Crystal structure of bis(cyclohexylammonium) diphenyldioxalatostannate(IV)

2015

In the title salt, (CyNH3)2[Sn(Ph2)(C2O4)2] (Cy is cyclo­hexyl and Ph is phen­yl), the SnPh2 moiety is chelated by two oxalate anions, leading to a cis arrangement within the distorted octa­hedral coordination sphere of the SnIV atom.

Organotin(IV) trifluoromethanesulfonates chemistry: Isolation and characterization of a new di-n-butyl derivative presenting a Sn3O3 core

2012

Abstract Reaction of the dimeric hydroxo di-n-butylstannane trifluoromethanesulfonato complex [n-Bu2Sn(OH)(H2O)(CF3SO3)]2 (1) with a mixture of anthracene (C14H10, Ant) and phenazine (C12H8N2, Phz) in dichloromethane at room temperature yielded the novel di-n-butyltin(IV) trifluoromethanesulfonate salt {[n-Bu2Sn(H2O)]2O·n-Bu2Sn(OH)2}(CF3SO3)2 (2), together with the co-crystallization of phenazinium trifluoromethanesulfonate salts ([C12H9N2][CF3SO3], PhzH) collected in the solid state in two distinct self-assembled architectures, 3 and 4, showing π–π stacking interactions, and involving the intercalation of free molecules of phenazine and anthracene, respectively. Complex 2 is a cationic tri…

Reactivity of di-tert-butyldimethoxystannane with carbon dioxide and methanol: X-ray structure of the resulting complex

2006

Abstract The synthesis of dimethyl carbonate from carbon dioxide and methanol was studied with ditert-butyldimethoxystannane under pressure at temperatures ⩽423 K. The formation of dimethyl carbonate is accompanied by transformation of the stannane into a trinuclear complex, the structure of which has been determined by single-crystal X-ray diffraction technique. The relevance of this specie in the catalytic cycle is demonstrated by conducting recycling runs. A preliminary kinetic study underlines the steric influence of the tert-butyl ancillary ligands in the stabilisation of intermediates, by comparison with the n-butyl homologue.

Efficient microwave-assisted synthesis of glycerol monodecanoate

2017

International audience; Solvent-free microwave-assisted synthesis was carried out to prepare 2,3-dihydroxypropyl decanoate, by esterification of decanoic acid in the presence of two distinct glycerol derivatives, glycidol, and glycerol carbonate, respectively. The process described is based on microwaves heating source with electrical power in the range of 200–400 W, involving stoichiometric proportions of decanoic acid and glycerol derivatives, and using catalytic amounts of TBAI used as organocatalyst. Conversion and selectivity rates of esterification reactions were monitored by 1H and 13C{1H} NMR spectroscopy. The predominantly formed ester, 2,3-dihydroxypropyl decanoate was fully chara…

Organocatalytic synthesis of new telechelic polycarbonates and study of their chemical reactivity

2015

Abstract A two-step versatile process for telechelic polycarbonates synthesis is described. 1-n-butyl-3-methylimidazolium-2-carboxylate (BMIM-2-CO2) was used as thermolabile precursor of N-heterocyclic carbene (NHC) organocatalyst. In a first step, synthesized branched fatty diols or commercially available linear diols were reacted with an excess of dimethylcarbonate (DMC) to afford oligocarbonates with methylcarbonate end-groups. Then, the methylcarbonate groups were reacted with hydroxyl groups of 9-decen-1-ol, 4-hexyn-1-ol and 4-hydroxybenzene ethanol leading to telechelic oligomers with alkene, alkyne and phenol functionalities. Reactivity of these end-groups towards polymerization was …

Undecylenic acid: A tunable bio-based synthon for materials applications

2016

International audience; An undecylenic acid-based monoglyceride prepared from glycidol and undecylenic acid is used as suitable and tunable synthon for polymerization applications. Epoxidation and acrylation reactions lead to photopolymerizable monomers while transesterification with dimethyl carbonate, metathesis and aminolysis reactions provide access to polyhydroxyurethane-based materials. The successive intermediates were synthesized according to a green chemistry approach implicating solvent-less and catalyzed reactions, and were at each step fully characterized by infrared, 1H and 13C{1H} NMR spectroscopy, elemental analysis and mass spectrometry. Analyses of the resulting polymer mat…

Tribenzylammonium chloride

2014

Single crystals of the title salt, C21H21NH+·Cl−, were isolated as a side product from the reaction involving [(C6H5CH2)3NH]2[HPO4] and Sn(CH3)3Cl in ethanol. Both the cation and the anion are situated on a threefold rotation axis. The central N atom in the cation has a slightly distorted tetrahedral environment, with angles ranging from 107.7 to 111.16 (10)°. In the crystal, the tribenzylammonium cations and chloride anions are linked through N—H...Cl and C—H...Cl hydrogen bonds, leading to the formation of infinite chains along [001]. The crystal studied was a merohedral twin.

Propane-1,3-diammonium molybdate

2019

The reaction between equimolar amounts of propane-1,3-diamine and molybdenum trioxide in water led to the formation of single crystals of the title salt, (C3H12N2)[MoO4]. The asymmetric unit is comprised of one propane-1,3-diammonium cation and one molybdate anion. The latter is isolated in the structure and has a slightly distorted tetrahedral configuration. An extensive network of N—H...O hydrogen bonds connects anions and cations, giving rise to a compact three-dimensional packing.

The skeleton of the staghorn coral Acropora millepora: molecular and structural characterization.

2014

15 pages; International audience; The scleractinian coral Acropora millepora is one of the most studied species from the Great Barrier Reef. This species has been used to understand evolutionary, immune and developmental processes in cnidarians. It has also been subject of several ecological studies in order to elucidate reef responses to environmental changes such as temperature rise and ocean acidification (OA). In these contexts, several nucleic acid resources were made available. When combined to a recent proteomic analysis of the coral skeletal organic matrix (SOM), they enabled the identification of several skeletal matrix proteins, making A. millepora into an emerging model for biomi…

Equilibrium solution coordination chemistry

2018

Welcome to this themed issue of New Journal of Chemistry entitled “Equilibrium Solution Coordination Chemistry”.

Synthesis of dimethyl carbonate in supercritical carbon dioxide

2006

The reactivity of carbon dioxide with methanol to form dimethyl carbonate was studied in the presence of the n-butylmethoxytin compounds n-Bu3SnOCH3, n-Bu2Sn(OCH3)2 , and [n-Bu2(CH3O)Sn]2 O. The reaction occurred under solventless conditions at 423 K and was produced by an increase in CO2 pressure. This beneficial effect is primarily attributed to phase behavior. The mass transfer under liquid-vapor biphasic conditions was not limiting when the system reached the supercritical state for a CO2 pressure higher than 16 MPa. Under these conditions, CO2 acted as a reactant and a solvent.

The shell organic matrix of the crossed lamellar queen conch shell (Strombus gigas)

2014

10 pages; International audience; In molluscs, the shell organic matrix comprises a large set of biomineral-occluded proteins, glycoproteins and polysaccharides that are secreted by the calcifying mantle epithelium, and are supposed to display several functions related to the synthesis of the shell. In the present paper, we have characterized biochemically the shell matrix associated to the crossed-lamellar structure of the giant queen conch Strombus gigas. The acid-soluble (ASM) and acid-insoluble (AIM) matrices represent an extremely minor fraction of the shell. Both are constituted of polydisperse and of few discrete proteins among which three fractions, obtained by preparative SDS-PAGE …

Crystal structure of 2-methyl-1H-imidazol-3-ium hydrogen oxalate dihydrate

2016

In the title mol­ecular salt 2-methyl-1H-imidazol-3-ium hydrogen oxalate dihydrate, N—H⋯(O,O) and O—H⋯O hydrogen bonds link the components into a bilayer-like assembly.

