Highly Selective Detection of Nerve‐Agent Simulants with BODIPY Dyes

Two chromo-fluorogenic probes, each based on the boron dipyrromethene core, have been developed for the detection of nerve-agent mimics. These chemosensors display both a color change and a significant enhancement of fluorescence in the presence of diethylcyanophosphonate (DCNP) and diisopropylfluorophosphate (DFP). No interference from other organophosphorus compounds or acids has been observed. Two portable chemosensor kits have been developed and tested to demonstrate its practical application in real-time monitoring.

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…

Chromogenic Detection of Nerve Agent Mimics by Mass Transport Control at the Surface of Bifunctionalized Silica Nanoparticles

Chemical warfare (CW) agents are toxic chemicals that have been used in several terrorist attacks in recent years. Among CW species, nerve agents are probably the most dangerous; their high toxicity and facile synthesis underscores the need to detect these lethal compounds with quick, reliable procedures. Analytical methods based on enzymatic assays and physical measurements have generally been used to detect these hazards. However, these protocols usually have limitations such as low selectivity, poor portability, and a certain level of complexity. In recent years, several chromogenic and fluorogenic sensors, and reagents for the detection of nerve agents have been described. For instance,…

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.

Sesquiterpene lactones from iranian Artemisia species

Abstract The aerial parts of Artemisia turcomanica and A. deserti yielded two new germacranolides, a new guaianolide, and several known mono- and sesquiterpenes.

Nerve agent simulant detection by using chromogenic triaryl methane cation probes

Two triaryl methane cations have been used as probes for colorimetric detection of nerve agent simulants. Buffered mixed aqueous solutions of 1 and 2 showed bathochromic shifts in the presence of DCNP (diethylcyanophosphonate) and DCP (diethylchlorophosphate). The colour modulation can be observed to the naked eye. Appropriate mechanisms for the recognition event are proposed. © 2012 Elsevier Ltd.

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…

Selective and sensitive colorimetric detection of the neurotransmitter serotonin based on the aggregation of bifunctionalised gold nanoparticles

[EN] We report a simple, sensitive and selective method for the colorimetric detection of serotonin (5-HT) in aqueous media using bifunctionalized gold nanoparticles (AuNPs). The probe (1) consisted of AuNPs functionalised with dithiobis(succinimidylpropionate) (DSP) and N-acetyl-l-cysteine (NALC). DSP was chosen to react with the amino group of 5-HT, whereas NALC was chosen to bind the hydroxyl group in 5-HT through hydrogen bonding and electrostatic interactions. A double interaction between nanoparticles and the hydroxyl and the amino group of serotonin led to interparticle-crosslinking aggregation. This, resulted in a colour change from red to blue that can be observed by the naked eye.…

A new selective fluorogenic probe for trivalent cations.

[EN] A new selective chromo-fluorogenic probe for Fe 3+, Cr 3+ and Al 3+ is reported. Detection limits are in the ¿M range and the fluorogenic sensing ability could be observed by the naked eye when illuminated with UV-light. No response is observed with divalent cations. © 2012 The Royal Society of Chemistry.

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

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…

Highly selective and sensitive chromo-fluorogenic detection of the Tetryl explosive using functional silica nanoparticles

Silica nanoparticles containing polyamines and thiol groups have been used as probes for the selective detection of Tetryl. © 2011 The Royal Society of Chemistry.

Hg2+ and Cu2+ selective detection using a dual channel receptor based on thiopyrylium scaffoldings

2,4,6-Triphenylthiopyrylium functionalized with an aza-oxa-thia macrocycle is able to selectively recognize Hg2+ cation by a color change and Cu2+ cation by a remarkable significant emission enhancement.

Sesquiterpenes from Centaurea aspera

Abstract The aerial parts of two subspecies of Centaurea aspera L. (Asteraceae) yielded the germacranolides 1a – h , 2 , 3 , 4 and 5 , the elemane derivatives 6d and 6f , the lignan matairesinol, the degraded terpene loliolide, and the onopordopicrin–valine dimeric adduct 7 . From these, compounds 1e , 3 and 6d are natural products. The chemical composition of the two subspecies is very similar, a circumstance which does not support a taxonomic subdivision of the species.

Controlled release using mesoporous materials containing gate-like scaffoldings.

The use of gated mesoporous silica solids as suitable systems for controlled-release protocols is reviewed. These materials are based on mesoporous silica supports that can be prepared with tailor-made pores of around 2 - 10 nm and that show a very large specific surface area (up to 1200 m(2)/g), thus having a large load capacity. The solids can be additionally functionalised in the external surface with gate-like systems that can be opened on command to allow cargo release. Light, redox reactions, pH, temperature, polarity and enzyme-driven protocols are shown. The possible application in drug delivery protocols is discussed.

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…

4,4′-bis(dimethylamino)biphenyl containing binding sites. A newfluorescent subunit for cation sensing

The emission behaviour of the 4,4′-bis(dimethylamino)biphenyl subunit covalently attached to aza-crown ethers is studied. Some new ligands have been synthesised in order to test the properties of this new fluorophore. The fluorescence of these new ligands and some other compounds previously described has been studied in acetonitrile in the presence of Ni2+, Cu2+, Zn2+, Hg2+, Pb2+, Cd2+ and also in the presence of some alkali and alkaline-earth cations.

