Rational design of aminoanthraquinones for colorimetric detection of heavy metal ions in aqueous solution
A family of water-soluble colorimetric chemosensors incorporating an anthraquinone signalling subunit functionalized with a polyamine chain that bears hydrophilic diethoxyphosphoryl moieties was prepared with the aim of assaying metal cations. The outstanding UV-Vis absorption properties of the 1-aminoanthraquinone chromophore allowed the efficient visual detection and quantification of copper(II) ions by chelators L(1)-L(3) in buffered aqueous solution. Moreover, the visible response of L(2) is not interfered by addition of large excesses of 13 common metal ions, whereas chemosensor L(3) produces also a color change in the presence of equimolar amounts of lead(II). Considering the 134 nm g…
Inside Cover: Hydrogen-Bonded Open-Framework with Pyridyl-Decorated Channels: Straightforward Preparation and Insight into Its Affinity for Acidic Molecules in Solution (Chem. Eur. J. 49/2017)
International audience; A hydrogen-bonded open framework with pores decorated by pyridyl groups was constructed by off-charge-stoichiometry assembly of protonated tetrakis(4-pyridyloxymethyl)methane and [Al(oxalate)(3)](3-), which are the H-bond donor and acceptor of ionic H-bond interactions, respectively. This supramolecular porous architecture (SPA-2) has 1nm-large pores interconnected in 3D with large solvent-accessible void (53%). It demonstrated remarkable affinity for acidic organic molecules in solution, which was investigated by means of various carboxylic acids including larger drug molecules. Competing sorption between acetic acid and its halogenated homologues evidenced good sel…
Towards sensory Langmuir monolayers consisting of macrocyclic pentaaminoanthraquinone
A pentaazamacrocycle incorporating an intracyclic anthraquinone fragment (PENTAQ) was synthesized with the aim of forming metal-responsive Langmuir monolayers. PENTAQ allows a good discrimination by naked eye of copper ions in methanol–water solutions (50 : 50 v/v). Spectrophotometric investigations of the protonation and Cu2+ binding properties of PENTAQ were undertaken in order to gain a deeper insight into the pH-dependent speciation as well as the color changing process. PENTAQ monolayers at air/water and air/methanol–water interfaces were prepared according to the Langmuir procedure. The structure of the monolayers can be tuned by varying the pH of the aqueous subphase, since it was fo…
Efficiency of dihydroxamic and trihydroxamic siderochelates to extract uranium and plutonium from contaminated soils
International audience; Actinide-based mineral phases occurring in contaminated soils can be solubilized by organic chelators excreted by plants, such as citrate. Herein, the efficiency of citrate towards U and Pu extraction is compared to that of siderophores, whose primary function is the acquisition of iron(III) as an essential nutrient and growth factor for many soil microorganisms. To that end, we selected desferrioxamine B (DFB) as an emblematic bacterial trishydroxamic siderophore and a synthetic analog, abbreviated (LCy,Pr)H2, of the tetradentate rhodotorulic acid (RA) produced by yeasts. Firstly, the uranyl speciation with both ligands was assessed in the pH range 2–11 by potentiom…
Synthesis, Characterization, and X-ray Crystal Structures of Cyclam Derivatives. 5. Copper(II) Binding Studies of a Pyridine-Strapped 5,12-Dioxocyclam-Based Macrobicycle1
The copper(II) binding properties of the macrobicyclic diamide 1,9,12,18,22-pentaazatricyclo[7.6.6.1(3,7)]docosa-3,5,7(22)-triene-13,19-dione (L1) have been fully investigated by spectroscopic (IR, UV-vis, EPR, MALDI-TOF MS), X-ray diffraction, potentiometric, electrochemical, and spectroelectrochemical methods. This constrained receptor possesses a hemispherical cavity created by cross-bridging the 1 and 8 positions of trans-dioxocyclam (1,4,8,11-tetraazacyclotetradecane-5,12-dione, L2) with a 2,6-pyridyl strap. Treatment of L1 with a copper salt in methanol produces a red complex of [Cu(L1H(-1))]+ formula in which the copper atom is embedded in a 13-membered ring and coordinated by both a…
Reduction of ferricytochrome c catalyzed by optically active chromium(III) complexes
The reduction rates of horse heart ferricytochrome c by amalgamated zinc or by electrolysis at fixed potential on a mercury pool as the cathode have been measured in a buffered solution at pH 7.5 by absorption spectrophotometry. In both cases, the reaction was strongly accelerated by the presence of the optically active complexes Lambda-[Cr(III)((S,S)-promp)H(2)O](+) (H(2)promp = N,N'-[(pyridine-2,6-diyl)bis(methylene)]-bis[(S)-proline]), Delta-[Cr(III)((R,R)-alamp)H(2)O](+) (H(2)alamp = N,N'-[(pyridine-2,6-diyl)bis(methylene)]-bis[(R)-alanine]) and Lambda-[Cr(III)((S,S)-alamp)(H(2)O)(2)](+). These were shown to undergo reversible one-electron reduction to the corresponding labile chromium(…
New Insights into the complexation of lead(II) by 1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane (DOTAM): structural, thermodynamic and kinetic studies
The lead(II) coordination properties of the tetrapodal ligand DOTAM [1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraaza-cyclododecane] have been investigated both in the solid state and in solution in order to ascertain the stereoactivity of the lone pair and to rationalize the structural effects of a cyclen-based scaffold on the metal uptake kinetics. The crystal structure of the free base shows that the pendant acetamide groups are not equivalent: two are folded over the macrocycle and maintained by an intramolecular hydrogen bond involving an amide hydrogen atom and a neighboring tertiary amine of the cyclen ring, while the other two are extended and point away from the macrocyclic cav…
Equilibrium solution coordination chemistry
Welcome to this themed issue of New Journal of Chemistry entitled “Equilibrium Solution Coordination Chemistry”.
