Attempts to Fill the Gap Between Enzymatic, Homogeneous, and Heterogeneous Catalysis

Abstract Bio‐inspired and single site metal complex catalysts have been discussed to direct towards a rational design of solid heterogeneous catalysts. When concepts derived from catalytic antibodies, molecular imprinting and molecular recognition, and site isolation and modification by appropriate ligands are combined, with new techniques to prepare, tailor made solid materials, catalysts can be prepared that improve reaction rate and selectivity by increasing the concentration and activation of reactants in the vicinity of the active sites, and by stabilizing transition states or intermediate products. It is also shown that enzymatic, homogeneous and hetergeneous catalysts can be combined to perform “one‐pot” cascade reactions.

[1]  C. Nájera,et al.  A convenient oxime-carbapalladacycle-catalyzed Suzuki cross-coupling of aryl chlorides in water. , 2002, Angewandte Chemie.

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

[3]  G. Paparatto,et al.  Process for producing olefin oxides , 2000 .

[4]  A. Corma,et al.  MCM-41–Quaternary organic tetraalkylammonium hydroxide composites as strong and stable Brønsted base catalysts , 1999 .

[5]  A. Suzuki,et al.  Design of catalytic sites at oxide surfaces by metal-complex attaching and molecular imprinting techniques , 2002 .

[6]  Raul F. Lobo,et al.  Zeolite and molecular sieve synthesis , 1992 .

[7]  Y. Iwasawa,et al.  Approaches to design of active structures by attaching and molecular imprinting of metal complexes on oxide surfaces , 2003 .

[8]  Buddy D. Ratner,et al.  Template-imprinted nanostructured surfaces for protein recognition , 1999, Nature.

[9]  R. Schoevaart,et al.  Galactose dialdehyde: the forgotten candidate for a protein cross-linker? , 2001, Carbohydrate research.

[10]  A. V. Ramaswamy,et al.  Synthesis and catalytic properties of large-pore Sn-β and Al-free Sn-β molecular sieves , 1997 .

[11]  K. Severin,et al.  Biomimetic catalysis with immobilised organometallic ruthenium complexes: substrate- and regioselective transfer hydrogenation of ketones. , 2000, Chemistry.

[12]  A. Corma,et al.  Periodic mesoporous organosilica incorporating a catalytically active vanadyl Schiff base complex in the framework , 2004 .

[13]  R. Haushalter,et al.  High-valent iron-porphyrin complexes related to peroxidase and cytochrome P-450 , 1981 .

[14]  C. Hill Activation and functionalization of alkanes , 1989 .

[15]  S. Srebnik Theoretical Investigation of the Imprinting Efficiency of Molecularly Imprinted Polymers , 2004 .

[16]  I. Karube,et al.  Carbon-carbon bond formation using substrate selective catalytic polymers prepared by molecular imprinting: an artificial class II aldolase , 1996 .

[17]  B. Gaber,et al.  Surface-imprinted silica particles: the effects of added organosilanes on catalytic activity , 2001 .

[18]  Q. Xin,et al.  Enantioselective epoxidation of olefins catalyzed by Mn (salen)/MCM-41 synthesized with a new anchoring method. , 2002, Chemical communications.

[19]  Y. Iwasawa,et al.  Performance and Kinetic Behavior of a New SiO2-Attached Molecular-Imprinting Rh-Dimer Catalyst in Size- and Shape-Selective Hydrogenation of Alkenes , 2002 .

[20]  O. Terasaki,et al.  Cubic Hybrid Organic−Inorganic Mesoporous Crystal with a Decaoctahedral Shape , 2000 .

[21]  A. Corma,et al.  Direct Synthesis and Characterization of Hydrophobic Aluminum-Free Ti−Beta Zeolite , 1998 .

[22]  A. Corma,et al.  On the atomic environment and the mode of action of the catalytic centre in an intercalated oxo–molybdenum complex [MoO2{O2CC(S)Ph2}2]2– for oxygen-transfer reactions , 1996 .

[23]  A. Corma,et al.  One-pot synthesis of phenols from aromatic aldehydes by Baeyer–Villiger oxidation with H2O2 using water-tolerant Lewis acids in molecular sieves , 2004 .

[24]  J. Suh,et al.  Macrocyclic metal complexes built on polyethylenimine , 1991 .

[25]  W. Hoelderich,et al.  ‘One-pot’ reactions: a contribution to environmental protection , 2000 .