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…

Toxicological assessment of mesoporous silica particles in the nematode Caenorhabditis elegans

[EN] Here we report the toxicological evaluation of mesoporous silica particles (MSPs) in the nematode C. elegans. Specifically, we have investigated the effect of bare micro- (M0) and nano-sized (N0) MSPs, and their corresponding functionalized particles with a starch derivative (Glu-N) (M1 and N1, respectively) on C. elegans ageing parameters. The toxicity of MSPs, their impact on C. elegans lifespan, movement capacity, progeny and ability to survive upon exposure to acute oxidative stress were assessed. This study demonstrated that both size particles assayed (M0 and N0), labeled with rhodamine and monitored through fluorescence microscopy, are ingested by the nematode. Moreover, toxicit…

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.

A Colorimetric Probe for the Selective Detection of Norepinephrine Based on a Double Molecular Recognition with Functionalized Gold Nanoparticles

[EN] A simple colorimetric probe for the selective and sensitive detection of neurotransmitter norepinephrine (NE), an important biomarker in the detection of tumors such as pheochromocytoma and paraganglioma, is described. The sensing strategy is based on the use of spherical gold nanoparticles functionalized with benzaldehyde and boronic acid-terminated moieties. A double molecular recognition involving on one hand the aromatic aldehyde and the aminoalcohol group of NE, and on the other hand the boronic acid and the catechol moiety of the neurotransmitter, results in analyte triggered aggregation of the gold nanoparticles, leading to a bathochromic shift of the SPR band in the UV-vis spec…

A Chromogenic Probe for the Selective Recognition of Sarin and Soman Mimic DFP

The synthesis, characterization and sensing features of a novel probe 1 for the selective chromogenic recognition of diisopropylfluorophosphate (DFP), a sarin and soman mimic, in 99:1 (v/ v) water/acetonitrile and in the gas phase is reported. Colour modulation is based on the combined reaction of phosphorylation of 1 and fluoride-induced hydrolysis of a silyl ether moiety. As fluoride is a specific reaction product of the reaction between DFP and the OH group, the probe shows a selective colour modulation in the presence of this chemical. Other nerve agent simulants, certain anions, oxidant species and other organophosphorous compounds were unable to induce colour changes in 1. This is one…

Sesquiterpene lactones and acetylenes from Artemisia reptans

Abstract The aerial parts of Artemisia reptans yielded a new thiophene acetylene, four new guaianolides, a new acyclic sesquiterpene related to davanone and several known compounds.

2,4,5-Triaryl imidazole probes for the selective chromo-fluorogenic detection of Cu(II). Prospective use of the Cu(II) complexes for the optical recognition of biothiols

The sensing behaviour toward metal cations and biothiols of two 2,4,5-triarylimidazole probes (3a and 3b) is tested in acetonitrile and in acetonitrile-water. In acetonitrile the two probes present charge-transfer absorption bands in the 320-350 nm interval. Among all cations tested only Cu(11) is able to induce bathochromic shifts of the absorption band in the two probes, which is reflected in marked colour changes. Colour modulations are ascribed to the formation of 1:1 Cu(II)-probe complexes in which the cation interacts with the imidazole acceptor heterocycle. Besides, the two probes present intense emission bands (at 404 and 437 nm for 3a and 3b respectively) in acetonitrile that are q…

Chromogenic detection of nerve agent mimics

The current rise in international concern over criminal terrorist attacks via chemical warfare (CW) agents has resulted in an increasing interest in the detection of these lethal chemicals. Among CW species, nerve agents are extremely dangerous and their high toxicity and ease of production underscore the need to detect these deadly chemicals via quick and reliable procedures. A number of detection systems have been developed, most of them based on enzymatic and physical methodologies. However, these usually show limitations such as low selectivity, lack of portability and a certain complexity in their use. An alternative to these classical methods that has been gaining interest in recent y…

Synthesis and In Vitro Evaluation of a Photosensitizer-BODIPY Derivative for Potential Photodynamic Therapy Applications

A new photosensitizer (1) based on the 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) scaffold has been synthesized. 1 is water soluble and showed an intense absorption band at 490 nm (e=77600 cm-1M-1) and an emission at 514 nm. In vitro toxicity of 1 in the presence of light and in darkness has been studied with HeLa, HaCaT, MCF-7, and SCC-13 cell lines. Moreover, internalization studies of 1 in these cell lines were also performed. These results suggested that 1 is more toxic for SCC-13 and HeLa carcinoma cells than for the HaCaT noncancerous immortal human keratinocytes. Toxicity upon light irradiation was due to the formation of singlet oxygen and reactive oxygen species (ROS). Cel…

Acetylcholinesterase-Capped Mesoporous Silica Nanoparticles That Open in the Presence of Diisopropylfluorophosphate (a Sarin or Soman Simulant)

Mesoporous silica nanoparticles loaded with rhodamine B and capped with acetylcholinesterase are able to be selectively opened and deliver their cargo in the presence of nerve agent simulant diisopropyl fluorophosphate (DFP).

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…

Oplopanone derivatives monoterpene glycosides from Artemisia sieberi

Abstract The aerial parts of Artemisia sieberi yielded three new oplopanone derivatives, three new monoterpene glycosides, a new germacrane alcohol and a monoterpene acid related to nerolidol.

