The Kirkwood-Buff theory and the effect of cosolvents on biochemical reactions

Cosolvents added to aqueous solutions of biomolecules profoundly affect protein stability, as well as biochemical equilibria. Some cosolvents, such as urea and guanidine hydrochloride, denature proteins, whereas others, such as osmolytes and crowders, stabilize the native structures of proteins. The way cosolvents interact with biomolecules is crucial information required to understand the cosolvent effect at a molecular level. We present a statistical mechanical framework based upon Kirkwood-Buff theory, which enables one to extract this picture from experimental data. The combination of two experimental results, namely, the cosolvent-induced equilibrium shift and the partial molar volume change upon the reaction, supplimented by the structural change, is shown to yield the number of water and cosolvent molecules bound or released during a reaction. Previously, denaturation experiments (e.g., m-value analysis) were analyzed by empirical and stoichiometric solvent-binding models, while the effects of osmolytes and crowders were analyzed by the approximate molecular crowding approach for low cosolvent concentration. Here we synthesize these previous approaches in a rigorous statistical mechanical treatment, which is applicable at any cosolvent concentration. The usefulness and accuracy of previous approaches was also evaluated.     

Estimation of excess solvation numbers of water and cosolvents from preferential interaction and volumetric experiments

To elucidate, at a molecular level, how cosolvents influence protein stability, it is indispensable to understand the distribution of water and cosolvent molecules around proteins. Calculation of excess solvation numbers of water and cosolvents serves this purpose, and I show that they can be extracted from preferential interaction parameter and volumeric data via the Kirkwood-Buff theory. This scheme was applied to trehalose and glycerol (stabilizers) and urea (denaturant). Important insights from the application include stabilizer-induced enhancement of protein hydration, which, together with the stabilizer's exclusion from protein surfaces, may contribute to protein stabilization at high osmolyte concentrations.     

The quasi-classical limit of quantum scattering theory

We study the quasi-classical limit of the quantum mechanical scattering operator for non-relativistic simple scattering system. The connection between the quantum mechanical and classical mechanical scattering theories is obtained by considering the asymptotic behavior as 0 of the quantum mechanical scattering operator on the state exp(—ip·a/)f(p) in the momentum representation.Partially supported by Fûjû-kai Foundation and Sakkô-kai Foundation     

Existence and Regularity of Propagators for Multi-Particle Schrödinger Equations in External Fields

We consider Schrödinger equations for N number of particles in (classical) electro-magnetic fields that are interacting with each other via time dependent inter-particle potentials. We prove that they uniquely generate unitary propagators \({\{U(t,s), t,s \in \mathbb{R}\}}\) on the state space \({\mathcal{H}}\) under the conditions that fields are spatially smooth and do not grow too rapidly at infinity so that propagators for single particles satisfy Strichartz estimates locally in time, and that local singularities of inter-particle potentials are not too strong that time frozen Hamiltonians define natural selfadjoint realizations in \({\mathcal{H}}\). We also show, under very mild additional assumptions on the time derivative of inter-particle potentials, that propagators possess the domain of definition of the quantum harmonic oscillator \({\Sigma(2)}\) as an invariant subspace such that, for initial states in \({\Sigma(2)}\), solutions are C¹ functions of the time variable with values in \({\mathcal{H}}\). New estimates of Strichartz type for propagators for N independent particles in the field will be proved and used in the proof.     

Synthetic studies on maitotoxin. 1. Stereoselective synthesis of the C'D'E'F'-ring system having a side chain

The stereoselective synthesis of the maitotoxin C'D'E'F'-ring system having a side chain has been accomplished through a convergent strategy. The key reactions include Horner-Wadsworth-Emmons coupling of the C'D'E'-ring and the side chain and subsequent construction of the F'-ring by silane reduction of dihydropyran.     