[26]  Börje Sellergren,et al.  Noncovalent molecular imprinting: antibody-like molecular recognition in polymeric network materials , 1997 .

[27]  A. Sayari,et al.  Periodic Mesoporous Silica-Based Organic−Inorganic Nanocomposite Materials , 2001 .

[28]  I. Nicholls,et al.  Chapter 1 - A historical perspective of the development of molecular imprinting , 2001 .

[29]  K. Wieghardt,et al.  Aerobic Oxidation of Primary Alcohols by a New Mononuclear Cu(II) -Radical Catalyst. , 1999, Angewandte Chemie.

[30]  Dae-Won Park,et al.  The catalytic activity of new chiral salen complexes immobilized on MCM-41 in the asymmetric hydrolysis of epoxides to diols , 2000 .

[31]  I. Vankelecom,et al.  Oxidation of cyclohexane using FePcY-zeozymes occluded in polydimethylsiloxane membranes , 1996 .

[32]  D. Avnir,et al.  Acids and Bases in One Pot while Avoiding Their Mutual Destruction , 2001 .

[33]  Y. Iwasawa,et al.  Design of a Novel Molecular-Imprinted Rh−Amine Complex on SiO2 and Its Shape-Selective Catalysis for α-Methylstyrene Hydrogenation , 2004 .

[34]  M. Laspéras,et al.  Design of Chiral Hybrid Organic-Inorganic Mesoporous Materials as Enantioselective Epoxidation and Alkylation Catalysts , 2005 .

[35]  Y. Fujii,et al.  Formation of a specific co-ordination cavity for a chiral amino acid by template synthesis of a polymer Schiff base cobalt(III) complex , 1985 .

[36]  V. Dufaud,et al.  Surface Organometallic Chemistry of Inorganic Oxides: The Synthesis and Characterization of (.tplbond.SiO)Ta(:CHC(CH3)3)(CH2C(CH3)3)2 and (.tplbond.SiO)2Ta(:CHC(CH3)3)(CH2C(CH3)3) , 1995 .

[37]  Robert G. Bell,et al.  Molecular-sieve catalysts for the selective oxidation of linear alkanes by molecular oxygen , 1999, Nature.

[38]  I. Nicholls,et al.  Spectroscopic Evaluation of Molecular Imprinting Polymerization Systems , 1997 .

[39]  A. Corma,et al.  Catalytic Air Oxidation of Thiols Mediated at a Mo(VI)O2 Complex Center Intercalated in a Zn(II)-Al(III) Layered Double Hydroxide Host , 1995 .

[40]  K. Shea,et al.  Designed catalysts. A synthetic network polymer that catalyzes the dehydrofluorination of 4-fluoro-4-(p-nitrophenyl)butan-2-one , 1994 .

[41]  D. Mansuy,et al.  Metalloporphyrinosilicas: a new class of hybrid organic–inorganic materials acting as selective biomimetic oxidation catalysts , 1996 .

[42]  K. Mosbach,et al.  Molecularly imprinted polymers and their use in biomimetic sensors. , 2000, Chemical reviews.

[43]  C. Baerlocher,et al.  Synthesis and Structural Characterization of MWW Type Zeolite ITQ-1, the Pure Silica Analog of MCM-22 and SSZ-25 , 1998 .

[44]  P. Mutin,et al.  Design of supported catalysts by surface functionalization of micelle- templated silicas , 2003 .

[45]  A. Bhaumik,et al.  Sn-ZSM-12, a new, large pore MTW type tin-silicate molecular sieve: synthesis, characterization and catalytic properties in oxidation reactions , 1995 .

[46]  A. Corma,et al.  Lewis acids as catalysts in oxidation reactions: from homogeneous to heterogeneous systems. , 2002, Chemical reviews.

[47]  T. Tatsumi,et al.  Synthesis and Catalytic Capability of Zeolite-Encapsulated Iron and Manganese Tetramethylporphine Complexes , 1990 .

[48]  J. W. Parker,et al.  Progress in Developing Nerve Agent Sensors Using Combinatorial Techniques , 2003 .

[49]  S. Marx,et al.  Molecular Imprinting of Sol Gel Polymers for the Detection of Paraoxon in Water , 2003 .

[50]  Päivi Jokela,et al.  Can we rationally design molecularly imprinted polymers , 2001 .