Bimetallic ruthenium-tin chemistry: synthesis and molecular structure of arene ruthenium complexes containing trichlorostannyl ligands

2010

A series of neutral, anionic and cationic arene ruthenium complexes containing the trichlorostannyl ligand have been synthesised from SnCl2 and the corresponding arene ruthenium dichloride dimers [(η6-arene)Ru(μ2-Cl)Cl]2 (arene = C6H6, PriC6H4Me). While the reaction with triphenylphosphine and stannous chloride only gives the neutral mono(trichlorostannyl) complexes [(η6-C6H6)Ru(PPh3)(SnCl3)Cl] (1) and [(η6-PriC6H4Me)Ru(PPh3)(SnCl3)Cl] (2), the neutral di(trichlorostannyl) complex [(η6-PriC6H4Me)Ru(NCPh)(SnCl3)2] (3) could be obtained for the para-cymene derivative with benzonitrile as additional ligand. By contrast, the analogous reaction with the benzene derivative leads to a salt compose…

Synthesis, spectroscopic study, and crystal structure of a new organotin(IV) selenate derivative

2018

Abstract The polymeric organotin(IV) selenate complex [(Me3Sn)3(SeO4)(OH)]n (1) has been isolated as single crystals from the reaction of [(Me2NH2)2SeO4] and Me3SnCl in methanol. In the solid state, compound 1 was characterized by X-ray diffraction analysis, Fourier transform-infrared spectroscopy, and elemental analysis. 1 crystallizes in the orthorhombic system space group Pbca with a=11.0231(2) Å, b=16.3461(3) Å, c=20.9945(4) Å, α=β=γ=90°, V=3782.89(12) Å3, and Z=8. Its structure can be described as a polymeric zigzag chain based on Me3Sn moieties linked by tridentate selenate anions. Pendant (Me3Sn)2OH groups are also connected to the chain, according to a syndiotactic organization, and…

Organo-catalyzed synthesis of aliphatic polycarbonates in solvent-free conditions

2012

A new efficient and expeditious route to the synthesis of aliphatic polycarbonates, in solvent-free conditions and using 1-n-butyl-3-methylimidazolium-2-carboxylate (BMIM-2-CO2) as a catalyst precursor, is described. The protocol consists of a two-step polymerization process involving the transesterification of dimethyl carbonate (DMC) with linear alkane diols and leading to high molecular weight homopolymers. The reaction went to completion quantitatively with the liberation of methanol as the only by-product. The in situ formation of N-heterocyclic carbene species resulting from BMIM-2-CO2 decarboxylation is suggested to be a key feature of the condensation process. The protocol was then …

Variability of shell repair in the Manila clam Ruditapes philippinarum affected by the Brown Ring Disease: A microstructural and biochemical study

2011

11 pages; International audience; For more than two decades, the Manila clam Ruditapes philippinarum has been regularly affected by Brown Ring Disease (BRD), an epizootic event caused by the bacterium Vibrio tapetis and characterized by the development of a brown deposit on the inner face of valves. Although BRD infection is often lethal, some clams recover by mineralizing a new repair shell layer, which covers the brown deposit and fully isolates it from living tissues. In order to understand this specific shell repair process, the microstructures of repaired zones were compared to those of shells unaffected by BRD. In addition, the organic matrix associated with unaffected shells and to r…

Carbon Dioxide as Chemical Feedstock. Edited by Michele Aresta.

2010

Bis(cyclohexylammonium) tetrachlorido(oxalato)stannate(IV)

2013

The title salt, (C6H14N)2[Sn(C2O4)Cl4], was obtained as a by-product from the reaction between 2C6H14N+·C2O42−·1.5H2O and SnCl2·2H2O. The cyclohexylammonium cation has a chair conformation. The complex anion consists of an oxalate anion chelating the SnCl4 moiety, resulting in a distorted octahedral coordination sphere of the SnIV atom with the O atoms in equatorial cis positions. In the crystal, cations and anions are linked through N—H...O and N—H...Cl interactions into a layered arrangement parallel to (100).

Spine and test skeletal matrices of the Mediterranean sea urchinArbacia lixula- a comparative characterization of their sugar signature

2015

15 pages; International audience; Calcified structures of sea urchins are biocomposite materials that comprise a minor fraction of organic macromolecules, such as proteins, glycoproteins and polysaccharides. These macromolecules are thought to collectively regulate mineral deposition during the process of calcification. When occluded, they modify the properties of the mineral. In the present study, the organic matrices (both soluble and insoluble in acetic acid) of spines and tests from the Mediterranean black sea urchin Arbacia lixula were extracted and characterized, in order to determine whether they exhibit similar biochemical signatures. Bulk characterizations were performed by mono-di…

Catalytic and anticancer activities of sawhorse-type diruthenium tetracarbonyl complexes derived from fluorinated fatty acids

2013

The reaction of fluorinated fatty acids, perfluorobutyric acid (C3F7CO2H), and perfluorododecanoic acid (C11F23CO2H), with dodecacarbonyltriruthenium (Ru3(CO)12) under reflux in tetrahydrofuran, followed by addition of two-electron donors (L) such as pyridine, 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]decane, or triphenylphosphine, gives stable diruthenium complexes Ru2(CO)4(μ2-η2-O2CC3F7)2(L)2 (1a, L = C5H5N; 1b, L = PTA; 1c, L = PPh3) and Ru2(CO)4(μ2-η2-O2CC11F23)2(L)2 (2a, L = C5H5N; 2b, L = PTA; 2c, L = PPh3). The catalytic activity of the complexes for hydrogenation of styrene under supercritical carbon dioxide has been assessed and compared to the analogous triphenylphosphine complexes w…

Crystal structure of bis­(2-methyl-1H-imidazol-3-ium) di­hydroxidobis(oxalato-κ2 O 1,O 2)stannate(IV) monohydrate

2016

The SnIV atom in the anion of the title compound is six-coordinated by two OH groups and four O atoms from two chelating oxalate ligands. Several N—H⋯O and O—H⋯O hydrogen bonds involving the stannate dianions, the cations and the water mol­ecules result into a three-dimensional network structure.

The shell of the invasive bivalve species Dreissena polymorpha: biochemical, elemental and textural Investigations.

2016

28 pages; International audience; The zebra mussel Dreissena polymorpha is a well-established invasive model organism. Although extensively used in environmental sciences, virtually nothing is known of the molecular process of its shell calcification. By describing the microstructure, geochemistry and biochemistry/proteomics of the shell, the present study aims at promoting this species as a model organism in biomineralization studies, in order to establish a bridge with ecotoxicology, while sketching evolutionary conclusions. The shell of D. polymorpha exhibits the classical crossed-lamellar/complex crossed lamellar combination found in several heterodont bivalves, in addition to an extern…

Crystal structure of the bis(cyclohexylammonium) succinate succinic acid salt adduct

2015

The title salt adduct comprises two cyclo­hexyl­ammonium cations, one succinate anion and one mol­ecule of succinic acid, linked together through inter­molecular hydrogen-bonding inter­actions giving a two-dimensional layer-like self-assembly lying parallel to (010).

The ‘Shellome’ of the Crocus Clam Tridacna crocea Emphasizes Essential Components of Mollusk Shell Biomineralization

2021

Molluscan shells are among the most fascinating research objects because of their diverse morphologies and textures. The formation of these delicate biomineralized structures is a matrix-mediated process. A question that arises is what are the essential components required to build these exoskeletons. In order to understand the molecular mechanisms of molluscan shell formation, it is crucial to identify organic macromolecules in different shells from diverse taxa. In the case of bivalves, however, taxon sampling in previous shell proteomics studies are focused predominantly on representatives of the class Pteriomorphia such as pearl oysters, edible oysters and mussels. In this study, we hav…

The shell matrix of the european thorny oyster, Spondylus gaederopus: microstructural and molecular characterization.

