From Raman spectra, the ${\nu}g$C=O frequencies of 4-substituted benzaldehydes were found to correlate with the ${\sigma}_p$ values of the 4-x atom or group as well as the acceptor number (AN) values of solvents. In various solvents, the ${\nu}g$C=O frequency of benzaldehyde decreased upon the increase of benzaldehyde concentration. This shift was mainly due to the hydrogen bonding between the carbonyl oxygen and/or aldehydic proton of benzaldehyde and the solvent molecules. Over the 1-80 volume % change, the ${\nu}g$C=O frequency of benzaldehyde down shifted from 1709.4 $cm^{-1}$ to 1700.2 $cm^{-1}$ in CCl4 solution and from 1703.0 $cm^{-1}$ to 1698.0 $cm^{-1}$ in $C_2H_5OH$ solution. This is due to the fact that hydrogen bonding between the benzaldehyde and C2H5OH was much stronger than that between the benzaldehyde and the other solvents.

The conformational transition of oligopeptide multimer,-(HPPHPPP)n-, is studied (H:hydrophobic amino acid, P:hydrophilic amino acid). The helix/coil transitions are detected in the multimer. The transition depends on the number of amino acid in the sequence, the concentration of the oligopeptide, and temperature which affects helix stability constant (${\xi}$) and hydrophobic interaction parameter (wj). In the thermodynamic equilibrium system jA${\rightarrow}$Aj (where A stands for oligopeptide monomer), Skolnick et al., explained helix/coil transition of dimer by the matrix method using Zimm-Bragg parameters ${\xi}$ and $\sigma$ (helix initiation constant). But the matrix method do not fully explain dangling H-bond effects which are important in oligopeptide systems. In this study we propose a general theory of conformational transitions of oligopeptides in which dimer, trimer, or higher multimer coexists. The partition of trimer is derived by using zipper model which account for dangling H-bond effects. The transitions of multimers which have cross-linked S-S bonds or long chains do not occur, because they keep always helical structures. The transitions due to the concentration of the oligopeptides are steeper than those due to the chain length or temperature.

The transition metal carbonylate, PPN+(${\eta}^5-MeCp)Mn(CO)_2Cl^-$ undergoes a novel ligand substitution reaction with PR3 (R=Me, Et, OEt, $C_6H_5$ in THF at elevated temperatures (40 $^{\circ}C$ up to 60 $^{\circ}C)$ under the pseudo-first-order reaction conditions (usually 20-fold excess of PR3 with respect to metal carbonylate concentrations) where chloride is displaced by PR3. The reaction follows overall first order dependence on [(${\eta}^5-MeCp)Mn(CO)_2Cl^-$]; however, the negative entropy changes of activation (${\Delta}S^{\neq}$=-19.3 e.u. for $P(OEt)_3$; ${\Delta}S^{\neq}$=-16.4 e.u. for $PPh_3$) suggest the existence of the intermediate, ((η3-MeCp)Mn(CO)2(THF)Cl-, which eventually transforms to the product (${\eta}^5-MeCp)Mn(CO)_2(PR_3)$.

A continuous potential pulse is applied to a silver-working electrode on a pulsed amperometric detector (PAD) for detection of free cyanide and sulfide. The moving phase is 0.1 M sodium hydroxide, 0.5 M sodium acetate and 5% (v/v) ethylenediamine mixture, and the flow rate is 0.7 mL/min. Optimized pulse conditions include a -200 mV (vs. Ag/AgCl reference electrode) detection potential(Ed) for 60 msec and 50 mV cleaning potential (Ec) for 120 msec. The silver working electrode surface is not poisoned by cyanide or sulfide, and the PAD maintains long-term stability without loss of sensitivity and reproducibility at these pulse conditions. The detection limit of cyanide and sulfide separated by ion chromatography using an anion exchange column is 0.1 ppm and 0.05 ppm, respectively.

To see the quantitative relationship between the structures of the C-7 substituted quinolones and their antibacterial activities, theoretical parameters such as the molecular van der Waals volume, surface area and some electrostatic parameters based on the molecular electrostatic potential, which represent lipophilicity, and some quantum mechanical parameters are introduced as descriptors. The sixteen substituted quinolone derivatives and twenty bacteria are used for the study. It is found that the QSARs of C-7 substituted quinolones are obtained for eleven bacteria and our descriptors are more useful for Gram positive organisms than negative ones. It is also shown that molecular surface area (or molecular Waals volume) of the C-7 substituent and net charge of C-7 atom of the quinolones are the descriptors of utmost importance.