Improving the performances of Diffusive Gradient in Thin-films (DGT) technique to measure the labile uranyl concentration in environmental waters by employing the chelating properties of siderochelates
Uranium (U) presents a unique challenge for ecological risk assessments around installations related to the nuclear fuel cycle because of both chemical and radiological toxicity. Their relative importance depends on the chemical speciation and isotopic composition of the radionuclide, the latter being strongly correlated to its natural or anthropogenic origin (enriched or depleted U) [1]. In this framework, the Diffusive Gradient in Thin-films (DGT) technique is an appealing tool for monitoring the water quality around uranium processing plants, nuclear facilities or mining areas. Indeed, the DGT sampling allows to preconcentrate in situ the labile U(VI) species, allowing to simultaneously …
Platinum( ) and palladium( ) complexes with electron-deficient -diethoxyphosphorylporphyrins: synthesis, structure and tuning of photophysical properties by varying peripheral substituents
The luminescence quenching by O and photodegradation of Pt( ) and Pd( ) phosphorylporphyrins are reported.
Capillary electrophoresis–inductively coupled plasma-mass spectrometry hyphenation for the determination at the nanogram scale of metal affinities and binding constants of phosphorylated ligands
Abstract A screening strategy based on hyphenated capillary electrophoresis and inductively coupled plasma mass spectrometry (CE–ICP-MS) was developed to classify phosphorylated ligands according to their europium(III) binding affinity in a hydro-organic medium (sodium formate, pH 3.7, H2O/MeOH 90:10, v/v). Taking advantage of the high sensibility of ICP-MS for detecting phosphorus, this method enabled to assess the affinity of a variety of phosphorylated compounds, including phosphine oxides, thiophosphines, phosphonates, and phosphinates, in less than 1 h and using less than 5 ng of substance. By varying the total europium concentration, complexation constants could be determined accordin…
Interaction of iron(II)-heme and artemisinin with a peptide mimic of Plasmodium falciparum HRP-II
Abstract The interaction of heme or heme-artemisinin adducts (heme-art) with different peptides mimicking repeat sequences of the Histidine-Rich-Protein-II of Plasmodium falciparum (PfHRP-II) was investigated. The pseudo-first order rate constants of the coordination of heme or heme-art onto a histidine rich peptide, used as a mimic of PfHRP-II putative heme binding sequence, are of the same order of magnitude, namely 42 and 14 s −1 , respectively. Despite the intrinsic reactivity of the carbonyl at C10 of heme-art toward a hydroxyl function, a peptide containing a serine or threonine residue does not readily react with heme-art adducts. Therefore, a much higher affinity of heme-art compare…
The ins and outs of proton complexation
Proton complexation differs from simple protonation by the fact that the coordinated hydrogen atom is bound intramolecularly to more than one donor atom. This is usually achieved by covalent bonding supplemented by hydrogen bonding. In a few cases, however, the complexed proton is hydrogen-bound to all donor atoms, which gives rise to single well (SWHB) and low barrier (LBHB) hydrogen bonds. This tutorial review highlights a full range of proton complexes formed with chelating and "proton-sponge"-type ligands, cryptand-like macropolycycles, and molecules of topological relevance, such as rotaxanes and catenanes. The concept of proton complexation can explain how the smallest cation possible…
A 4-tert-butylcalix[4]arene tetrahydroxamate podand based on the 1-oxypiperidine-2-one (1,2-PIPO−) chelate. Self-assembly into a supramolecular ionophore driven by coordination of tetravalent zirconium or hafnium(iv)
An octadentate tetrahydroxamic calix[4]arene podand incorporating 1-hydroxypiperidine-2-one (1,2-PIPOH) binding units has been designed as a specific chelator for tetravalent metal cations like Zr4+ or Hf4+. This receptor, which can be considered as the first ever abiotic ligand possessing only cyclic six-membered hydroxamate groups, has been synthesized and characterized in its tetraprotonated form (1H4). Contrary to expectation, however, this new chelator did not form a 1 : 1 complex upon reaction with M(acac)4 (M = Zr and Hf; acac = acetylacetonate), but rather self-assembled into a dimeric species of 2 : 2 stoichiometry. The latter could be characterized in solution by mass spectrometry…
Design and evaluation of sensory systems based on amphiphilic anthraquinones molecular receptors
A new paradigm is described that allows one to create different types of sensors: from highly sensitive ones to practical household devices. Our approach relies on modular molecular receptors incorporating an intensely-colored aminoanthraquinone signaling unit equipped with both hydrophilic and hydrophobic modules, the number and size of which being configured in accordance with the targeted analyte and the sought detection method. An important advantage is the compliance with some principles of green chemistry, avoiding the use of toxic organic solvents. The proper functionalization of the anthraquinone scaffold afforded water-soluble chromoinophores capable of quantifying selectively Hg2+…
On the physicochemical properties of pyridohelicenes.