2020

17 pages; International audience; Molluscs, the largest marine phylum, display extraordinary shell diversity and sophisticated biomineral architectures. However, mineral-associated biomolecules involved in biomineralization are still poorly characterised.We report the first comprehensive structural and biomolecular study of Spondylus gaederopus, a pectinoid bivalve with a peculiar shell texture. Used since prehistoric times, this is the best-known shell of Europe’s cultural heritage. We find that Spondylus microstructure is very poor in mineral-bound organics, which are mostly intercrystalline and concentrated at the interface between structural layers.Using high-resolution liquid chromatog…

Tris(cyclo-hexyl-ammonium) cis-di-chlorido-bis-(oxalato-κ(2) O (1),O (2))stann-ate(IV) chloride monohydrate.

2013

The crystal structure of the title compound, (C6H14N)3[Sn(C2O4)2Cl2]Cl·H2O, contains three cyclohexylammonium cations, one stannate(IV) dianion, one isolated chloride anion and one lattice water molecule. The cyclohexylammonium cations adopt chair conformations. In the complex anion, two bidentate oxalate ligands and two chloride anions incispositions coordinate octahedrally to the central SnIVatom. The cohesion of the molecular entities is ensured by the formation of N—H...O, O—H...O, O—H...Cl and N—H...Cl interactions involving cations, anions and the lattice water molecule, giving rise to a layer-like arrangement parallel to (010).

Self-assembly of 1D- and 3D-networks through non-coordination intermolecular forces: synthesis and crystal structures of copper(I) complexes based on…

2007

Reaction of [Cu2(H3CCN)2(μ-pydz)3][PF6]2 (1) with an excess of pyridazine or phthalazine yielded the novel dinuclear complexes [Cu2(μ-pydz)3(pydz)2][PF6]2 (2) and [Cu2 (μ- pydz)(μ-phtz)2(phtz)2][PF6]2 (5), respectively. Depolymerisation of the coordination polymer 1 ∞ {[Cu(μ-pydz)2][PF6]} (3) in dichloromethane by addition of an excess of benzo[c]cinnoline afforded the dinuclear copper(I) salt [Cu2(μ-pydz)2(pydz)2(benzo[c]cinnoline)2][PF6]2 (4). Furthermore, a new route for the preparation of bis(benzonitrile)tris(μ-phthalazine)dicopper(I) bis(trifluoromethanesulfonate), [Cu2(C6H5CN)2(μ-phtz)3][CF3SO3]2 (7), was established from {[Cu(CF3SO3)]2 ・C6H5Me}, phthalazine and benzonitrile via the …

Pearl grafting: tracking the biological origin of nuclei by straightforward immunological methods.

2018

9 pages; International audience; French Polynesia is renowned for the production of Tahitian black pearl. These gems are obtained by grafting a nucleus into the gonad of a receiving oyster together with a graft, i.e. a small section of mantle tissue of a donor oyster. This procedure initiates the formation of a pearl sack around the nucleus, and subsequently, the deposition of concentric layers of nacre. The nucleus plays a key-role in pearl formation and its characteristics influence markedly the quality of the final product. As it is manufactured from mollusc shells, it contains a small percentage of organics. In the present paper, we used a set of biochemical techniques to characterize a…

Design and synthesis of biobased epoxy thermosets from biorenewable resources

2017

International audience; Biobased diepoxy synthons derived from isoeugenol, eugenol or resorcinol (DGE-isoEu, DGE-Eu and DGER, respectively) have been used as epoxy monomers in replacement of the diglycidyl ether of bisphenol A (DGEBA). Their curing with six different biobased anhydride hardeners leads to fully biobased epoxy thermosets. These materials exhibit interesting thermal and mechanical properties comparable to those obtained with conventional petrosourced DGEBA-based epoxy resins cured in similar conditions. In particular, a high Tg in the range of 90–130 °C and instantaneous moduli higher than 4.3 GPa have been recorded. These good performances are very encouraging, making these n…

Biochemical characterization of the skeletal matrix of the massive coral, Porites australiensis - The saccharide moieties and their localization.

2018

11 pages; International audience; To construct calcium carbonate skeletons of sophisticated architecture, scleractinian corals secrete an extracellular skeletal organic matrix (SOM) from aboral ectodermal cells. The SOM, which is composed of proteins, saccharides, and lipids, performs functions critical for skeleton formation. Even though polysaccharides constitute the major component of the SOM, its contribution to coral skeleton formation is poorly understood. To this end, we analyzed the SOM of the massive colonial coral, Porites australiensis, the skeleton of which has drawn great research interest because it records environmental conditions throughout the life of the colony. The coral …

Characterization of the teeth skeletal matrix from Arbacia lixula.

2015

15 pages; International audience

Bromide hydrogen oxalate salts with the diprotonated 1,4-diazabicyclo[2.2.2]octane counterion

2020

Abstract Two new salts composed of the diprotonated 1,4-diazabicyclo[2.2.2]octane (DABCO) molecule as the cations and bromide and hydrogen oxalate as the anions have been isolated and structurally characterized by X-ray diffraction analysis. The salt [DABCOH2]{[HC2O4][Br]} (1) crystallizes in the orthorhombic system, space group P212121 with a = 9.0809(7), b = 9.5156(7), c = 12.3558(9) Å, V = 1067.67(14) Å3 and Z = 4. The salt [DABCOH2]2{[HC2O4][Br]3}·H2O (2) crystallizes in the orthorhombic system, space group Pnma with a = 26.6554(17), b = 7.3711(4), c = 10.7421(7) Å, V = 2110.6(2) Å3 and Z = 4. The compounds were prepared from ethanolic solutions of [DABCOH2][HC2O4]2 (L 1 ) and ZnBr2 in …

Unprecedented Hexa- and Undecanuclear Frameworks of Two New Tin(IV) Oxo Clusters Resulting from Partial Debenzylation Reactions

2010

A new and facile synthetic route to the known neutral cluster ((PhCH2)2SnO)6[((PhCH2)2SnOH)2- (CO3)]2 (2) as well as its reactivity toward trifluoromethanesulfonic acid (HO3SCF3, TfOH) are reported. The solid-state structure of the new solvate 2·6C7H8 has been determined by single-crystal X-ray diffraction. The core of 2 can be described as a pair of coplanar pentanuclear [(PhCH2)2SnO]5 ladders bridged at their ends by two carbonate groups. Successive additions of TfOH to a suspension of 2 in CD3CN were monitored by 119Sn{1H} NMR spectroscopy showing the transformation of the fingerprint of 2 (δ = −244, −246, −306 ppm), via new upfield signals, to a final broad resonance located at δ = −474…

s-Block metal scorpionates – A new sodium hydrido-tris(3,5-dimethyl-1-pyrazolyl)borate salt showing an unusual core stabilized by bridging and termin…

2020

Abstract Dissolution of [(μ-Me2CO)3(NaTp*)2] (1) (Tp* = hydrido-tris(3,5-dimethyl-1-pyrazolyl)borate) in DMSO at room temperature leads to the growth of colourless crystals characterized as the new salt [Na2Tp*(μ-Me2SO)3(Me2SO)3] [NaTp* 2] (2). 2 crystallized in the trigonal space group R3 with Z = 3, a = 14.1227(2) Å, b = 14.1227(10) Å, c = 33.9685(2) Å, and V = 5867.35(17) Å3. Interestingly, anion and cation of 2 both contain the Tp* ligand. Moreover, the cationic moiety highlights an unusual sodium atom hexacoordinated by six DMSO molecules acting as O-bonded ligands. Three of which exhibit a bridging coordination mode and three are in terminal position. To the best of our knowledge, the…

Genesis of amorphous calcium carbonate containing alveolar plates in the ciliate Coleps hirtus (Ciliophora, Prostomatea).

