(bipy)(3)](2+) in the pores (solid S1; bipy = 2,2'-bipyridyl). For this hybrid system, the inhibition of mass transport of the dye from the pore voids to the bulk solution in the presence of borate is demonstrated in water at neutral pH. The formation of the corresponding boroester derivative is related to the selective reaction of borate with the appended saccharides. This control is selective and only anion borate, among several anions and cations, can act as a molecular tap and inhibit the delivery of the entrapped guest. Additionally, the S1-borat…

Soft hydrothermal synthesis of new microporous materials based on phosphate-like species

ABSTRACTFactors controlling hydrothermal synthetic procedures are not well understood. A good knowledge of the solution chemistry of precursor species is the best reference for the design of rational procedures. Examples of the predictive character of simple models in order to rationalize complex syntheses are discussed in detail.

Reversible Solvatomagnetic Switching in a Spongelike Manganese(II)-Copper(II) 3D Open Framework with a Pillared Square/Octagonal Layer Architecture

The concept of "molecular magnetic sponges" was introduced for the first time in 1999 by the creative imagination of the late Olivier Kahn. It refers to the exotic spongelike behavior of certain molecule-based materials that undergo a dramatic change of their magnetic properties upon reversible dehydration/rehydration processes. Here we report a unique example of a manganese(II)-copper(II) mixed-metal-organic framework of formula [Na(H(2)O)(4)](4)[Mn(4){Cu(2)(mpba)(2)(H(2)O)(4)}(3)]·56.5H(2)O (1) (mpba=N,N'-1,3-phenylenebis(oxamate)). Compound 1 possesses a 3D Mn(II)(4)Cu(II)(6) pillared layer structure with mixed square and octagonal pores of approximate dimensions 1.2×1.2 nm and 2.1×3.0 n…

Synthesis and Crystal Structure of a Novel Lamellar Barium Derivative:  Ba(VOPO4)2·4H2O. Synthetic Pathways for Layered Oxovanadium Phosphate Hydrates M(VOPO4)2·nH2O

A unified synthetic strategy has allowed us to rationalize the preparative chemistry of the layered oxovanadium phosphates M(VOPO4)2·nH2O. Thus, we have been able to isolate as single phases with reasonable yields both all the previously characterized phosphates and a new solid containing Ba2+ cations as guest species as well as to prepare new related derivatives involving arsenate anions. In order to organize the experimental results, we have used two complementary models:  a simple restatement of the partial charge model (PCM), and the valence matching principle (VMP) (derived from the bond valence method). The crystal structure of the new barium lamellar derivative, Ba(VOPO4)2·4H2O, has …

Efficient boron removal by using mesoporous matrices grafted with saccharides.

Highly efficient boron removal from water was achieved by using mesoporous silica materials functionalised with saccharides. Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Enhanced antifungal efficacy of tebuconazole using gated pH-driven mesoporous nanoparticles

Núria Mas,1–3 Irene Galiana,3 Silvia Hurtado,† Laura Mondragón,1–3 Andrea Bernardos,1–3 Félix Sancenón,1–3 María D Marcos,1–3 Pedro Amorós,4 Nuria Abril-Utrillas,5 Ramón Martínez-Máñez,1–3 José Ramón Murguía1,3 1Centro de Reconocimiento Molecular y Desarrollo Tecnológico (IDM), Centro Mixto Universidad Politécnica de Valencia, Universidad de Valencia, Valencia, Spain; 2Departamento de Química, Universidad Politécnica de Valencia, Valenci…

AlTf-UVM-7—Highly active catalysts for the synthesis of long chain symmetrical ethers and non-ionic surfactant structures

New Lewis acid AlTf-UVM-7 catalysts with bimodal pore system and different Si to Al ratios were prepared in a two-step synthesis in which triflic acid (Tf) was incorporated into previously synthesized mesoporous aluminum-containing silica. The Al incorporation inside the pore walls was carried out through the Atrane method. The characterization of the resulted catalysts showed that the triflic acid treatment step did not damage the texture or the structure of the catalysts. These materials were used as green catalysts for the etherification of fatty alcohols and the conversion of ethylene glycol (EG) with n-octanol resulting in mixtures of short ethoxylated structures with a large distribut…

Improving epoxide production using Ti-UVM-7 porous nanosized catalysts

Nanosized Ti-UVM-7 materials with a hierarchical system of pores at two different length scales have been prepared through a one-pot procedure by using a simple template agent; the catalytic activity and selectivity of the resulting materials in bulky olefin epoxidation by organic peroxides are the highest reported to date.

Synthetic Pathways for New Tubular Transition Metal Hydroxo- and Fluoro-Selenites: Crystal Structures ofM12(X)2(SeO3)8(OH)6(M=Co2+,Ni2+;X= OH−)

The dumortierite-family structuresM12X2(SeO3)8(OH)6(M= Co2+and Ni2+;X= OH−and F−) have been synthesized. The crystal structures of the hydroxo-derivatives have been refined from X?ray powder diffraction data in the space groupP63mc(Z= 1) witha= 12.887(3) A andc= 4.981(4) A (M= Co2+,X= OH−or F−) anda= 12.704(5) A andc= 4.925(6) A (M= Ni2+,X= OH−or F−). Application of the Partial Charge Transference Model allows the understanding of the selenite derivatives crystal chemistry.

Chromo-Fluorogenic Detection of Nitroaromatic Explosives by Using Silica Mesoporous Supports Gated with Tetrathiafulvalene Derivatives

[EN] Three new hybrid gated mesoporous materials (SN3-1, SNH2-2, and SN3-3) loaded with the dye [Ru(bipy)(3)](2+) (bipy=bipyridine) and capped with different tetrathiafulvalene (TTF) derivatives (having different sizes and shapes and incorporating different numbers of sulfur atoms) have been prepared. The materials SN3-1 and SN3-3 are functionalized on their external surfaces with the TTF derivatives 1 and 3, respectively, which were attached by employing the click chemistry reaction, whereas SNH2-2 incorporates the TTF derivative 2, which was anchored to the solid through an amidation reaction. The final gated materials have been characterized by standard techniques. Suspensions of these s…

Antibody-Capped Mesoporous Nanoscopic Materials: Design of a Probe for the Selective Chromo-Fluorogenic Detection of Finasteride

[EN] The synthesis of capped mesoporous silica nanoparticles (MSN) conjugated with an antibody (AB) as a gatekeeper has been carried out in order to obtain a delivery system able to release an entrapped cargo (dye) in the presence of a target molecule (antigen) to which the conjugated antibody binds selectively. In particular, MSN loaded with rhodamine B and functionalized on the external surface with a suitable derivative of N-(t-butyl)- 3-oxo-(5a,17b)-4-aza-androst-1-ene-17-carboxamide (finasteride) have been prepared (S1). The addition of polyclonal antibodies against finasteride induced capping of the pores due to the interaction with the anchored hapten-like finasteride derivative to g…

Cyclodextrins as a Key Piece in Nanostructured Materials: Quantitation and Remediation of Pollutants

Separation and pre-concentration of trace pollutants from their matrix by reversible formation of inclusion complexes has turned into a widely studied field, especially for the benefits provided to different areas. Cyclodextrins are non-toxic oligosaccharides that are well known for their host–guest chemistry, low prices, and negligible environmental impact. Therefore, they have been widely used as chiral selectors and delivery systems in the pharmaceutical and food industry over time. However, their use for extraction purposes is hampered by their high solubility in water. This difficulty is being overcome with a variety of investigations in materials science. The setting-up of novel solid…

Mesoporous Materials Incorporating Metal Triflates

Metal triflates attracted a large interest as catalysts in the past three decades especially due to the Lewis acid properties exhibited by these compounds and the variety of the functional group transformations. This chapter proposes an overview presenting the catalytic performances of triflates both as molecular compounds and as triflates dispersed in different solid matrices. In the first part the performances of molecular triflates in organic reactions carried out in the presence of water or water as solvent considering both water-sensitive and -insensitive metals are discussed. Then, the importance of materials incorporating triflates is demonstrated for catalysts obtained via immobiliz…

Enzyme-responsive intracellular-controlled release using silica mesoporous nanoparticles capped with ε-poly-L-lysine.

The synthesis and characterization of two new capped silica mesoporous nanoparticles for controlled delivery purposes are described. Capped hybrid systems consist of MCM-41 nanoparticles functionalized on the outer surface with polymer epsilon-poly-L-lysine by two different anchoring strategies. In both cases, nanoparticles were loaded with model dye molecule [Ru(bipy)(3)](2+). An anchoring strategy involved the random formation of urea bonds by the treatment of propyl isocyanate-functionalized MCM-41 nanoparticles with the lysine amino groups located on the epsilon-poly-L-lysine backbone (solid Ru-rLys-S1). The second strategy involved a specific attachment through the carboxyl terminus of…

Mesoporous aluminum phosphite

Abstract High surface area pure mesoporous aluminum-phosphorus oxide-based derivatives have been synthesized through an S+I− surfactant-assisted cooperative mechanism by means of a one-pot preparative procedure from aqueous solution and starting from aluminum atrane complexes and phosphoric and/or phosphorous acids. A soft chemical extraction procedure allows opening the pore system of the parent as-prepared materials by exchanging the surfactant without mesostructure collapse. The nature of the pore wall can be modulated from mesoporous aluminum phosphate (ALPO) up to total incorporation of phosphite entities (mesoporous aluminum phosphite), which results in a gradual evolution of the acid…

Confined growth of carbon nanoforms in one-dimension by fusion of anthracene rings inside the pores of MCM-41

We report a simple two-step procedure that uses anthracene, a cheap polyaromatic hydrocarbon with low melting point, as a molecular precursor to produce carbon nanoforms (CNFs). First, we describe the chemical synthesis of graphite from the fusion of anthracene rings at relatively low temperature (520 °C) followed by cyclodehydrogenation. Next, we extend this protocol to the synthesis of CNFs by confining the molecular precursor in a mesoporous host like MCM-41. The confined environment favors one-dimensional growth of CNFs with sizes controlled by the pores of the mesoporous host.