[51]  S. Kurihara,et al.  Footprint Catalysis. I. A New Method for Designing “Tailor-Made” Catalysts with Substrate Specificity: Silica (Alumina) Catalysts for Butanolysis of Benzoic Anhydride , 1988 .

[52]  Mark E. Davis,et al.  Rational Catalyst Design via Imprinted Nanostructured Materials , 1996 .

[53]  R. Sheldon,et al.  A four-step enzymatic cascade for the one-pot synthesis of non-natural carbohydrates from glycerol. , 2000, The Journal of organic chemistry.

[54]  Börje Sellergren,et al.  Enantioselective ester hydrolysis catalyzed by imprinted polymers. , 2000 .

[55]  A. Corma,et al.  Intercalation of [MoVIO2(O2CC)(S)Ph2)2]2- in a Zn(II)-Al(III) layered double hydroxide host : a strategy for the heterogeneous catalysis of the air oxidation of thiols , 1994 .

[56]  Jordi Rius,et al.  Pure Polymorph C of Zeolite Beta Synthesized by Using Framework Isomorphous Substitution as a Structure-Directing Mechanism. , 2001, Angewandte Chemie.

[57]  E. Sastre,et al.  Synthesis, characterization and catalytic activity of MCM-41-type mesoporous silicas functionalized with sulfonic acid , 2001 .

[58]  Dewi W. Lewis,et al.  Predicting the Templating Ability of Organic Additives for the Synthesis of Microporous Materials , 1995 .

[59]  B. J. Melde,et al.  Mesoporous sieves with unified hybrid inorganic/organic frameworks , 1999 .

[60]  C. Brinker,et al.  Microporous Silica Prepared by Organic Templating: Relationship Between the Molecular Template and Pore Structure , 1999 .

[61]  J. F. Young,et al.  The preparation and properties of tris(triphenylphosphine)halogenorhodium(I) and some reactions thereof including catalytic homogeneous hydrogenation of olefins and acetylenes and their derivatives , 1966 .

[62]  M. Lam,et al.  A Sol-gel Derived Molecular Imprinted Luminescent PET Sensing Material for 2,4-Dichlorophenoxyacetic Acid , 2001 .

[63]  Y. Iwasawa,et al.  Novel SiO2-attached molecular-imprinting Rh-monomer catalysts for shape-selective hydrogenation of alkenes; preparation, characterization and performance , 2002 .

[64]  A. Cammidge,et al.  Synthesis of heterogeneous palladium catalyst assemblies by molecular imprinting , 2001 .

[65]  P. Schultz,et al.  A new strategy for the generation of catalytic antibodies , 1989, Nature.

[66]  Karl Wieghardt,et al.  Synthesis, crystal structures, reactivity, and magnetochemistry of a series of binuclear complexes of manganese(II), -(III), and -(IV) of biological relevance. The crystal structure of [L'MnIV(.mu.-O)3MnIVL'](PF6)2.H2O containing an unprecedented short Mn.cntdot..cntdot..cntdot.Mn distance of 2.296 , 1988 .

[67]  Kevin M Smith,et al.  Biochemistry and binding : activation of small molecules , 2000 .

[68]  Giorgio Strukul,et al.  Transition Metal Catalysis in the Baeyer-Villiger Oxidation of Ketones. , 1998, Angewandte Chemie.

[69]  J. Moulijn,et al.  Direct Epoxidation of Propene Using Gold Dispersed on TS-1 and Other Titanium-Containing Supports , 1999 .

[70]  D. Spivak,et al.  Enhanced Enantioselectivity of Molecularly Imprinted Polymers Formulated with Novel Cross-Linking Monomers , 2003 .

[71]  D. D. De Vos,et al.  Heterogeneous Enzyme Mimics Based on Zeolites and Layered Hydroxides , 2002 .

[72]  T. Ohsuna,et al.  Novel Mesoporous Materials with a Uniform Distribution of Organic Groups and Inorganic Oxide in Their Frameworks , 1999 .

[73]  J. Mayoral,et al.  Bis(oxazoline)–Copper Complexes, Supported by Electrostatic Interactions, as Heterogeneous Catalysts for Enantioselective Cyclopropanation Reactions: Influence of the Anionic Support , 1999 .

[74]  Mizuo Maeda,et al.  Molecular and ionic recognition with imprinted polymers , 1998 .

[75]  A. Corma,et al.  Al-free Sn-Beta zeolite as a catalyst for the selective reduction of carbonyl compounds (Meerwein-Ponndorf-Verley reaction). , 2002, Journal of the American Chemical Society.