2013

7 pages; International audience; In the protist world, the ciliate Coleps hirtus (phylum Ciliophora, class Prostomatea) synthesizes a peculiar biomineralized test made of alveolar plates, structures located within alveolar vesicles at the cell cortex. Alveolar plates are arranged by overlapping like an armor and they are thought to protect and/or stiffen the cell. Although their morphology is species-specific and of complex architecture, so far almost nothing is known about their genesis, their structure and their elemental and mineral composition. We investigated the genesis of new alveolar plates after cell division and examined cells and isolated alveolar plates by electron microscopy, e…

Nautilin-63, a novel acidic glycoprotein from the shell nacre of Nautilus macromphalus

2011

In molluscs, and more generally in metazoan organisms, the production of a calcified skeleton is a complex molecular process that is regulated by the secretion of an extracellular organic matrix. This matrix constitutes a cohesive and functional macromolecular assemblage, containing mainly proteins, glycoproteins and polysaccharides that, together, control the biomineral formation. These macromolecules interact with the extruded precursor mineral ions, mainly calcium and bicarbonate, to form complex organo-mineral composites of well-defined microstructures. For several reasons related to its remarkable mechanical properties and to its high value in jewelry, nacre is by far the most studied …

The test skeletal matrix of the black sea urchin Arbacia lixula

2015

11 pages; International audience; In the field of biomineralization, the past decade has been marked by the increasing use of high throughput techniques, i.e. proteomics, for identifying in one shot the protein content of complex macromolecular mixtures extracted from mineralized tissues. Although crowned with success, this approach has been restricted so far to a limited set of key-organisms, such as the purple sea urchin Strongylocentrotus purpuratus, the pearl oyster or the abalone, leaving in the shadow non-model organisms. As a consequence, it is still unknown to what extent the calcifying repertoire varies, from group to group, at high (phylum, class), median (order, family) or low (g…

A minimal molecular toolkit for mineral deposition? Biochemistry and proteomics of the test matrix of adult specimens of the sea urchin Paracentrotus…

2016

12 pages; International audience; The sea urchin endoskeleton consists of a magnesium-rich biocalcite comprising a small amount of occluded organic macromolecules. This structure constitutes a key-model for understanding the mineral - organics interplay, and for conceiving in vitro bio-inspired materials with tailored properties. Here we employed a deep-clean technique to purify the occluded proteins from adult Paracentrotus lividus tests. We characterized them by 1- and 2D-electrophoreses, ELISA and immunoblotting, and using liquid chromatography coupled with Mass Spectrometry (nanoLC-MS/MS), we identified two metalloenzymes (carbonic anhydrase and MMP), a set of MSP130 family members, sev…

The shell matrix and microstructure of the Ram's Horn squid: Molecular and structural characterization.

2020

20 pages; International audience; Molluscs are one of the most diversified phyla among metazoans. Most of them produce an external calcified shell, resulting from the secretory activity of a specialized epithelium of the calcifying mantle. This biomineralization process is controlled by a set of extracellular macromolecules, the organic matrix. In spite of several studies, these components are mainly known for bivalves and gastropods. In the present study, we investigated the physical and biochemical properties of the internal planispiral shell of the Ram's Horn squid Spirula spirula. Scanning Electron Microscope investigations of the shell reveal a complex microstructural organization. The…

Self-assembly through non-coordinating intermolecular forces, part 2 [1]. Synthesis, crystal structure and packing of [Cu2(μ-phthalazine) 3(phthalazi…

2008

Abstract Treatment of the copper(I) trifluoromethanesulphonate toluene complex {[Cu(CF3SO3)]2 · C6H5Me} (1) with phthalazine (phtz, C8H6N2) in dichloromethane-acetonitrile solution yielded, via the bis(acetonitrile)tris(μ-phthalazine)dicopper(I) trifluoromethanesulphonate intermediate (2), the novel bis(phthalazine)tris(μ-phthalazine)dicopper(I) trifluoromethanesulphonate salt (3). Compound 3 was completely characterised and the molecular structure determined by single-crystal X-ray diffraction. Complex 3 crystallises in the monoclinic system, space group C2/c, with a = 26.9527(10), b = 10.9558(7), c = 19.2104(10) Å , β = 127.268(2)◦, V = 4514.3(4) Å3 and Z = 4. The copper(I) coordination g…

Biomass-derived phenylpropenes as precursors of thermosetting epoxy resins : from synthesis to materials

2019

International audience; As demonstrated by the current international awareness, and supported by several independent studies, the replacement of fossil fuels and the need to find competitive alternatives are crucial issues to reduce global warming, and to limit the consequences for life on Earth [1]. As part of this challenge, the biomass and molecules from the living can be considered as providential pools of renewable building blocks dedicated to the chemistry of the future. This is particularly true in polymer science, where the use of renewable resources for the synthesis of fully or partially biobased materials arouses a great deal of interest, in academia and industry [2].

'Palaeoshellomics' reveals the use of freshwater mother-of-pearl in prehistory

2019

The extensive use of mollusc shell as a versatile raw material is testament to its importance in prehistoric times. The consistent choice of certain species for different purposes, including the making of ornaments, is a direct representation of how humans viewed and exploited their environment. The necessary taxonomic information, however, is often impossible to obtain from objects that are small, heavily worked or degraded. Here we propose a novel biogeochemical approach to track the biological origin of prehistoric mollusc shell. We conducted an in-depth study of archaeological ornaments using microstructural, geochemical and biomolecular analyses, including ‘palaeoshellomics’, the first…

New acridinium trifluoromethanesulfonate stacks induced in the presence of organotin(IV) complexes

2013

Abstract Three new crystalline architectures based on acridinium trifluoromethanesulfonate salts [C13H10N]+[CF3SO3]– have been isolated as single crystals from the reaction of the dimeric hydroxo di-n-butylstannane trifluoromethanesulfonato complex [n-Bu2Sn(OH)(H2O)(CF3SO3)]2 (1) with acridine (C13H9N, Acr), in dichloromethane at room temperature. When an equimolar mixture of anthracene (C14H10, Ant) and acridine is initially used, the crystallization of a sandwich-type arrangement occurs, leading to the intercalation of one molecule of anthracene between two acridium trifluoromethanesulfonate salt molecules. In the three X-ray structures reported, the crystal packing involves the contribut…

Insertion reaction of carbon dioxide into Sn-OR bond. Synthesis, structure and DFT calculations of di- and tetranuclear isopropylcarbonato tin(IV) co…

2006

The reaction of carbon dioxide with the stannane nBu2Sn(OiPr)2 and distannoxane [nBu2(iPrO)Sn]2O leads to the selective insertion into one Sn-OiPr bond generating the corresponding nBu2Sn(OiPr)(OCO2(i)Pr) and nBu2(iPrO)SnOSn(OCO2(i)Pr)nBu2 species. Both compounds are characterised by multinuclear NMR, FT-IR and single-crystal X-ray crystallography. In the solid state, they adopt a dimeric arrangement with bridging isopropoxy and terminal isopropylcarbonato ligands. The X-ray crystal structure of the dinuclear stannane shows that the Sn2O2 ring and the two Sn-OCO2C fragments are nearby coplanar. The same holds for the ladder-type tetranuclear distannoxane. The dimeric structures are also evi…