A comprehensive study on the physicochemical properties of a series of mono- and diaza[5]helicenes as well as mono- and diaza[6]helicenes is reported. Through the use of both computational and experimental methods, these helically chiral pyridohelicenes with the nitrogen atom(s) in various positions are characterised according to their inversion barriers, protonation constants and redox potentials. By using DFT calculations, kinetic measurements, UV/Vis titrations, cyclic voltammetry and EPR spectroscopy, a self-contained picture of their behaviour under conventional treatment by heat, acids and oxidising/reducing agents is provided.
(Strept)avidin as host for biotinylated coordination complexes: stability, chiral discrimination, and cooperativity
Incorporation of a biotinylated ruthenium tris(bipyridine) [Ru(bpy)₂(Biot-bpy)]²⁺ (1) in either avidin or streptavidin-(strept)avidin-can be conveniently followed by circular dichroism spectroscopy. To determine the stepwise association constants, cooperativity, and chiral discrimination properties, diastereopure (Λ and δ)-1 species were synthesized and incorporated in tetrameric (strept)avidin to afford (δ-[Ru(bpy)₂(Biot-bpy)]²⁺)x⊂avidin, (Λ- [Ru(bpy)₂(Biot-bpy)]²⁺)x⊂avidin, (δ-[Ru(bpy)₂(Biot- bpy)]²⁺)x⊂streptavidin, and (Λ-[Ru(bpy)₂(Biot-bpy)]²⁺) x⊂streptavidin (x = 1-4) For these four systems, the overall stability constants are log β₄ = 28.6, 30.3, 36.2, and 36.4, respectively. Critical…
Some factors affecting the removal of lead(II) ions from aqueous solution by porous hydroxyapatite: relationships between surface and adsorption properties
A porous hydroxyapatite (p-HAp) was prepared and employed for the removal of lead(II) ions at different concentrations from aqueous solution to determine the adsorption properties of p-HAp and compare them with those of a commercial hydroxyapatite (CAp) sample. The kinetic data obtained indicated that the adsorption performances of the adsorbents depended both on their specific surface area and crystallinity. Complexation of the Pb(II) ion on the adsorbent surface favoured the dissolution of hydroxyapatites characterized by a Ca/Pb molar ratio in the 0.85–1.5 range. The maximum adsorption capacity of p-Hap for Pb(II) ions at 30 ± 2°C was 2.30 mmol/g relative to 1.38 mmol/g for the commercia…
Assessing the quality of dissolved organic matter in forest soils using ultraviolet absorption spectrophotometry
Abbreviations: DOC, dissolved organic carbon; SUVA, specifi c ultraviolet absorbance; UV, ultraviolet. Ultraviolet spectrophotometry was used to investigate the effects, 30 yr after planting, of tree species substitution on the aromatic C content and related properties of dissolved organic carbon (DOC). Precautions were taken to correct measurements for the absorbance of NO 3 and dissolved Fe. In litter leachates, a signifi cant reduction in the aromatic content of DOC was found in the Douglas-fi r [Pseudotsuga menziesii (Mirb.) Franco] plantation but not in the beech (Fagus sylvatica L.) plantation. The disturbance of short-term C dynamics thus revealed agreed well with fi eld observations…
Synthesis, characterization and X-ray crystal structures of cyclam derivatives. Part VI. Proton binding studies of a pyridine-strapped 5,12-dioxocyclam based macrobicycle
The 14-membered cyclic diamide 1,4,8,11-tetraazacyclotetradecane-5,12-dione (5,12-dioxocyclam) can be considered as a trans-autodiprotected tetraazamacrocycle and provides a convenient starting material for the preparation of macrobicyclic receptors. As an example, the secondary amine nitrogen atoms located at the 1 and 8 positions were cross-bridged with a 1,3-pyridyl strap, affording the constrained ansa-dioxocyclam ligand 1,9,12,18,22-pentaazatricyclo[7.6.6.13,7]docosa-3,5,7(22)-triene-13,19-dione (L1). The proton binding properties of this cage-type compound, which possesses a hemispherical cavity, were fully investigated by spectroscopic (IR, NMR, UV, MALDI-TOF MS), quantum chemical, a…
