Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and $\gamma$-hydrogen abstraction pathways.

Unfunctionalized biaryl compounds were parallelly and combinatorially prepared by the traceless hydrogenolysis of biarylsulfonates supported on pentaerythritol. The hydrogenolysis using 2-propylmagnesium chloride in the presence of $dppfNiCl_2$ efficiently generated corresponding biaryl derivatives without any memory of the support. The strategy using pentaerythritol as a small soluble support was disclosed to have a potential to combine the benefits of both SPOS and solution-phase reaction with fast reaction rate, facile isolation of intermediates, easy analysis of intermediates and atom economical manner. The novel tetrapodal support is expected to be an efficient substitute for polymeric supports in many circumstances.

Twenty novel tetramic acid derivatives (E)-3-(1-(alkyloxyamino)ethylidene)-1-alkylpyrrolidine-2,4-diones were synthesized by the reaction of 3-(1-hydroxyethylidene)pyrrolidine-2,4-diones with O-alkyl hydroxylamines. The title compounds were confirmed by IR, $^1H$ NMR, MS and elemental analysis. The structure of compound 6r was further verified by X-ray diffraction crystallography. The bioassays showed that most of the title compounds exhibited noticeable herbicidal and fungicidal activities.

Novel 1'-methyl-5'-norcarbocyclic adenosine phosphonic acid analogues were synthesized using an acyclic stereoselective route from commercially available 3,3-diethoxy-propan-1-ol 4. The synthesized nucleoside phosphonate 19 and phosphonic acid 21 were subjected to antiviral screening against various viruses.

Using a pinhole-type glass nozzle equipped for a corona-excited supersonic expansion (CESE), precursor 2,6-dichlorotoluene seeded in a large amount of inert carrier gas helium was discharged to produce jet-cooled but electronically excited benzyl-type radicals. The visible vibronic emission spectrum was recorded with a long-path monochromator to observe vibronic bands in the $D_1{\rightarrow}D_0$ electronic transition of benzyl-type radicals. The spectral analysis revealed the generation of not only the 2,6-dichlorobenzyl radical as a typical product, but also the o-chlorobenzyl radical as an unexpected species, which indicates the possible molecular rearrangement in eliminating a chlorine atom from the benzene ring. A possible mechanism is proposed for the formation of the o-chlorobenzyl radical from the precurs or in the gas phase.

Pseudo-first-order rate constants ($k_{obsd}$) were measured spectrophotometrically for nucleophilic substitution reactions of 4-nitrophenyl picolinate (6) with alkali metal ethoxides (EtOM, $M^+\;=\;K^+$, $Na^+$ and $Li^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOM] exhibits upward curvature regardless of the nature of $M^+$ ions. However, the plot for the reaction of 6 with EtOK is linear with significantly decreased $k_{obsd}$ values when 18-crown-6-ether (18C6, a complexing agent for $K^+$ ion) is added in the reaction medium. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that ion-paired EtOM is 3~17 times more reactive than dissociated $EtO^-$. The reaction has been proposed to proceed through a 5-membered cyclic transition state, in which $M^+$ ion increases the electrophilicity of the reaction site. Interestingly, $Na^+$ ion exhibits the largest catalytic effect. The presence of a nitrogen atom in the pyridine moiety of 6 has been suggested to be responsible for the high $Na^+$ ion selectivity.

A method is described for the determination of the Po nuclides in a water sample. After the Po nuclides were purified from interfering elements in a water sample using a manganese dioxide precipitation followed by a solvent extraction method, the Po nuclides were deposited onto the silver plate. A large volume of the water sample was effectively pretreated with manganese dioxide precipitation method. To determine the optimum conditions for plating Po, the effects of the pH, volume, temperature and time on the Po deposition were investigated in hydrochloric acid solution. The investigated determination method of Po nuclides with solvent extraction was applied to a tap water sample.