Triorganotin( iv ) cation-promoted dimethyl carbonate synthesis from CO 2 and methanol: solution and solid-state characterization of an unexpected di…

2018

Two novel C,N-chelated organotin(IV) complexes bearing weakly coordinating carborane moieties were prepared by the reaction of the corresponding C,N-chelated organotin(IV) chloride (i.e. LCNR2SnCl, R = n-Bu (1) and Ph (2); LCN = 2-(N,N-dimethylaminomethyl)phenyl)) with monocarba-closo-dodecaborate silver salt (AgCB11H12; Ag·3). Both products of the metathesis, [LCN(n-Bu)2Sn]+[CB11H12]− (4) and [LCNPh2Sn]+ [CB11H12]− (5), respectively, were characterized by both multinuclear NMR spectroscopy and elemental analysis. The instability of 4 and 5 towards water is discussed. The solid-state structure of LCN(n-Bu)2SnOH·B(C6F5)3 (4a) as a model compound with a Sn–O(H)⋯B linkage is also reported. The…

High-pressure NMR spectroscopy: An in situ tool to study tin-catalyzed synthesis of organic carbonates from carbon dioxide and alcohols. Part 2 [1]

2015

Dialkoxide diorganotin(IV) complexes are known to readily react with carbon dioxide under pressure and they are considered as suitable catalyst precursor models for the direct synthesis of organic carbonates. To gain a better understanding of CO2 insertion processes with Sn-OR bonds, the reactivity of n-Bu2Sn(OCH(CH3)(2))(2) (2) was investigated using high-pressure NMR (HP-NMR) spectroscopy. In deuterated solvents (isopropanol-d(8) and toluene-d(8)) under 50 bar of CO2 pressure at 80 degrees C, Sn-119{H-1} NMR experiments revealed the exclusive formation of an unprecedented tetraorganodistannoxane species, characterized as the bis[diisopropycarbonatotetrabutyldistannoxane] complex, {[n-Bu2S…

The role of distannoxanes in the synthesis of dimethyl carbonate from carbon dioxide

2003

Abstract The synthesis, characterization, and reactivity of 1,3-dimethoxytetrabutyldistannoxane were investigated in connection to the mechanism of the selective synthesis of dimethyl carbonate from CO2 and methanol. A new distannoxane, 1-methoxy-3-methylcarbonatotetrabutyldistannoxane, resulting from a 1:1 adduct with CO2 was isolated and characterised by volumetry, multinuclear NMR and IR spectroscopies. When this compound was submitted to 20 MPa of CO2 at 423 K in toluene no dimethyl carbonate was formed, conversely to dibutyldimethoxystannane. However, when methanol was the solvent, dimethyl carbonate was selectively produced. A promoting effect of Si(OCH3)4 was evidenced through methox…

Tris(cyclohexylammonium) cis-dichloridobis(oxalato-κ2O1,O2)stannate(IV) chloride monohydrate

2013

The crystal structure of the title compound, (C6H14N)3[Sn(C2O4)2Cl2]Cl·H2O, contains three cyclohexylammonium cations, one stannate(IV) dianion, one isolated chloride anion and one lattice water molecule. The cyclohexylammonium cations adopt chair conformations. In the complex anion, two bidentate oxalate ligands and two chloride anions in cis positions coordinate octahedrally to the central SnIV atom. The cohesion of the molecular entities is ensured by the formation of N—H...O, O—H...O, O—H...Cl and N—H...Cl interactions involving cations, anions and the lattice water molecule, giving rise to a layer-like arrangement parallel to (010).

Di-n-butyltin oxide as a chemical carbon dioxide capturer

2010

Abstract Several synthetic routes to the decakis(di-n-butyltin(IV)) oxocluster, (n-Bu2SnO)6[(n-Bu2SnOCH3)2(CO3)]2 (1), a diorganotin compound previously shown to belong to the class of organotins able to store carbon dioxide, as well as its reactivity toward dimethyl carbonate (DMC), are described. The synthetic route from n-Bu2SnO and DMC was applied for the preparation of the ethoxy analogue of 1, oxocluster 2, using diethyl carbonate. The structural relationship connecting cluster 1, with its precursor PRE-1 isolated from recycling experiments and n-Bu2SnO is discussed. For this purpose, the reactivity of PRE-1 with trifluoromethanesulfonic acid was investigated in order to trace structu…

Direct synthesis of dimethyl carbonate with supercritical carbon dioxide: characterization of a key organotin oxide intermediate

2006

The direct synthesis of dimethyl carbonate (DMC) using carbon dioxide as solvent and reagent for its fixation to methanol was explored with din-butyldimethoxystannane in order to get insight into the reaction mechanism for activity improvement. Catalytic runs including recycling experiments allowed isolation and characterization by NMR, IR, and single-crystal X-ray diffraction of a new tin complex containing 10 tin atoms. This compound could be prepared independently and is considered as a resting species. The yield of DMC is highest under 20 MPa pressure that fits with a monophasic supercritical medium in agreement with fluid phase equilibria calculations. In line, preliminary kinetics and…

Organotin(IV) Complexes Containing Sn–O–Se Moieties: A Structural Inventory

2018

This review focuses on organotin compounds exhibiting Sn–O–Se moieties, the molecular structures of which have been previously resolved by single-crystal X-ray diffraction analysis. Three distinct classes of compounds have been identified. Thus, the various modes of coordination of selenite, selenate and organoseleninate anions with tin atoms of organotin(IV) fragments are illustrated and detailed.1 Introduction2 Organotin(IV) Selenite Complexes3 Organotin(IV) Selenate Complexes4 Organotin(IV) Organoseleninate Complexes5 Summary

Imidazolium-2-carboxylate as an afficient, expeditious and eco-friendly organocatalyst for glycerol carbonate synthesis

2009

An improved and greener approach towards the synthesis of glycerol carbonate, via transesterification, using 1-n-butyl-3-methylimidazolium-2-carboxylate as catalyst is described. The catalyst loading as low as 1% was sufficient to yield quantitative conversions. A plausible mechanism is proposed for the catalytic cycle leading to product formation.

Reactivity of bis(cyclohexylammonium) 4-nitrophenylphosphate with SnMe3 Cl. X-ray structure of 4-NO2 C6 H4 PO4(SnMe3)2·H2 O

2014

The reaction of bis(cyclohexylammonium) 4-nitrophenylphosphate with Me3 SnCl (1:2) under reflux in ethanol yielded the title compound 4-NO2 C6 H4 PO4(SnMe3)2H2 O (1). The X-ray crystallographic analysis achieved on single crystals obtained by slow evaporation at room temperature revealed the formation of an unexpected supramolecular coordination network. The elementary building block can be viewed as two Me3 Sn moieties linked by a bridging 4-nitrophenylphosphate ligand. The two tin atoms are five-coordinated and describe a trans-Me3 SnO2 geometry in a trigonal bipyramidal arrangement. However, the Sn atoms are distinct, exhibiting two different environments. Thus, one is linked to two axia…

New reactive isoeugenol based phosphate flame retardant : toward green epoxy resins

2019

A biobased reactive phosphate flame retardant derived from isoeugenol was synthesized and fully characterized (1H, 13C, 31P NMR, FTIR, MS) with the aim of improving flame retardancy behavior of bio...

