Mesostructured fatty acid-tethered silicas: sustaining the order by co-templating with bulky precursors.

The co-condensation of functional alkoxysilanes with tetraethoxysilane in the presence of a structure directing agent under sol-gel process chemistry is a common way to access functional organosilica with an ordered mesostructure. In this report, bulky silylated fatty acid methyl esters were used both as co-templating bio-molecules and functionalizing agents in the process of supra-molecular silica mineralization. The highest structural regularity in terms of pore size distribution and channel size homogeneity was observed for carboxy-tethered silica possessing SBA-15-type architecture due to an enhanced fatty acid precursor-surfactant interaction. The carboxylic surface embedded within the hydrophobic environment of the fatty compounds confers to these materials interesting reactive-surface properties with promising applications as drug-delivery systems and bio-catalytic nanoreactors.

[1]  Brandon M. Vogel,et al.  Interfacial modification of silica surfaces through γ-isocyanatopropyl triethoxy silane–amine coupling reactions , 2008 .

[2]  Brian J. Melde,et al.  Hybrid Inorganic–Organic Mesoporous Silicates—Nanoscopic Reactors Coming of Age , 2000 .

[3]  M. Jaroniec,et al.  Synthesis and Properties of Ordered Mesoporous Organosilicas with Vinyl and Mercaptopropyl Surface Groups: The Effect of Ligand Concentration on Pore Structure , 2009 .

[4]  P. Voort,et al.  Silylation of the silica surface a review , 1996 .

[5]  S. Che,et al.  Supramolecular chiral transcription and recognition by mesoporous silica prepared by chiral imprinting of a helical micelle. , 2009, Angewandte Chemie.

[6]  Bradley F. Chmelka,et al.  Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant Syntheses of Highly Ordered, Hydrothermally Stable, Mesoporous Silica Structures , 1998 .

[7]  Lai-Kwan Chau,et al.  Novel Sol−Gel-Derived Material for Separation and Optical Sensing of Metal Ions: Propyl-ethylenediamine Triacetate Functionalized Silica , 1999 .

[8]  M. Ferrari,et al.  Tailoring of the nanotexture of mesoporous silica films and their functionalized derivatives for selectively harvesting low molecular weight protein. , 2010, ACS nano.

[9]  M. Davis,et al.  Design and preparation of organic-inorganic hybrid catalysts. , 2002, Chemical reviews.

[10]  T. Ohsuna,et al.  An ordered mesoporous organosilica hybrid material with a crystal-like wall structure , 2002, Nature.

[11]  G. Mckay,et al.  Selective Adsorbents from Ordered Mesoporous Silica , 2003 .

[12]  J. Mayoral,et al.  Immobilizing a single pybox ligand onto a library of solid supports , 2004, Molecular Diversity.

[13]  Dietmar Seyferth,et al.  Comprehensive Organometallic Chemistry , 1984 .

[14]  A. El Kadib,et al.  SBA-15-type organosilica with 4-mercapto-N,N-bis-(3-Si-propyl)butanamide for palladium scavenging and cross-coupling catalysis. , 2011, Chemistry.

[15]  F. Renzo,et al.  Intrusion and Retraction of Fluids in Nanopores: Effect of Morphological Heterogeneity , 2009 .

[16]  J. Rosenholm,et al.  Amino-functionalization of large-pore mesoscopically ordered silica by a one-step hyperbranching polymerization of a surface-grown polyethyleneimine. , 2006, Chemical communications.

[17]  J. Broekhoff Studies on pore systems in catalysts: XIII. Pore distributions from the desorption branch of a nitrogen sorption isotherm in the case of cylindrical pores B. Applications , 1968 .

[18]  P. Hesemann,et al.  Preparation and optical properties of hybrid sol–gel systems containg doubly anchored oligoarylenevinylenes , 1996 .

[19]  Avelino Corma,et al.  From Microporous to Mesoporous Molecular Sieve Materials and Their Use in Catalysis. , 1997, Chemical reviews.

