"Naked" hydrogencarbonate ion as a bifunctional catalyst toward amide substrates. Nucleophilic ion pairs. 9.
スポンサーリンク
概要
- 論文の詳細を見る
The cleavage of amide substrates (<I>p</I>-nitro-<I>N</I>-methyltrifiuoroacetanilide and <I>p</I>-nitro-<I>N</I>-methyldichloroacetanilide) with anionic nucleophiles was studied at 30 °C in aprotic (acetonitrile and <I>N</I>,<I>N</I>-dimethylformamide) and protic(ethanol) media. Hydrogencarbonate ion acted as catalyst much more efficiently in the aprotic solvents (about 10<SUP>3</SUP> fold) than expected from its aqueous p<I>K</I><SUB>a</SUB>, but in ethanol, its reactivity was close to those of simple nucleophiles (<I>p</I>-cyanophenolate anion and <I>N</I>-hydroxysuccinimide anion) that possess analogous p<I>K</I><SUB>a</SUB> values in water. The reaction rate in the aprotic solvents was sensitive to small amounts of water. The kinetic isotope effect showed that proton transfer was involved (at least partially) in the rate-determining step. Thus, hydrogencarbonate ion behaves in aprotic media as a nucleophilic-general acid catalyst for the amide cleavage. The biochemical implication with regard to the action of biotin was discussed.
- 公益社団法人 日本化学会の論文
著者
-
Kunitake Toyoki
Department Of Chemical Engineering & Technology Faculty Of Engineering Kyushu University
-
Shinkai Seiji
Department Of Applied Chemistry Faculty Of Engineering Kyushu University
-
Nakashima Naotoshi
Department Of Applied Chemistry Faculty Of Engineering Kyushu University
関連論文
- Delivery of Antisense Oligonucleotides to Nuclear Telomere RNA by Use of a Complex between Polysaccharide and Polynucleotide
- Molecular Association of Water-Soluble Calixarenes with Several Stilbene Dyes and Its Application to the Facile Determination of Cationic Surfactant Concentrations
- TICT Induced Fluorescence Color Change Actualized in an Organogel System
- Electropolymerization of Bithienyl-appended Cerium(III) Triple Decker Porphyrin Complex
- Porphyrin Polygons: A New Synthetic Strategy for Cyclic Porphyrin Oligomers Utilizing a Porphyrin Double Decker Structure
- Hydrogen Adsortion in Periodic Mesoporous Organic- and Inorganic-Silica Materials at Room Temperature
- Ultrastable Steroidal Nanotube Formed in Organic Solvents
- 共有結合と非共有結合で連結したミオグロビン基体での電子伝達系の超分子的構築
- Coupling Covalent and Noncovalent Electron Transfer in a Catenane-type Donor-Sensitizer-Acceptor Triad
- A Convenient Synthesis of a Ru(bpy)_3 - based Catenane - type Triad and Its Incorporation into a Protein Scaffold
- ジフェニルスルフィド基を含む両親媒性化合物の合成と2分子膜特性 (高機能両親媒性化合物の合成とその高次構造) -- (ベシクル系)
- Optical Second Harmonic Generation in Alternately Assembled Dye-Polyion Multilayers
- ドキュメント 「研究室の電子化」大作戦! (特集 「研究室の電子化」大作戦!)