Catena-poly[[di-n-butyltin(IV)]-mu-trifluoromethanesulfonato-[[di-n-butyl(trifluoromethanesulfonato)tin(IV)]-di-mu-hydroxo]]

2006

International audience

Di-n-butyltin(IV)-catalyzed dimethyl carbonate synthesis from carbon dioxide and methanol: An in situ high pressure 119Sn{1H} NMR spectroscopic study

2011

The reactivity of five di-n-butyltin(IV) complexes, n-Bu2Sn(OR)(2) (1), n-Bu2SnO (3), [n-Bu2Sn(OR)](2)O (4), (n-Bu2SnO)(2)(CO2) (6) and (n-Bu2SnO)(6)[(n-Bu2SnOR)(2)(CO3)](2) (7) (R = CH3), with CO2, suggested as possible catalyst precursors and key-intermediates for the direct synthesis of dimethyl carbonate from carbon dioxide and methanol, has been investigated using high-pressure Sn-119{H-1} NMR (HP-NMR) spectroscopy. Four of the five precursors studied, i.e. 3, 4, 6 and 7 give rise to an identical Sn-119{H-1} NMR pattern which can be explicitly attributed to the fingerprint of the dimeric form of the 1-methoxy-3-methylcarbonatotetrabutyldistannoxane {5}(2). However, with 1, a new pair o…

ChemInform Abstract: Imidazolium and Potassium Hydrogen Carbonate Salts as Ecofriendly Organocatalysts for Oxazolidinone Synthesis.

2016

Although oxazolidinones are valuable intermediate compounds for industrial applications, no synthetic method is suitable for their production on a large scale owing to the use of reagents/catalysts that are hazardous or toxic to human health or ecotoxic for the environment. In this manuscript, we describe new and efficient catalysts, that is, the nontoxic hydrogen carbonate anion in combination with a potassium or diisobutylimidazolium ([iBu(2)IM]) countercation, for the conversion of -amino alcohols into cyclic oxazolidinones in high yields of 69 to 90%. Depending on the catalytic conditions, both catalysts could be easily recovered from the crude reaction products and reused several times…

In VitroRelease of Local Anaesthetic and Anti-Inflammatory Drugs from Crosslinked Collagen Based Device

2012

The drug delivery systems that are the object of this article take the form of a hydrophilic matrix (collagen or crosslinked collagen) containing a drug. These devices can be used as The model active agents, were chosen from the range of local anaesthetics (lidocaine hydrochloride), anti-inflammatory (diclofenac sodium salt) and antioxydant (caffeic acid). Whatever the drug affinity for water, in the first time of the experiments, the release appears to be systematically delayed when the matrix is crosslinked. For lidocaine hydrochloride based systems, as the amount of drug increases in the matrix, the high gap concentration between the matrix and the buffer solution promote the diffusion a…

A novel two-dimensional organostannoxane coordination network promoted by phenazine: Synthesis, characterization and X-ray structure of

2009

Abstract Reaction of the dimeric hydroxo di-n-butylstannane trifluoromethanesulfonato complex [n-Bu2Sn(μ-OH)(H2O)0.5(η1-O3SCF3)]2 (1) with phenazine (C12H8N2, Phz) (2) in dichloromethane at room temperature in a 1:3 molar ratio yielded the novel two-dimensional organometallic coordination polymer 2 ∞ { [ n - Bu 2 ( μ -OH ) SnOSn ( μ - η 2 - O 3 SCF 3 ) n - Bu 2 ] 2 [ n - Bu 2 ( μ -OH ) SnOSn ( η 1 - O 3 SCF 3 ) n - Bu 2 ] 2 } (3), together with the phenazinium trifluoromethanesulfonate salt [C12H9N2]+ [CF3SO3]−, crystallographically isolated in two different structural arrangements, free 4 and in π–π aromatic stacking interaction with independent intercalated non-protonated phenazine molecu…

Ethylammonium hydrogen oxalate–oxalic acid (2/1)

2019

The reaction between ethylamine and oxalic acid in water in a 1:1 molar ratio afforded the title salt, C2H8N+·C2HO4 −·0.5C2H2O4. The hydrogen oxalate anions interact through hydrogen bonding and are organized into a chains propagating along the c-axis direction. The chains are connected to the neighbouring cations and oxalic acid molecules by N—H...O and O—H...O hydrogen bonds and N...O dipole–dipole contacts, leading to a supramolecular three-dimensional network.

Crystal structure of dimethylammonium hydrogen oxalate hemi(oxalic acid)

2015

The title salt consists of a di­methyl­ammonium cation (Me2NH2 +), an hydrogenoxalate anion (HC2O4 −), and half a mol­ecule of oxalic acid (H2C2O4) situated about an inversion center. They are linked together through inter­molecular hydrogen bonds, forming a two-dimensional bilayer-like self-assembly.

Author response: 'Palaeoshellomics’ reveals the use of freshwater mother-of-pearl in prehistory

2019

( n ‐Bu 2 Sn) 2 O(CO 3 ): An active, robust and recyclable organotin(IV) for the direct synthesis of linear organic carbonates from carbon dioxide an…

2017

Organotin(IV) compounds are known to promote the direct synthesis of organic carbonates from carbon dioxide and alcohols. In the past, structural studies have highlighted that the carbonato moiety is a recurring ligand of tin species collected during CO2 pressurized reactions. In a mimetic approach and in order to achieve an available and recyclable precursor, the title compound (n-Bu2Sn)2O(CO3) (1) was prepared in a single step by reacting commercial di-n-butyltin dichloride with an aqueous solution of sodium carbonate. Compound 1 was characterized using infrared spectroscopy and thermogravimetric and elemental analyses. Multinuclear NMR investigations in solution were also conducted. Comp…

Tin-based mesoporous silica for the conversion of CO2 into dimethyl carbonate.

2011

Sn-based SBA-15 was prepared by reacting di-n-butyldimethoxystannane with SBA-15 pretreated with trimethylchlorosilane (TMCS) to cap the external hydroxyl groups. Small-angle X-ray diffraction (SXRD), infrared spectroscopy (IR), nitrogen adsorption/desorption, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and inductively coupled plasma atomic emission (ICP-AES) measurements allow us to propose that the organotin species are located within the pore channels of the mesoporous host. This novel material catalyzes selectively the coupling of CO(2) with methanol to dimethyl carbonate (DMC). The reaction time-conversion dependence shows that a turnover number (TON) of 1…

Imidazolium and Potassium Hydrogen Carbonate Salts as Ecofriendly Organocatalysts for Oxazolidinone Synthesis

2016

International audience; Although oxazolidinones are valuable intermediate compounds for industrial applications, no synthetic method is suitable for their production on a large scale owing to the use of reagents/catalysts that are hazardous or toxic to human health or ecotoxic for the environment. In this manuscript, we describe new and efficient catalysts, that is, the nontoxic hydrogen carbonate anion in combination with a potassium or diisobutylimidazolium ([iBu(2)IM]) countercation, for the conversion of -amino alcohols into cyclic oxazolidinones in high yields of 69 to 90%. Depending on the catalytic conditions, both catalysts could be easily recovered from the crude reaction products …

Structural characterization of 2,2-di-n-butyl-4-methyl-1,3,2-dioxastannolane isolated from supercritical CO2 conditions

2009

The title compound has been isolated as single crystals from the synthesis of propylene carbonate from racemic 1,2-propanediol and carbon dioxide using n-Bu2SnO as a catalyst precursor. The X-ray crystallographic structure analysis revealed the self-assembly of di-n-butyltin(IV) 1,2-propanediolate units, linked together through long-distance Sn-O interactions leading to a one-dimensional polymeric architecture organized in a syndiotactic arrangement. The coordination geometry around the tin atoms can be described as an unusual faced-capped trigonal bipyramidal environment.

Crystal structure of 2-methyl-1H-imidazol-3-ium aquatrichlorido(oxalato-κ2O,O′)stannate(IV)

2015

N—H⋯O, N—H⋯Cl and O—H⋯O hydrogen bonds between cations and anions in the complex salt (C4H7N2)+[Sn(H2O)Cl3(C2O4)]− are responsible for the formation of a three-dimensional network structure.