[20]  B. Hatton,et al.  Past, Present, and Future of Periodic Mesoporous OrganosilicasThe PMOs , 2005 .

[21]  A. Mandoli,et al.  First example of a silica gel-supported optically active Mn(III)–salen complex as a heterogeneous asymmetric catalyst in the epoxidation of olefins , 1999 .

[22]  D. Gertner,et al.  Hydrosilylation of long chain unsaturated fatty acid esters , 1974 .

[23]  A. Corma,et al.  On the activity of chiral chromium salen complexes covalently bound to solid silicates for the enantioselective epoxide ring opening , 2002 .

[24]  M. Wirth,et al.  Horizontal polymerization of mixed trifunctional silanes on silica. 2. Application to chromatographic silica gel , 1993 .

[25]  F. Gasparrini,et al.  Synthesis of sugar-based silica gels by copper-catalysed azide-alkyne cycloaddition via a single-step azido-activated silica intermediate and the use of the gels in hydrophilic interaction chromatography. , 2010, Chemistry.

[26]  Q. Cai,et al.  New mineralization agents for the synthesis of MCM-41 , 1999 .

[27]  A. Ulman,et al.  Formation and Structure of Self-Assembled Monolayers. , 1996, Chemical reviews.

[28]  R. Corriu,et al.  Organic-inorganic hybrid materials : hydrolysis and polycondensation of 1,1'-bis-silylated ferrocene derivatives , 1993 .

[29]  O. Terasaki,et al.  A novel anionic surfactant templating route for synthesizing mesoporous silica with unique structure , 2003, Nature materials.

[30]  G. W. Anderson,et al.  The Use of Esters of N-Hydroxysuccinimide in Peptide Synthesis , 1964 .

[31]  Jun Liu,et al.  Local release of highly loaded antibodies from functionalized nanoporous support for cancer immunotherapy. , 2010, Journal of the American Chemical Society.

[32]  Yingchun Zhu,et al.  Chitosan enclosed mesoporous silica nanoparticles as drug nano-carriers: Sensitive response to the narrow pH range , 2012 .

[33]  Bruce M. Novak,et al.  Hybrid nanocomposite materials―between inorganic glasses and organic polymers , 1993 .

[34]  D. D. De Vos,et al.  Ordered mesoporous and microporous molecular sieves functionalized with transition metal complexes as catalysts for selective organic transformations. , 2002, Chemical reviews.

[35]  Jianlin Shi,et al.  The effect of PEGylation of mesoporous silica nanoparticles on nonspecific binding of serum proteins and cellular responses. , 2010, Biomaterials.

[36]  S. Coluccia,et al.  On the compatibility criteria for protein encapsulation inside mesoporous materials. , 2010, Chemphyschem : a European journal of chemical physics and physical chemistry.

[37]  G. Hoatson,et al.  Modelling one‐ and two‐dimensional solid‐state NMR spectra , 2002 .

[38]  A. Walcarius,et al.  Voltammetric detection of copper(II) at a carbon paste electrode containing an organically modified silica , 2001 .

[39]  A. Corma,et al.  Chiral copper(II) bisoxazoline covalently anchored to silica and mesoporous MCM-41 as a heterogeneous catalyst for the enantioselective Friedel-Crafts hydroxyalkylation. , 2002, Chemical communications.

[40]  D. Brunel,et al.  CHIRAL MESOPOROUS TEMPLATED SILICAS AS HETEROGENEOUS INORGANIC-ORGANIC CATALYSTS IN THE ENANTIOSELECTIVE ALKYLATION OF BENZALDEHYDE , 1998 .

[41]  S. Che,et al.  Synthesis of Carboxylic Group Functionalized Monodispersed Mesoporous Silica Spheres (MMSSs) via Costructure Directing Method , 2009 .

[42]  A. Behr,et al.  The synthesis of silicon oleochemicals by hydrosilylation of unsaturated fatty acid derivatives , 2002 .

[43]  Joop A. Peters,et al.  Comparison of two MCM-41 grafted TEMPO catalysts in selective alcohol oxidation , 2001 .