Nanoparticulated Silicas with Bimodal Porosity: Chemical Control of the Pore Sizes

Nanoparticulated bimodal porous silicas (NBSs) with pore systems structured at two length scales (meso- and large-meso-/macropores) have been prepared through a one-pot surfactant-assisted procedure by using a simple template agent and starting from silicon atrane complexes as hydrolytic inorganic precursors. The final bulk materials are constructed by an aggregation of pseudospherical mesoporous primary nanoparticles process, over the course of which the interparticle (textural) large pore system is generated. A fine-tuning of the procedural variables allows not only an adjustment of the processes of nucleation and growth of the primary nanoparticles but also a modulation of their subseque…

Enhancing extraction performance of organophosphorus flame retardants in water samples using titanium hierarchical porous silica materials as sorbents.

Abstract A sorbent for the extraction of organophosphorus flame retardants has been proposed, based on UVM-7 (University of Valencia Materials) mesoporous silica doped with titanium. Designed cartridges have been applied to the extraction and preconcentration of flame retardants in water samples, followed by gas chromatography coupled to a mass spectrometry detector. Firstly, UVM-7 materials with different contents of titanium were synthesized and characterized by several techniques, thus confirming the proper mesoporous architecture. The potential of these materials was assessed in comparison with their morphological properties, resulting Ti50-UVM-7 the best solid phase. Several extraction…

A new method for fluoride determination by using fluorophores and dyes anchored onto MCM-41Electronic supplementary information (ESI) available: IR spectra, SEM images, X-ray diffraction patterns and TG/TD analysis. See http://www.rsc.org/suppdata/cc/b1/b111128k/

A new colourimetric and fluorimetric method for fluoride determination in aqueous samples based on the specific reaction between fluoride and silica has been developed and applied on real samples.

The Li Ni0.2Mn0.2Co0.6O2 electrode materials: A structural and magnetic study

Graphical abstract: EPR signal of the Li{sub 0.6}Co{sub 0.6}Ni{sub 0.2}Mn{sub 0.2}O{sub 2} composition showing that Mn{sup 4+} ions are the solely paramagnetic ions in the structure. Highlights: Black-Right-Pointing-Pointer LiCo{sub 0.6}Ni{sub 0.2}Mn{sub 0.2}O{sub 2} was prepared by the combustion method with sucrose as a fuel. Black-Right-Pointing-Pointer Chemical delithiaition was performed by using NO{sub 2}BF{sub 4} oxidizing agent. Black-Right-Pointing-Pointer The rhombohedral symmetry was preserved upon lithium removal. Black-Right-Pointing-Pointer Lithium extraction leads to Ni{sup 2+} oxidation to Ni{sup 4+} followed by Co{sup 3+} oxidation. Black-Right-Pointing-Pointer The EPR narr…

Delivery modulation in silica mesoporous supports via alkyl chain pore outlet decoration

This article focuses on the study of the release rate in a family of modified silica mesoporous supports. A collection of solids containing ethyl, butyl, hexyl, octyl, decyl, octadecyl, docosyl, and triacontyl groups anchored on the pore outlets of mesoporous MCM-41 has been prepared and characterized. Controlled release from pore voids has been studied through the delivery of the dye complex tris(2,2¿-bipyridyl)ruthenium(II). Delivery rates were found to be dependent on the alkyl chain length anchored on the pore outlets of the mesoporous scaffolding. Moreover, release rates follow a Higuchi diffusion model, and Higuchi constants for the different hybrid solids have been calculated. A decr…

The Determination of Methylmercury in Real Samples Using Organically Capped Mesoporous Inorganic Materials Capable of Signal Amplification

Nitroarene hydrogenation catalysts based on Pd nanoparticles glued with PDA on inorganic supports: Multivariate Curve Resolution as an useful tool to compare the catalytic activity in multi-step reactions

[EN] Two green catalysts based on Pd(0) nanoparticles (Pd NPs) anchored through PDA on porous silica and magnetite have been synthesized using a generalized simple and reproducible "two-step" methodology. Both catalysts were tested for a model reaction, the hydrogenation of 4-nitrophenol using NaBH4 as the hydrogenating agent, and especially good activity has been achieved in the case of the catalysts containing magnetite as inorganic core (Pd NPs-PDA@Fe3O4). We analyzed the effect associated with the catalyst separation method (centrifugation or magnetically) that affect to the distribution and aggregation degree of the Pd NPs. In addition, we also correlate the final catalyst morphology w…

ChemInform Abstract: Enhanced Surface Area in Thermally Stable Pure Mesoporous TiO2.

Abstract We describe here for the first time the surfactant-assisted synthesis of thermally stable mesoporous pure TiO 2 having a high surface area. Our synthetic approach to the chemistry of this system is based on the equilibrium between the hydrolysis and condensation reactions of the inorganic species and the organic–inorganic self-assembling processes. The use of titanatrane complexes helps to retard the hydrolysis and condensation reactions, thus allowing us to overcome the difficulties in preparing titanium dioxide mesoporous materials starting from highly reactive Ti-alkoxides. The mesoporous material has been characterized by TEM, XRD and N 2 adsorption–desorption isotherms and dis…

Ordered Mesoporous Silicon Oxynitrides

Recent Progress of Microwave-Assisted Synthesis of Silica Materials.

Microwaves are a source of energy of great interest for chemical synthesis. Among nanomaterials, few are as versatile as silica—it forms mesoporous materials and nanoparticles, it can be incorporated as shells or loaded in composites, it can also be functionalized. Despite the relevant properties of silica, and the advantages of the use of microwave as energy source, its use in silica-based materials is not frequent. We report herein a compilation of the research results published in the last 10 years of microwave assisted synthesis of silica based materials. This review includes examples of mesoporous materials for waste removal, catalysis, drug release, and gas adsorption applications, to…

Hierarchical bimodal porous silicas and organosilicas for enzyme immobilization

This work shows the ability of a hierarchical porous silica-based network with pore systems at two different length scales for enzyme immobilization. Two different enzymes have been selected, lysozyme, a relatively small globular enzyme, and α-L-arabinofuranosidase, a large enzyme of interest in the winemaking industry. The lysozyme immobilization on several silica supports (bimodal porous silicas denoted UVM-7 materials and conventional silica xerogels) has been studied and the loading amounts can be correlated to the open nature and accessibility of the internal surface area. Bimodal UVM-7 silicas present a very quick adsorption rate and high enzyme loading. α-L-Arabinofuranosidase has be…

Insights into the Dynamics of Grotthuss Mechanism in a Proton-Conducting Chiral bioMOF

Proton conduction in solids attracts great interest, not only because of possible applications in fuel cell technologies, but also because of the main role of this process in many biological mechanisms. Metal–organic frameworks (MOFs) can exhibit exceptional proton-conduction performances, because of the large number of hydrogen-bonded water molecules embedded in their pores. However, further work remains to be done to elucidate the real conducting mechanism. Among the different MOF subfamilies, bioMOFs, which have been constructed using biomolecule derivatives as building blocks and often affording water-stable materials, emerge as valuable systems to study the transport mechanisms involve…

Vanadyl phosphate dihydrate, a solid acid: the role of water in VOPO4�2H2O and its sodium derivatives Na x (VIV x VV 1?x O)PO4�(2?x)H2O

Sodium-containing intercalates having as general formula Na x VOPOP4·(2−x)H2O (0.25≤x<0.50) have been obtained and characterized. Orthorhombic phases, which essentially maintain the structure of the layered oxide hydrate VOPO4·2H2O result. Intercalated sodium ions act as ‘pillars’. The presence of H3O+ ions in the parent VOPO4·2H2O and also in some reduced phases, is detected. The understanding of the structural role of the water molecules is advanced and the topotactic dehydration/rehydration processes are studied. The formation of a new metastable VOPO4·H2O phase is established.

Hydrolysis of DCNP (a Tabun mimic) catalyzed by mesoporous silica nanoparticles

[EN] The hydrolysis of diethylcyanophosphonate, DCNP (a Tabun simulant) in the presence of mesoporous silica nanoparticles (MSN) has been studied in acetonitrile:water (99.5:0.5 v/v) mixtures using 31P NMR as a suitable technique to follow the DCNP hydrolysis. MSN alone was not capable to induce DCNP hydrolysis, yet MSN in combination with the presence of the bases potassium carbonate, triethylamine or DABCO enhanced DCNP degradation. When MSN was used combined with K2CO3, a hydrolysis of ca. 95% of the initial DCNP after 60 min was observed. In the presence of DABCO, MSN was able to induce the hydrolysis of ca. 90% of DCNP after the same time. However, the DCNP hydrolysis using MSN in the …

Interface charge density matching as driving force for new mesostructured oxovanadium phosphates with hexagonal structure, [CTA]xVOPO4·zH2O

Hexagonal mesostructured mixed-valence oxovanadium phosphates [CTA]xVOPO4·zH2O, in short ICMUV-2, have been synthesized through a S+I- cooperative mechanism using cationic surfactant (cetyltrimethylammonium, CTAB) rodlike micelles as a template. On the lines of the hypothesis that the driving force leading to the formation of mesostructured solids is the charge density matching at the interface between the supramolecular−organic and supramolecular−inorganic moieties, the self-assembling process between CTA+ micelles and VOPO4q- planar anions can be thought of as consequence of the adequate adjustment of the metal mean oxidation state. X-ray powder diffraction and TEM techniques show that th…

Glucose-triggered release using enzyme-gated mesoporous silica nanoparticles.

[EN] A new gated nanodevice design able to control cargo delivery using glucose as a trigger and cyclodextrin-modified glucose oxidase as a capping agent is reported.

A new efficient, highly dispersed, Pd nanoparticulate silica supported catalyst synthesized from an organometallic precursor. Study of the homogeneous vs. heterogeneous activity in the Suzuki-Miyaura reaction

[EN] A new Pd(0) catalyst supported on silica UVM-7 has been synthesized from the organometallic [Pd-2(mu-(C6H4) Pp(2))(2)(CH3CN)(4)](BF4)(2) precursor, characterized by the high dispersion, activity, and small size of the palladium nanoclusters fixed on the silica surface. The catalyst was tested for the Suzuki-Miyaura (SM) reaction of different 4-substitutedphenyl halides with phenylboronic acid. The kinetic study concurs with most of the catalytic action was carried out by Pd species originated by the partial solubilization of Pd immobilized on mesoporous silica. The Schmidt's analysis of differential selectivity (SADS) in several competitive SM reactions, together the STEM-HAADF and HRT…

Ordered mesoporous materials: composition and topology control through chemistry

Abstract The atrane route constitutes a very versatile technique to obtain ordered mesoporous materials. A wide diversity of silica and silica-doped materials can be prepared by bringing into play fundamental synthesis parameters (like temperature, concentration and pH) which, in turn, allow modulation of the resulting material topology.