[76]  P. Gallezot,et al.  Preparation and utilization of molecularly imprinted silicas , 1997 .

[77]  J. Silvestre-Albero,et al.  Chemoselective hydrogenation catalysts: Pt on mesostructured CeO2 nanoparticles embedded within ultrathin layers of SiO2 binder. , 2004, Journal of the American Chemical Society.

[78]  M. Jaroniec,et al.  Recent developments in the synthesis and chemistry of periodic mesoporous organosilicas , 2002 .

[79]  K. Severin,et al.  Biomimetic Catalysis with an Immobilised Chiral Rhodium(III) Complex , 2000 .

[80]  S. Gatley Activities of the enantiomers of cocaine and some related compounds as substrates and inhibitors of plasma butyrylcholinesterase. , 1991, Biochemical pharmacology.

[81]  Avelino Corma,et al.  Strategies to improve the epoxidation activity and selectivity of Ti-MCM-41 , 1998 .

[82]  D. Avnir,et al.  Pore Size Distribution Induced by Microphase Separation: Effect of the Leaving Group during Polycondensation , 2001 .

[83]  K. Mizuno,et al.  PHOTO-INDUCED CYCLODIMERIZATION OF ELECTRON-RICH AROMATIC OLEFINS IN THE PRESENCE OF TRANSITION METAL COMPLEXES , 1979 .

[84]  B. Pugin,et al.  More than 100,000 Turnovers with Immobilized Ir‐Diphosphine Catalysts in an Enantioselective Imine Hydrogenation , 2002 .

[85]  A. Corma,et al.  Ultra fast and efficient synthesis of Ti-ITQ-7 and positive catalytic implications , 2000 .

[86]  C. Che,et al.  Asymmetric epoxidation of alkenes catalysed by chromium binaphthyl Schiff base complex supported on MCM-41 , 1999 .

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

[88]  B. Sellergren,et al.  Enantioselective ester hydrolysis catalyzed by imprinted polymers. , 1994, The Journal of organic chemistry.

[89]  Martha Sibrian-Vazquez,et al.  Molecular imprinting made easy. , 2004, Journal of the American Chemical Society.

[90]  A. Corma,et al.  Hydrogenation of aromatics under mild conditions on transition metal complexes in zeolites. A cooperative effect of molecular sieves , 1995 .

[91]  P. Schultz,et al.  An antibody-catalyzed bimolecular Diels-Alder reaction , 1990 .

[92]  A. Corma,et al.  Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer–Villiger oxidations , 2001, Nature.

[93]  Jun Liu,et al.  Molecular Recognition of Organic Compounds by Imprinted Silica , 1999 .

[94]  A. Corma,et al.  MCM‐41—Quaternary Organic Tetraalkylammonium Hydroxide Composites as Strong and Stable Broensted Base Catalysts. , 1999 .

[95]  Miguel A. Camblor,et al.  Synthesis and catalytic activity of Ti-ITQ-7: a new oxidation catalyst with a three-dimensional system of large pore channels , 2000 .

[96]  Jonathan S. Dordick,et al.  Catalytic Silica Particles via Template-Directed Molecular Imprinting , 2000 .

[97]  A. Corma,et al.  Hybrid organic—inorganic catalysts: a cooperative effect between support, and palladium and nickel salen complexes on catalytic hydrogenation of imines , 2004 .

[98]  T. Sagawa,et al.  Catalytic activity of a novel water-soluble cross-linked polymer imprinted by a transition-state analogue for the stereoselective hydrolysis of enantiomeric amino acid esters , 1996 .

[99]  A. Corma,et al.  Delaminated zeolite precursors as selective acidic catalysts , 1998, Nature.

[100]  K. Mosbach,et al.  Study of the nature of recognition in molecularly imprinted polymers , 1996, Journal of molecular recognition : JMR.

[101]  A. Corma,et al.  Electrostatic and covalent immobilisation of enzymes on ITQ-6 delaminated zeolitic materials , 2001 .

[102]  A. Corma,et al.  Water-resistant solid Lewis acid catalysts: Meerwein–Ponndorf–Verley and Oppenauer reactions catalyzed by tin-beta zeolite , 2003 .

[103]  R. Lerner,et al.  Bait and switch strategy for obtaining catalytic antibodies with acyl-transfer capabilities , 1990 .