[44]  D. Brunel Functionalized micelle-templated silicas (MTS) and their use as catalysts for fine chemicals , 1999 .

[45]  R. Sheldon,et al.  Chiral catalysts confined in porous hosts: 1. Synthesis , 2003 .

[46]  M. Popall,et al.  Applications of hybrid organic–inorganic nanocomposites , 2005 .

[47]  S. Polarz,et al.  Amino acid silica hybrid materials with mesoporous structure and enantiopure surfaces. , 2008, Angewandte Chemie.

[48]  Carl P. Tripp,et al.  Reaction of chloromethylsilanes with silica: a low-frequency infrared study , 1991 .

[49]  H. Mayer,et al.  Applications of sol-gel-processed interphase catalysts. , 2002, Chemical reviews.

[50]  Jian Liu,et al.  Functionalized periodic mesoporous organosilicas for catalysis , 2009 .

[51]  C. Brinker,et al.  Synthesis and characterization of highly ordered mesoporous thin films with -COOH terminated pore surfaces. , 2003, Chemical communications.

[52]  T. Coradin,et al.  Turning biopolymer particles into hybrid capsules: the example of silica/alginate nanocomposites , 2006 .

[53]  F. Schüth,et al.  A novel synthetic route for negatively charged ordered mesoporous silica SBA-15 , 2003 .

[54]  A. Chan,et al.  Recoverable catalysts for asymmetric organic synthesis. , 2002, Chemical reviews.

[55]  M. Haas,et al.  Customizing lipases for biocatalysis: a survey of chemical, physical and molecular biological approaches , 2000 .

[56]  Shiori Kubo,et al.  Salt-induced formation of uniform fiberlike SBA-15 mesoporous silica particles and application to toluene adsorption. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[57]  Improvement of hydrothermal stability of MCM-41 mesoporous molecular sieve , 1999 .

[58]  K. Ariga,et al.  Recent advances in functionalization of mesoporous silica. , 2005, Journal of nanoscience and nanotechnology.

[59]  N. Marcotte,et al.  Nanocomposites from natural templates based on fatty compound-functionalised siloxanes , 2009 .

[60]  E. Ruiz-Hitzky,et al.  Rhodium Complexes with Nitrogen-Donor Ligands Anchored on Silicic Supports. 1. Synthesis and Characterization , 1992 .

[61]  D. Vos,et al.  Mesoporous Sulfonic Acids as Selective Heterogeneous Catalysts for the Synthesis of Monoglycerides , 1999 .

[62]  M. C. Bruzzoniti,et al.  Direct synthesis of large-pore ethane-bridged mesoporous organosilica functionalized with carboxylic groups. , 2009, Chemical communications.

[63]  A. Stein,et al.  Synthesis of Ordered Microporous Silicates with Organosulfur Surface Groups and Their Applications as Solid Acid Catalysts , 1998 .

[64]  J. M. Córdoba,et al.  The effects on pore size and particle morphology of heptane additions to the synthesis of mesoporous silica SBA-15 , 2010 .

[65]  Hcl Erik Abbenhuis,et al.  Hierarchical fabrication of silica cocoon with hexagonally ordered channel constructed wall via an emulsion-assisted process , 2012 .

[66]  S. Kaliaguine,et al.  Perspectives in catalytic applications of mesostructured materials , 2001 .

[67]  P. Kralchevsky,et al.  Kinetics of Triglyceride Solubilization by Micellar Solutions of Nonionic Surfactant and Triblock Copolymer. 2. Theoretical Model , 2002 .

[68]  A. E. Kadib,et al.  Hydrosilylation of unsaturated fatty acid N-phenyl amides , 2007 .

[69]  David Grosso,et al.  Mesostructured hybrid organic–inorganic thin films , 2005 .

[70]  Jiyong Park,et al.  Triblock Copolymer Synthesis of Highly Ordered Large-Pore Periodic Mesoporous Organosilicas with the Aid of Inorganic Salts , 2003 .

