Sulconazole nitrate, C18H16Cl3N3O3S, crystallizes in monoclinic, space group C2/c, with a=14.401(1), b=8.051(1), c=34.861(2) Å, β=95.9(1)°, g=0.58 mm-1, Dc=1.523 g/cm3, Dm=1.522 g/cm3, F(000)=1888.0, and z=8. Intensities for 2460 unique reflections were measured on a CAD4 diffractometer with graphited-monochromated Mo-Kα radiation. The structure was solved by direct method and refined by full matrix least squares to a final R=0.071 for 2182 reflections (Io > 2σIo). The bond lengths and angles are comparable with the values found in the analogues imidazole derivatives. The 2,4-dichlorophenyl ring(A) and the p-chlorophenyl ring(B) are almost planar with different heights [dihedral angle 17.3°] while the imidazole ring(C) is nearly perpendicular to the two phenyl rings[dihedral angles about the two rings A, B are 110.8° and 96.1° respectively]. In order to understand the overall conformation we calculated the selected distances (l1, l2, l3) among the center of the three rings and considered the imaginary plan D[C(7), C(9) and C(16)]. The two polar group S(8) and N(19) do not have gauche conformation and l2 value (4.47 Å) is shorter than the other imidazole derivatives. One -NO3 group are hydrogen bonded the two neighbored sulconazole molecules. The molecular crystal packing is also formed by two hydrogen bondings and van der Waals forces.

Data from structure/activity studies in vir gene induction system have led to evaluate the working hypothesis of interaction between phenolic inducers and phenol binding proteins. The primary specificity in the association of a phenolic inducer with its receptor in our system is hypothesized to be the hydrogen bonding interactions through the ortho methoxy substituents as well as the proton transfer between the inducer and the binding protein. In this paper the proposed working model for phenol-mediating signal transduction was evaluated in several ways. The importance of the general acid-base catalysis was first addressed by the presence of an acidic residue and a basic residue in the phenol binding protein. Series of compounds were tested for vir gene expression activity to confirm the generation of a strong nucleophile by an acidic residue and an involvement of a basic residue as a proton acceptor. An attempt was made to correlate the pKa values of the phenolic compounds with vir gene induction activities as inducers to further support the proposed proton transfer mechanism. Finally, it was also observed that the regioselectively attached methoxy group on phenol compounds is required as the proper hydrogen bond acceptor.

The luminescence and excitation spectra of [Cr(trans-diammac)](ClO4)3 (trans-diammac=trans-6, 3-dimethyl-l, 4, 8, 11-tetraazacyclotetradecane-6, 13-diamine) taken at 77 K are reported. The mid and far-infrared spectra at room-temperature are also measured between 4000 cm-1and 50 cm-1. In the excitation spectrum the 2Eg components are splitted by 102 cm-1. Using the observed electronic transitions, a ligand field analysis was performed to determine more detailed bonding properties of the coordinated atoms toward chromium(Ⅲ). According to the results, we can confirm that the six nitrogen atoms have a strong σ-donor character, and the trans-diammac secondary amine has a greater value of eσ than does the primary amine.

The geometries and energies of the isomers in alkyne complexes MCl(PH3)2(η2-C2H2), M=Rh and Ir, are theoretically investigated using ab initio methods at the Hartree-Fock and up to MP4 level of theory and relativistic effective core potentials for Rh and Ir metals. The optimized structures of Rh complexes, 1-3 at MP2/ECP1 level are in good agreement with the related experimental data. The binding energies of C2H2 to d8-metal fragments are computed to be ∼55 kcal/mol. The vinylidene complexes for Rh and Ir metals are calculated to be much lower in energy than the alkyne complexes. The alkyne-vinylidene rearrangement is possible to proceed exothermically through the intermediate hydrido-alkynyl complexes, 2 or 9. Detailed comparison is given about the geometries and relative energies on Rh and Ir isomers at the various level ab initio calculations with orbital analysis.

We have built a laser ionization mass spectrometer (LIMS) for chemical composition analysis of solid samples, which employs an Nd:YAG laser and a time-of-flight mass analyzer. In this spectrometer, the maximum mass we identified clearly is higher than 2000 amu. A mass resolution of 230 has been achieved at m/z 208 (Pb element) in the linear TOFMS and can be even improved up to 1550 by employing a reflectron. The detection limit is determined to be on the order of ppm for Fe and In. The depth resolution is found to be about 20Å/spectrum with a laser power of 0.5 J/cm2. We also report a preliminary application of the LIMS to identifying impurities resident in several solid samples.