The Chemo- and Stereoselective Formation of Pallado- and Platinocryptophanes
International audience
Thermodynamic studies of actinide complexes. 1. A reappraisal of the solution equilibria between plutonium(IV) and ethylenediaminetetraacetic acid (EDTAH4) in nitric media
Abstract A detailed reevaluation of the complexation equilibria of plutonium(IV) with the polyaminocarboxylic sequestering agent EDTA4− has been performed in 1 M (H,K)NO3 media at 298 K by means of visible absorption spectrophotometry and glass-electrode potentiometry at millimolar concentration levels. The high binding affinity even under strongly acidic conditions supports the exclusive formation of the neutral Pu(EDTA) complex over the range 0.01 ≤ [H+] ≤ 0.9 M with an apparent formation constant of log β110 = 25.8(1) at 0.9 M HNO3. Extrapolation to zero ionic strength using the SIT approach provides the first ever-reported NEA–TDB compliant estimate of β 110 0 ( log β 110 0 = 32.2 ( 3 )…
Minor changes in the macrocyclic ligands but major consequences on the efficiency of gold nanoparticles designed for radiosensitization
International audience; Many studies have been devoted to adapting the design of gold nanoparticles to efficiently exploit their promising capability to enhance the effects of radiotherapy. In particular, the addition of magnetic resonance imaging modality constitutes an attractive strategy for enhancing the selectivity of radiotherapy since it allows the determination of the most suited delay between the injection of nanoparticles and irradiation. This requires the functionalization of the gold core by an organic shell composed of thiolated gadolinium chelates. The risk of nephrogenic systemic fibrosis induced by the release of gadolinium ions should encourage the use of macrocyclic chelat…
Identification of hexanuclear Actinide(IV) carboxylates with Thorium, Uranium and Neptunium by EXAFS spectroscopy
International audience; Hydrated actinide(IV) ions undergo hydrolysis and further polymerization and precipitation with increasing pH. The resulting amorphous and partly crystalline oxydydroxides AnO(n)(OH)(4-2n)center dot xH(2)O can usually be observed as colloids above the An(IV) solubility limit. The aging process of such colloids results in crystalline AnO(2). The presence of carboxylates in the solution prevents the occurrence of such colloids by formation of polynuclear complexes through a competing reaction between hydrolysis and ligation. The majority of recently described carboxylates reveals a hexanuclear core of [An(6)(mu(3)-O)(4)(mu(3)-OH)(4)](12+) terminated by 12 carboxylate l…
Conformations and coordination schemes of carboxylate and carbamoyl derivatives of the tetraazamacrocycles cyclen and cyclam, and the relation to their protonation states
Abstract This paper discusses and rationalizes the metal coordination pattern of 12- and 14-membered tetraazamacrocyclic carboxylate and carbamoyl ligands based on the cyclen and cyclam framework in light of their acido–basic properties. Structural and protonation data are reviewed in order to illustrate the influence of the free ligand's protonation state and of the pH conditions during the complexation reaction on the final coordination mode of the metallic cations.
[(1,4,8,11-Tetraazacyclotetradeca-1,4,8,11-tetrayl)tetraacetamide-kappa6N1,N4,N8,N11,O1,O8]copper(II) sulfate 4.5-hydrate.