[71]  H. Kao,et al.  A simple one-pot route to mesoporous silicas SBA-15 functionalized with exceptionally high loadings of pendant carboxylic acid groups. , 2009, Chemical communications.

[72]  A. El Kadib,et al.  Silylation of triacylglycerol: an easy route to new biosiloxanes. , 2007, Chemistry and physics of lipids.

[73]  Tetsuo Sato,et al.  Morphological Control of Rod- and Fiberlike SBA-15 Type Mesoporous Silica Using Water-Soluble Sodium Silicate , 2004 .

[74]  Karine Molvinger,et al.  Hybrid materials and periodic mesoporous organosilicas containing covalently bonded organic anion and cation featuring MCM-41 and SBA-15 structure. , 2009, Journal of the American Chemical Society.

[75]  F. Renzo,et al.  Transition-metal ligands bound onto the micelle-templated silica surface , 1998 .

[76]  O. Terasaki,et al.  Carboxylic group functionalized ordered mesoporous silicas , 2011 .

[77]  S. Inagaki,et al.  Self-Organization of Organosilica Solids with Molecular-Scale and Mesoscale Periodicities† , 2008 .

[78]  M. Stébé,et al.  Amphiphilic and cation-complexing compounds based on peptidoamines , 2000 .

[79]  G. W. Anderson,et al.  N-Hydroxysuccinimide Esters in Peptide Synthesis , 1963 .

[80]  Bénédicte Lebeau,et al.  Chemical strategies to design textured materials: from microporous and mesoporous oxides to nanonetworks and hierarchical structures. , 2002, Chemical reviews.

[81]  E. Barrett,et al.  (CONTRIBUTION FROM THE MULTIPLE FELLOWSHIP OF BAUGH AND SONS COMPANY, MELLOX INSTITUTE) The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms , 1951 .

[82]  E. Garrone,et al.  In situ infrared study of SBA-15 functionalized with carboxylic groups incorporated by a co-condensation route. , 2005, The journal of physical chemistry. B.

[83]  J. Clark,et al.  Preparation of a silica-supported peroxycarboxylic acid and its use in the epoxidation of alkenes† , 1998 .

[84]  A. E. Kadib,et al.  Highly Selective C-Silylation of Fatty Acid Methyl Esters , 2005 .

[85]  Fredrickson,et al.  Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores , 1998, Science.

[86]  S. Che,et al.  DNA transcription into diverse porous silicas by a co-structure directing route: chiral, ring and ordered nanochannel arrays. , 2009, Chemical communications.

[87]  Stephen Mann,et al.  Bio-inspired materials chemistry , 2002 .

[88]  W. A. Aue,et al.  Preparation and chromatographic uses of surface-bonded silicones , 1969 .

[89]  Isabelle Migneault,et al.  Glutaraldehyde: behavior in aqueous solution, reaction with proteins, and application to enzyme crosslinking. , 2004, BioTechniques.

[90]  M. Yokoyama,et al.  Chemical modification of sol-gel-derived glass by a neutral carrier for ion sensors , 1996 .

[91]  J. Nagy,et al.  29Si and 13C MAS-NMR characterization of surface modification of micelle-templated silicas during the grafting of organic moieties and end-capping , 1999 .

[92]  P. Walde,et al.  Fatty acid vesicles , 2007 .

[93]  D. Lerner,et al.  Immobilisation of a biological chelate in porous mesostructured silica for selective metal removal from wastewater and its recovery , 2005 .

[94]  B. Limoges,et al.  Synthesis of nitroxides for use as procationic labels and their incorporation into nafion films , 1993 .

[95]  N. Patil,et al.  Synthesis and Characterization of Biopolymer Composites from the Inside Out , 2009 .

[96]  O. Terasaki,et al.  Synthesis of carboxylic group functionalized mesoporous silicas (CFMSs) with various structures , 2007 .

[97]  F. Xiao,et al.  pH-responsive carrier system based on carboxylic acid modified mesoporous silica and polyelectrolyte for drug delivery , 2005 .

