A method for the determination of cobalt(Ⅱ) by differential pulse voltammetry using a carbon paste electrode constructed by incorporating 1-(2-pyridylazo)-2-naphthol(PAN) into a conventional carbon paste mixture composed of graphite powder and Nujol oil has been developed. Several influencing factors for the determination of cobalt(Ⅱ) were studied in detail and the optimum analytical conditions were found to be as follows: pH, 4.6; composition of electrode, 20%; temperature of deposition, 43 ℃; time of preconcentration, 15 min. Regeneration of the electrode surface for the continuous uses of the electrode was achieved by exposing the carbon paste electrode to an acidic solution. Response of the electrode was reproducible for the uses of five times and the relative standard deviations were 6.7 and 4.6% for 2.0×10-5 M and 4.0×10-6 M cobalt(Ⅱ), respectively. The calibration curve for cobalt(Ⅱ) obtained by differential pulse voltammetry was divided into two linear ranges of 1.7× 10-6-1.3×10-4 M and 2.0×10-7-8.0×10-7 M. The detection limit was estimated to be 1.3×10-7 M. The effects of coexisting ions were also investigated to test the applicability of the proposed method to the determination of cobalt(Ⅱ) in real samples.

A random walk simulation was used to determine the triplet exciton density and annihilation rate for a two dimensional lattice of naphthalene choleic acid with small amount of β-methylnaphthalene (BMN). The results demonstrate that energy transfer efficiency (α) increases as density increases and the annihilation begins to become significant at triplet exciton densities higher then 10-3/sites. Another simulation was carried out to determine annihilation rate and unimolecular decay rate in the absence of BMN. The results indicate that the annihilation rate is equal to the unimolecular decay rate at the density of 1.2×10-3/sites.

The interactions between a rod-coil liquid crystalline oligomer, ethyl 4-[4'-oxy-4-biphenylcarbonyloxy]-4'-biphenylcarboxylate with poly(ethylene oxide) (DP=12) (12-4) and LiCF3SO3 have been characterized by using Raman spectroscopy. Band assignments were made comparing the spectrum of 12-4 with those of the poly(ethylene glycol) monomethyl ether(PEGME) (Mw=550) and the ethyl-4'-hydroxybiphenyl-4-carboxylate (EHBPC), which are the coil and mesogen analogues, respectively. Analyzing characteristic bands of the 12-4-salt complex, we have found that the bands belonging to the coil and mesogenic units are changed in both intensities and frequencies. The spectral changes were interpreted from the viewpoint of the complexation between 12-4 and the Li+ ion. However, the possibility that the spectral changes in the mesogenic unit are not due to the complexation with the Li+ ion, but due to the conformational changes by the intercalation of nondissociated LiCF3SO3, is not ruled out.

A study on the application of vinyl radical cyclization via free radical allylation reaction in the synthesis of various carbocyclic compounds is described. In connection with this study, a new allyl transfer reagent, 2-bromo-3-(phenylthio)propene 1 is developed and it was shown that vinyl radical cyclization through free radical allylation reaction using reagent 1 provides a valuable approach to carbocyclic systems with a reactive exo-alkylidene moiety, which is advantageous for further transformations.

Adenosine deaminase (ADA) has been utilized as the label in devising a potentiometric homogeneous assay for riboflavin and riboflavin binding protein (RBP). The proposed homogeneous assay method employs an ADA-biotin conjugate as the signal generator and an avidin-riboflavin conjugate as the signal modulator in the solution phase. The catalytic activity of the ADA-biotin conjugate is inhibited in the presence of an excess amount of the avidin-riboflavin conjugate, and the observed inhibition is reversed in an amount proportional to the concentration of RBP added. When the analyte riboflavin is added to this mixture of ADA-biotin, avidin-riboflavin and RBP, the activity of the enzyme conjugate is re-inhibited in an amount proportional to the concentration of riboflavin. Since the enzyme label used in this system is ADA, an ammonia-producing enzyme, a potentiometric rather than photometric detection scheme is used to monitor the enzymatic activity in the assay.