The crystal structure of the title copper(II) complex, [Cu(C(18)H(36)N(8)O(4))]SO(4).4.5H(2)O, formed with the tetraamide cyclam derivative 2-(4,8,11-triscarbamoylmethyl-1,4,8,11-tetraazacyclotetradec-1-yl)acetamide (TETAM), is described. The macrocycle lies on an inversion centre occupied by the hexacoordinated Cu atom. The four macrocyclic tertiary amines form the equatorial plane of an axially Jahn-Teller elongated octahedron. Two O atoms belonging to two diagonally opposite amide groups occupy the apical positions, giving rise to a trans-III stereochemistry, while both the remaining pendant side arms extend outwards from the macrocyclic cavity and are engaged in hydrogen bonds with sulf…
Effects of preorganization in the chelation of UO22+ by hydroxamate ligands: cyclic PIPO– vs linear NMA–
International audience; Many siderophores incorporate as bidentate chelating subunits linear and more seldomly cyclic hydroxamate groups. In this work, a comparative study of the uranyl binding properties in aqueous solution of two monohydroxamic acids, the prototypical linear N-methylacetohydroxamic acid (NMAH) and the cyclic analog 1-hydroxypiperidine-2-one (PIPOH), has been carried out. The complex [UO2(PIPO)(2)(H2O)] crystallized from slightly acidic water solutions (pH < 5), and its molecular structure was determined by X-ray diffraction. The uranyl speciation in the presence of both ligands has been thoroughly investigated in a 0.1 M KNO3 medium at 298.2 K by the combined use of four …
Acta of the International Symposia on Metal Complexes ISMEC 2017
International audience; This book gathers the abstracts of the 5 plenary lectures, 10 keynotes, 43 oral communications, and of the 86 posters that have been presented during the International Symposium on Metal Complexes (ISMEC 2017) hold at the Université de Bourgogne – Franche-Comté in Dijon, France on June 11-15, 2017.
Assignment of complex species by affinity capillary electrophoresis: The case of Th(IV)‐desferrioxamine B
International audience; The electrophoretic mobility change of desferrioxamine B (DFO) was monitored by UV absorption spectrophotometry upon increasing the thorium(IV) concentration in the background electrolyte at two acidities ([HClO4]Tot = 0.0316 and 0.0100 M). These data enabled to assess the speciation model and to determine the equilibrium constant of [Th(DFO)H2]3+ at fixed ionic strength (I = 0.1 M (H,Na)ClO4). Affinity capillary electrophoresis (ACE) turned out to be most helpful in identifying the complexed species by ascertaining its charge and protonation state. The assignment of the correct stoichiometry relied on the reliable estimation of the electrophoretic mobility by assumi…
Synthesis, Characterization, and X-ray Crystal Structures of Cyclam Derivatives. 8. Thermodynamic and Kinetic Appraisal of Lead(II) Chelation by Octadentate Carbamoyl-Armed Macrocycles1
En route toward the development of hybrid organic−inorganic extracting materials incorporating lead-selective chelators and their implementation in water purification processes, the lead(II) binding properties of three N-carbamoylmethyl-substituted 1,4,8,11-tetraazacyclotetradecanes (cyclams) have been fully investigated by spectroscopic (IR, UV−vis, MALDI-TOF MS, 1H and 13C NMR), X-ray crystallographic, potentiometric, and kinetic methods. Solution NMR studies revealed that the Pb2+ ion is entrapped in a molecular cage constituted by the four macrocyclic nitrogen and four amidic oxygen atoms. Protonation and lead binding constants determined in aqueous solution were shown to be linearly de…
Hydrogen-Bonded Open-Framework with Pyridyl-Decorated Channels: Straightforward Preparation and Insight into Its Affinity for Acidic Molecules in Solution.
International audience; An hydrogen-bonded open framework with pores decorated by pyridyl groups has been constructed following an off-charge-stoichiometry assemblage of protonated tetrakis(4-pyridyl-oxymethyl)methane and [Al(oxalate)3]3-, respectively the H-bond donor and acceptor of the ionic H-bond interactions. This supramolecular porous architecture (SPA-2) possesses 1 nm-large pores interconnected in 3D with high solvent accessible void (53%). It demonstrated remarkable affinity for acidic organic molecules in solution, which was investigated by the means of various carboxylic acids including larger drug molecules. Noteworthy, competing sorption between acetic acid and its halogenated…
Conformational and structural studies of N-methylacetohydroxamic acid and of its mono- and bis-chelated uranium(VI) complexes
The thermodynamics and kinetics of the cis/trans isomerism of N-methylacetohydroxamic acid (NMAH) and its conjugated base (NMA(-)) have been reinvestigated in aqueous media by (1)H NMR spectroscopy. Hindered rotation around the central C-N bond due to electronic delocalization becomes slow enough on the NMR time scale to observe both rotamers in equilibrium in D2O at room temperature. By properly assigning the methyl group resonances, evidence for the prevalence of the E over the Z form is unambiguously provided [K300=[E]/[Z]=2.86(2) and 9.63(5) for NMAH and NMA(-), respectively], closing thereby a long-lasting dispute about the most stable conformer. To that end, calculations of the chemic…
Synthesis and Structural Study of Tetravalent (Zr 4+ , Hf 4+ , Ce 4+ , Th 4+ , U 4+ ) Metal Complexes with Cyclic Hydroxamic Acids
Six- and seven-membered cyclic hydroxamic acids, such as 1-hydroxypiperidine-2-one (1H, 1,2-PIPOH) and 1-hydroxyazepan-2-one (2H), have recently been identified in some mixed siderophores as one of their three chelating subunits. Compared to their ubiquitous noncyclic counterparts, cyclic hydroxamates are preorganized for metal binding. Surprisingly, the coordination chemistry of these bidentate, monoanionic ligands remains virtually unknown, even in the case of iron(III). We report herein the first structural study of the complexes of 1– and of 6–, an unsaturated seven-membered ring analog of 2–, with tetravalent cations of transition metals (zirconium and hafnium), lanthanide (cerium), an…
A metal-responsive interdigitated bilayer for selective quantification of mercury( ii ) traces by surface plasmon resonance
Reusable surface plasmon resonance chips allowing the quantitative and selective detection of mercury(II) ions in water at the 0.01 nM level are reported. The surface-modified gold sensor consists of a rarefied self-assembled monolayer of octanethiol topped with a Langmuir–Blodgett monolayer of an amphiphilic and highly-specific chelator. The interdigitated architecture confers to the bilayer a high packing density, surface coverage, and binding-group accessibility.