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

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 …

Double Drug Delivery Using Capped Mesoporous Silica Microparticles for the Effective Treatment of Inflammatory Bowel Disease

[EN] Silica mesoporous microparticles loaded with both rhodamine B fluorophore (S1) or hydrocortisone (S2), and capped with an olsalazine derivative, are prepared and fully characterized. Suspensions of Si and S2 in water at an acidic and a neutral pH show negligible dye/drug release, yet a notable delivery took place when the reducing agent sodium dithionite is added because of hydrolysis of an azo bond in the capping ensemble. Additionally, olsalazine fragmentation induced 5-aminosalicylic acid (5-ASA) release. In vitro digestion models show that S1 and S2 solids are suitable systems to specifically release a pharmaceutical agent in the colon. In vivo pharmacokinetic studies in rats show …

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…

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

Functional Magnetic Mesoporous Silica Microparticles Capped with an Azo-Derivative: A Promising Colon Drug Delivery Device

[EN] Magnetic micro-sized mesoporous silica particles were used for the preparation of a gated material able to release an entrapped cargo in the presence of an azo-reducing agent and, to some extent, at acidic pH. The magnetic mesoporous microparticles were loaded with safranin O and the external surface was functionalized with an azo derivative 1 (bearing a carbamate linkage) yielding solid S1. Aqueous suspensions of S1 at pH 7.4 showed negligible safranin O release due to the presence of the bulky azo derivative attached onto the external surface of the inorganic scaffold. However, in the presence of sodium dithionite (azoreductive agent), a remarkable safranin O delivery was observed. A…

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…

Surfactant-assisted chromogenic sensing of cyanide in water

Chromogenic cyanide recognition in water was achieved by the use of a hydrophobic dye in micellar containers.

Ex Vivo Tracking of Endogenous CO with a Ruthenium(II) Complex.

[EN] A two-photon fluorescent probe based on a ruthenium(II) vinyl complex is capable of selectively detecting carbon monoxide in cells and ex vivo using mice with a subcutaneous air pouch as a model for inflammation. This probe combines highly selective and sensitive ex vivo detection of endogenous CO in a realistic model with facile, inexpensive synthesis, and displays many advantages over the widely used palladium-based systems.

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…

ChemInform Abstract: Optical Chemosensors and Reagents to Detect Explosives

This critical review is focused on examples reported from 1947 to 2010 related to the design of chromo-fluorogenic chemosensors and reagents for explosives (141 references).

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…

Mesoporous Silica-Based Materials with Bactericidal Properties

[EN] Bacterial infections are the main cause of chronic infections and even mortality. In fact, due to extensive use of antibiotics and, then, emergence of antibiotic resistance, treatment of such infections by conventional antibiotics has become a major concern worldwide. One of the promising strategies to treat infection diseases is the use of nanomaterials. Among them, mesoporous silica materials (MSMs) have attracted burgeoning attention due to high surface area, tunable pore/particle size, and easy surface functionalization. This review discusses how one can exploit capacities of MSMs to design and fabricate multifunctional/controllable drug delivery systems (DDSs) to combat bacterial …

A Synthetic Model for the [4+2] Cycloaddition in the Biosynthesis of the Brevianamides, Paraherquamides, and Related Compounds

Abstract The reactivity of model systems for the proposed [4+2] cycloaddition in the biosynthesis of the brevianamides, paraherquamides, and marcfortines is explored. The model for the intermolecular reaction reveals that the cycloaddition takes place under mild conditions only if activated, very reactive dienophiles are used. When relatively unreactive dienophiles such as cyclopentene and cyclohexene are used, harsh reaction conditions and/or a Lewis acid catalyst are necessary for the reaction. In contrast, the model for the intramolecular reaction demonstrates that the cycloaddition takes place within a few hours at room temperature, even in the absence of a Lewis acid catalyst. Conclusi…

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…

A chalcone-based highly selective and sensitive chromofluorogenic probe for trivalent metal cations

[EN] Anew chalcone-based probe for the chromofluorogenic sens-ing of trivalent (Al3 +,Fe3+,Cr3+,Ga3+,In3+and As3 +)overmono-and divalent cationsand anionsisreported. In the presence of trivalent metal cations,the probe was able to displayaremarkable color change from yellow to colorless that wasclearly visible to the naked eye. Also, the initial strongyellowemission was gradually quenched and substituted by aweaklyshifted band.

A l-glutamate-responsive delivery system based on enzyme-controlled self-immolative arylboronate-gated nanoparticles

We report herein a L-glutamate (L-Glu)-responsive delivery system. It consists of Janus Au–mesoporous silica (MS) nanoparticles functionalized with L-glutamate oxidase on the Au face and with self-immolative arylboronate derivatives as caps on the MS face. The MS face is additionally loaded with a cargo. The delivery paradigm is based on the recognition of L-Glu by the enzyme and the subsequent formation of H2O2, which induces the cleavage of the self-immolative gate and the uncapping of the pores. Given the importance of L-Glu as a key neurotransmitter, we hope that these findings will help in designing new therapeutic strategies for nervous system diseases.