- Spectral Characteristics and Molecular Orientation of Azobenzene-Containing Hydrogen-Bond-Mediated Bilayer Membranes
- Thermal Stability and Specific Dye Binding of a Hydrogen-Bond-Mediated Bilayer Membrane^
- Enhancement of the Antisense Effect of Polysaccharide-Polynucleotide Complexes by Preventing the Antisense Oligonucleotide from Binding to Proteins in the Culture Medium
- Influence of Added Saccharides on the Conformation of Boronic-Acid-Appended Poly(L-lysine). Attempts to Control a Helix-Coil Transition by Sugars
- Alternating Molecular Arrangements in Paired Bilayers of Oppositely Charged Amphiphiles
- Heat-Induced Structural Changes of Multibilayer Films of Benzylideneaniline- and Salicylideneaniline-Containing Ammonium Amphiphiles
- 分子集合体を利用した2次元重合反応の制御 (精密重合) -- (構造構築の制御)
- Preparation of Cross-Linked Ultrathin Films Based on Layer-by-Layer Assembly of Polymers
- Molecular Weight Control of Curdlan (β-1, 3-Glucan Polysaccharide) Provides Unique Polynucleotide Binding Properties
- Polysaccharide-Polynucleotide Complexes Part 17. Solvent Effects on Conformational-Transition of Polydeoxyadenylic Acid in the Complexes with Schizophyllan
- Polysaccharide-polynucleotide Interaction (XI) ; Novel Separation System of RNAs by Using Schizophyllan-appended Column
- Chemical Modification of Curdlan to Induce an Interaction with Poly(C)^1
- Polysaccharide-Polynucleotide Complexes (III): A Novel Interaction between the β-1,3-Glucan Family and the Single-Stranded RNA Poly(C)
- Formation of Ordered Monolayer of Anionic Silica Particles on a Cationic Molecular Layer
- Template-Synthesis of Dimension-Diminished Lead Halide Clusters at the Interlayer of Multibilayer Cast Films
- Layer-by-Layer Assembly of Aqueous Bilayer Membranes on Charged Surfaces
- Practical Preparation of Size-Controlled Gold Nanoparticles in Water
- Enantioselective Binding of Amino Acid Derivatives onto Imprinted TiO_2 Ultrathin Films^1
- Molecular Imprinting of Protected Amino Acids in Ultrathin Multilayers of TiO_2 Gel
- AFM Observation of Organogel Nanostructures on Graphite in the Gel-Assisted Transfer Technique
- Chiral Synthesis of a Co(III) Complex on Ammonium Bilayer Templates
- Protein Assembly on Solid Surfaces by Gel-Assisted Transfer (GAT) Technique
- Bilayer Formation in Ethanol from Dialkylammomium Amphiphile Appended with Nitroaniline Moiety
- Selective Transport of Alkali Metal Ions Across Black Lipid Membranes(BLM)Composed of Ionophilic Amphiphiles^1
- Aniline - Hydroxylase Activity of Myoglobin by Coupling with a Membrane - Bound Electron Transport System^1
- Enhanced Peroxidase Activity of Cytochrome c by Phosphate Bilayer Membrane
- Energy Transfer from Zinc-Myoglobin to a Cyanine Dye Facilitated by Their Simultaneous Binding to a Phosphate Bilayer Membrane
- Lipid Anchored Myoglobin 2. Effect of the Anchor Structure on Membrane Binding
- Preparation and Molecular Orientation of a Regular Cast Film of Fluorocarbon Bilayers
- A Hexagonally Organized Elemental Supramolecular Structure of a Sugar-Appended Organogelator Observed by Synchrotron X-ray Source (SPring-8)^1
- 直鎖状アニオン性高分子としてのDNAを用いた金ナノ粒子の一次元配列
- 組織化の楽しさ, これから
- Activity and Stability of Glucose Oxidase in Molecular Films Assembled Alternately with Polyions
- 二分子膜の形成する極微空間を鋳型としたナノ構造体の合成
- 気-水界面における多成分分子認識の可能性と問題点
- Molecularly Flat Films of Linear Polyions and Proteins Obtained by the Alternate Adsorption Method
- 二分子膜キャストフィルムを鋳型とする無機構造制御ならびに分子膜/無機複合超格子の構築
- Alternately Assembled Ultrathin Film of Silica Nanoparticles and Linear Polycations
- Alternate Layer-by-Layer Assembly of Organic Dyes and Proteins is Facilitated by Pre-mixing with Linear Polyions
- タンパク質を自在に並べる--次世代の薄膜作製法,交互積層法
- 2分子膜における機能分子の配向制御 (1988年の化学-8-)
- Preparation of Cationic Gold Nanoparticles and Their Monolayer Formation on an Anionic Amphiphile Layer
- Sequential Reaction and Product Separation on Molecular Films of Glucoamylase and Glucose Oxidase Assembled on an Ultrafilter