Stability of different mesoporous silica particles during an in vitro digestion

Mesoporous silica materials have the ability to entrap drugs, nutrients and functional biomolecules and can be able to act as smart delivery systems capable to control and target the release of their cargo in a particular part of the gastrointestinal tract when administrated orally. However, the aptness of these encapsulation supports in in vivo oral controlled release relies on their chemical stability through the digestive tube. In this context, we have evaluated the stability of four different mesoporous silica particles, frequently used as encapsulating supports, during an in vitro digestion process comprising buccal, stomach and intestinal phases. Results showed that after 4 h of diges…

Comparative hydroamination of aniline and substituted anilines with styrene on different zeolites, triflate based catalysts and their physical mixtures

Abstract Catalytic performances of different zeolites (Beta and mordenites), scandium triflate based catalysts, mesoporous UVM-7 encapsulated scandium triflate and physical mixtures prepared under ultrasound irradiation were evaluated in the hydroamination of aniline and substituted anilines with styrene. The performances of these catalysts were controlled by the type of acidity and strength. Thus, the conversion was mainly controlled by the strength of the acid sites and their accessibility, while the selectivity appeared to be controlled by the Lewis/Bronsted type of acidity. Lewis acid catalysts directed the reactions mainly to the formation of the Markovnikov adducts while Bronsted acid…

Dual Enzyme-Triggered Controlled Release on Capped Nanometric Silica Mesoporous Supports

The development of nanoscopic hybrid materials equipped with “molecular gates” showing the ability of releasing target entrapped guests upon the application of an external trigger has attracted great attention and has been extensively explored during recent years.1 These nanodevices are composed of two subunits, namely, a suitable support and certain capping entities grafted on the surface of the scaffolding.2 The support is used as a suitable reservoir in which certain chemicals can be stored whereas the molecules grafted in the outer surface act as a “gate” and can control the release of the entrapped molecules at will. Both components are carefully selected and arranged in order to achie…

A new proposal for the determination of polychlorinated biphenyls in environmental water by using host-guest adsorption

Abstract Polychlorinated biphenyls (PCBs) are ubiquitous environmental pollutants whose wide industrial use has been banned over the years in most countries due to their persistence and bioaccumulation. In fact, the International Agency for Research on Cancer defined them in 2016 as carcinogenic to humans based on sufficient evidence of an increased risk of cancer, being children and pregnant or lactating women the most vulnerable population subgroups. In this work, a new alternative for the determination of polychlorinated biphenyls (PCB28, PCB52, PCB101, PCB138, PCB153, and PCB180) in water samples has been developed by using a cyclodextrin-containing silica microparticulated material as …

Synthesis and crystal structure of α-NH4(VO2)(HPO4)

Abstract Hydrothermal synthesis starting from β-NH 4 (VO 2 )(HPO 4 ) leads to α-NH 4 (VO 2 )(HPO 4 ): orthorhombic, space group Pb 2 1 a ; Z = 4; a = 6.830(1) A, b = 9.233(2) A, c = 8.817(2) A; R = 0.037 for 3371 reflections. NH + 4 cations connect isolated chains of trans -corner sharing VO 5 square pyramids running along the a -axis. The a -phase transforms irreversibly into the β-form by heating near 200°C. Comparison is made between the two phases.

Enzyme-responsive silica mesoporous supports capped with azopyridinium salts for controlled delivery applications

11 páginas, 7 figuras, 3 tablas y 2 esquemas

Enhanced surface area in thermally stable pure mesoporous TiO2

Abstract We describe here for the first time the surfactant-assisted synthesis of thermally stable mesoporous pure TiO 2 having a high surface area. Our synthetic approach to the chemistry of this system is based on the equilibrium between the hydrolysis and condensation reactions of the inorganic species and the organic–inorganic self-assembling processes. The use of titanatrane complexes helps to retard the hydrolysis and condensation reactions, thus allowing us to overcome the difficulties in preparing titanium dioxide mesoporous materials starting from highly reactive Ti-alkoxides. The mesoporous material has been characterized by TEM, XRD and N 2 adsorption–desorption isotherms and dis…

Poly(N-isopropylacrylamide)-gated Fe3O4/SiO2 core shell nanoparticles with expanded mesoporous structures for the temperature triggered release of lysozyme

Core-shell nanoparticles comprised of Fe3O4 cores and a mesoporous silica shell with an average expanded pore size of 6.07 nm and coated with a poly(N-isopropylacrylamide) (PNIPAM) layer (CS MSNs EP PNIPAM) were prepared and characterized. The nanoparticles was loaded with (Ru(bipy)3 2+) dye or an antibacterial enzyme, lysozyme, to obtain CS MSNs EP PNIPAM Ru(bipy)3 2+ and CS MSNs EP PNIPAM Lys, respectively. The lysozyme loading was determined to be 160 mg/g of nanoparticle. It was seen that Ru(bipy)3 2+ and lysozyme release was minimal at a room temperature of 25 ºC while at physiological temperature (37 º C), abrupt release was observed. The applicability of the CS MSNs EP PNIPAM Lys was…

Use of Silica Based Materials as Modulators of the Lipase Catalyzed Hydrolysis of Fats under Simulated Duodenal Conditions

[EN] The effect of silica materials and their functionalization in the lipase catalyzed fat hydrolysis has been scarcely studied. Fifteen silica materials were prepared and their effect on the fat hydrolysis was measured, under simulated duodenal conditions, using the pH-stat method. The materials are composed of the combination of three supports (Stober massive silica nanoparticles, Stober mesoporous nanoparticles and UVM-7) and four surface functionalizations (methyl, trimethyl, propyl and octyl). In addition, the non-functionalized materials were tested. The functional groups were selected to offer a hydrophobic character to the material improving the interaction with the fat globules an…

The First Pure Mesoporous Aluminium Phosphonates and Diphosphonates − New Hybrid Porous Materials

Organophosphorus moieties have been incorporated into mesoporous ALPOs through a one-pot surfactant-assisted procedure leading, for the first time, to periodic mesoporous aluminium phosphonates and diphosphonates. The number of organic groups on the surface or in the network can be modulated continuously up to the maximum incorporation level of the respective organophosphorus entities (100 %). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Incorporation of Mn12single molecule magnets into mesoporous silica

The incorporation of four Mn12 derivatives, namely [Mn12O12(O2CR)16(H2O)4] (R = CH3 (1), CH3CH2 (2), C6H5 (3), C6F5 (4)), into the hexagonal channels of the MCM-41 mesoporous silica has been studied. Only the smallest clusters 1 and 2, i.e. those with compatible size with the pores of MCM-41, could enter into the mesoporous silica. Powder X-ray diffraction analysis, HRTEM images and N2 adsorption–desorption isotherm experiments show that the well-ordered hexagonal structure of MCM-41 is preserved and that the Mn12 clusters are inside the pores. The magnetic properties of the MCM-41/2b nanocomposite material obtained in CH2Cl2 indicate that the structure of the cluster is maintained after in…

Heterogeneous Gold Catalyst: Synthesis, Characterization, and Application in 1,4-Addition of Boronic Acids to Enones

The new 1 wt % Au/TiO2–UVM-7 catalyst was prepared and fully characterized. This heterogeneous catalyst proved to be active, selective and recyclable for the unprecedented gold-catalyzed 1,4-addition of various functionalized arylboronic acids to 2-cyclohexen-1-one and other selected enones using toluene as a solvent. The gold-based catalyst was recycled two times and played an active role in this reaction, and the nature of the solvent determined a remarkable change in the products’ selectivities.

New heterogeneous catalysts for greener routes in the synthesis of fine chemicals

Abstract New strong Lewis acid SnTf-MCM-41 and SnTf-UVM-7 catalysts with unimodal and bimodal pore systems were prepared in a two-step synthesis in which the triflic acid (Tf) was incorporated to previously synthesized mesoporous tin-containing silicas. The Sn incorporation inside the pore walls was carried out through the Atrane method. The SnTf-UVM-7 catalysts were prepared by aggregating nanometric mesoporous particles defining a hierarchic textural-type additional pore system. Following these procedures, catalysts with different Si/Sn ratios—21.8 to 50.8 for SnTf-MCM-41 and 18.4 for SnTf-UVM-7—were prepared. These new materials were tested in the acylation of aromatic sulfonamides using…

New tubular transition metal oxoanionic derivatives: a systematic approach to condensed phases of the dumortierite family

Abstract An unified synthetic approach has allowed us to isolate a wide set of highly condensed oxoanionic derivatives of transition metals by using solution chemistry procedures. New phases are described [Ni 12+ x H 6−2 x (AsO 4 ) 8 (OH) 6 . Ni 6 (SeO 3 ) 4 (OH) 4 ], and the preparation of other already known [Ni 12+ x H 6−2 x (PO 4 ) 8 (OH) 6 , Ni 3 Te 2 O 6 (OH) 2 ] is significantly simplifi ed. The structure of these derivatives, as well as that of other phases such as M 11 (HPO 3 ) 8 (OH) 6 (M=Zn, Co, Ni), previously characterized by us, can be related to that of the dumortierite mineral. The main features of the tubular channels that characterize this structure and the possibility to …

Layered-Expanded Mesostructured Silicas: Generalized Synthesis and Functionalization

Mesostructured layered silicas have been prepared through a surfactant-assisted procedure using neutral alkylamines as templates and starting from atrane complexes as hydrolytic inorganic precursors. By adjusting the synthetic parameters, this kinetically controlled reproducible one-pot method allows for obtaining both pure and functionalized (inorganic or organically) lamellar silica frameworks. These are easily deconstructed and built up again, which provides a simple way for expanding the interlamellar space. The materials present high dispersibility, which results in stable colloidal suspensions.