Erythropoietin (EPO) is mainly produced in kidney and stimulates erythropoiesis. The use of recombinant EPOs for doping is prohibited because of its performance enhancing effect. This study investigated whether biosimilar EPOs could be differentiated from endogenous one by iso-electro-focusing plus double blotting and SDS-PAGE for antidoping analysis. The established method was validated with positive control urine. The band patterns were reproducible and meet the criteria, which was made by world anti doping agency (WADA). Isoelectric focusing was conducted in pH range 2 to 6. Recormon (La Roche), Aropotin (Kunwha), Epokine (CJ Pharm Co.), Eporon (Dong-A), Espogen (LG Life Sciences), and Dynepo (Shire Pharmaceuticals) were detected in basic region. All biosimilars showed discriminative isoelectric profiles from endogenous EPO profiles, but they showed different band patterns with the reference one except Epokine (CJ Pharm Co.). Next, SDS-PAGE of biosimilar EPOs resulted in different molecular weight patterns which were distributed higher than endogenous EPO. Commercial immune assay kit as an immune affinity purification tool and immobilized antibody coated magnetic bead were tested for the purification and concentration of EPO from urinary matrix. The antibody-coated magnetic bead gave better purification yield. The IEF plus double blotting and SDS-PAGE with immunoaffinity purification method established can be used to discriminate biosimilar EPOs from endogenous EPO.

Arg13 is a conserved active-site residue in all known Pi class glutathione S-transferases (GSTs) and in most Alpha class GSTs. To evaluate its contribution to substrate binding and catalysis of this residue, three mutants (R13A, R13K, and R13L) were expressed in Escherichia coli and purified by GSH affinity chromatography. The substitutions of Arg13 significantly affected GSH-conjugation activity, while scarcely affecting glutathione peroxidase or steroid isomerase activities. Mutation of Arg13 into Ala largely reduced the GSH-conjugation activity by approximately 85 - 95%, whereas substitutions by Lys and Leu barely affected activity. These results suggest that, in the GSH-conjugation activity of hGST P1-1, the contribution of Arg13 toward catalytic activity is highly dependent on substrate specificities and the size of the side chain at position 13. From the kinetic parameters, introduction of larger side chains at position 13 results in stronger affinity (Leu > Lys, Arg > Ala) towards GSH. The substitutions of Arg13 with alanine and leucine significantly affected $k_{cat}$, whereas substitution with Lys was similar to that of the wild type, indicating the significance of a positively charged residue at position 13. From the plots of log ($k_{cat}/{K_m}^{CDNB}$) against pH, the $pK_a$ values of the thiol group of GSH bound in R13A, R13K, and R13L were estimated to be 1.8, 1.4, and 1.8 pK units higher than the $pK_a$ value of the wild-type enzyme, demonstrating the contribution of the Arg13 guanidinium group to the electrostatic field in the active site. From these results, we suggest that contribution of Arg13 in substrate binding is highly dependent on the nature of the electrophilic substrates, while in the catalytic mechanism, it stabilizes the GSH thiolate through hydrogen bonding.

ZnO thin films were grown on Si or $SiO_2$/Si substrates, at growth temperatures ranging from 150 to $400^{\circ}C$, by atomic layer deposition (ALD) using diethylzinc and water. Despite the large band gap of 3.3 eV, the ALD ZnO films show high n-type conductivity, i.e. low resistivity in the order of $10^{-3}\;{\Omega}cm$. In order to understand the high conductivity of ALD ZnO films, the films were characterized with X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, elastic recoil detection, Rutherford backscattering, Photoluminescence, and Raman spectroscopy. In addition, the various analytical data of the ZnO films were compared with those of ZnO single crystal. According to our analytical data, metallic zinc plays an important role for the high conductivity in ALD ZnO films. Therefore when the metallic zinc was additionally oxidized with ozone by a modified ALD sequence, the resistivity of ZnO films could be adjusted in a range of $3.8{\times}10^{-3}\;{\sim}\;19.0\;{\Omega}cm$ depending on the exposure time of ozone.