[98]  D. Brunel,et al.  Preparation of MCM-41 type silica-bound manganese(III) Schiff-base complexes , 1996 .

[99]  K. Ghebreyessus,et al.  Isomerizing-Hydroboration of the Monounsaturated Fatty Acid Ester Methyl Oleate† , 2006 .

[100]  K. Tsutsumi,et al.  Adsorption characteristics of organosilica based mesoporous materials. , 2004, Langmuir.

[101]  Christopher W. Jones,et al.  Effect of the synthetic method and support porosity on the structure and performance of silica‐supported CuBr/pyridylmethanimine atom transfer radical polymerization catalysts. I. Catalyst preparation and characterization , 2004 .

[102]  Bozhi Tian,et al.  Morphology development of mesoporous materials: a colloidal phase separation mechanism , 2004 .

[103]  J. Vinh,et al.  Comparison of two glutaraldehyde immobilization techniques for solid‐phase tryptic peptide mapping of human hemoglobin by capillary zone electrophoresis and mass spectrometry , 2004, Electrophoresis.

[104]  S. Mann,et al.  Synthesis and shape modification of organo-functionalised silica nanoparticles with ordered mesostructured interiors , 2003 .

[105]  Can Li Chiral Synthesis on Catalysts Immobilized in Microporous and Mesoporous Materials , 2004 .

[106]  Q. Xue,et al.  Preparation and self-assembly of carboxylic acid-functionalized silica. , 2007, Journal of colloid and interface science.

[107]  D. Brunel,et al.  Organo-lined alumina surface from covalent attachment of alkylphosphonate chains in aqueous solution , 2010 .

[108]  V. S. Lin,et al.  Fine-tuning the degree of organic functionalization of mesoporous silica nanosphere materials via an interfacially designed co-condensation method. , 2005, Chemical communications.

[109]  María Vallet-Regí,et al.  Revisiting ceramics for medical applications. , 2006, Dalton transactions.

[110]  E. Teller,et al.  ADSORPTION OF GASES IN MULTIMOLECULAR LAYERS , 1938 .

[111]  S. Mann,et al.  Synthesis of hybrid inorganic–organic mesoporous silica by co-condensation of siloxane and organosiloxane precursors , 1996 .

[112]  C. Bied,et al.  Preparation and Characterization of New Templated Hybrid Materials Containing a Chiral Diamine Ligand , 2001 .

[113]  M. Jaroniec,et al.  Adsorption Characterization of Octyl Bonded Phases for High Performance Liquid Chromatography , 1996 .

[114]  J. Devoisselle,et al.  Synthesis and characterisation of ibuprofen-anchored MCM-41 silica and silica gel , 2003 .

[115]  Marc Lemaire,et al.  Enantioselective catalysis using heterogeneous bis(oxazoline) ligands: which factors influence the enantioselectivity? , 2002, Chemical reviews.

[116]  P. Orth,et al.  Alkoxy Silanes for the Preparation of Silica Based Stationary Phases with Bonded Polar Functional Groups , 1987 .

[117]  K. Unger,et al.  Role of solvent and base in the silanization reaction of silicas for reversed-phase high-performance liquid chromatography , 1984 .

[118]  D. Macquarrie Direct preparation of organically modified MCM-type materials. Preparation and characterisation of aminopropyl–MCM and 2-cyanoethyl–MCM , 1996 .

[119]  M. Fröba,et al.  Silica-based mesoporous organic-inorganic hybrid materials. , 2006, Angewandte Chemie.

[120]  G. Vigier,et al.  Dissipative water intrusion in hydrophobic MCM-41 type materials. , 2002, Chemical communications.

[121]  J. Devoisselle,et al.  Porous chitosan-silica hybrid microspheres as a potential catalyst , 2004 .

[122]  A. Corma,et al.  Silica-Bound Homogenous Catalysts as Recoverable and Reusable Catalysts in Organic Synthesis , 2006 .