Caspase 3 Targeted Cargo Delivery in Apoptotic Cells Using Capped Mesoporous Silica Nanoparticles

[EN] Excessive apoptotic cell death is at the origin of several pathologies, such as degenerative disorders, stroke or ischemia-reperfusion damage. In this context, strategies to improve inhibition of apoptosis and other types of cell death are of interest and may represent a pharmacological opportunity for the treatment of cell-death-related disorders. In this scenario new peptide-containing delivery systems (solids S1-P1and S1-P2) are described based on meso-porous silica nanoparticles (MSNs) loaded with a dye and capped with the KKGDEVDKKARDEVDK (P1) peptide that contains two repeats of the DEVD target sequence that are selectively hydrolyzed by caspase3 (C3). This enzyme plays a central…

An aptamer-gated silica mesoporous material for thrombin detection.

An aptamer-capped mesoporous material for the selective and sensitive detection of &-thrombin in human plasma and serum has been prepared and characterised.

Surfactant-Assisted Synthesis of Mesoporous Alumina Showing Continuously Adjustable Pore Sizes

Porous materials displaying tailor-made pore sizes and shapes are particularly interesting in a great variety of real and potential applications where molecular recognition is needed, such as shape-selective catalysis, molecular sieving, and selective adsorption. Classically, apart from silica, materials most commonly used for catalysis and catalyst supports have been those based on high surface aluminas, owing to their thermal, chemical, and mechanical stability and their low cost. Earlier aluminas with high surface areas (~500 m/g) had been prepared using structure-directing agents. However, they were X-ray amorphous materials and their porosity was purely textural, characterized by wide …

Tetrathiafulvalene-Capped Hybrid Materials for the Optical Detection of Explosives

[EN] Mesoporous silica microparticles capped with TTF moieties and containing a ruthenium dye in the pores were used for the turn-on optical detection of the nitroaromatic explosives Tetryl and TNT via a selective pore uncapping and release of the entrapped dye.

Synthesis and crystal structure of Na1+xV4P4O17(OH) (x ≈ 1.44)

Abstract Hydrothermal synthesis starting from Na0.46VOPO4 · 1.58H2O leads to a new mixed-valence sodium vanadium phosphate: Na2.44V4P4O17(OH) (orthorhombic, space group Pnma; Z = 4; a = 13.723(5) A, b = 6.314(2) A, c = 16.139(4) A; R = 0.032 for 2659 reflections). In this phase, the interconnection of three complex types of infinite chains, built from VO6 octahedra and PO4 tetrahedra, sometimes edgeshared, defines tunnels partly occupied by a portion of the sodium atoms.

Towards the Loewenstein limit (Si/Al = 1) in thermally stable mesoporous aluminosilicates

The use of complexing agents to generate polynuclear precursor species containing both Al and Si allows the synthesis of thermally stable mesoporous aluminosilicates including solely tetrahedrally coordinated aluminium, in which the Si/Al ratio can be modulated down to a minimum Si/Al value of 1.06(4). Cabrera Medina, Saul, Saul.Cabrera@uv.es ; El Haskouri, Jamal, Jamal.Haskouri@uv.es ; Latorre Saborit, Julio, Julio.Latorre@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Amidase-responsive controlled release of antitumoral drug into intracellular media using gluconamide-capped mesoporous silica nanoparticles

MCM-41 silica nanoparticles were used as inorganic scaffolding to prepare a nanoscopic-capped hybrid material S1, which was able to release an entrapped cargo in the presence of certain enzymes, whereas in the absence of enzymes, a zero release system was obtained. S1 was prepared by loading nanoparticles with Safranine O dye and was then capped with a gluconamide derivative. In the absence of enzymes, the release of the dye from the aqueous suspensions of S1 was inhibited as a result of the steric hindrance imposed by the bulky gluconamide derivative, the polymerized gluconamide layer and the formation of a dense hydrogen-bonded network around the pore outlets. Upon the addition of amidase…

Temperature-controlled release by changes in the secondary structure of peptides anchored onto mesoporous silica supports

Changes in the conformation of a peptide anchored onto the external surface of mesoporous silica nanoparticles have been used to design novel temperature-controlled delivery systems.

Stable anchoring of dispersed gold nanoparticles on hierarchic porous silica-based materials

The nanometric organization of MOx (M = Co, Zn, Ni) domains partially embedded inside the mesoporous silica walls but accessible to the pore voids, which is achieved through a simple one-pot surfactant-assisted procedure, define optimal anchors for the nucleation and growth of gold nanoparticles, which in turn favours an exceptional thermal stability for the final Au-supported materials. As silica support we have selected a UVM-7 silica having a highly accessible architecture defined by two hierarchic pore systems. The combination of nanometric pore length, tortuous mesopores and MOx inorganic anchors favours the stability of the final Au/CoOx-UVM-7 nanocomposites.

Silica-based powders and monoliths with bimodal pore systemsElectronic supplementary information (ESI) available: UV–Vis spectrum of sample 3. See http://www.rsc.org/suppdata/cc/b1/b110883b/

Porous pure and doped silicas with pore sizes at two length scales (meso/macroporous) have been prepared and shaped both as powders and monoliths through a one-pot surfactant assisted procedure by using a simple template agent and starting from atrane complexes as inorganic precursors.

Epoxidation of dibenzocycloalkenes on Ti–Ge-MCM-41 and Ti-SBA-15 catalysts

Abstract Epoxidation of a series of dibenzocycloalkenes: phenanthrene, 5H-dibenzo[ a , e ]cycloheptene, 5H-dibenzo[ a , c ] cycloheptene, 5,6-dihydrodibenzo[ a , e ]cyclo-octene, and dibenzo[ a , e ]cyclooctene with hydrogen peroxide was investigated on Ti- and Ge-modified Ti-incorporated-type mesoporous catalysts including MCM-41 and SBA-15 structures looking for the effect of the porous texture and Ge-promoting on both activity and selectivity to epoxide and H 2 O 2 efficiency. Ti–Ge-MCM-41 catalysts (Si/Ti = 43; Si/Ge = 85 and Si/Ti = 41; Si/Ge = 62) were prepared by a one-pot surfactant-assisted procedure based on the use of a cationic surfactant (CTAB, cetyltrimethylammonium bromide), …

Efficient Sc triflate mesoporous-based catalysts for the synthesis of 4,4′-methylenedianiline from aniline and 4-aminobenzylalcohol

Abstract Sc triflate mesoporous-based catalysts have been prepared using a two-step strategy (i.e., Atrane method) based on the formation of the hierarchic bimodal porosity in the first step and the formation of Sc triflate complexes at the materials surface in the second step. All solids were analyzed by EPMA, surface area, and pore size values, XRD, TEM, FTIR, and 45Sc NMR static spectra. The catalysts have been investigated in the synthesis of 4,4′-methylenedianiline (4,4′-MDA) from aniline and 4-aminobenzylalcohol. 4,4′-MDA was obtained with selectivities over 85.0% for a conversion of aniline of 31%, at 80 °C and after 24 h. Using microwaves, selectivities of 90% in 4,4′-MDA were reach…

High content and dispersion of Gd in bimodal porous silica: T2 contrast agents under ultra-high magnetic fields

Silica-based UVM-7-type bimodal mesoporous materials with high gadolinium content (∞ ≥ Si/Gd ≥ 13) have been synthesized through a one-pot surfactant-assisted procedure from hydroalcoholic solution using a cationic surfactant as template, and starting from atrane complexes of Gd and Si as inorganic precursors. The novel synthetic pathway developed in the study preserves the UVM-7-type architecture while optimizing the dispersion of the Gd-guest species at the nanoscale and even at atomic level. It has been determined that the number of Gd atoms forming clusters is always less than 10. The behaviour under exposure to ultra-high magnetic fields reveals a significant increase in the transversa…

High-Temperature Stable Gold Nanoparticle Catalysts for Application under Severe Conditions: The Role of TiO2 Nanodomains in Structure and Activity

Metal nanoparticles with precisely controlled size are highly attractive for heterogeneous catalysis. However, their poor thermal stability remains a major concern in their application at realistic operating conditions. This paper demonstrates the possibility of synthesizing gold nanoparticles with exceptional thermal stability. This has been achieved by using a simple conventional deposition–precipitation technique. The material employed as catalyst consists of gold supported on a TiO2-impregnated SiO2 bimodal mesoporous support. The resulting material shows gold nanoparticles with a narrow size distribution around 3.0 nm, homogeneously dispersed over the TiO2/SiO2 material. Most interesti…

Nano-sized mesoporous carbon particles with bimodal pore system and semi-crystalline porous walls

Acetylene CVD carbon replication of a hierarchical pore silica-based material, Fe-UVM-7, is reported. The original template organization, which is based on the aggregation of mesoporous nanoparticles, is accurately replicated in the final carbon material: a bimodal porous carbon combining mesoporous nanoparticles and inter-particle textural-like pores which provide high surface area, a highly accessible pore system and semi-crystalline pore walls in the form of graphitic-like nanodomains is presented.

High‐Zirconium‐Content Nano‐Sized Bimodal Mesoporous Silicas

Silica-based nanoparticulated bimodal mesoporous materials with high Zr content (43 ≥ Si/Zr ≥ 4) have been synthesized by a one-pot surfactant-assisted procedure from a hydroalcoholic medium using a cationic surfactant (CTMABr = cetyltrimethylammonium bromide) as structure-directing agent, and starting from molecular atrane complexes of Zr and Si as hydrolytic inorganic precursors. This preparative technique allows optimization of the dispersion of the Zr guest species in the silica walls. The bimodal mesoporous nature of the final high surface area nano-sized materials is confirmed by XRD, TEM, and N2 adsorption–desorption isotherms. The small intraparticle mesopore system (with pore sizes…

New Methods for Anion Recognition and Signaling Using Nanoscopic Gatelike Scaffoldings

Comparison of the solid-phase extraction efficiency of a bounded and an included cyclodextrin-silica microporous composite for polycyclic aromatic hydrocarbons determination in water samples.

Solid-phase extraction is one of the most important techniques for sample purification and concentration. A wide variety of solid phases have been used for sample preparation over time. In this work, the efficiency of a new kind of solid-phase extraction adsorbent, which is a microporous material made from modified cyclodextrin bounded to a silica network, is evaluated through an analytical method which combines solid-phase extraction with high-performance liquid chromatography to determine polycyclic aromatic hydrocarbons in water samples. Several parameters that affected the analytes recovery, such as the amount of solid phase, the nature and volume of the eluent or the sample volume and …

Comparison of silica-based materials for organophosphorus pesticides sampling and occupational risk assessment.