Chromo-Fluorogenic Detection of Nerve-Agent Mimics Using Triggered Cyclization Reactions in Push-Pull Dyes

A family of azo and stilbene derivatives (1-9) are synthesized, and their chromo-fluorogenic behavior in the presence of nerve-agent simulants, diethylchlorophosphate (DCP), diisopropylfluorophosphate (DFP), and diethylcyanophosphate (DCNP) in acetonitrile and mixed solution of water/acetonitrile (3:1 v/v) buffered at pH 5.6 with MES, is investigated. The prepared compounds contain 2-(2-N,N-dimethylaminophenyl)ethanol or 2-[(2-N,N-dimethylamino)phenoxy]ethanol reactive groups, which are part of the conjugated pi-system of the dyes and are able to give acylation reactions with phosphonate substrates followed by a rapid intramolecular N-alkylation. The nerve-agent mimic-triggered cyclization …

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

Overview of the Evolution of Silica-Based Chromo-Fluorogenic Nanosensors

[EN] This review includes examples of silica-based, chromo-fluorogenic nanosensors with the aim of illustrating the evolution of the discipline in recent decades through relevant research developed in our group. Examples have been grouped according to the sensing strategies. A clear evolution from simply functionalized materials to new protocols involving molecular gates and the use of highly selective biomolecules such as antibodies and oligonucleotides is reported. Some final examples related to the evolution of chromogenic arrays and the possible use of nanoparticles to communicate with other nanoparticles or cells are also included. A total of 64 articles have been summarized, highlight…

Self-Immolative Linkers as Caps for the Design of Gated Silica Mesoporous Supports

A new hybrid material based on sulforhodamine-B dye-loaded silica mesoporous nanoparticles capped with a self-immolative gate has been synthesized and characterized. The gated material's controlled release behavior is monitored under different pH conditions. Under acidic and neutral conditions, a low level of dye release is detected. However, at slightly basic pH, significant dye release occurs owing to deprotonation of the phenol moiety in the capping molecule, which results in its disassembly.

Multi-channel receptors based on thiopyrylium functionalised with macrocyclic receptors for the recognition of transition metal cations and anions.

We report herein the synthesis and characterization of a family of ligands containing different cation binding sites covalently connected to a thiopyrylium signalling reporter. The receptors L1–L6 are able to signal the presence of certain metal cations via three different channels; i.e. electrochemically, fluorogenically and chromogenically. An acetonitrile solution of L1–L6 shows a bright blue colour due to a charge-transfer band in the 575–585 nm region. The colour variation in acetonitrile of L1–L6 in the presence of the metal cations Ag+, Cd2+, Cu2+, Fe3+, Hg2+, Ni2+, Pb2+ and Zn2+ has been studied. A selective hypsochromic shift of the blue band was found for the systems L4-Pb2+ and L…

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 …

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.

Enzyme-Controlled Nanodevice for Acetylcholine-Triggered Cargo Delivery Based on Janus Au–Mesoporous Silica Nanoparticles

[EN] This work reports a new gated nanodevice for acetylcholine-triggered cargo delivery. We prepared and characterized Janus Au-mesoporous silica nanoparticles functionalized with acetylcholinesterase on the Au face and with supramolecular b-cyclodextrin: benzimidazole inclusion complexes as caps on the mesoporous silica face. The nanodevice is able to selectively deliver the cargo in the presence of acetylcholine via enzyme-mediated acetylcholine hydrolysis, locally lowering the pH and opening the supramolecular gate. Given the key role played by ACh and its relation with Parkinson's disease and other nervous system diseases, we believe that these findings could help design new therapeuti…

A new 8-oxo-7,8-2 ' deoxyguanosine nanoporous anodic alumina aptasensor for colorectal cancer diagnosis in blood and urine

Many important human diseases, and especially cancer, have been related to the overproduction of 8-oxo-7,8-dihydro-2 '-deoxyguanosine (8-oxo-dG). This molecule is a product of oxidative stress processes over nucleophilic bases in DNA. In this work, an aptasensor for the rapid, selective and accurate detection of this oncomarker is presented. The aptasensor consists of a nanoporous anodic alumina material loaded with a dye and is functionalized with an aptamer-based "molecular gate". In the presence of target 8-oxo-dG, the capping aptamer displaces from the surface due to the high affinity of the analyte with the capping aptamer, thus inducing delivery of the preloaded fluorescent dye. In co…

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…

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…

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

11 páginas, 7 figuras, 3 tablas y 2 esquemas

Frontispiece: Self-Immolative Linkers as Caps for the Design of Gated Silica Mesoporous Supports

Highly selective fluorescence detection of hydrogen sulfide by using an anthracene-functionalized cyclam-CuII complex

An anthracene-functionalised cyclam-copper(II) complex for the detection of HS- in aqueous environments has been prepared. This probe displays poor fluorescence but can selectively and sensitively detect HS- anions in water over other anions, biothiols and common oxidants such as H2O2 through remarkably enhanced emission. This turn-on response in the presence of the HS- anion is ascribed to a demetallation reaction that inhibits emission quenching observed in the initial complex as a result of the presence of the paramagnetic Cu2+ centre. Moreover, real-time fluorescence imaging measurements confirm that probe [Cu(1)](2+) can be easily used to detect intracellular HS- at micromolar concentr…

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…

Selective and Sensitive Chromogenic Detection of Cyanide and HCN in Solution and in Gas Phase

Two triphenylmethane based chemodosimeters for selective and chromogenic sensing of cyanide anions in aqueous environments and of hydrogen cyanide in gas phase were prepared and studied.