Separation of CO2 and CH4 by a DDR membrane

The permeation of CO₂ and CH₄ and their binary mixtures through a DDR membrane has been investigated over a wide range of temperatures and pressures. The synthesized DDR membrane exhibits a high permeance and maintains a very high selectivity for CO₂. At a total pressure of 101 kPa, the highest selectivity for CO₂ in a 50∶50 feed mixture was found to be over 4000 at 225 K. This is ascribed to the higher adsorption affinity, as well as to the higher mobility for the smaller CO₂ molecules in the zeolite, preventing the bypassing of the CH₄ through the membrane. An engineering model, based on the generalized Maxwell-Stefan equations, has been used to interpret the transport phenomena in the membrane. The feasibility of DDR membranes as applied to CO₂ removal from natural gas or biogas is anticipated.     

Optical resolution of (+/-)-1,2-Bis(2-methylphenyl)ethylene-1,2-diamine as a chiral framework for 2-iminoimidazolidine with 2-methylphenyl pendant and the guanidine-catalyzed asymmetric michael reaction of tert-butyl diphenyliminoacetate and ethyl acrylate

(+/-)-1,2-Bis(2-methylphenyl)ethylene-1,2-diamine, prepared from benzil and ammonium acetate, was optically resolved as a chiral framework for 2-(1-benzyl-2-hydroxyethyl)imino-1,3-dimethylimidazolidine with 2-methylphenyl pendants at the 4,5-positions. Catalysis ability of the 1,3-dimethyl-4,5-bis(2-methylphenyl)imidazolidine and the related 1,3-dibenzyl-4,5-diphenylimidazolidine was examined in the asymmetric Michael reaction of t-butyl diphenyliminoacetate and ethyl acrylate.     

Development of Electrophilic Radical Perfluoroalkylation of Electron-Deficient Olefins

Fluorinated organic compounds have attracted significant attention over the past few decades owing to their unique properties and versatility. An established method for the synthesis of fluorinated organic compounds involves radical perfluoroalkylation reactions towards double bonds. In this radical pathway, electrophilic perfluoroalkyl radicals exhibit excellent reactivity towards electron-rich olefins. Therefore, several splendid perfluoroalkylation reactions of electron-rich olefins have been reported. However, there are only a few examples of reaction involving electron-deficient olefins because of their poor electronic compatibility with perfluoroalkyl radicals. This review focuses on the reports that challenge this long-standing issue. Radical perfluoroalkylation/bifunctionalization reactions of electron-deficient olefins are described according to the radical generation methods.     

Time-delayed interferometry with nuclear resonant scattering

Hyperfine Interactions - Experimental results of “time-delayed interferometry” with nuclear resonances at KEK are reported. Mössbauer nuclei were used as a cavity for X-rays in...     

Extraction of Alkali Metal (Na—Cs) Picrates with Dibenzo-18-crown-6 into Various Organic Solvents. Elucidation of Fundamental Equilibria which Govern the Extraction-Ability and -Selectivity

In order to quantitatively investigate effects of the size, the structuralrigidity, and the lipophilicity of dibenzo-18-crown-6 (DB18C6) on itsextraction-ability and -selectivity for alkali metal ions, constants of theoverall extraction (Kex), the distribution for various diluents of lowdielectric constants (K_D,MLA), and the aqueous ion-pairformation (K_MLA) of DB18C6-alkali metal (Na-—Cs) picrate 1:1:1 complexes were determined at 25°C; the partition constants of DB18C6 itself were also measured at 25°C. The log K_MLA of Na, K, Rb, and Cs are -0.14 ± 0.11, 1.30 ± 0.10, 1.00 ± 0.09, and 0.24 ± 0.11, respectively. The partition behavior of DB18C6 and its1:1:1 complexes with the alkali metal picrates can be clearly explained byregular solution theory, except for chloroform. The molar volumes andsolubility parameters of DB18C6 and the 1:1:1 complexes were determined.A relation between molar volumes of the complexes and K_MLAis discussed. The magnitude of Kex is largely determined by that ofK_D,MLA. For every diluent, the extraction selectivity of DB18C6increases in the order Na > Cs > Rb > K. The K extraction-selectivity of DB18C6 over Na is the highest among all the combinations of the two neighboring alkali metals in the periodic table. The extraction-ability and -selectivity for the alkalimetal picrates and their change with the diluent of DB18C6 were completely elucidated by the four fundamental equilibria and regular solution theory.