Abstract A novel air sampler has been designed containing a sorbent based on UVM-7 mesoporous silica doped with Ti. The sorbent has been applied for the determination of organophosphorus pesticides in occupational air, followed by gas chromatography with mass spectrometry detection. Thus, several silica materials with different structures (mesoporous UVM-7 and microporous xerogels) were synthesized, and modified with the addition of Ti and Fe. The structure of these materials was proved by transmission electronic microscopy, energy-dispersive X-ray, X-ray diffraction, nitrogen adsorption-desorption and UV–Vis and Raman spectroscopy. The potential of these materials for the retention of pest…

Refractive index controlled by film morphology and free carrier density in undoped ZnO through sol-pH variation

Abstract Zinc oxide thin films, prepared by the sol-gel process, were deposited on glass substrate using spin coating technique. The sol-pH effect on the optical parameters was studied for alkaline sol. The surface roughness was investigated by atomic force microscopy (AFM) and varied from 20 to 40 nm. The optical transmission measurements were carried out to evaluate the behavior of the extinction coefficient and the refractive index. An exponential decay of the refractive index ‘n’ as a function of wavelength was observed. The refractive index increases slightly when the pH increases to pH = 9.5 where it reaches its maximum. Beyond this value, it decreases sharply. This behavior has been …

Scale-up low-cost synthesis of bimodal mesoporous silicas

Porous pure and doped silicas with pore sizes at two length scales (meso/macroporous) have been prepared through a large scale one-pot surfactant assisted reproducible procedure by using a simple template agent and starting from non-expensive sodium silicate as silicon source. Together with the relative low-cost of the reagents we have used, the simplicity of this method, which moreover is scalable and provides high yields, could be a strong argument for considering its suitability for the production of bimodal porous silicas. Additionally, we present a simple chemical scheme that allows directing the synthesis towards different related materials including both bimodal nanoparticulated meso…

Encapsulation of folic acid in different silica porous supports: A comparative study.

Although folic acid is essential to numerous bodily functions, recent research indicates that a massive exposition to the vitamin could be a double-edged sword. In this study, the capacity of different caped mesoporous silica particles (i.e. Hollow Silica Shells, MCM-41, SBA-15 and UVM-7) to dose FA during its passage through the gastrointestinal tract has been evaluated. Results confirmed that the four capped materials were capable to hinder the delivery of FA at low pH (i.e. stomach) as well as able to deliver great amounts of the vitamin at neutral pH (i.e. intestine). Nevertheless, the encapsulation efficiency and the deliver kinetics differed among supports. While supports with large p…

One‐Pot Synthesis of Superparamagnetic CoO‐MCM‐41 Nanocomposites with Uniform and Highly Dispersed Magnetic Nanoclusters

Superparamagnetic CoO-MCM-41 mesoporous nanocomposites, with variable cobalt amounts, in the form of well-dispersed CoO-like clusters, were prepared in a large compositional range by a one-step reproducible procedure employing co-hydrolysis and co-condensation of the inorganic precursors in a water/triethanolamine medium. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Theoretical study of oligomeric alumatranes present in the chemistry of materials from micro to mesoporous molecular sieves and alumina composites

Quantum chemical calculations using density functional theory have been carried out to investigate molecular precursors based on alumatranes which are one of the components with silatranes for the preparation of mesoporous aluminosilicate materials. In the same way, some oligomeric alumatranes of this study take part in chemical syntheses related to materials such as zeolites and alumina composite. Gas phase and solution equilibrium geometries of the alumatrane precursors were fully optimized at B3LYP level, modeling solvent effects using a self-consistent reaction field (SCRF). From these optimized geometries, calculations of the 1 H, 13 C and 27 Al NMR chemical shifts at GIAO/B3LYP/6-31G(…

Bases for the synthesis of nanoparticulated silicas with bimodal hierarchical porosity

Porous silicas with pore sizes at two length scales (meso and large meso/macroporous) have been prepared through a one-pot surfactant assisted procedure by using a simple template agent and starting from silicon atrane complexes as hydrolytic inorganic precursors. The special organization of these bimodal porous silicas can be related to the nanometric character of their constituent mesoporous particles. Whereas the small intra-particle mesopore system is generated by the templating effect of the surfactant, the large pore system is defined by inter-particle voids. We have studied the effect of different procedural parameters on the small pore system and also on the nucleation and growth of…

Novel Phases in the V-P-O Catalytic System from Oxovanadium Hydrogenphosphate Precursors

ABSTRACTSeveral biphasic VOP04/(VO)2P2O7 redox partners seem to be active in the catalytic cycles involved in the mild oxidation of simple hydrocarbons to maleic anhydride. The present X-ray time resolved thermal-diffractometric study reveals the existence of a new anhydrous variety of the oxidized form, ω-VOPO4, which may appear as an intermediate in the formation of the well known β-VOPO4. This new phase only remains well crystallized at relatively high temperatures, and when it is allowed to cool down in wet air VOPO4·2H2O results. In turn, another well defined phase, VOPO4·1.58H2O, can be recognized in the course of the hydration process.

Design of enzyme-mediated controlled release systems based on silica mesoporous supports capped with ester-glycol groups

[EN] An ethylene glycol-capped hybrid material for the controlled release of molecules in the presence of esterase enzyme has been prepared. The final organic-inorganic hybrid solid S1 was synthesized by a two-step procedure. In the first step, the pores of an inorganic MCM-41 support (in the form of nanoparticles) were loaded with [Ru(bipy) 3]Cl 2 complex, and then, in the second step, the pore outlets were functionalized with ester glycol moieties that acted as molecular caps. In the absence of an enzyme, release of the complex from aqueous suspensions of S1 at pH 8.0 is inhibited due to the steric hindrance imposed by the bulky ester glycol moieties. Upon addition of esterase enzyme, del…

Anthrylmethylamine functionalised mesoporous silica-based materials as hybrid fluorescent chemosensors for ATP

A number of functionalised mesoporous solids containing anchored anthrylmethylamine groups have been prepared using different co-hydrolysis or grafting synthetic routes. The solids have been characterised using standard solid-state techniques. Solids with a low loading of the anthrylmethylamine probe show typical well defined and structured emission bands centred at ca. 415 nm. Addition of ATP to suspensions of these solids at pH 2.8 resulted in a quenching of the anthracene emission. These solids showed a cooperative effect that resulted in quite a remarkable improvement in ATP response with respect to the free anthrylmethylamine probe in solution. Certain prepared solids showed a remarkab…

A New Approach to Chemosensors for Anions Using MCM-41 Grafted with Amino Groups

Mesoporous silica microparticles gated with a bulky azo derivative for the controlled release of dyes/drugs in colon.

[EN] Mesoporous silica microparticles were prepared, loaded with the dye safranin O (M-Saf) or with the drug budesonide (M-Bud) and capped by the grafting of a bulky azo derivative. Cargo release from M-Saf at different pH values (mimicking those found in the gastrointestinal tract) in the absence or presence of sodium dithionite (a reducing agent mimicking azoreductase enzyme present in the colon) was tested. Negligible safranin O release was observed at pH 6.8 and 4.5, whereas a moderate delivery at pH 1.2 was noted and attributed to the hydrolysis of the urea bond that linked the azo derivative onto the external surface of the inorganic scaffold. Moreover, a marked release was observed w…

Preparation of multi-nanocrystalline transition metal oxide (TiO2–NiTiO3) mesoporous thin films

Ordered mesoporous TiO2–NiTiO3 thin films, with nickel content x < 0.5, were prepared by dip-coating an acidic solution of hydrolysed transition metal chlorides in controlled humidity, followed by a very careful annealing treatment. These latter treatments were studied by in situ SAXS-WAXS experiments involving synchrotron radiation and TEM analysis. They revealed that the walls can be composed of amorphous, single crystalline or multi crystalline nanoparticles depending on x and the conditions applied during the thermal treatment.

Magnetic and structural approach for understanding the electrochemical behavior of LiNi0.33Co0.33Mn0.33O2 positive electrode material

Abstract A systematic study has been performed to investigate the structural and magnetic changes in LiNi 0.33 Mn 0.33 Co 0.33 O 2 , a member of the LiNi y Mn y Co 1–2 y O 2 series, upon chemical lithium deintercalation. Structural characterization of the chemically delithiated Li x Ni 0.33 Mn 0.33 Co 0.33 O 2 samples indicates that the initial rhombohedral symmetry (α-NaFeO 2 type structure) is maintained in the whole 0.3 ≤  x  ≤ 1.0 composition range. Less than 1% variation in the hexagonal unit cell volume was evidenced showing a good structural stability of this sample. SEM pictures of the delithiated phases confirm this stability. Indeed, the particle size average undergoes a small dec…

Organic-Inorganic Hybrid Mesoporous Materials as Regenerable Sensing Systems for the Recognition of Nitroaromatic Explosives

[EN] Fluorescent organic-inorganic mesoporous hybrid materials have been prepared and characterised, and their behaviour against nitroaromatic explosives have been tested. MCM-41 silica was used as an inorganic scaffold and pyrene (P derivative containing trialkoxysilane moieties), dansyl and fluorescein (D and F derivatives also containing trialkoxysilane groups, respectively) fluorophores have been anchored on hybrid materials by a co-condensation method to obtain a homogenous distribution of dyes into the pores of the support. Six sensing materials have been prepared, of which SP, SD, SF were hydrophilic and SPh, SDh, SFh were hydrophobic. Template-free hydrophilic materials (SP, SD, SF)…

Selektiver, hoch empfindlicher und schneller Nachweis genomischer DNA mit gesteuerten Materialien am Beispiel vonMycoplasma

[DE] Mit DNA verschlossene und mit Farbstoff beladene mesoporöse Siliciumdioxid-Nanopartikel wurden zum Nachweis von Mycoplasma bis zu einer Nachweisgrenze von ca. 70 genomischen DNA-Kopien pro mu-L in real kontaminierten Zellkulturmedien ohne die Hilfe von PCR-Techniken eingesetzt.