- Layer-by-Layer Assembly of Alternate Protein/Polyion Ultrathin Films
- 界面における分子認識
- Spatially Controlled Synthesis of Protein/Inorganic Nano-assembly:Alternate Molecular Layers of Cyt c and TiO_2 Nanoparticles
- Supramolecular Assemblies Comprised of One-Dimensional Mixed Valence Platinum Complex and Anionic Amphiphiles in Organic Media
- Improved Stability of a Polyion-Complexed Monolayer of a Maleic Acid Copolymer by Using Alkoxyethyldimethylamines as Hydrophobic Counterparts at the Air-Water Interface
- Ordering of Dipeptide Molecules on Guanidinium Bilayer Membrane
- Controlled Growth of Polypyrrole Thin Films by Polymerization-induced Adsorption
- Lanthanide Ion-Mediated Hydrolysis of DNA on Phosphate Bilayer Membrane
- 新構造高分子とは
- 水を含む溶媒中での水素結合を利用した分子認識と超分子構築 (1994年の化学-12-)
- 有機分子集合体を用いた無機物の構造制御 (1993年の化学-10-)
- 2分子膜,単分子膜における分子集合構造の構築とその制御--分子設計と集合構造設計
- 2分子膜のつくるらせん超構造 (1987年の化学-7-)
- Stepwise Adsorption of Metal Alkoxides on Hydrolyzed Surfaces : A Surface Sol-Gel Process
- 二分子膜および関連する分子集合体の組織構造とその利用
- 非水媒体中での分子集合体形成 (1992年の化学-9-)
- 2分子膜・単分子膜によるタンパク質の配向組織化 (1991年の化学-8-)
- 分子鋳型としての2分子膜 (1990年の化学-8-)
- 界面単分子膜による分子認識 (1989年の化学-8-)
- 接着研究者・技術者のための分子設計シリ-ズ-11-合成2分子膜の最近の展開--分子設計と応用
- フルオロカ-ボン超薄膜の作製とガス透過特性
- Correlation between Physicochemical Characteristics of Synthetic Cationic Amphiphiles and Their DNA Transfection Ability.
- Fluorescence behavior and energy transfer of cyanine dyes bound to bilayer membranes of double-chain ammonium amphiphiles.
- Coenzyme Models. II. Effect of Micellar Environments on the Acid-Catalyzed Hydration of 1,4-Dihydropyridine Derivatives
- Multifunctional hydrolytic catalyses. V. The reaction of o-substituted benzohydroxamic acids and p-nitrophenyl acetate.
- Reaction of the azomethine moiety buried in bilayer membranes.
- Coenzyme Models. III. Enhanced Charge Transfer Interaction between the Oxidized and Reduced Forms of Nicotinamide in Micellar and Polymeric Systems. NAD Coenzyme Model
- Excimer formation and phase separation of hydrocarbon and fluorocarbon bilayer membranes.
- Coenzyme models. VIII. Reduction of the Schiff base of pyridoxal analogs by 1,4-dihydronicotinamide.
- Simultaneous Fixation of Orientation of Myoglobin and Metalloporphyrins by Synthetic Bilayer Membrane.
- Nucleophilic ion pairs. 8. Facile nucleophilic cleavage of dinitrophenyl sulfate in the presence of micellar zwitterionic hydroxamates.
- Nucleophilic ion pairs. I. Enhanced esterolytic reactivity of hydrophobic ion paors in micellar systems.
- Micellar activation of nucleophilic reactivity of coenzyme A and glutathione toward p-nitrophenyl acetate.
- Coenzyme models. VII. Micellar catalysis of acid-catalyzed hydration of 1-dodecyl-1,4-dihydronicotinamide.
- Nucleophilic ion pairs. 6. Catalytic hydrolysis of p-nitrophenyl acetate by zwitterionic hydroxamate nucleophiles in representative micellar systems.
- Catalytic hydrolysis of p-nitrophenyl esters in the presence of representative ammonium aggregates. Specific activation of a cholesteryl nucleophile bound to a dialkylammonium bilayer membrane.
- The Reaction of the Hydroxamic Acid Group in Polymer with p-Nitrophenyl Acetate
- Coenzyme models. IX. Micellar catalysis of isoalloxazine (flavin) oxidation of dithiol.
- Catalytic hydrolysis of dinitrophenyl sulfate by poly(ethylenimine) derivatives.
- "Naked" hydrogencarbonate ion as a bifunctional catalyst toward amide substrates. Nucleophilic ion pairs. 9.
- Nucleophilic cleavage of phosphate triesters in dialkylammonium bilayer membranes.
- Synthetic bilayer membranes with anionic head groups.
- Imidazole Catalyses in Aqueous Systems. VIII. Spontaneous Hydrolysis and Michaelis-Menten-type Catalytic Hydrolysis of Phenyl Esters in the Presence of Cholic Acid and Its Histamine Derivative
- Imidazole Catalyses in Aqueous Systems. IV. Bimolecular and Michaelis-Menten-Type Catalyses of a Phenyl Ester Hydrolysis by Some Hydrophobic Imidazole Derivatives