C,N-chelated organotin(IV) trifluoroacetates. Instability of the mono- and diorganotin(IV) derivatives.

2011

Abstract The C,N-chelated tri-, di- and monoorganotin(IV) halides react with equimolar amounts of CF3COOAg to give corresponding C,N-chelated organotin(IV) trifluoroacetates. The set of prepared tri-, di- and monoorganotin(IV) trifluoroacetates bearing the LCN ligand (where LCN is 2-(N,N-dimethylaminomethyl)phenyl-) was structurally characterized by X-ray diffraction analyses, multinuclear NMR and IR spectroscopy. In the case of triorganotin(IV) trifluoroacetates and (LCN)2Sn(OC(O)CF3)2, no tendency to form hydrolytic products, or instability towards the moisture was observed. LCNRSn(OC(O)CF3)2 (where R is n-Bu or Ph) and LCNSn(OC(O)CF3)3 forms upon crystallization from THF in the air mainl…

Crystal structure of the diglycidyl ether of eugenol

2017

The diep­oxy monomer (DGE-Eu) was synthesized from eugenol by a three-step reaction. It consists of a 1,2,4-tris­ubstituted benzene ring substituted by diglycidyl ether, a meth­oxy group and a methyl­oxirane group. The three-membered oxirane rings are inclined to the benzene ring by 61.0 (3) and 27.9 (3)°. In the crystal, mol­ecules are linked by C—H⋯O hydrogen bonds, forming layers parallel to the ab plane.

Organotin(IV) selenate derivatives – Crystal structure of [{(Ph 3 Sn) 2 SeO 4 } ⋅ CH 3 OH] n

2021

Abstract Crystallization of [(Ph3Sn)2SeO4] ⋅ 1.5H2O in methanol leads to the formation of [{(Ph3Sn)2SeO4} ⋅ CH3OH] n (1) which constitutes a new specimen of organotin(IV) selenate derivatives. In the solid state, complex 1 is arranged in polymeric zig-zag chains, composed of alternating Ph3Sn and SeO4 groups. In addition, pendant Ph3Sn ⋅ CH3OH moieties are branched along chains according to a syndiotactic organization and via Sn-O-Se connections. From a supramolecular point of view, intermolecular hydrogen bonds established between the selenate groups (uncoordinated oxygen) and the hydroxyl functions (CH3OH) of the pendant groups link the chains together.

C,N-chelated organotin(IV) trifluoromethanesulfonates: Synthesis, characterization and preliminary studies of its catalytic activity in the direct sy…

2012

Abstract C,N-chelated tri- and diorganotin(IV) halides react with 1 or 2 mol equiv of silver trifluoromethanesulfonate (triflate, AgOTf, OTf = OSO2CF3−) to give corresponding C,N-chelated organotin(IV) triflates. The triorganotin(IV) triflates of general formula LCNR2SnOTf (R = n-Bu (1), Ph (2)) are presumably more stable towards hydrolysis than the diorganotin(IV) triflates LCNRSn(OTf)2 (R = n-Bu (3), Ph (4)). All prepared organotin(IV) triflates bearing the LCN ligand (where LCN is 2-(N,N-dimethylaminomethyl)phenyl-) were characterized by multinuclear NMR spectroscopy and elemental analysis. In addition, the structure of 3 was determined by the X-ray diffraction analysis. The catalytic ac…

Characterization of the Teeth Skeletal Matrix from <i>Arbacia lixula</i>

2016

The teeth of sea urchins are highly complex composite structures, composed predominantly of high magnesium calcite, and of a minor heterogeneous assemblage of organic macromolecules that are occluded within the mineral. The organic matrix fulfils important functions in mineralization, in addition to giving the mineral phase peculiar mechanical properties, different from that of purely inorganic calcite. Nevertheless, the composition and function of individual components of the organic matrix still remains largely unknown. Up to now, the detailed protein repertoire of teeth from a single sea urchin species (Strongylocentrotus purpuratus, order Camarodonta) was investigated. In this study, we…

Two new organic-selenate salts: syntheses and crystal structures of bis(di-iso-propylammonium) selenate and di-n-butylammonium hydrogenoselenate

2017

Abstract Two new dialkyammonium selenate salts [i-Pr2NH2]2[SeO4] (1) and [n-Bu2NH2][HSeO4] (2) have been isolated and characterized by single-crystal X-ray diffraction. Salt 1 crystallizes in the monoclinic system, space group P21/n with a=8.7190(5), b=8.8500(4), c=22.5953(9) Å, β=94.6290(17)°, V=1737.84(14) Å3 and Z=4. Salt 2 crystallizes in the monoclinic system space group P21/n with a=10.9328(9), b=8.1700(6), c=13.8095(11) Å, β=97.130(3)°, V=1223.94(17) Å3 and Z=4. In both salts, dialkylammonium cations and selenate anions are connected through NH···O and OH···O hydrogen bonds. In the crystal structure, 1 and 2 are organized in layer-like arrangements. Structural characterizations were …

1-n-Butyl-3-methylimidazolium-2-carboxylate: a versatile precatalyst for the ring-opening polymerization of ε-caprolactone and rac-lactide under solv…

2013

The ring-opening polymerization of ε-caprolactone (ε-CL) and rac-lactide (rac-LA) under solvent-free conditions and using 1-n-butyl-3-methylimidazolium-2-carboxylate (BMIM-2-CO2) as precatalyst is described. Linear and star-branched polyesters were synthesized by successive use of benzyl alcohol, ethylene glycol, glycerol and pentaerythritol as initiator alcohols, and the products were fully characterized by 1H and 13C{1H} NMR spectroscopy, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). BMIM-2-CO2 acts as an N-heterocyclic carbene precursor, resulting from in situ decarboxylation, either by heating under vacuo (method A) or by addition of NaBPh4 (method B)…

The ionic tin(IV) complex tri-μ2-methoxy-μ3-oxo-tris[di-tert-butyltin(IV)] tri-μ2-methoxy-bis[tert-butyldimethoxystannate(IV)]

2004

The solid-state of the title compound, [Sn3(C4H9)6(CH3O)3O][Sn2(C4H9)2(CH3O)7], consists of distinct [tBu6Sn3(μ-OCH3)3(μ3-O)]+ cations and [tBu2Sn2(OCH3)4(μ-OCH3)3]− anions, apparently formed as a result of slow hydro­lysis of pure di(tert-butyl)­di­methoxy­stannane, tBu2Sn(OCH3)2. In the monocation, the coordin­ation about the Sn atoms is distorted trigonal bipyramidal, and, in the monoanion, distorted octahedral. The trigonal bipyramidal arrangement induces planarity of the Sn3O4 motif.

Novel molluskan biomineralization proteins retrieved from proteomics: a case study with upsalin.

2012

12 pages; International audience; The formation of the molluskan shell is regulated by an array of extracellular proteins secreted by the calcifying epithelial cells of the mantle. These proteins remain occluded within the recently formed biominerals. To date, many shell proteins have been retrieved, but only a few of them, such as nacreins, have clearly identified functions. In this particular case, by combining molecular biology and biochemical approaches, we performed the molecular characterization of a novel protein that we named Upsalin, associated with the nacreous shell of the freshwater mussel Unio pictorum. The full sequence of the upsalin transcript was obtained by RT-PCR and 5'/3…

Vieillissement environnemental accéléré et propriétés mécaniques des fibres issues du chanvre

2016

International audience; Ce travail a pour objectif de caractériser l’influence d’un vieillissement environnemental accéléré sur les propriétés mécaniques de fibres extra-xylémiennes issues du chanvre. Le protocole de vieillissement accéléré proposé dans cette étude consiste en des cycles de 24h comprenant une phase d’immersion de 12h dans une eau distillée à 70°C et une phase de séchage de 12h dans une étuve contrôlée à 50°C. Les résultats montrent une perte de masse significative et une diminution des propriétés de rigidité et de résistance en traction de l’ordre de 50% après 30 cycles de vieillissement.