A Sensitive Nanosensor for the In Situ Detection of the Cannibal Drug.

[EN] A bio-inspired nanodevice for the selective and sensitive fluorogenic detection of 3,4- methylenedioxypyrovalerone (MDPV), usually known as Cannibal drug, is reported. The sensing nanodevice is based on mesoporous silica nanoparticles (MSNs), loaded with a fluorescent reporter (rhodamine B) and functionalized on their external surface with a dopamine derivative (3), which specifically interacts with the recombinant human dopamine transporter (DAT), capping the pores. In the presence of MDPV, DAT detaches from the MSNs consequently causing rhodamine B release and allowing drug detection. The nanosensor shows a detection limit of 5.2 µM and it is able to detect the MDPV drug both in sali…

CO-releasing binuclear rhodium complexes as inhibitors of nitric oxide generation in stimulated macrophages.

Nontoxic CO-releasing dirhodium complexes act as inhibitors of NO in stimulated macrophage cells, suggesting that novel antiinflammatory treatments could involve the use of these types of binuclear complexes.

Efficacy of budesonide-loaded mesoporous silica microparticles capped with a bulky azo derivative in rats with TNBS-induced colitis.

Abstract A colon targeted drug delivery system for inflammatory bowel diseases (IBD), consisting in budesonide loaded mesoporous silica microparticles functionalized with a selective azo-molecular gate (M-Bud), has been evaluated for in vivo efficacy. Experimental colitis in male Wistar rats was induced by rectal instillation of 2,4,6-trinitrobenzenesulfonic acid (TNBS). M-Bud was orally administered to the rats as a suspension in water. Colon/body weight ratio, clinical activity score, and histological evaluation were used as inflammatory indices to measure the performance of the microparticles. The formulation was compared with a suspension prepared from the commercial drug Entocord®. Sta…

Colorimetric detection of normetanephrine, a pheochromocytoma biomarker, using bifunctionalised gold nanoparticles.

[EN] A simple and effective colorimetric method for the detection of normetanephrine (NMN), an O-methylated metabolite of norepinephrine, using functionalised gold nanoparticles is described. This metabolite is an important biomarker in the diagnosis of adrenal tumours such as pheocromocytoma or paraganglioma. The colorimetric probe consists of spherical gold nanoparticles (AuNPs) functionalised with two different ligands, which specifically recognize different functional groups in normetanephrine. Thus, a benzaldehyde-terminated ligand was used for the recognition of the amino alcohol moiety in NMN, by forming the corresponding oxazolidine. On the other hand, N-acetyl-cysteine was chosen f…

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.

Biomimetic diels–alder cyclizations for the construction of the brevianamide, paraherquamide, sclerotamide, asperparaline and VM55599 ring systems

Abstract A potentially bio-mimetic Diels–Alder cyclization to construct the bicyclo[2.2.2] ring system common to the paraherquamides, marcfortines, sclerotamides, brevianamides, VM55599, and asperparaline is reported. Epi-deoxybrevianamide E (22) is converted into the corresponding lactim ether (23) and then oxidized with DDQ to provide an azadiene (24) which is tautomerized in the presence of base to azadiene 25 which, spontaneously cyclizes to give a 2:1 mixture of cycloadducts 26 and 27. These cycloadducts are each in turn, converted into d , l -C-19-epi-brevianamide A (20) and d , l -brevianamide B (6). The stereochemical implications of the [4+2] cycloaddition is discussed in the conte…

A new fluorescent "turn-on" chemodosimeter for the detection of hydrogen sulfide in water and living cells

[EN] A new fluorescent turn-on probe for the selective detection of hydrogen sulfide in water and living cells based on a 8-hydroxyquinoline fluorophore functionalized with a 2,6-dinitrophenyl ether moiety has been developed.

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.

A Chemosensor Bearing Sulfonyl Azide Moieties for Selective Chromo-Fluorogenic Hydrogen Sulfide Recognition in Aqueous Media and in Living Cells

A simple chemodosimeter based on a sulfonyl azide dye (1-Az), which displayed a highly selective response toward hydrogen sulfide anion in mixed aqueous media, was synthesised and characterised. Addition of hydrogen sulfide to acetonitrile/HEPES 1:1 solutions of 1-Az induced a clear colour change from red-orange to yellow, which was easily detected by the naked eye, and by an enhancement in the emission intensity. Other common anions, thiol-containing biomolecules and oxidants did not induce any noticeable colour or fluorescence modulation in the probe. The chemodosimeter also showed a good sensitivity, with limits of detection of 11.91 and 0.63 μM by using UV/Vis or fluorescence measuremen…

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.

Chromo-fluorogenic BODIPY-complexes for selective detection of V-type nerve agent surrogates

Two new Eu3+ and Au3+ BODIPY-complexes capable of chromofluorogenically detecting micromolar concentrations of V-type nerve agent surrogates by a simple displacement assay are described

Selective chromo-fluorogenic detection of trivalent cations in aqueous environments using a dehydration reaction

[EN] Trivalent cations (Al3+, Fe3+, Cr3+, As3+, In3+ and Ga3+) induced a dehydration reaction of a chemodosimeter in water that is coupled with colour and emission changes.