In order to increase protease stability of a novel Trp-rich model antimicrobial peptide, $K_6L_2W_3$ (KLWKKWKKWLK-$NH_2$)and investigate the effect of L-amino acid to peptoid residue conversion on biological functions, we synthesized its antimicrobial peptoid, $k_6l_2w_3$. Peptoid $k_6l_2w_3$ had similar bacterial selectivity compared to peptide $k_66L_2W_3$. The bactericidal rate of $k_6l_2w_3$ was somewhat slower than that of $K_6L_2W_3$. Peptoid $k_6l_2w_3$ exhibited very little dye leakage from bacterial outer-membrane mimicking PE/PG liposomes, as observed in $K_6L_2W_3$, indicating that the major target site of $K_6L_2W_3$ and $k_6l_2w_3$ may be not the cell membrane but the cytoplasm of bacteria. Trypsin treatment of $K_6L_2W_3$ completely abolished antimicrobial activities against Escherichia coli and Staphylococcus aureus. In contrast, the antimicrobial activity of $k_6l_2w_3$ was completely preserved after trypsin treatment. Taken together, our results suggested that antimicrobial peptoid $k_6l_2w_3$ can potentially serves as a promising therapeutic agent for the treatment of microbial infection.

A very simple synthetic route of a novel SATE prodrug type of 6'-fluoro-6'-methyl-5'-noradeonosine carbocyclic nucleoside phosphonic acid is described. The key fluorinated alcohol intermediate 7 was prepared from the epoxide intermediate 6a via selective ring-opening of epoxide. Coupling of 7 with $N^6$-bis-Boc-adenine under a Mitsunobu reaction followed by phosphonation and deprotection afforded the carbocyclic phosphonic acid. The chemical stability of the bis(SATE) derivative 13 was measured at neutral (pH 7.2) and slightly acidic (Milli-Q water, pH 5.5) pH. The antiviral activity test of the SATE prodrug 13 and its parent nucleoside phosphonic acid 11 were evaluated against HIV-1.

Silane-based self-assembly was employed for the surface modification of carbon-coated Si electrodes and their surface chemistry and electrochemical performance in battery electrolyte depending on the molecular structure of silanes was studied. IR spectroscopic analyses revealed that siloxane formed from silane-based self-assembly possessed Si-O-Si network on the electrode surface and high surface coverage siloxane induced the formation of a stable solid-electrolyte interphase (SEI) layer that was mainly composed of organic compounds with alkyl and carboxylate metal salt functionalities, and PF-containing inorganic species. Scanning electron microscopy imaging showed that particle cracking were effectively reduced on the carbon-coated Si when having high coverage siloxane and thickened SEI layer, delivering > 1480 mAh/g over 200 cycles with enhanced capacity retention 74% of the maximum discharge capacity, in contrast to a rapid capacity fade with low coverage siloxane.

The stereoselectivity of the intramolecular Diels-Alder reactions of 1 and its derivatives were investigated by ab initio calculations. The stereoselectivity mainly originates from the steric repulsion and the orbital interactions. The additional s-cis and s-trans conformations by introducing the carbonyl group at the neighbor of diene or dienophile may change the stereoselectivity, hence this kind of substitution can be utilized for stereoselectivive asymmetric synthesis.

Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations have been employed to investigate the molecular structures and absorption spectra of two dyes containing diphenylaniline and 4-diphenylamino-diphenylaniline as donor moiety (TPA1 and TPA3). The geometries indicate that the strong conjugation is formed in the dyes. The electronic structures suggest that the intramolecular charge transfer from the donor to the acceptor occurs, and the electron-donating capability of 4-diphenylamino-diphenylaniline is stronger than that of diphenylaniline. The computed highest occupied molecular orbital (HOMO) energy levels are -5.31 and -4.90 eV, while the lowest unoccupied molecular orbital (LUMO) energies are -2.29 and -2.26 eV for TPA1 and TPA3, respectively, revealing that the interfacial charge transfer between the dyes and the semiconductor electrode are electron injection processes from the photon-excited dyes to the semiconductor conduction band. Furthermore, all the experimental absorption bands of TPA1 and TPA3 have been assigned according to the TDDFT calculations.