Poly(ethylene 2, 6-naphthalate-co-tetramethylene 2, 6-naphthalate) (PEN/PBN) copolymers were synthesized and studied by 13C NMR spectroscopy, DSC analysis and X-ray diffraction. A minimum in the melting point vs. composition curve was found at approximately 60 mol% tetramethylene 2, 6-naphthalate. The PEN/PBN copolymers were shown to be statistically random throughout the range of 1, 4-butanediol compositions. The melting point depression behavior of annealed PEN/PBN copolymers depended upon the sequence propagation probability, PS, which is suggested by indivisual crystal formation of two pure comonomers; that is, ethylene-naphthalate-ethylene, EE, and tetramethylene-naphthalate-tetramethylene, BB. However, it can be seen from the X-ray curve that the peaks of PEN/PBN copolymers appear from a crystal lattice which is governed only by the rich component between two different aliphatic units in the copolymer composition.

A method of dual-signal generation from two different enzymes was developed and utilized to simultaneously perform dual immunoassays in a single microwell. Two enzymes selected as tracers were horseradish peroxidase (HRP) and β-galactosidase (GAL). 3, 3', 5, 5'-Tetramethylbenzidine (TMB) and chlorophenolred-β-galactopyranoside (CPRG) as chromogenic substrates for the respective enzyme were used. Although the two enzymes showed their maximum activities at distinct pH conditions (pH 5.1 for HRP and 7.5 for GAL), the enzyme reactions were able to be concurrently carried out at pH 5.75 in a dual-substrate solution without signal loss. This performance was achieved by increasing TMB concentration two-fold, introducing potassium salt as activator of GAL reaction, and extending total reaction time 50%. The signal generation method was then used for dual-enzyme immunoassays to detect antibodies with co-immobilized Hepatitis C virus antigens (core and NS5) and a Hepatitis B virus antigen (PreS(2)) in a microwell. Dose-response curves of the assays revealed cooperativity between different antigen-antibody complex formation, which suggested that dual immunoassays can only be used for qualitative screening tests unless the antigens immobilized were spatially separated.

The mode of action of mastoparan B, an antimicrobial cationic tetradecapeptide amide isolated from the hornet Vespa basalis, toward phospholipid bilayers was studied with synthetic mastoparan B and its analogs with individual Ala instead of hydrophobic amino acids (1-Ile, 3-Leu, 6-Leu, 7-Val, 9-Trp, 13-Val, 14-Leu) in mastoparan B. Mastoparan B and its analogs were synthesized by the solid-phase method. Circular dichroism spectra showed that mastoparan B and its analogs adopted an unordered structure in buffer solution. In the presence of neutral and acidic liposomes, most of the peptides took an α-helical structure. The calcein leakage experiment indicated that mastoparan B interacted strongly with neutral and acidic lipid bilayers than its analogs. Mastoparan B also showed a more or less highly antimicrobial activity and hemolytic activity for human erythrocytes than its analogs. These results indicate that the hydrophobic face in the amphipathic α-helix of mastoparan B critically affect biological activity and helical contents.

Lead zirconate titanate (PZT) thin fills were deposited onto the Pt/Ti/SiO2/Si substrate by the pulsed laser deposition with the second harmonic wavelength (532 nm) of Nd:YAG laser. In order to determine the optimum conditions for the film deposition, the phase of the films were investigated as functions of ambient oxygen pressure, substrate temperature, and laser fluence. Also the chemical composition analysis was conducted for the PZT films deposited under various ambient oxygen pressure. When the distance between substrate and bulk PZT target is set to 20 mm, the optimum conditions have been determined to be 3 torr of oxygen pressure, 1.5 J/cm2 of laser fluence, and 823-848(±10) K range of substrate temperature. At these conditions, perovskite phase PZT films were obtained on platinized silicon. The chemical composition of the films is very similar to that of PZT bulk target. The physical structure of the deposited films analyzed by scanning electron microscopy shows a columnar morphology perpendicular to the substrate surface. Capacitance-Voltage hysteresis loop measurements show also a typical characteristics of ferroelectric thin film. The dielectric constant is found to be 528 for the 0.48 μm thickness of PZT thin film.

The electrochemical properties of LixCoyNi1-yO2 compounds (y=0.1, 0.3, 0.5, 0.7, 1.0) prepared by citrate sol-gel method have been investigated. The LixCoyNi1-yO2 compounds were annealed at 850 ℃ for 20 h after preheating at 650 ℃ for 6 h, in air. The x-ray diffraction (XRD) patterns for LixCoyNi1-yO2 have shown that these compounds have a well developed layered structure (R&bar{3} m). From the scanning electron microscopy of LixCoyNi1-yO2, particle size was estimated less than 5 μm. The Li//LixCoyNi1-yO2 electrochemical cell consists of Li metal anode and 1 M LiClO4-propylene carbonate (PC) solution as the electrolyte. The differences in intercalation rate of the LixCoyNi1-yO2 in the first charge/discharge cycle were less than 0.05 e-. The first discharge capacities of LixCoO2 and LixCo0.3Ni0.7O2 were ∼130 mAh/g and ∼160 mAh/g, respectively.