Dual emission of a bis(pyrene)-functionalized, perbenzylated beta-cyclodextrin
A bis(pyrene)-functionalized β-cyclodextrin (1) has been prepared in two steps from perbenzylated β-cyclodextrin. This compound shows dual emission properties, which arise from the pyrenyl chromophores. Upon excitation of 1 at 355 nm, monomer blue fluorescence (386, 407 and 428 nm) is observed in DMSO solution, whereas excimer green fluorescence (477 nm) is seen upon addition of ≥20 vol% water in DMSO. This suggests that modified β-cyclodextrin 1 changes its shape in response to the environment. The sensing properties of 1 towards carboxylic acids and alcohols were investigated in H2O–DMSO (80 : 20 v/v). Monomer fluorescence is restored selectively by medium length normal carboxylic acids, …
Factors affecting copper(II) binding to multiarmed cyclam-grafted mesoporous silica in aqueous solution
Single- as well as multi-anchored cyclam-functionalized silica samples have been prepared by grafting amorphous silica gel (K60) and mesostructured silica (SBA-15) with silylated cyclam precursors bearing one, two, or four triethoxysilyl groups, respectively ascribed to cyclam-mono, cyclam-di, and cyclam-tetra. Their reactivity toward copper(II) has been thoroughly investigated in aqueous solution and discussed with respect to the number of arms tethering the ligand to the silica surface and the structural ordering of the adsorbent in terms of capacity, long-term stability, and speed of access to the binding sites. Less-than-complete metal ion uptake was always observed, even in excess of c…
Real-Time Observation of “Soft” Magic-Size Clusters during Hydrolysis of the Model Metallodrug Bismuth Disalicylate
International audience; Colloidal bismuth therapeutics have been used for hundreds of years, yet remain mysterious. Here we report an X-ray pair distribution function (PDF) study of the solvolysis of bismuth disalicylate, a model for the metallodrug bismuth subsalicylate (Pepto-Bismol). This reveals catalysis by traces of water, followed by multistep cluster growth. The ratio of the two major species, {Bi9O7} and {Bi38O44}, depends on exposure to air, time, and the solvent. The solution-phase cluster structures are of significantly higher symmetry in comparison to solid-state analogues, with reduced off-center Bi3+ displacements. This explains why such “magic-size” clusters can be both stab…
Interfacial Self-Assembly of Water-Soluble Cationic Porphyrins for the Reduction of Oxygen to Water
Meet at the border: Assembly of the water-soluble cobalt tetrakis(N-methylpyridinium-4-yl)porphyrin [CoTMPyP]4+ at soft interfaces is enhanced and stabilized by its interfacial interaction with the lipophilic anion (C6F5)4B−. The supramolecular structure thus formed (see picture) provides excellent catalytic activity in the four-electron reduction of oxygen.
Chelation of toxic metals: from fundamental advances in macrocyclic chemistry to extracting materials
Exposure to lead-contaminated tap water is a persistent issue in many western countries. In the context of the 98/83/EU directive, we got involved in the design of a cartridge-based purification system that could be mounted directly on a kitchen faucet. Solid-phase extraction by covalent attachment of a lead-selective sequestering agent to the surface of silica gel was thought as an efficient method to reduce the lead level below the new parametric value, as shown by pipe-loop tests.1 High binding affinity, selectivity, and fast uptake kinetics are of crucial importance. This fine-tuning was most conveniently achieved by taking advantage of the outstanding coordination properties displayed …
Coordination Chemistry of a Bis(Tetrazine) Tweezer: A Case of Host-Guest Behavior with Silver Salts
The carbon-carbon cross-coupling of phenyl s-tetrazine (Tz) units at their ortho-phenyl positions allows the formation of constrained bis(tetrazines) with original tweezer structures. In these compounds, the face-to-face positioning of the central tetrazine cores is reinforced by π-stacking of the electron-poor nitrogen-containing heteroaromatic moieties. The resulting tetra-aromatic structure can be used as a weak coordinating ligand with cationic silver. This coordination generates a set of bis(tetrazine)-silver(I) coordination complexes tolerating a large variety of counter anions of various geometries, namely, PF6−, BF4−, SbF6−, ClO4−, NTf2−, and OTf−. These compounds were characterized…
Synthesis, characterization and X-ray crystal structures of cyclam derivatives. 7. Hydrogen-bond induced allosteric effects and protonation cooperativity in a macrotricyclic bisdioxocyclam receptor
The unprecedented cooperative protonation properties displayed by a barrel-shaped macrotricyclic tetraamine incorporating two 14-membered bisamide rings maintained in a face-to-face arrangement is rationalized in terms of allosteric effects upon binding of the first and third protons.