[104]  N. Minoura,et al.  Synthesis of Polymer-Coated Silica Particles with Specific Recognition Sites for Glucose Oxidase by the Molecular Imprinting Technique. , 1998 .

[105]  J. Heilmann,et al.  Selective Catalysis on Silicon Dioxide with Substrate-Specific Cavities† , 1994 .

[106]  Bruno Notari,et al.  Microporous Crystalline Titanium Silicates , 1996 .

[107]  D. Landry,et al.  Anti-Cocaine Catalytic Antibodies: A Synthetic Approach to Improved Antibody Diversity. , 1996 .

[108]  D. Riley,et al.  Manganese macrocyclic ligand complexes as mimics of superoxide dismutase , 1994 .

[109]  A. Corma,et al.  Computational and Experimental Approach to the Role of Structure-Directing Agents in the Synthesis of Zeolites: The Case of Cyclohexyl Alkyl Pyrrolidinium Salts in the Synthesis of β, EU-1, ZSM-11, and ZSM-12 Zeolites , 2003 .

[110]  A. Corma,et al.  Oxime carbapalladacycle covalently anchored to high surface area inorganic supports or polymers as heterogeneous green catalysts for the Suzuki reaction in water. , 2004, The Journal of organic chemistry.

[111]  Uday S. Racherla,et al.  Efficient manganese catalysts for low-temperature bleaching , 1994, Nature.

[112]  Peng Wu,et al.  A Novel Titanosilicate with MWW Structure. I. Hydrothermal Synthesis, Elimination of Extraframework Titanium, and Characterizations , 2001 .

[113]  P. A. Barrett,et al.  ITQ-7: A New Pure Silica Polymorph with a Three-Dimensional System of Large Pore Channels. , 1999, Angewandte Chemie.

[114]  A. Corma,et al.  Vanadyl salen complexes covalently anchored to single-wall carbon nanotubes as heterogeneous catalysts for the cyanosilylation of aldehydes , 2004 .

[115]  O. Brüggemann,et al.  Catalyzing a cycloaddition with molecularly imprinted polymers obtained via immobilized templates , 2004 .

[116]  M. Finn,et al.  Mechanism of asymmetric epoxidation. 2. Catalyst structure , 1991 .

[117]  R. Schoevaart,et al.  Combined Catalytic Reactions: Nature′s Way. , 2002 .

[118]  John Meurig Thomas,et al.  Influence of Organic Templates on the Structure and on the Concentration of Framework Metal Ions in Microporous Aluminophosphate Catalysts , 1996 .

[119]  D. Alonso,et al.  Highly active oxime-derived palladacycle complexes for Suzuki-Miyaura and Ullmann-type coupling reactions. , 2002, The Journal of organic chemistry.

[120]  I. Nicholls Can we rationally design molecularly imprinted polymers? Fundamentals of molecularly imprinted polymer design , 2000 .

[121]  K. Severin,et al.  Molecular imprinting with an organometallic transition state analogue , 1999 .

[122]  M. Olivucci,et al.  An innovative approach to the design of plastic antibodies: molecular imprinting via a non-polar transition state analogue , 2004 .

[123]  C. Alexander,et al.  Directed nucleation of calcite at a crystal-imprinted polymer surface , 1999, Nature.

[124]  P. A. Jacobs,et al.  Iron-Phthallocyanines Encaged in Zeolite Y and Vpi-5 Molecular Sieve as Catalysts for the Oxyfunctionalization of n-Alkanes , 1991 .

[125]  T. Akiyama,et al.  Molecular Imprinting of Cyclodextrins Leading to Synthetic Antibodies , 2002 .

[126]  A. Corma,et al.  Delaminated zeolites: An efficient support for enzymes , 2002 .

[127]  J. Smith,et al.  Alkene epoxidation with iodosylbenzene catalysed by polyionic manganese porphyrins electrostatically bound to counter-charged supports , 2001 .

[128]  F. H. Dickey,et al.  The Preparation of Specific Adsorbents. , 1949, Proceedings of the National Academy of Sciences of the United States of America.

[129]  M. R. Gagné,et al.  Toward the Molecular Imprinting of Titanium Lewis Acids: Demonstration of Diels−Alder Catalysis , 1998 .

[130]  Chi‐Huey Wong,et al.  Complex carbohydrate synthesis tools for glycobiologists: enzyme-based approach and programmable one-pot strategies. , 2000, Glycobiology.