The polymerization of 4, 4-bis(acetoxymethyl)-1, 6-heptadiyne (BAH) was carried out by MoCl5 and WCl6 with various organometallic cocatalysts. MoCl5-based catalysts were more effective than WCl6-based ones for the cyclopolymerization of BAH. Poly(BAH) was characterized to have polymer backbone with conjugated double bond and cyclic structure by IR, UV-visible, and 1H-and 13C NMR spectroscopies. The polymer was stable up to 310 ℃ and 5 % weight loss show up at 350 ℃. The resulting dark violet polymer exhibited good solubility in common organic solvents and could be cast on a glass plate to give film with good mechanical properties. It was found that oxygen permeability (PO2) and permselectivity (PO2/PN2) of the resulting polymer were 15.2 barrer and 2.84, respectively.

A wide range (10 < Si/V) of mesoporous vanadium silicate molecular sieves with the MCM-41 structure have been synthesized using vanadyl sulfate as the source of vanadium and characterized by XRD, 51V MAS NMR and 29Si MAS NMR. The increase of the unit cell parameter and the decrease of Q3/Q4 ratio of 29Si spectra with the vanadium content suggest the incorporation of vanadium in the framework of MCM-41 structure. 51V MAS NMR demonstrates that vanadiums in as-synthesized V-MCM-41 are present in the chemical environment of octahedra and octahedral vanadium is decreased and tetrahedral vanadium is increased inversely with raising the calcination temperature. Though the thermal treatment in rotor of hydrated sample resulted in the change from tetrahedral environment to octahedral one and the steaming and the acid treatment affect to the chemical environment of vanadium, the spectrum similar to originally calcined sample is regenerated after recalcination. This indicates that the vanadium is belong to the framework in a relatively exposed site. The best quality XRD pattern of the product of Si/V=27 may be attributable to heterogeneous nucleation mechanism. V-MCM-41's having the Si/V ratio lower than 20 are completely collapsed after calcination.

Preparation and properties of Eu(hfa)3·L (Hhfa = hexafluoroacetylacetone, L = bis(2-methoxyethyl)ether, diglyme, and 2, 2':6', 2"-terpyridine, tpy), which are potential CVD precursors for europium, were investigated. The reaction of the Eu2O3 with Hhfa in the presence of tridentate neutral ligand yielded the nine-coordinated Eu(hfa)3·L. Eu(hfa)3·diglyme is air- and moisture-stable and most importantly has good volatility and thermal stability. Eu(hfa)3·tpy shows no sublime intact. The complex Eu(hfa)3·diglyme has been characterized by an X-ray structure determination; monoclinic P21/n, a=10.252(1), b=16.051(6), c=19.392(8) Å, β=96.10(2)°, V=3173(2) Å3. The europium atom in Eu(hfa)3·diglyme adopts a square-antiprismatic geometry with the ninth coordinating oxygen atom capping one of the square faces. All the adducts have been characterized by IR, TGA/DTA.

Nine new solubility-increased container hosts having eight undecyl substituents were synthesized and characterized. 1H NMR spectral data showed integral inclusion state of carceplexes and their stability. 1H NMR chemical shifts of guest DMA were correlated to the host's cavity dimensions shrinked by constrictive binding. Carceplex and hemicarcerand showed their distinctive FD mass spectra.

Complexation of primary alkylammonium ions by 1, 3-distal calix[4]arene diesters was studied by NMR spectroscopy. The guest alkylammonium ions are found to bind mainly to the two ester moieties and are oriented outward with respect to the cone cavity of the host, forming exo-type complexes unlike the case of alkylammonium-calix[6]arene systems. Measurement of T1 also revealed that the primary binding site is the two ester moities and phenolic OH groups. The temperature dependence of the chemical shifts of phenolic OH protons in these diesters correlates with the basicity of the solvent moderately well and the temperature coefficients of their chemical shifts are found to significantly decrease upon complexation with propylammonium ion.

In the course of magnetic study on several perovskite-type oxides, A2Fe(Ⅲ)BO6 (A = Ca, Sr, Ba and B = Sb, Bi), we have observed a strong irreversibility in their dc-magnetizations. When the structural data and the Mossbauer spectra are considered, such an irreversibility is to be associated with some competitions between the nearest-neighbors (nn) and the next-nearest-neighbors (nnn) in their magnetic sublattices. Particularly, the Mossbauer spectra indicate that Sr2FeBiO6 of cubic perovskite-structure is apparently well ordered crystalline compound. Nontheless this antiferromagnet shows a magnetic property which resembles that of a spin-glass. The strong history dependence is observed below 91 K and the irreversible magnetic behavior is also observed from the measurement of hysteresis loops at 10 K after zero-field-cooled (zfc) and field-cooled (fc) processes. Considering the nn and the nnn superexchanges of almost same order in ordered perovskite, it is proposed that there exists a competition and cancellation of antiferromagnetic and ferromagnetic superexchange between the nearest-neighbors and the next-nearest-neighbors, thus introducing a certain degree of frustration.