A new synthetic route for the lanthanum β-diketonate compounds via in-situ formed lanthanum alkyl complexes was developed in the process for the development of suitable MOCVD (metal-organic chemical vapor deposition) precursors of PLT, one of the promising material for the ferroelectric film. A series of lanthanum β-diketonate compounds were successfully synthesized by this method. This new method is found to have some merits; versatile method for almost every β-diketone, β-hydroxyketone, and β-hydroxyaldehyde, short reaction time, easy purification for high purity, moderate to high yield, and easy access to anhydrous compounds. In some cases, anhydrous oligomeric products fail to show the higher volatility. On the other hand, some lanthanum β-diketonates with aromatic groups such as La(1,3-biphenyl-l,3-propandione)3 are found to have favorable properties for a precursor of lanthanum oxide, one of major components of PLT, such as low melting point, and much higher decomposition temperature. A plausible pyrolysis mechanism is proposed by the TGA, where consecutive dissociation of R, CO, CH, C, and O fragments occurs.

The synthesis and characterization of diastereomeric dodecanucleotides, d[GATCp(S)TCGAGATC], containing recognition sequence of the XhoI restriction endonuclease with a phosphorothioate internucleotidic linkage the cleavage site are described. Rp and Sp form of diastereomerically pure dinucleoside phosphorothioates d[Cp(S)T] were presynthesized and used for the addition to the growing oligonucleotide chain as a block. The stereochemistry of dinucleoside phosphorothioate was assigned by 31P NMR spectroscopy, enzyme digestion, and reverse-phase HPLC. XhoI restriction endonuclease cut only Rp diastereomer d[GATCp(S))TCGAGATC]. The rate of hydrolysis is slower than that of the unmodified dodecamer d[GATCTCGAGATC]. The phosphorothioate nucleotide is using for determination of the stereochemical course of the XhoI catalyzed reaction.

Synthetic lipoidal peptides based on viral protein sequences have been prepared. These peptides contain an N-palmitoyl group at the N-terminal residue, which is a modified cysteine, containing a S-[2,3-bis(acyloxy)-(2-R,S)-propyl] moiety. When this residue (Pam3Cys) is at the N-terminus of a synthetic peptide, it acts as potent immunoadjuvant to enhance both IgM and IgG antibody responses to the attached peptide. Conventional analytical procedures (e.g., Edman degradation and amino acid analysis) are either not applicable due to the N-terminal modification, or do not provide confirmation of the intact structure. Chromatographic analysis is also hindered by the tendency of these lipoidal Pam3Cys peptides to form large aggregates, and in some cases to be permanently adsorbed on reversed phase columns. We have applied several mass spectrometric techniques, including fast atom bombardment (FAB), electrospray ionization (ESI) and matrix assisted laser desorption ionization (MALDI) to characterize the intact structures of a number of different Pam3Cys synthetic peptides. The MALDI-MS has been found to be the most sensitive for the analysis of the structure of Pam3Cys peptides.

The catalytic dehydrocoupling of bis(1-sila-3-butyl)benzene, 1 by Cp2ZrCl2/Red-Al and Cp2ZrCl2/n-BuLi combination catalysts yielded a mixture of oily and solid polymers. While the catalytic dehydrocoupling of 2-phenyl-l,3-disilapropane, 2 by Cp2ZrCl2/n-BuLi combination catalyst produced a mixture of oily and solid polymers, the catalytic redistribution/dehydrocoupling of 2 by Cp2ZrCl2/Red-Al combination catalyst gave oily polymer. The dehydrocoupling of 1 and 2, unless the prior silane redistribution occurs, seems to initially produce a low-molecular-weight polymer, which then undergoes an extensive cross-linking reaction of backbone Si-H bonds, leading to an insoluble polymer.

The effects of G-T mismatches on thermal stability, the base-pair lifetime and the global structure of a d(GCGTGCGC)2 duplex were studied by using 1H NMR, UV and CD spectroscopy. The existence of G-T mismatches was found to cause a noticeable change in the chemical environment of imino protons associated with significant decrease in the base-pair lifetime at the mismatched site as well as in thermal stability of the duplex itself. The melting transition of d(GCGTGCGC)2 was not cooperative at all at 100 mM or lower concentration of NaCl, but became cooperative at 500 mM or higher NaCl concentration. The melting temperature (Tm) of this duplex was 32℃ at 500 mM concentration of NaCl, which is much lower than that of d(GCGCGCGC)2 at the same NaCl concentration. This suggests that the decrease in stability may be ascribed to the decrease in the base-pair lifetime and the deviation from the normal structure due to the G-T mismatches. Adding berenil to d(GCGTGCGC)2 caused no observable change in the global structure but the large decrease in the base-pair lifetime and the stability of the duplex.