[131]  Ivo F. J. Vankelecom,et al.  An efficient mimic of cytochrome P-450 from a zeolite-encaged iron complex in a polymer membrane , 1994, Nature.

[132]  O. Baffa,et al.  Study of the catalytical intermediates of metalloporphyrins supported on imidazole propyl gel , 1997 .

[133]  D. Riley Rational design of synthetic enzymes and their potential utility as human pharmaceuticals , 2000 .

[134]  I. Wilson,et al.  Routes to catalysis: structure of a catalytic antibody and comparison with its natural counterpart. , 1994, Science.

[135]  D. Barthomeuf,et al.  Change in benzene adsorption with acidobasicity of (Cs,Na)X zeolites studied by i.r. spectroscopy , 1988 .

[136]  P G Schultz,et al.  At the crossroads of chemistry and immunology: catalytic antibodies. , 1991, Science.

[137]  A. Corma,et al.  AlITQ-6 and TiITQ-6: Synthesis, Characterization, and Catalytic Activity We thank the Spanish CICYT for financial support (project MAT97-1016-C02-01 and project MAT97-1207-C03-01). U.D. and M.E.D. thank the M.E.C. and M.E.A., respectively, for funding their doctoral fellowships. , 2000, Angewandte Chemie.

[138]  J. Barciszewski,et al.  Native transfer RNA catalyzes Diels-Alder reaction. , 2002, Biochemical and biophysical research communications.

[139]  Kim D. Janda,et al.  Catalytic Antibody Mediated Hydrolysis of Paraoxon. , 1996, The Journal of organic chemistry.

[140]  Tohru Yamada,et al.  Oxidation of Aldehydes into Carboxylic Acids with Molecular Oxygen Using Nickel(II) Complex Catalyst , 1991 .

[141]  S. Campestrini,et al.  Olefin epoxidation and alkane hydroxylation catalyzed by robust sulfonated manganese and iron porphyrins supported on cationic ion-exchange resins , 1992 .

[142]  B. Meunier Metalloporphyrins as versatile catalysts for oxidation reactions and oxidative DNA cleavage , 1992 .

[143]  Jihoon Shin,et al.  Application of new unsymmetrical chiral Mn(III), Co(II,III) and Ti(IV) salen complexes in enantioselective catalytic reactions , 1999 .

[144]  A. Corma,et al.  An oxime-carbapalladacycle complex covalently anchored to silica as an active and reusable heterogeneous catalyst for Suzuki cross-coupling in water. , 2003, Chemical communications.

[145]  B. Gates Models of metal catalysts: beyond single crystals , 2000 .

[146]  A. Corma,et al.  Model Reactions of Molybdo-Reductase. A Novel and Highly Efficient Reduction of Nitrobenzene to Aniline Catalyzed by a Molybdenum-Mediated Oxygen Atom Transfer Reaction , 1995 .

[147]  A. Corma,et al.  On the Preferential Location of Al and Proton Siting in Zeolites: A Computational and Infrared Study , 2002 .

[148]  Avelino Corma,et al.  Delaminated Zeolites: Combining the Benefits of Zeolites and Mesoporous Materials for Catalytic Uses , 1999 .

[149]  A. Togni,et al.  Chiral Xyliphos Complexes for the Catalytic Imine Hydrogenation Leading to the Metolachlor Herbicide: Isolation of Catalyst–Substrate Adducts , 2004 .

[150]  James H. Clark,et al.  Solid acids for green chemistry. , 2002, Accounts of chemical research.

[151]  F. Bigi,et al.  Heterogeneous enantioselective epoxidation of olefins catalysed by unsymmetrical (salen)Mn(III) complexes supported on amorphous or MCM-41 silica through a new triazine-based linker. , 2002, Chemical communications.

[152]  T. Shimada,et al.  Enzyme-like enantioselective catalysis over chiral ‘molecular footprint’ cavities on a silica (alumina) gel surface , 1992 .

[153]  J. Groves,et al.  Hydroxylation and epoxidation catalyzed by iron-porphine complexes. Oxygen transfer from iodosylbenzene , 1979 .

[154]  Mark E. Davis,et al.  Transesterification on “imprinted” silica , 1996 .

[155]  I. P. Rothwell,et al.  Surface-supported group 5 metal organometallic compounds for catalytic arene hydrogenation , 1993 .

[156]  Erik H. Anderson,et al.  Nanoscale molecular-switch devices fabricated by imprint lithography , 2003 .