Design and development of 100 % bio-based high-grade hemp/epoxy composites

2017

International audience; In order to develop 100% bio-based high-grade epoxy composites, in this study, bio-based epoxy thermosets and hemp slivers are processed and characterized by different technologies. Epoxy resins are synthesized from the diglycidylether of Eugenol, extracted from cloves. They are cured with bio-based acid anhydrides. The physicochemical properties of the resulting epoxy resins are characterized using thermogravimetric analyses (TGA), differential scanning calorimetry (DSC), and nanoindentation. The mechanical properties of hemp fibres extracted from the slivers are also determined using tensile tests. After their processing and characterization, these bio-based consti…

Development and characterization of a bio-based epoxy matrix for high-grade bio-based composites

2019

This study aims to develop 100% bio-based hemp/epoxy composites for semi-structural and structural applications. The thermal and mechanical performances of a 100% bio-based matrix derived from biomassare evaluated and reveal properties in the same order of magnitude as those obtained for polyepoxides based on DGEBA, that means a glass transition temperature of approximately 150°C and mechanical properties in the order of 120MPa for the maximum stress and 3.2 GPa for the tangent apparent modulus. This natural origin matrix is then used for the manufacture of composites reinforced with hemp rovings. The bending properties of these 100% bio-based materials are equivalent to those determined fo…

Towards Fully Bio-Based Thermosets: From Prepolymers Synthesis to Composite Applications

2017

International audience

Development and characterization of a bio-based epoxy matrix for high-grade bio-based composites

2019

This study aims to develop 100% bio-based hemp/epoxy composites for semi-structural and structural applications. The thermal and mechanical performances of a 100% bio-based matrix derived from biomassare evaluated and reveal properties in the same order of magnitude as those obtained for polyepoxides based on DGEBA, that means a glass transition temperature of approximately 150°C and mechanical properties in the order of 120MPa for the maximum stress and 3.2 GPa for the tangent apparent modulus. This natural origin matrix is then used for the manufacture of composites reinforced with hemp rovings. The bending properties of these 100% bio-based materials are equivalent to those determined fo…

Étude d'un procédé de traitement innovant des fibres de chanvre sous condition de fluide supercritique et propriétés induites

2017

International audience

Vieillissement accéléré et propriétés mécaniques des fibres issues du chanvre

2016

International audience; L’objectif de ce colloque est de regrouper les personnes du monde académique et de l’industrie intéressées par le comportement en fatigue et la durabilité des composites biosourcés et de leurs constituants. Ce colloque permettra de faire un état des lieux sur les connaissances actuelles, de partager les dernières avancées effectuées dans le domaine et d’échanger sur les principaux verrous à lever pour accéder à une utilisation pérenne des composites biosourcés dans les applications structurales.

CCDC 1590298: Experimental Crystal Structure Determination

2018

Related Article: Petr Švec, Hélène Cattey, Zdeňka Růžičková, Josef Holub, Aleš Růžička, Laurent Plasseraud|2018|New J.Chem.|42|8253|doi:10.1039/C7NJ05058E

CCDC 891928: Experimental Crystal Structure Determination

2013

Related Article: Laurent Plasseraud, Helene Cattey|2013|Comptes Rendus Chimie|16|613|doi:10.1016/j.crci.2012.12.006

CCDC 891929: Experimental Crystal Structure Determination

2013

Related Article: Laurent Plasseraud, Helene Cattey|2013|Comptes Rendus Chimie|16|613|doi:10.1016/j.crci.2012.12.006

CCDC 1590299: Experimental Crystal Structure Determination

2018

Related Article: Petr Švec, Hélène Cattey, Zdeňka Růžičková, Josef Holub, Aleš Růžička, Laurent Plasseraud|2018|New J.Chem.|42|8253|doi:10.1039/C7NJ05058E

CCDC 1847278: Experimental Crystal Structure Determination

2021

Related Article: Waly Diallo, Libasse Diop, Cheikh Abdoul Khadir Diop, H��l��ne Cattey, Laurent Plasseraud|2018|Main Group Met.Chem.|41|183|doi:10.1515/mgmc-2018-0029

CCDC 1985584: Experimental Crystal Structure Determination

2020

Related Article: Laurent Plasseraud, Hélène Cattey|2020|Main Group Met.Chem.|43|102|doi:10.1515/mgmc-2020-0012

CCDC 1835271: Experimental Crystal Structure Determination

2021

Related Article: Mamadou Ndiaye, Mouhamadou Birame Diop, Abdoulaye Samb, Libasse Diop, Allen G. Oliver, Laurent Plasseraud|2020|Zeitschrift fuer Naturforschung, Teil B. Anorganische Chemie, Organische Chemie|75|815 |doi:10.1515/znb-2020-0097

CCDC 1590300: Experimental Crystal Structure Determination

2018

Related Article: Petr Švec, Hélène Cattey, Zdeňka Růžičková, Josef Holub, Aleš Růžička, Laurent Plasseraud|2018|New J.Chem.|42|8253|doi:10.1039/C7NJ05058E

CCDC 1835272: Experimental Crystal Structure Determination

2021

Related Article: Mamadou Ndiaye, Mouhamadou Birame Diop, Abdoulaye Samb, Libasse Diop, Allen G. Oliver, Laurent Plasseraud|2020|Zeitschrift fuer Naturforschung, Teil B. Anorganische Chemie, Organische Chemie|75|815 |doi:10.1515/znb-2020-0097

CCDC 1533770: Experimental Crystal Structure Determination

2019

Related Article: Waly Diallo, Libasse Diop, Cheikh Abdoul Khadir Diop, Laurent Plasseraud, Hélène Cattey|2017|Z.Naturforsch.,B:Chem.Sci.|72|425|doi:10.1515/znb-2017-0032

CCDC 891927: Experimental Crystal Structure Determination

2013

Related Article: Laurent Plasseraud, Helene Cattey|2013|Comptes Rendus Chimie|16|613|doi:10.1016/j.crci.2012.12.006

CCDC 789750: Experimental Crystal Structure Determination

2015

Related Article: Waly Diallo, Libasse Diop, Kieran C. Molloy, Mary F. Mahon, Laurent Plasseraud|2014|Main Group Met.Chem.|37|33|doi:10.1515/mgmc-2013-0058

CCDC 1533769: Experimental Crystal Structure Determination

2019

Related Article: Waly Diallo, Libasse Diop, Cheikh Abdoul Khadir Diop, Laurent Plasseraud, Hélène Cattey|2017|Z.Naturforsch.,B:Chem.Sci.|72|425|doi:10.1515/znb-2017-0032

CCDC 914515: Experimental Crystal Structure Determination

2013

Related Article: Justin P. Johnpeter, Laurent Plasseraud, Frédéric Schmitt, Lucienne Juillerat-Jeanneret, Bruno Therrien|2013|J.Coord.Chem.|66|1753|doi:10.1080/00958972.2013.790020

CCDC 914514: Experimental Crystal Structure Determination

2013

Related Article: Justin P. Johnpeter, Laurent Plasseraud, Frédéric Schmitt, Lucienne Juillerat-Jeanneret, Bruno Therrien|2013|J.Coord.Chem.|66|1753|doi:10.1080/00958972.2013.790020