Inside Cover: A Boron Dipyrromethene (BODIPY)-Based CuII-Bipyridine Complex for Highly Selective NO Detection (Chem. Eur. J. 44/2015)

Halogen-containing BODIPY derivatives for photodynamic therapy

Abstract Two iodinated (1 and 2) and two brominated (3 and 4) BODIPY-based photosensitizers are prepared and characterized using slightly modified synthetic procedures previously described. 1–4 present intense absorption bands in the 510–540 nm interval and very weak emissions due to the presence of halogen atoms in their structure. Irradiation of aqueous solutions of 1–4 with visible light (wavelength > 475 nm) induce the generation of singlet oxygen with quantum yields of ca. 0.62–0.66 for the photosensitizers containing iodine atoms (1 and 2) and of ca. 0.16–0.21 for the brominated counterparts (3 and 4). In vitro studies carried out with HeLa, SCC-13 and HaCaT cell lines and the four ph…

Off–on BODIPY-based chemosensors for selective detection of Al3+ and Cr3+versus Fe3+ in aqueous media

[EN] Two new off-on BODIPY-based chemosensors that are highly sensitive for trivalent cations in aqueous solutions are described. Compound 2 exhibits selective sensing of Al3+ and Cr3+ versus Fe3+ through two different channels (UV-vis and fluorescence).

Aryl carbinols as nerve agent probes. Influence of the conjugation on the sensing properties

Two new aryl carbinols (1 and 3) have been synthesised and characterised and their ability as OFF-ON probes for the chromogenic detection of the nerve agent simulant in acetonitrile has been tested. In addition compound 2 has been also studied. The carbinols suffered a phosphorylation reaction followed by an elimination process giving rise to the corresponding carbocations. This transformation of the carbinol into the carbocation is responsible for a significant color change. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012.

Selective chromo-fluorogenic detection of DFP (a Sarin and Soman mimic) and DCNP (a Tabun mimic) with a unique probe based on a boron dipyrromethene (BODIPY) dye.

[EN] A novel colorimetric probe (P4) for the selective differential detection of DFP (a Sarin and Soman mimic) and DCNP (a Tabun mimic) was prepared. Probe P4 contains three reactive sites; i.e. (i) a nucleophilic phenol group able to undergo phosphorylation with nerve gases, (ii) a carbonyl group as a reactive site for cyanide; and (iii) a triisopropylsilyl (TIPS) protecting group that is known to react with fluoride. The reaction of P4 with DCNP in acetonitrile resulted in both the phosphorylation of the phenoxy group and the release of cyanide, which was able to react with the carbonyl group of P4 to produce a colour modulation from pink to orange. In contrast, phosphorylation of P4 with…

New Insights of Oral Colonic Drug Delivery Systems for Inflammatory Bowel Disease Therapy

[EN] Colonic Drug Delivery Systems (CDDS) are especially advantageous for local treatment of inflammatory bowel diseases (IBD). Site-targeted drug release allows to obtain a high drug concentration in injured tissues and less systemic adverse effects, as consequence of less/null drug absorption in small intestine. This review focused on the reported contributions in the last four years to improve the effectiveness of treatments of inflammatory bowel diseases. The work concludes that there has been an increase in the development of CDDS in which pH, specific enzymes, reactive oxygen species (ROS), or a combination of all of these triggers the release. These delivery systems demonstrated a th…

A dual channel sulphur-containing a macrocycle functionalised BODIPY probe for the detection of Hg(II) in a mixed aqueous solution

We report herein the synthesis and chromo-fluorogenic behaviour of a new probe 1 containing a boron-dipirromethene (BODIPY) unit electronically connected with a dithia-dioxa-aza macrocycle. Acetonitrile and water-acetonitrile 95:5 v/v solutions of the probe showed an ICT band in the visible zone and are nearly non-emissive. When acetonitrile was used as solvent, addition of Hg(II) and trivalent metal cations induced an hypsochromic shift of the absorption band and moderate emission enhancements. A highly selective response was obtained when using competitive media such as wateracetonitrile 95:5 v/v. In this case only Hg(II) induced a hypsochromic shift of the absorption band and a marked em…

New Methods for Anion Recognition and Signaling Using Nanoscopic Gatelike Scaffoldings

Sesquiterpene lactones from Artemisia species

Abstract The aerial parts of Artemisia spicigera yielded two new eudesmanolides as well as three known ones. The aerial parts of Artemisia verlotiorum yielded four known germacranolides and two known eudesmanolides.

Co2+ Translocation in a Terpyridine−Cyclam Ditopic Receptor

The coordination behaviour of the ditopic receptor of 1-[p-(2,2′:6′,2′′-terpyrid-4′-yl)tolyl]-1,4,8,11-tetraazacyclotetradecane (L1) towards Co2+ in acetonitrile/water (70:30, v/v) has been investigated. At acidic pH values, the L1−H+−Co2+ system shows an oxidation wave at 150 mV vs. SCE, characteristic of Co2+ in a bis(terpyridine) environment. Upon addition of OH−, a reduction in the intensity of the wave at 150 mV is observed and a new oxidation wave appears at 1.30 V. This new wave is close to that found for [Co(cyclam)]2+ under similar working conditions. The electrochemical data thus suggest that there is a pH-controlled translocation of the Co2+ ion from the bis(terpyridine) to the c…

Selective opening of nanoscopic capped mesoporous inorganic materials with nerve agent simulants; an application to design chromo-fluorogenic probes.