Über den chemischen Informationsaustausch zwischen gesteuerten Nanopartikeln

Das Design von vergleichsweise einfachen und modular konfigurierbaren k nstlichen Systemen, die ber den Austausch von chemischen Botenstoffen miteinander kommunizieren kçnnen, ist unseres Wissens ein bislang unerforschtes Gebiet. In einer grundlegenden Arbeit pr sentieren wir hier eine Serie von Nanopartikeln, die in hierarchischer Art und Weise miteinander kommunizieren kçnnen. Das Konzept beruht auf gedeckelten mesoporçsen Silikat-Tr gern, bei denen der aus einem ersten Typ von gesteuerten Nanopartikeln freigesetzte chemische Botenstoff einen zweiten Typ von gedeckelten Nanopartikeln çffnet, welche wiederum einen anderen Botenstoff freisetzen, die eine dritte Gruppe von gesteuerten Nanoob…

Fluorogenic detection of Tetryl and TNT explosives using nanoscopic-capped mesoporous hybrid materials

[EN] A hybrid capped mesoporous material, which was selectively opened in the presence of Tetryl and TNT, has been synthesised and used for the fluorogenic recognition of these nitroaromatic explosives.

Selective and Sensitive Chromofluorogenic Detection of the Sulfite Anion in Water Using Hydrophobic Hybrid Organic-Inorganic Silica Nanoparticles

[EN] In water and wine: Chromofluorogenic detection of the sulfite anion in pure water was accomplished by using a new hybrid organic-inorganic material that contained a probe entrapped in hydrophobic biomimetic cavities. This material was used for the detection of sulfite in red wine. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective oxidative activation of isobutane on a novel vanadium-substituted bimodal mesoporous oxide V-UVM-7

Abstract New vanado-silicates with a bimodal mesoporous system (V-UVM-7) and high vanadium contents (Si/V ≥ 7) have been prepared by a modification of the so-called atrane method. Its morphology consists of aggregation of nano-particles with V-MCM-41 structure, creating a second broader porous system in their interparticle space. Its structure allows to incorporate a high V contents into tetrahedral sites of the framework while keeping vanadium dispersion. V-UVM-7 catalysts are very active and selective for the direct transformation of isobutane to isobutene and methacrolein. Total conversion and methacrolein-to-isobutene ratio in the products increased with increasing vanadium contents. Th…

Fluorogenic Sensing of Carcinogenic Bisphenol A using Aptamer-Capped Mesoporous Silica Nanoparticles

[EN] Mesoporous silica nanoparticles loaded with rhodamine B and capped with a bisphenol A aptamer were used for the selective and sensitive detection of this lethal chemical. The pores of the nanoparticles are selectively opened in the presence of bisphenol A (through its selective coordination with the aptamer) with subsequent rhodamine B delivery. With this capped material a limit of detection as low as 3.5 mu m of bisphenol A was measured.

Fatty Acid Carboxylate- and Anionic Surfactant-Controlled Delivery Systems That Use Mesoporous Silica Supports

We report the preparation of a MCM-41 mesoporous material that contains the dye [Ru(bipy) 3 ]Cl 2 (bipy= bipyridine) inside the mesopores and functionalised with suitable binding groups at the entrance of the pores. Solids S1―S3 were obtained by the reaction of the mesoporous material with N-methyl-N'-propyltrimethoxysilylimidazolium chloride, N-phenyl-N'-[3-(trimethoxysilyl)propyl]thiourea, or N-phenyl-N'-[3-(trimethoxysilyl)propy1]urea, respectively. A study of the dye delivery of these systems in buffered water (pH 7.0, 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid (HEPES), 10 ―3 mol dm ―3 ) in the presence of a family of carboxylate ions was carried out. In the interaction of …

Design, characterization and comparison of materials based on β and γ cyclodextrin covalently connected to microporous silica for environmental analysis

Abstract Determination of organic pollutants in environmental samples presents great difficulties due to the lack of sensitivity and selectivity in many of the existing analytical methods. In this work, the efficiency of materials based on silica structures containing bounded γ-cyclodextrin has been evaluated to determinate phenolic compounds and polycyclic aromatic hydrocarbons in air and water samples, respectively, in comparison with materials made of β-cyclodextrin. According to the results obtained for the material characterization, the new γ-cyclodextrin solid phase does not apparently present any porosity when used in air samples, but it has been shown to work efficiently for the pre…

X-ray powder diffraction data for some transition metal phosphites and hypophosphites

A set of nine transition metal oxophosphorous compounds, consisting of four hypophosphites and five phosphites has been synthesized and studied using X-ray powder diffraction techniques. The compounds are α-Mn(H2PO2)2·H2O, Co(H2PO2)2 ·0.53H2O, MCl(H2PO2)2·H2O (M = Co2+, Ni2+), M2(HPO3)2·2H2O (M = Co2+, Ni2+), and M11 (HPO3)8(OH)6 (M = Zn2+, Co2+, Ni2+). Unit cells and X-ray powder patterns are reported.

Synthesis, characterization and catalytic behavior of AlTf/UVM-7 as new green catalysts for the glycols etherification reactions

Abstract Bimodal porous Al–UVM-7 system materials with different Si-to-Al ratios were prepared using the Atrane route. These were converted in strong acid heterogeneous AlTf-based catalysts after the treatment with methanolic solutions of triflic acid. The materials so obtained were used as catalysts for the conversion of ethylene glycol (EG) and propylene glycol (PG) with octanol under solvent-free conditions. The process is selective to short ethoxylated structures resulting in the corresponding monoethers. While the conversion of EG and PG was very high (>94%) irrespective of the support characteristics, 1-octanol was transformed only in low degree (3–35%), and its conversion depends on …

Combination of silica nanoparticles with hydroxyapatite reinforces poly (l-lactide acid) scaffolds without loss of bioactivity

Composite scaffolds of poly(l-lactide acid) and hydroxyapatite are of great interest in bone tissue engineering, but their mechanical properties are typically inferior to scaffolds of pure poly(l-lactide acid) due to agglomeration of the particles and weak interfacial component interaction. Fabrication strategies like double sonication of hydroxyapatite or increasing the amount of this inorganic filler do not effectively enhance the mechanical performance. In this study, poly(l-lactide acid) composites combining two types of fillers, mesoporous silica (SiO2) nanoparticles and hydroxyapatite, were developed to reinforce the poly(l-lactide acid) scaffold without any loss of bioactivity. A 5%…

Enzyme-Responsive Controlled Release Using Mesoporous Silica Supports Capped with Lactose

Crystal structure and magnetism of Co(HPO3)⋅H2O : A novel layered compound of Co(II)

Under the terms of the Creative Commons Attribution (CC BY) license to their work.-- et al.

Heterogeneous oxidation of pyrimidine and alkyl thioethers in ionic liquids over mesoporous Ti or Ti/Ge catalysts.

Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)-imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions p…

Controlled delivery using oligonucleotide-capped mesoporous silica nanoparticles.

Control of the pore wall thickness and thermal stability in low-cost bimodal porous silicas

Abstract A new hierarchical bimodal mesoporous silica, labelled as UVM-12 (acronym of University of Valencia Materials), has been prepared by using a solution of sodium silicate as low-cost silicon source. The final self-assembling between cationic micelles of CTAB and anionic inorganic Si-based oligomers occurs in a homogeneous aqueous medium. The reaction is carried out from low-sized building blocks through a bottom-up approach. The UVM-12 solids combine two mesopore systems according to N2 adsorption–desorption isotherms, what is corroborated by TEM micrographs and XRD patterns. This material has been inorganically modified by incorporation of Al or Ti (M-UVM-12, M = Al, Ti) without alt…

Mn 12 single-molecule magnets incorporated into mesoporous MCM-41 silica

Abstract The incorporation of four Mn12 derivatives, namely [Mn12O12(O2CR)16(H2O)4] (R=CH3 (1), CH3CH2 (2), C6H5 (3), C6F5 (4)), into the hexagonal channels of the MCM-41 mesoporous silica have been studied. Only the smallest clusters 1 and 2 that are those with compatible size with the pores of MCM-41 could be incorporated into the mesoporous silica. Powder X-ray diffraction (XRD) analysis and N2 adsorption–desorption isotherm experiments show that the well-ordered hexagonal structure of MCM-41 is preserved and that the Mn12 clusters are inside the pores. The magnetic properties of the MCM-41/1 nanocomposite material indicate that the structure of the cluster is maintained after incorporat…

Samplers for VOCs in air based on cyclodextrin–silica hybrid microporous solid phases

Samplers for VOCs in air based on cyclodextrin-silica hybrid microporous solid phases are proposed. The solid phase preparation is very easy and inexpensive. Proposed samplers compared with other solid phases present the advantages of a wider range of operative conditions for VOCs desorption. Samplers are tested based on results for the determination of benzene, toluene, ethylbenzene and o-xylene, m-xylene and p-xylene (BTEX) in air. Operational parameters are optimized and quantitative recovery is obtained using a solid phase from 2-hydroxypropyl-β-cyclodextrin and acetonitrile as the extraction solvent. The recoveries obtained are 89 ± 4%, 90 ± 6%, 91 ± 2%, 87.0 ± 0.9%, 88 ± 4%, and 88 ± …

Sensory hybrid host materials for the selective chromo-fluorogenic detection of biogenic amines

[EN] Pyrylium-containing mesoporous materials have been used for the chromo-fluorogenic sensing of biogenic amines in an aqueous environment.

Biomimetic chitosan-mediated synthesis in heterogeneous phase of bulk and mesoporous silica nanoparticles

Both bulk and mesoporous silica nanoparticles can be obtained in the form of granular aggregates using chitosan flakes as additive under very soft biomimetic reaction conditions. Puchol Estors, Victoria, Victoria.Puchol@uv.es ; El Haskouri, Jamal, Jamal.Haskouri@uv.es ; Latorre Saborit, Julio, Julio.Latorre@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Tuning the pore size from micro- to meso-porous in thermally stable aluminophosphates

Thermally stable porous aluminophosphates (ICMUV-3) with P/Al molar ratios in the range 0.15 <= P/Al <= 0.75 and showing continuously adjustable pore sizes from 13 to 37 Å have been prepared through a surfactant-assisted procedure without changing the surfactant length and/or addition of organic expansors. Cabrera Medina, Saul, Saul.Cabrera@uv.es ; El Haskouri, Jamal, Jamal.Haskouri@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Supplementary Material from Mesoporous silica microparticles gated with a bulky azo derivative for the controlled release of dyes/drugs in colon

Mesoporous silica microparticles were prepared, loaded with the dye safranin O (M-Saf) or with the drug budesonide (M-Bud) and capped by the grafting of a bulky azo derivative. Cargo release from M-Saf at different pH values (mimicking those found in the gastrointestinal tract (GIT)) in the absence or presence of sodium dithionite (a reducing agent mimicking azoreductase enzyme present in the colon) was tested. Negligible safranin O release was observed at pH 6.8 and 4.5, whereas a moderate delivery at pH 1.2 was noted and attributed to the hydrolysis of the urea bond that linked the azo derivative onto the external surface of the inorganic scaffold. Moreover, a marked release was observed …

Transition metal derivatives of low oxidation state phosphorus oxoacids: synthetic pathways and structural studies

Abstract A general synthetic approach intended to rationalize the solution preparative chemistry of transition metal phosphites and hypophosphites is presented. As previously shown for other derivatives containing also tetrahedral or pseudotetrahedral oxoanions, the hydrolytic processes affecting the cationic moieties play a determinant role on the very nature of the final solid. In fact, despite the limited number of donor atoms in the anions, the crystal chemistry of these compounds is quite intricate because of both the variety of possible cationic aggregates and the many ways to interconnect them through pseudotetrahedral anionic groups.