The synthesis of common skeleton of podosporin A and aureol was studied through cationic olefin cyclization as a key step. The generation of thermodynamic silyl enol ether or enol acetate under known conditions gave regioselectivity of 88:12. The enolate alkylation of 2,3-dimethylcyclohexanone with 2,5-dimethoxybenzyl bromide at the more substituted site via lithium enolate gave poor yield. In this case an organozincate or an ammonium enolate also proved to be ineffective or not practical in terms of yield. Side chain elongation of the substituted cyclohexanone 13 through Grignard reaction, Wittig reaction, or Shappiro reaction did not proceed because of steric hindrance and side reactions. However, Stille coupling reaction via enol triflate produced the desired product 18 in high yield. The advanced intermediate 22, which was efficiently synthesized from 18, produced 24 instead of the desired product under a cationic olefin cyclization condition, indicating that the cyclization occurred in a stepwise mannervia the organomercury intermediate 23.

The steady-state emission and fluorescence lifetimes of 1,3-dipyrenylpropane were measured in silicate sol-gel and xerogel matrices. In sol solution, the fluorescence emission spectra of monomer and excimer resemble those in hydrocarbon solvents. In gel and xerogel condition, however, the fluorescence spectra exhibit significant change, largely confirming the intramolecular motions in gel pores are influenced by microviscosity. The rate constants for intramolecular excimer formation were obtained from the measured fluorescence lifetimes and the rate processes for excimer forming in silicate sol-gel are described by a simple kinetic scheme.

Two redox processes of methyl viologen (+2/+, +/0) in acetonitrile were investigated by using channel electrode voltammetric and in situ electrochemical ESR methods. Two separated unequal plateau currents of the first (+2/+) and second (+/0) redox processes of the viologen were observed in the channel electrode voltammograms and showed a cube-root depedndence on the electrolyte flow rate, respectively. The simple Levich analysis resulted in two different diffusion coefficients of $D_{+2}=2.2{\times}10^{-5}\;cm^2/s$ and $D_+=3.0{\times}10^{-5}cm^2/s$ from the limiting currents. In situ electrochemical ESR studies were performed for the monocation radicals generated at the potentials of the two plateau currents in the electrolyte flow range $1.3{\times}10^{-1}{\geq}v_f{\geq}2.7{\times}10^{-3}\;cm^3/s$. Backward implicitfinite difference method was employed to simulate the electrochemical kinetic problem of two sequential electron transfers ($MV^{+2}+e{\leftrightarrows}MV^+,\;MV^{+}+e{\leftrightarrows}MV^0$) coupled with reversible comproportionation ($MV^{2+}+MV^0{{\leftrightarrows}^{k_f}_{k_b}}2MV^+$). $k_f$ was found to be greater than ($10^6M^{-1}s^{-1}.

The variations of the structural detail of layered perovskite-type oxides, Na2Ln2Ti3O10 (Ln=La, Nd, Sm, Gd), have been refined by Rietveld analyses of their powder X-ray diffraction data. Although the c-axis strongly decreases from Ln=La to Nd, Sm, or Gd, the length of Na-O bond along the c-axis that is regarded as the sodium layer spacing is not dependent on the unit cell parameter. Such a behavior is explained by the fact that Na-O bond is in competition with Ti-O one of the perovskite slab. Increased covalency of this Ti-O bond by the lattice contraction leads to weakening of the attaching strength of Na ion. This picture is consistent with the experimental observation that Na ion conductivity of Na2Ln2Ti3O10 increases from Ln=La to Nd, Sm, or Gd despite strong contraction of the unit cell volume.

A series of tetradentate Schiff base ligands; [1,2-bis(naphthylideneimino)ethane, 1,3-bis(naphthylideneimino)propane, 1,4-bis(naphthylideneimino)butane, and 1,5-bis(naphthylideneimino)pentane] and their Ni(Ⅱ) complexes have been synthesized. The properties of these ligands and their Ni(Ⅱ) complexes have been characterized by elemental analysis, IR, NMR, UV-vis spectra, molar conductance, and thermogravimetric analysis. The mole ratio of Schiff base to Ni(Ⅱ) metal was found to be 1:1. The electrochemical redox process of the ligands and their Ni(Ⅱ) complexes in DMF and DMSO solution containing 0.1 M tetraethyl ammonium perchlorate (TEAP) as a supporting electrolyte have been investigated by cyclic voltammetry, chronoamperometry, differential pulse voltammetry, and controlled potential coulometry at glassy carbon electrode. The redox process of the ligands was highly irreversible, whereas redox process of Ni(Ⅱ) complexes were observed as one electron transfer process in quasi-reversible and diffusion-controlled reaction. The electrochemical redox potentials of the Ni(Ⅱ) complexes were affected by the chelate ring size of ligands. The diffusion coefficients of Ni(Ⅱ) complexes containing 0.1 M TEAP in DMSO solution were determined to be 5.7-6.9 × 10-6 cm2/sec. Also the exchange rate constants were determined to be 1.8-9.5 × 10-2 cm2/sec. These values were affected by the chelate ring size of ligands.