The effects of β-CD, Me-β-CD, and biphenyl capped β-CD on 1H NMR spectra of mandelic acid 1, α-methylbenzylamine 2 and 2-phenylpropionic acid 3 were investigated. Enantiomeric recognition was observed for mandelic acid 1 by all the hosts used, for α-methylbenzylamine 2 by β-CD and Me-β-CD, and for 2-phenylpropionic acid 3 by Me-β-CD. In the presence of biphenyl-capped β-CD, ο-, m-, and p-protons of the phenyl groups of the guests are discriminated due to ring current of the capped biphenyl group. The splitting pattern of the phenyl protons indicates that the phenyl group of the guests is inserted into the β-CD cavity from the secondary hydroxyl side and positioned in close proximity to the capped biphenyl ring. The magnitude of the upfield shifts of H3 and H5 protons of β-CD upon binding of guests 1-3 is similar to that caused by ephedrine or pseudoephedrine, suggesting that the substitution at benzylic carbon atom has little effect on the depth of the insertion of the phenyl group into the β-CD cavity and stability of the inclusion complexes.

Solvolysis rates of 1-(4-methoxyphenyl)-l-phenyl-2,2,2-trifiuoroethyl chloride (1) and 1-(4-methoxyphenyl)-1-phenylethyl chloride (2) were measured in a variety of aqueous binary solvents, and the solvent effect was treated with the Grunwald-Winstein equation. The solvent effect on the solvolysis of 1 failed to give a single linear correlations using the ordinary Y or YCl, but exhibited the wide split pattern which could not be related to the solvent nucleophilicity. The improved correlations with YBnCl and extended dual-parameter treatment, log (k/k0)=mYCl+hI (mΔYΔ), were observed for the solvolysis of 1. These results suggest that the incipient cationic charge in the solvolysis of 1 is delocalized strongly into the aryl-rings in the transition state. While the solvent effect on the solvolysis of 2 is better correlated with Y or YCl than YBnCl but the linearity is not satisfactory. The correlation is comparably improved by the use of the extended Grunwald-Winstein equation, log (k/k0)=0.81YCl+0.26NOTs (R=0.994, SD=±0.12), indicating the cationic charge of reaction center of 2 was localized mostly in the transition state.

The charge transfer compounds of tetrathiafulvalene (TTF) with the general formula of (TTF)mMCln, (M=Au, Pt, Ir, Os) were prepared by the direct reaction using excess HAuCl4·3H2O, H2PtCl6·xH2O, H2IrCl6·xH2O and H2OsCl6 respectively. The powdered electrical conductivities (σrt) at room temperature are given as follows; (TTF)3AuCl2, 4.53×10-3; (TTF)3.5AuCl2, 6.37×10-3; (TTF)3PtCl4, 5.51×10-4; (TTF)2IrCl4, 2.40×10-5; (TTF)OsCl4·1/2C2H5OH, 4.46×10-7 Scm-1. Magnetic susceptibility, electronic (UV-Vis.), vibrational (IR) and EPR spectroscopic evidences indicate that there is incomplete charge transfer from the TTF donor to gold, platinum, and iridium respectively, and that there is essentially complete charge transfer to osmium, thereby resulting a relatively low electrical conductivity in osmium compound. The EPR and magnetic susceptibility data reflect that the metals are in diamagnetic Au(Ⅰ), Pt(Ⅱ), Ir(Ⅲ), and Os(Ⅱ) oxidation states, and the odd electrons are extensively delocalized over the TTF lattices in each compound.

The dissociative recombination of O2+(v+)＋e-→O(1S)＋O(1D) has been theoretically investigated using the multichannel quantum defect theory (MQDT). Cross sections and rate coefficients at various electron energies are calculated. The resonant structures in cross section profile, which are hardly measurable in experiments, are also determined and the existence of Rydberg states is found to affect the rates. The theoretical rate coefficients are computed to be smaller than experimental ones. The reasons for this difference are explained. The two-step MQDT procedure is found to be very useful and promising in calculating the state-to-state rates of the dissociative recombination reaction which is a very important and frequently found phenomenon in Earth's ionosphere.