ChemInform Abstract: Transition Metal Derivatives of Low Oxidation State Phosphorus Oxoacids: Synthetic Pathways and Structural Studies

Abstract A general synthetic approach intended to rationalize the solution preparative chemistry of transition metal phosphites and hypophosphites is presented. As previously shown for other derivatives containing also tetrahedral or pseudotetrahedral oxoanions, the hydrolytic processes affecting the cationic moieties play a determinant role on the very nature of the final solid. In fact, despite the limited number of donor atoms in the anions, the crystal chemistry of these compounds is quite intricate because of both the variety of possible cationic aggregates and the many ways to interconnect them through pseudotetrahedral anionic groups.

Oxidative dehydrogenation of isobutane over Co-MCM-41 catalysts

Abstract Cobalt-containing mesoporous silicates with MCM-41-like structure, with Si/Co≥49, are active and selective catalysts for the oxidative dehydrogenation (ODH) of isobutane. The formation of dehydrogenation products is analysed in terms of the nature of the cobalt species, tetrahedral Co(II), and heterogeneously initiated gas-phase reactions inside the mesopores.

Supramolecular capping-ligand effect of lamellar silica mesostructures for the one-pot synthesis of highly dispersed ZnO nanoparticles

ZnO?SiO2 lamellar nanocomposites with high zinc content (5?Si/Zn?50) have been synthesized through a one-pot surfactant-assisted procedure from aqueous solution and starting from molecular atrane complexes of Zn and Si as inorganic hydrolytic precursors. This approach allows optimization of the dispersion of the ZnO nanodomains in the silica sheets. The nature of the layered silica materials has been confirmed by x-ray diffraction. Spectroscopic (ultraviolet?visible and photoluminescence) study of these layered silica materials shows that, regardless of the Si/Zn ratio, Zn atoms are organized in well-dispersed, uniform ZnO nanodomains (about 1.2?nm) partially embedded within the silica shee…

Gated mesoporous silica nanoparticles for the controlled delivery of drugs in cancer cells

In recent years, mesoporous silica nanoparticles (MSNs) have been used as effective supports for the development of controlled-release nanodevices that are able to act as multifunctional delivery platforms for the encapsulation of therapeutic agents, enhancing their bioavailability and overcoming common issues such as poor water solubility and poor stability of some drugs. In particular, redox-responsive delivery systems have attracted the attention of scientists because of the intracellular reductive environment related to a high concentration of glutathione (GSH). In this context, we describe herein the development of a GSH-responsive delivery system based on poly(ethylene glycol)- (PEG-)…

Thalassiosira pseudonana diatom as biotemplate to produce a macroporous ordered carbon-rich material

Abstract Ordered macroporous–mesoporous carbonaceous materials were produced as a direct replica of the Thalassiosira pseudonana diatom by infiltration of the skeleton with furfuryl alcohol. The final carbon-rich material preserves the macropores of the diatom acting as bio-template and new hierarchical macro–mesopores appears as the silica is eliminated through chemical etching. The final solid can be described as an organized array of carbon macrotubes. In order to understand the progressive silica etching and the subsequent effect on the final carbon material, different etching reagents have been used. Moreover, the similar pore topology of T. pseudonana and the well known MCM-41 mesopor…

Photochemical and Chemical Two-Channel Control of Functional Nanogated Hybrid Architectures

Prediction of Magnetic Properties in Oxovanadium(IV) Phosphates: The Role of the Bridging PO4 Anions

Oxovanadium phosphates constitute a crystallochemically very rich family that, in turn, results in a seemingly intricate magnetochemistry including from isolated dimers to 3-D systems. This magnetic diversity is due, in part, to the possible participation of phosphate groups in the spin transfer between VIV centers. This way, 31P solid-state NMR becomes a key tool in determining the exchange paths involving phosphorus orbitals. The magnetic behavior of several layered oxovanadium phosphates M(VOPO4)2·4H2O (M = Na+, Ca2+, Ba2+, and Pb2+) has been investigated. Like it occurs in the case of other previously studied lamellar derivatives, the best fit of the temperature-dependent magnetic susce…

Generalised syntheses of ordered mesoporous oxides: the atrane route

Abstract A new simple and versatile technique to obtain mesoporous oxides is presented. While implying surfactant-assisted formation of mesostructured intermediates, the original chemical contribution of this approach lies in the use of atrane complexes as precursors. Without prejudice to their inherent unstability in aqueous solution, the atranes show a marked inertness towards hydrolysis. Bringing kinetic factors into play, it becomes possible to control the processes involved in the formation of the surfactant–inorganic phase composite micelles, which constitute the elemental building blocks of the mesostructures. Independent of the starting compositional complexity, both the mesostructu…

Hybrid materials with nanoscopic anion-binding pockets for the colorimetric sensing of phosphate in water using displacement assays

Mesoporous amino-functionalised solids containing certain dyes have been used as suitable anion hosts in displacement assays for the colorimetric signalling of phosphate in water. Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Ordered mesoporous silicas as host for the incorporation and aggregation of octanuclear nickel(ii) single-molecule magnets: a bottom-up approach to new magnetic nanocomposite materials

Silica-based mesoporous materials have been employed as the support host for a suitably designed small octanuclear nickel(II) guest complex with a moderately anisotropic S = 4 ground spin state (D = −0.23 cm−1), which behaves as a single-molecule magnet at low temperature (TB = 3.0 K). Both unimodal MCM-41 and bimodal UVM-7 porous silica provide appropriate template conditions for the incorporation and aggregation of the Ni8 complex precursor into larger complex aggregates, showing slow relaxation of the magnetization at higher blocking temperatures than the crystalline material. By playing with the initial complex vs. silica concentration, two series of samples with varying complex loading…

Synthesis of a new mesostructured lamellar oxovanadium phosphate assembled through an S+X-I0 Mechanism

A new lamellar mesostructured oxovanadium(V) phosphate, (DDAH)0.9(Cl)0.9VOPO4·1.5H2O (DDA = dodecylamine), has been synthesized through a S+X-I0 cooperative mechanism using protonated dodecylamine ...

Total oxidation of VOCs on Au nanoparticles anchored on Co doped mesoporous UVM-7 silica

Abstract Gold deposited on a cobalt containing siliceous mesoporous structure, UVM-7, presents a good catalytic performance in the total oxidation of propane and toluene. The presence of both gold and cobalt is necessary as bimetallic Au/Co-UVM-7 catalysts are remarkably more active than monometallic Au/UVM-7 or Co-UVM-7 catalysts. The improved activity of the bimetallic AuCo-samples if compared to gold free cobalt catalysts can be explained on the basis of the enhanced reducibility of some cobalt species in the presence of gold, which facilitates the redox cycle. This high reducibility of cobalt species in the bimetallic samples is probably due to the formation of Co 3 O 4 domains at the g…

Crystal structure of a new polytype in the V–P–O system: is ω-VOPO4 a dynamically stabilised metastable network?

Abstract ω-VOPO 4 has been prepared by thermal decomposition of different oxovanadium hydrogen phosphates, namely VO(HPO 4 ) n H 2 O ( n =2( α ), 2(β) and 4) and β-NH 4 (VO 2 )(HPO 4 ). The ω-VOPO 4 phase only remains well crystallised at relatively high temperatures. Its crystal structure has been determined ab initio from X-ray powder diffraction data collected at 475°C. The cell is tetragonal (space group P4 2 /mmc) with a =4.8552(3) A and c =8.4301(6) A. Starting positional parameters were obtained by direct methods, and the structure was refined using Rietveld profile refinement principles. Disorder of two oxygen sublattices is observed. To rationalise some features of the crystal stru…

Enhanced Efficacy and Broadening of Antibacterial Action of Drugs via the Use of Capped Mesoporous Nanoparticles

[EN] A novel nanodevice consisting of mesoporous nanoparticles loaded with vancomycin and capped with epsilon-poly-L-lysine (epsilon-PL) was prepared and its interaction with different Gram-negative bacteria studied. A remarkable improvement in the efficacy of the antimicrobial drug epsilon-PL and a broadening of the antimicrobial spectrum of vancomycin is demonstrated.

Atrane complexes chemistry as a tool for obtaining trimodal UVM-7-like porous silica

[EN] The use of atrane complexes as hydrolytic precursors enables the homogeneous incorporation of manganese (25Si/Mn48) throughout the porous walls of the nanoparticles of a surfactant-templated bimodal mesoporous silica (UVM-7). The subsequent leaching of the manganese nanodomains allows adding controlled microporosity to the host silica framework. The resulting final silica material presents three pore systems structured at different length scales: interparticle textural-type macroporosity (ca. 43.2nm), ordered intraparticle mesoporosity (ca. 2.63nm; after template removal), and well-dispersed microporosity (< 2nm; as consequence of the lixiviation of the Mn-rich domains). The good dispe…

Finely Tuned Temperature-Controlled Cargo Release Using Paraffin-Capped Mesoporous Silica Nanoparticles

[EN] Trapped: Mesoporous silica nanoparticles were loaded with a fluorescent guest and functionalized with octadecyltrimethoxysilane. The alkyl chains interact with paraffins, which build a hydrophobic layer around the particle (see picture). Upon melting of the paraffin, the guest molecule is released, as demonstrated in cells for the guest doxorubicin. The release temperature can be tuned by choosing an appropriate paraffin. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mesosynthesis of ZnO-SiO(2) porous nanocomposites with low-defect ZnO nanometric domains.