Hydrodediazoniation product (3a-d) was found to be the major product in the reaction of arenediazonium tetrafluoroborate (1a-d) with triethylamine (2) in methanol under nitrogen at room temperature. A quantitative study on the title reaction was investigated in detail and two remarks were noteworthy. One was the linear increase in the yield of 3a-d by increasing the molar concentration of 2 until equimolar concentration was reached between 1a-d and 2. The other was the suppression of the formation of 3a-d in the presence of oxygen. Based on these results, the title reaction was better understood by 1:1 electron transfer reaction between reactants (1a-d and 2) rather than by radical chain mechanism proposed in the reaction of arenediazonium tetrafluoroborate and triphenylphosphine.

Early attempts to identify plausible conformations of a linear octapeptide hormone, angiotensin-II (Asp-Arg-Val-Tyr-Ile-His-Pro-Phe), using various theoretical and experimental methods, have led to various conformational models. So far, no consensus has been made about the solution phase structure and the receptor binding structure of angiotensin-II. The ultimate goal for the conformation study of the peptide hormone is to develop a new potent drug. Therefore, we have devised a strategy for designing the pharmacophore by studying thermodynamically possible conformations of various kinds of angiotensin-II antagonists and angiotensin-II.

It is shown that the inversion of the undamped Bloch equation for an amplitude-modulated broadband π/2 pulse can be precisely treated as an inverse scattering problem for a Schrodinger equation on the positive semiaxis. The pulse envelope is closely related to the central potential and asymptotically the wave function takes the form of a regular solution of the radial Schrodinger equation for s-wave scattering. An integral equation, which allows the calculation of the pulse amplitude (the potential) from the phase shift of the asymptotic solution, is derived. An exact analytical inversion of the integral equation shows that the detuning-independent π/2 pulse amplitude is given by a delta function. The equation also provides a means to calculate numerically approximate π/2 pulses for broadband excitation.

We present a theoretical formulation of diffusion process on solid surface based on multidimensional transition state theory (TST). Surface diffusion of single adatom results from hopping processes on corrugated potential surface and is affected by surface vibrations of surface atoms. The rate of rare events such as hopping between lattice sites can be calculated by transition state theory. In order to include the interactions of the adatom with surface vibrations, it is assumed that the coordinates of adatom are coupled to the bath of harmonic oscillators whose frequencies are those of surface phonon modes. When nearest neighbor surface atoms are considered, we can construct Hamiltonians which contain terms for interactions of adatom with surface vibrations for the well minimum and the saddle point configurations, respectively. The escape rate constants, thus the surface diffusion parameters, are obtained by normal mode analysis of the force constant matrix based on the Hamiltonian. The analysis is applied to the diffusion coefficients of W, Ir, Pt and Ta atoms on the bcc(110) plane of W in the zero-coverage limit. The results of the calculations are encouraging considering the limitations of the model considered in the study.

The resonance width may be directly determined by solving an eigenvalue equation for width operator which is derived in this work based on the method of complex scaling transformation. The width operator approach is advantageous to the conventional rotating coordinate method in twofold; 1) calculation can be done in real arithmetics and, 2) so-called θ-trajectory is not required for determining the resonance widths. Application to one- and two-dimensional model problems can be easily implemented.

The crystal and molecular structure of thiourea dioxide, (NH2)2CSO2, was determined by x-ray single crystal diffraction techniques. Lattice constants are a=10.669(2), b=10.119(2), and c=3.9151(5) Å with the space group Pnma and Z=4. The thiourea portion of the molecule has a planar conformation. When the two oxygen atoms are included, the sulfur atom is at the apex of a trigonal pyramid formed with the two oxygen atoms and the carbon atom as the base. The crystal structure is stabilized by strong intermolecular hydrogen bonds. Ab initio calculations were performed to investigate the bonding features and reactivity of thiourea dioxide. The calculated bond order of S-C is only 0.481. The hydrogen bond energy was computed to be 22.3 kcal/mol for dimer. MEP analysis reveals that the sites on nucleophilic reactions are S and C atoms.