A hybrid nanoscopic capped mesoporous material, that is selectively opened in the presence of nerve agent simulants, has been prepared and used as a probe for the chromo-fluorogenic detection of these chemicals. © 2011 The Royal Society of Chemistry.

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…

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…

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…

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)…

A Boron Dipyrromethene (BODIPY)-Based Cu(II) -Bipyridine Complex for Highly Selective NO Detection.

[EN] A BODIPY-containing Cu-II-bipyridine complex for the simple selective fluorogenic detection of NO in air and in live cells is reported. The detection mechanism is based on NO-promoted Cu-II to Cu-I reduction, followed by demetallation of the complex, which results in the clearly enhanced emission of the boron dipyrromethene (BODIPY) unit.

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.

Biocompatibility and internalization assessment of bare and functionalised mesoporous silica nanoparticles

[EN] We report herein an evaluation of the effect of several mesoporous silica nanoparticles (MSNs) on the cellular uptake and in vitro cytotoxicity in human cells. Bare MSNs and MSNs functionalized with polyethylene glycol or hyaluronic acid are employed to evaluate uptake efficiency and mechanisms of endocytosis in cancer (MDA-MB-231) and non-cancer (MCF10A) cells. Moreover, changes in viability, cell cycle, oxidative stress, and mitochondrial membrane potential are evaluated. Our results confirm that MSNs are internalized efficiently by human cells and that uptake mechanisms differ for cell types and particles. We also confirm that MSNs are biocompatible materials that do not induce ROS/…

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.

Chromogenic and fluorogenic reagents for chemical warfare nerve agents' detection

The ease of production, the extreme toxicity of organophosphorus-containing nerve agents, and their facile use in terrorism attacks underscores the need to develop accurate systems to detect these chemicals. Among different technologies we review here recent advances in the design of chromo-fluorogenic methods for the specific detection of nerve agents. Optical sensing (especially colorimetric detection) requires usually low-cost and widely used instrumentation and offers the possibility of so-called “naked eye detection”. Recent reported examples suggest that the application of chromo-fluorogenic supramolecular concepts for the chromogenic or fluorogenic sensing of nerve agents might be an…

Biphenyl derivatives containing trimethylsilyl benzyl ether or oxime groups as probes for NO2 detection

[EN] Four probes based in the use of a biphenyl moiety and functionalized with trimethylsilyl benzyl ether (P1 and P3) and oxime (P2 and P4) groups have been prepared and tested as optical probes for the detection of NO2. Reaction of NO2 with acetonitrile solutions of P2-P4 resulted in the formation of aldehydes 7 and 8 with a concomitant redshift of the absorption bands. Probe P2 displayed a bathochromic shift of 45 nm upon reaction with NO2 and was able to detect this poisonous gas at concentrations as low as 0.02 ppm. P2 was highly selective against NO2 and other gases (i.e. NO, CO2, H2S, SO2) and vapours of organic solvents (i.e. acetone, hexane, chloroform, acetonitrile or toluene) had…

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 …

Chromogenic Detection of Aqueous Formaldehyde Using Functionalized Silica Nanoparticles

Silica nanoparticles functionalized with thiol reactive units and bulky polar polyamines were used for the selective colorimetric detection of formaldehyde. The reaction of thiols groups in the nanoparticles surface with a squaraine dye resulted in loss of the pi-conjugation of the chromophores, and the subsequent bleaching of the solution. However, when formaldehyde was present in the suspension, the thiol-squaraine reaction was inhibited and a chromogenic response was observed. A selective response to formaldehyde was observed only when the thiol and polyamine groups were anchored to the silica surface. The observed selective response was ascribed to the fact that bulky polyamines generat…

Discrimination of nerve gases mimics and other organophosphorous derivatives in gas phase using a colorimetric probe array.

A colorimetric array for the chromogenic discrimination of organophosphorous derivatives in gas phase has been developed. The array allows us to classify the nerve agent simulants DFP, DCP and DCNP.

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

NO2-controlled cargo delivery from gated silica mesoporous nanoparticles

[EN] Cargo delivery from mesoporous silica nanoparticles loaded with sulforhodamine B and capped with a difluoroboron-dipyrromethene (BODIPY) derivative was triggered by a NO2-induced oxidative process.

Controlled delivery using oligonucleotide-capped mesoporous silica nanoparticles.

Towards the design of organocatalysts for nerve agents remediation: The case of the active hydrolysis of DCNP (a Tabun mimic) catalyzed by simple amine-containing derivatives

We report herein a study of the hydrolysis of Tabun mimic DCNP in the presence of different amines, aminoalcohols and glycols as potential suitable organocatalysts for DCNP degradation. Experiments were performed in CD3CN in the presence of 5% D2O, which is a suitable solvent mixture to follow the DCNP hydrolysis. These studies allowed the definition of different DCNP depletion paths, resulting in the formation of diethylphosphoric acid, tetraethylpyrophosphate and phosphoramide species as final products. Without organocatalysts, DCNP hydrolysis occurred mainly via an autocatalysis path. Addition of tertiary amines in sub-stoichiometric amounts largely enhanced DCNP depletion whereas non-te…

Sesquiterpene lactones and lignans from Centaurea species

Abstract The aerial parts of Centaurea calcitrapa yielded cnicin, cnicin 4′-acetate, melitensin, a related elemanolide, the two new germacranolides 11α,13- and 11β,13-dihydrosalonitenolide, and the lignans arctigenin, pinoresinol and 7′( S )-hydroxyarctigenin. The latter compound is described for the first time as a natural product. The aerial parts of Centaurea pabotii yielded 11,13-dihydrodeacylcynaropicrin, aguerin A and a new guaianolide related to cynaropicrin.