Silica-based ZnO-MCM-41 mesoporous nanocomposites with high Zn content (5≤Si/Zn≤50) have been synthesized by a one-pot surfactant-assisted procedure from aqueous solution using a cationic surfactant (CTMABr = cetyltrimethylammonium bromide) as structure-directing agent, and starting from molecular atrane complexes as inorganic hydrolytic precursors. This preparative technique allows optimization of the dispersion of the ZnO nanodomains in the silica walls. The mesoporous nature of the final materials is confirmed by x-ray diffraction (XRD), transmission electron microscopy (TEM) and N(2) adsorption-desorption isotherms. The ZnO-MCM-41 materials show unimodal pore size distributions without …

Direct oxidation of isobutane to methacrolein over V-MCM-41 catalysts

High vanadium content mesoporous vanado-silicates with MCM-41-like structure, obtained by the atrane route, catalyse the direct oxidation of isobutane to methacrolein with 30% selectivity, and a total dehydrogenation (olefin plus methacrolein) selectivity up to 74%.

Synthesis and Characterization of SiC/MC/C Ceramics (M = Ti, Zr, Hf) Starting from Totally Non-oxidic Precursors

The reaction of poly(dimethylsilane) (PDMS) and poly(dimethylcarbosilane) (PCS) with bis(cyclopentadienyl)M dichloride Cp2MCl2 (M ) Ti, Zr, Hf) complexes has been used as a new route to obtain ceramic materials based on SiC-containing M. The reaction is completed at a relatively low temperature, 900 °C, yielding the corresponding amorphous SiC/MC ceramics which have been characterized by means of 29 Si MAS NMR. These amorphous materials have been treated at higher temperatures, 1350 °C, under a purified argon atmosphere, yielding partially crystallized products which have been studied by X-ray powder diffraction and 29 Si MAS NMR. The effect of the composition of the mixture of precursors is

ChemInform Abstract: New Trends in V-P-O Solids

On the basis of the industrial interest of the oxovanadium phosphate catalysts, current research effort in this field is focused mainly on the development of synthetic strategies directed towards obtaining open-framework materials. There is a growing body of work describing preparations using hydrothermal procedures under a diversity of conditions. A great number of new solids, whose nets range from lamellar arrays to micro- and mesostructured organizations, has been prepared in last years. In this context, the applicability of concepts and procedures from the zeolites chemistry to systems involving transition elements is critically analyzed.

Not always what closes best opens better: mesoporous nanoparticles capped with organic gates

ABSTRACT Four types of calcined MCM-41 silica nanoparticles, loaded with dyes and capped with different gating ensembles are prepared and characterized. N1 and N2 nanoparticles are loaded with rhodamine 6G and capped with bulky poly(ethylene glycol) derivatives bearing ester groups (1 and 2). N3-N4 nanoparticles are loaded with sulforhodamine B and capped with self-immolative derivatives bearing ester moieties. In the absence of esterase enzyme negligible cargo release from N1, N3 and N4 nanoparticles is observed whereas a remarkable release for N2 is obtained most likely due to the formation of an irregular coating on the outer surface of the nanoparticles. In contrast, a marked delivery i…

Generalized “one-pot” preparative strategy to obtain highly functionalized silica-based mesoporous spherical particles

In this work we present a synthesis strategy for the preparation of Stöber-type mesoporous particles functionalized with inorganic species. The procedure is based on a combination of the Atrane and the Stöber methods. Both as a source of silicon and of the incorporated heteroelements (Fe, Zn, Al, Ti) the corresponding atrane complexes are used as hydrolytic reagents. These complexes are easily formed by reaction with triethanolamine. Mesoporosity is achieved using surfactant micelles as templates. Obtaining uniform spherical particles is achieved by optimizing the amount of water-ethanol in the reaction medium. The particle sizes have been modulated by controlling simple parameters such as …

A Metallacryptand-Based Manganese(II)–Cobalt(II) Ferrimagnet with a Three-Dimensional Honeycomb Open-Framework Architecture

A photoactivated molecular gate.

Light-controlled gate: A novel capped silica nanoscopic mesoporous hybrid material for photo-driven cargo release applications has been designed and prepared. The capped system, which shows a zero release, contains a photo-cleavable bulky o-methoxybenzylamine derivative. Upon irradiation at 254¿nm, photo-degradation of the o-methoxybenzylamine framework and the subsequent delivery of a fluorescent cargo were observed

Determination of phenolic compounds in air by using cyclodextrin-silica hybrid microporous composite samplers

An analytical method for the determination of phenolic compounds in air samples based on the use of cyclodextrin-silica hybrid microporous composite samplers is proposed. The method allows the determination of phenol, guaiacol, cresol isomers, eugenol, 4-ethylphenol and 4-ethylguaiacol in workplaces according to the Norm UNE-EN 1076:2009 for active sampling. Therefore, the proposed method offers an alternative for the assessment of the occupational exposure to phenol and cresol isomers. The detection limits of the proposed method are lower than those for the NIOSH Method 2546. Storage time of samples almost reaches 44 days. Recovery values for phenol, guaiacol, o-cresol, m-cresol, p-cresol,…

A Mesoporous 3D Hybrid Material with Dual Functionality for Hg2+Detection and Adsorption

Dual-function hybrid material U1 was designed for simultaneous chromofluorogenic detection and removal of Hg(2+) in an aqueous environment. Mesoporous material UVM-7 (MCM41 type) with homogeneously distributed pores of about 2-3 nm in size, a large specific surface area exceeding 1000 m(2) g(-1), and nanoscale particles was used as an inorganic support. The mesoporous solid is decorated with thiol groups that were treated with squaraine dye III to give a 2,4-bis(4-dialkylaminophenyl)-3-hydroxy-4-alkylsulfanylcyclobut-2-enone (APC) derivative that is covalently anchored to the inorganic silica matrix. The solid was characterised by various techniques including X-ray diffraction, transmission…

Low-Cost Synthesis of Bimodal Mesoporous Silica-Based Materials by Pseudomorphic Transformation.

Nanoparticulate bimodal porous silica-based materials have been prepared through a surfactant-assisted procedure by using a simple template and starting from inexpensive sodium silicate as silicon source. Different procedural variables, such as pH or the nature and concentration of the surfactant, have been explored to optimize the preparative protocol, which allows, in turn, improved understanding of the formation process. The final bulk materials (called UVM-10 or M-UVM-10) are formed by pseudomorphic transformation of fresh silica-based xerogels under mild basic conditions. The UVM-10 architecture is constructed from small mesoporous nanoparticles, the aggregation of which generates a di…

Microwave-Assisted Synthesis of Covalent OrganicFrameworks: A Review

[EN] Covalent organic frameworks (COFs) are relatively recent materials. They have received great attention due to their interesting properties. However, the application of microwaves in their synthesis, despite its advantages such as faster and more reproducible processes, is a minority. Herein, a comprehensive compilation of the research results published in the microwave-assisted synthesis (MAS) of COFs is presented. This review includes articles of 2D and 3D COFs prepared using microwaves as source of energy. The articles have been classified depending on the functional groups including boronate ester, imines, enamines, azines, and triazines, among others. It compiles the main parameter…

Superexchange pathways in oxovanadium(IV) phosphates

Abstract Oxovanadium(IV) phosphates show a diversity of magnetic behaviours that cannot be deduced from their respective structural features only. In part, this is due to the involvement of phosphate bridges in the spin transfer between V(IV) centres, and 31P solid state nuclear magnetic resonance becomes a key tool in determining the exchange mechanisms. The magnetic properties of a wide set of vanadium(IV) containing derivatives can be explained by realizing that a good overlap of the magnetic orbits may be achieved through paths involving phosphorus d orbitals.

Study of silica-structured materials as sorbents for organophosphorus pesticides determination in environmental water samples

Abstract A novel sorbent based on a UVM-7 mesoporous silica doped with Ti has been synthesized and used for solid-phase extraction of several organophosphorus pesticides in environmental water samples followed by gas chromatography coupled to a nitrogen-phosphorus selective detector. Thus, mesoporous silica materials doped with Ti and Fe as well as immobilized cyclodextrin silica-based supports were prepared and morphologically characterized by several techniques such as transmission electronic microscopy, nitrogen adsorption-desorption and X-ray diffraction. These sorbents were comparatively evaluated, and Ti25-UVM-7 material was selected as the best solid phase. After optimization of extr…

CCDC 1530054: Experimental Crystal Structure Determination

Related Article: Tamires S. Fernandes, Wanessa D. C. Melo, Lucas H. G. Kalinke, Renato Rabelo, Ana K. Valdo, Cameron C. da Silva, Felipe T. Martins, Pedro Amorós, Francesc Lloret, Miguel Julve, Danielle Cangussu|2018|Dalton Trans.|47|11539|doi:10.1039/C8DT01686K

CCDC 1530055: Experimental Crystal Structure Determination

Related Article: Tamires S. Fernandes, Wanessa D. C. Melo, Lucas H. G. Kalinke, Renato Rabelo, Ana K. Valdo, Cameron C. da Silva, Felipe T. Martins, Pedro Amorós, Francesc Lloret, Miguel Julve, Danielle Cangussu|2018|Dalton Trans.|47|11539|doi:10.1039/C8DT01686K

CCDC 891353: Experimental Crystal Structure Determination

Related Article: Consuelo Yuste-Vivas, Manuela Ramos Silva, Pablo Martín-Ramos, Laura C.J. Pereira, Jesús Ferrando-Soria, Pedro Amorós, Miguel Julve|2015|Polyhedron|87|220|doi:10.1016/j.poly.2014.11.026

CCDC 1530056: Experimental Crystal Structure Determination

Related Article: Tamires S. Fernandes, Wanessa D. C. Melo, Lucas H. G. Kalinke, Renato Rabelo, Ana K. Valdo, Cameron C. da Silva, Felipe T. Martins, Pedro Amorós, Francesc Lloret, Miguel Julve, Danielle Cangussu|2018|Dalton Trans.|47|11539|doi:10.1039/C8DT01686K