ChemInform Abstract: The Ins and Outs of Proton Complexation
Proton complexation differs from simple protonation by the fact that the coordinated hydrogen atom is bound intramolecularly to more than one donor atom. This is usually achieved by covalent bonding supplemented by hydrogen bonding. In a few cases, however, the complexed proton is hydrogen-bound to all donor atoms, which gives rise to single well (SWHB) and low barrier (LBHB) hydrogen bonds. This tutorial review highlights a full range of proton complexes formed with chelating and “proton-sponge”-type ligands, cryptand-like macropolycycles, and molecules of topological relevance, such as rotaxanes and catenanes. The concept of proton complexation can explain how the smallest cation possible…
Biomimetic oxygen reduction by cofacial porphyrins at a liquid-liquid interface.
Oxygen reduction catalyzed by cofacial metalloporphyrins at the 1,2-dichlorobenzene−water interface was studied with two lipophilic electron donors of similar driving force, 1,1'-dimethylferrocene (DMFc) and tetrathiafulvalene (TTF). The reaction produces mainly water and some hydrogen peroxide, but the mediator has a significant effect on the selectivity, as DMFc and the porphyrins themselves catalyze the decomposition and the further reduction of hydrogen peroxide. Density functional theory calculations indicate that the biscobaltporphyr- in, 4,5-bis(5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl))-9,9-dimethylxanthene, Co2(DPX), actually catalyzes oxygen reduction to hydrogen p…
Chemical modification of porous calcium hydroxyapatite surfaces by grafting phenylphosphonic and phenylphosphite acids
Abstract It is well known that the incorporation of organic molecules can provide an effective route to modify the surface properties of apatite ceramics. The present study shows that phosphonates can react with calcium ions to control the formation of the hydroxyapatite structures. The grafting of C6H5PO(OH)2 (PPOH) and C6H5PO(OH)H (PPH) was used to increase the specific surface area as well as the porosity of hydroxyapatite materials. The higher specific surface area for HAp treated by PPOH is around 267 m2/g compared to the pure HAp (140 m2/g). The phenyl (C6H5) groups are removed by thermal treatment around 500 °C. After treatment at 800 °C, organoapatites (PP-HAp) are converted to stoi…
Cavitands incorporating a Lewis acid dinickel chelate function as receptors for halide anions.
The halide binding properties of the cavitand [Ni2(L(Me2H4))](2+) (4) are reported. Cavitand 4 exhibits a chelating N3Ni(μ-S)2NiN3 moiety with two square-pyramidal Ni(II)N3S2 units situated in an anion binding pocket of ∼4 Å diameter formed by the organic backbone of the (L(Me2H4))(2-) macrocycle. The receptor reacts with fluoride, chloride (in MeCN/MeOH), and bromide (in MeCN) ions to afford an isostructural series of halogenido-bridged complexes [Ni2(L(Me2H4))(μ-Hal)](+) (Hal = F(-) (5), Cl(-) (6), and Br(-) (7)) featuring a N3Ni(μ-S)2(μ-Hal)NiN3 core structure. No reaction occurs with iodide or other polyatomic anions (ClO4(-), NO3(-), HCO3(-), H2PO4(-), HSO4(-), SO4(2-)). The binding ev…
Functionalization of Bambusurils by a Thiol-Ene Click Reaction and a Facile Method for the Preparation of Anion-Free Bambus[6]urils
Sulfide-functionalized bambus[4]urils ((RS)8 BU[4]) and bambus[6]urils ((RS)12 BU[6]) were synthesized through thiol-ene click coupling reactions (TEC) of allylbambus[n]urils. Thiosugars were grafted to BU[4] and BU[6]. Synthesis of BU[6] derivatives always requires the use of a template anion (iodide, chloride, or bromide), which is enclosed in the cavity of BU[6]. We show that this anion influences the reactivity of bambus[6]urils. An encapsulated iodide makes allyl functions of allyl12 BU[6] less reactive towards TEC and hydrogenation reactions in comparison to the corresponding chloride or bromide inclusion complexes. This is critical for the chemical reactivity of BU[6] and even more t…
Azide Binding Controlled by Steric Interactions in Second Sphere. Synthesis, Crystal Structure, and Magnetic Properties of [Ni II 2 (L)(μ 1,1 -N 3 )][ClO 4 ] (L = Macrocyclic N 6 S 2 Ligand)
International audience; The dinuclear Ni-II complex [Ni-2(L-2)][ClO4](2) (3) supported by the 28-membered hexaaza-dithiophenolate macro-cycle (L-2)(2-) binds the N-3(-) ion specifically end-on yielding [Ni-2(L-2)(mu(1,1)-N-3)] [ClO4] (7) or [Ni-2(L-2)(mu(1,1)-N-3)][BPh4] (8), while the previously reported complex [Ni2L1(mu(1,3)-N-3)][ClO4] (2) of the 24-membered macrocycle (L-1)(2-) coordinates it in the end-to-end fashion. A comparison of the X-ray structures of 2, 3, and 7 reveals the form-selective binding of complex 3 to be a consequence of its preorganized, channel-like binding pocket, which accommodates the azide anion via repulsive CH center dot center dot center dot pi interactions …
Voltammetric Detection of Lead(II) Using Amide-Cyclam- Functionalized Silica-Modified Carbon Paste Electrodes