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.

Oligonucleotide-capped nanoporous anodic alumina biosensor as diagnostic tool for rapid and accurate detection of Candida auris in clinical samples.

[EN] Candida auris has arisen as an important multidrug-resistant fungus because of several nosocomial outbreaks and elevated rates of mortality. Accurate and rapid diagnosis of C. auris is highly desired; nevertheless, current methods often present severe limitations and produce misidentification. Herein a sensitive, selective, and time-competitive biosensor based on oligonucleotide-gated nanomaterials for effective detection of C. auris is presented. In the proposed design, a nanoporous anodic alumina scaffold is filled with the fluorescent indicator rhodamine B and the pores blocked with different oligonucleotides capable of specifically recognize C. auris genomic DNA. Gate opening modul…

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 …

Optical chemosensors and reagents to detect explosives

[EN] This critical review is focused on examples reported from 1947 to 2010 related to the design of chromo-fluorogenic chemosensors and reagents for explosives (141 references). © 2012 The Royal Society of Chemistry.

Acetylcholine-responsive cargo release using acetylcholinesterase-capped nanomaterials

[EN] Mesoporous silica nanoparticles capped with acetylcholinesterase, through boronic ester linkages, selectively release an entrapped cargo in the presence of acetylcholine.

A gated material as immunosensor for in-tissue detection of IDH1-R132H mutation in gliomas

[EN] A nanodevice consisted on nanoporous anodic alumina (NAA) supports functionalized with specific and selective antibody-based gatekeepers for the detection of IDH1-R132H mutant enzyme is here reported. Molecular profile and tissue mutations of the tumours (such as IDH1/IDH2 mutations in gliomas) are a great source of information that already make a difference in terms of prognosis and prediction of response to combined therapy. However, standardized methodologies to determine this mutation are time-consuming and cannot provide information before or during surgical intervention, which significantly limits their utility in terms of intraoperative decisionmaking. To solve this limitation, …

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-)…

A new simple chromo-fluorogenic probe for NO2 detection in air.

[EN] A new chromo-fluorogenic probe, consisting of a biphenyl derivative containing both a silylbenzyl ether and a N,N-dimethylamino group, for NO2 detection in the gas phase has been developed. A clear colour change from colourless to yellow together with an emission quenching was observed when the probe reacted with NO2. A limit of detection to the naked eye of about 0.1 ppm was determined and the system was successfully applied to the detection of NO2 in realistic atmospheric conditions.

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

Protection against chemical submission: naked-eye detection of γ-hydroxybutyric acid (GHB) in soft drinks and alcoholic beverages

Two new oxazole derivatives, able to detect γ-hydroxybutyric acid (GHB) in soft drinks and alcoholic beverages, by color and fluorescence changes, are reported.

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

Azide and sulfonylazide functionalized fluorophores for the selective and sensitive detection of hydrogen sulfide

[EN] Three fluorescent probes (1–3) for the selective and sensitive detection of hydrogen sulfide have been synthesized and characterized. Probe 1 is a coumarin derivative functionalized with an azide moiety whereas 2 contain the azide reactive group into a naphthalene fluorophore backbone. Probe 3 is composed also by a naphthalene fluorophore but, in this case, functionalized with a sulfonylazide reactive moiety. Probes 1 and 3 are non-fluorescent whereas 2 is weakly emissive in HEPES (10 mM, pH 7.4)–DMSO 99:1 (v/v). The emission behavior of the three probes was tested against selected anions, bio-thiols and oxidant molecules. Of all the chemical species tested, only HS− is able to induce …

A new chromo-fluorogenic probe based on BODIPY for NO2 detection in air

[EN] A novel colorimetric probe for the selective and sensitive detection of NO2 in solution and in air based on a BODIPY core containing an oxime group has been prepared.

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.

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.

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…

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

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…

Nanosensor for Sensitive Detection of the New Psychedelic Drug 25I-NBOMe.

[EN] This work reports the synthesis, characterization, and sensing behavior of a hybrid nanodevice for the detection of the potent abuse drug 25I-NBOMe. The system is based on mesoporous silica nanoparticles, loaded with a fluorescent dye, functionalized with a serotonin derivative and capped with the 5-HT2A receptor antibody. In the presence of 25I-NBOMe the capping antibody is displaced, leading to pore opening and rhodamine B release. This delivery was ascribed to 5-HT2A receptor antibody detachment from the surface due to its stronger coordination with 25I-NBOMe present in the solution. The prepared nanodevice allowed the sensitive (limit of detection of 0.6 mm) and selective recogniti…

CCDC 1819378: Experimental Crystal Structure Determination

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CCDC 1498393: Experimental Crystal Structure Determination

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CCDC 1498394: Experimental Crystal Structure Determination

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CCDC 1819380: Experimental Crystal Structure Determination

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CCDC 1819381: Experimental Crystal Structure Determination

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CCDC 1498392: Experimental Crystal Structure Determination

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