[157]  Patrick Gamez,et al.  Molecular imprinting of polymerised catalytic complexes in asymmetric catalysis , 1998 .

[158]  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.

[159]  G. Hutchings,et al.  Catalytic asymmetric heterogeneous aziridination of alkenes using zeolite CuHY with [N-(p-tolylsulfonyl)imino]phenyliodinane as nitrene donor , 1999 .

[160]  Burkhard König,et al.  Synthetic creatinine receptor: imprinting of a Lewis acidic zinc(II)cyclen binding site to shape its molecular recognition selectivity. , 2004, Journal of the American Chemical Society.

[161]  J. Smith,et al.  Model systems for cytochrome P450 dependent monooxygenases. Part 8. A study of the epoxidation of (Z)-cyclooctene by iodosylbenzene catalysed by cationic iron(III) tetra(N-methylpyridyl)porphyrins adsorbed on Dowex MSC1 , 1991 .

[162]  K. Mosbach,et al.  Molecularly imprinted polymers facilitating a β-elimination reaction , 1993 .

[163]  F. Vizza,et al.  Liquid-Biphase Hydrogenolysis of Benzo[b]thiophene by Rhodium Catalysis , 1997 .

[164]  D. Landry,et al.  Antibody-catalyzed degradation of cocaine. , 1993, Science.

[165]  J. Bäckvall,et al.  Ruthenium- and enzyme-catalyzed dynamic kinetic resolution of secondary alcohols , 1999 .

[166]  A. Corma,et al.  Chiral vanadyl Schiff base complex anchored on silicas as solid enantioselective catalysts for formation of cyanohydrins: optimization of the asymmetric induction by support modification , 2003 .

[167]  D. Alonso,et al.  Oxime-Derived Palladium Complexes as Very Efficient Catalysts for the Heck–Mizoroki Reaction , 2002 .

[168]  R. Bloch,et al.  Estimation and disposition of [3H]benzoylecgonine and pharmacological activity of some cocaine metabolites , 1975, The Journal of pharmacy and pharmacology.

[169]  R. Lerner,et al.  From molecular diversity to catalysis: lessons from the immune system. , 1995, Science.

[170]  A. Fitch,et al.  Localization of benzene in sodium-Y-zeolite by powder neutron diffraction , 1986 .

[171]  G. Wulff,et al.  Catalytic Molecularly Imprinted Polymers Using Conventional Bulk Polymerization or Suspension Polymerization: Selective Hydrolysis of Diphenyl Carbonate and Diphenyl Carbamate , 2000 .

[172]  J. Smith,et al.  Alkene epoxidation catalysed by ligand-bound supported metalloporphyrins , 1992 .

[173]  A. Corma,et al.  Synthesis, Characterization, and Catalytic Activity of a Large‐Pore Tridirectional Zeolite, H‐ITQ‐7 , 2000 .

[174]  K. Balkus,et al.  Mesoporous molecular sieve immobilized enzymes , 1998 .

[175]  Mark E. Davis,et al.  Molecular imprinting of bulk, microporous silica , 2000, Nature.

[176]  D. Sasaki Chapter 8 - Molecular imprinting approaches using inorganic matrices , 2001 .

[177]  UchidaShogo,et al.  NEW DOUBLE SALT OF SULFAMIC ACID AND POTASSIUM SULFATE , 1972 .

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

[179]  O. Lev,et al.  Toward establishing criteria for polymer imprinting using mean-field theory , 2002 .

[180]  T. Tatsumi,et al.  A New Generation of Titanosilicate Catalyst: Preparation and Application to Liquid-Phase Epoxidation of Alkenes , 2004 .

[181]  R. Schoevaart,et al.  Combined catalytic conversion involving an enzyme, a homogeneous and a heterogeneous catalyst: one-pot preparation of 4-deoxy-d-glucose derivatives from d-galactose , 2002 .

[182]  R. Breslow,et al.  Cleavage of Phosphate Esters by a Cyclodextrin Dimer Catalyst That Binds the Substrates Together with La3+ and Hydrogen Peroxide , 1994 .

[183]  A. Corma,et al.  Heterogeneized Brönsted base catalysts for fine chemicals production : grafted quaternary organic ammonium hydroxides as catalyst for the production of chromenes and coumarins , 2000 .

[184]  A. Corma,et al.  Synthesis and catalytic activity of a chiral periodic mesoporous organosilica (ChiMO). , 2003, Chemical communications.