2-(4,8,11-Triscarbamoylmethyl-1,4,8,11-tetraazacyclotetradec-1-yl)acetamide (TETAM) derivatives bearing 1, 2, or 4 silylated arms have been synthesized and grafted to the surface of silica gel and ordered mesoporous silica samples. The resulting organic-inorganic hybrids have been incorporated into carbon paste electrodes and applied to the preconcentration electroanalysis of Pb(II). The attractive recognition properties of these cyclam derivatives functionalized with amide pendent groups toward Pb(II) species and the highly porous structure of the adsorbents can be exploited for the selective and sensitive detection of the target analyte. Various parameters affecting the preconcentration a…
A molecular approach to remove lead from drinking water
Abstract Corrosion of lead-containing plumbings is responsible for significant contamination of tap water, which can reach several hundreds of micrograms per liter. According to a decision of the European Council applicable in 2013, the maximal lead level in tap water should not exceed 10 μg l −1 . A new concept has been explored that relies on solid-phase extraction by covalent attachment of a lead-selective macrocyclic sequestering agent onto the surface of silica gel. An N -carbamoylmethyl substituted 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative was shown to exhibit favorable protonation properties together with an almost 10 6 -fold selectivity for lead over calcium. Structural …
CCDC 1553488: Experimental Crystal Structure Determination
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CCDC 908612: Experimental Crystal Structure Determination
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CCDC 1042533: Experimental Crystal Structure Determination
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CCDC 908613: Experimental Crystal Structure Determination
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CCDC 1537659: Experimental Crystal Structure Determination
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CCDC 917925: Experimental Crystal Structure Determination
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CCDC 1904438: Experimental Crystal Structure Determination
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CCDC 945040: Experimental Crystal Structure Determination
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CCDC 938729: Experimental Crystal Structure Determination
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CCDC 983068: Experimental Crystal Structure Determination
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CCDC 1537661: Experimental Crystal Structure Determination
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CCDC 966355: Experimental Crystal Structure Determination
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CCDC 966357: Experimental Crystal Structure Determination
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CCDC 1042608: Experimental Crystal Structure Determination
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CCDC 1537660: Experimental Crystal Structure Determination
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CCDC 915779: Experimental Crystal Structure Determination
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CCDC 1537663: Experimental Crystal Structure Determination
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CCDC 937567: Experimental Crystal Structure Determination
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CCDC 937568: Experimental Crystal Structure Determination
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CCDC 966356: Experimental Crystal Structure Determination
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CCDC 908614: Experimental Crystal Structure Determination
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CCDC 1579042: Experimental Crystal Structure Determination
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CCDC 1904436: Experimental Crystal Structure Determination
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CCDC 1904437: Experimental Crystal Structure Determination
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CCDC 1437970: Experimental Crystal Structure Determination
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CCDC 945039: Experimental Crystal Structure Determination
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CCDC 1537662: Experimental Crystal Structure Determination
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CCDC 908617: Experimental Crystal Structure Determination
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CCDC 937569: Experimental Crystal Structure Determination
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CCDC 908616: Experimental Crystal Structure Determination
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CCDC 1042532: Experimental Crystal Structure Determination
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CCDC 1553489: Experimental Crystal Structure Determination
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CCDC 915780: Experimental Crystal Structure Determination
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CCDC 908615: Experimental Crystal Structure Determination
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