We chose a fluorescent pentapeptide sensor (-CPGHE) containing a dansyl fluorophore as a model peptide and investigated whether the selectivity and sensitivity of the peptides for heavy and transition metal ions could be tuned by changing amino acid sequence. In this process, we developed a selective peptide sensor, Cp1-d (-HHPGE, $K_d\;=\;670\;nM$) for detection of $Zn^{2+}$ in 100% aqueous solution and a selective and sensitive peptide sensor, Cp1-e (-CCHPGE, $K_d\;=\;24\;nM$) for detection of $Cd^{2+}$ in 100% aqueous solution. Overall results indicate that the selectivity and sensitivity of the metallopeptide sensors to specific heavy and transition metal ions can be tuned by changing amino acid sequence.

The objective of this paper was to investigate the effect of dextran gel on preparation of nano-liposomes loaded with ginkgolide. During preparation, Sephadex G75, G50 and G25 were added in the aqueous phase respectively. From the experiment, nano-liposomes prepared by dextran gels were found spherical and smooth. The result indicated that aperture of dextran gels were narrower, particle size of nano-liposomes was smaller (207.13 ~ 89.16 nm) and zeta potential was greater (-36.2 ~ -29.5 mV) in more negative. The study also revealed that differences of the entrapment efficiency and drug loading among the three types of nano-liposomes were not significant. In vitro drug release test demonstrated that nano-liposomes had a better controlled release. To conclude, by using dextran gel in the preparation of nano-liposome loaded with ginkgolide, the particle size could be effectively controlled and the drug stability could be improved.

CdS nano-particulate films were prepared at the air/water interface under Langmuir monolayers of arachidic acid (AA) via interfacial reaction between $Cd^{2+}$ ions in the subphase and $H_2S$ molecules in the gaseous phase. The films were made up of fine CdS nanoparticles with hexagonal Wurtzite crystal structure after reaction. It was revealed that the formation of CdS nano-particulate films depends largely on the experimental conditions. When the films were ripened at room temperature or an increased temperature ($60^{\circ}C$) for one day, numerous holes were appeared due to the dissolution of smaller nanoparticles and the growth of bigger nanoparticles with an improved crystallinity. When the films were ripened further, CdS rodlike nanoparticles with cubic zinc blende crystal structure appeared due to the re-nucleation and growth of CdS nanoparticles at the stacking faults and defect structures of the hexagonal CdS grains. These structures were characterized by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and X-ray diffraction (XRD). These results declare that CdS semiconductor nanoparticles formed at the air/water interface change their morphologies and crystal structures during the ripening process due to dissolution and recrystallization of the particles.

On the basis of a simple modified Poisson-Boltzmann (SMPB) theory, taking into account the finite ionic size, the analytic expression for the effect of ionic size on the diffuse layer potential drop at negative charge densities has been given for the simple 1:1 electrolyte. It is shown that the potential drop across the diffuse layer depends on the size of the ions in the electrolyte. For a given electrolyte concentration and electrode charge density, the diffuse layer potential drop in a small ion system is smaller than that in a large ion system. It is also displayed that the diffuse layer potential drop is always less than the value of the Gouy-Chapman (GC) theory, and the deviation increases as the electrode charge density increases for a given electrolyte concentration. These theoretical results are consistent with the results of the Monte-Carlo simulation [Fawcett and Smagala, Electrochimica Acta 53, 5136 (2008)], which indicates the importance of including steric effects in modeling diffuse layer properties.

To assay for antioxidant capacity of natural products considered important in producing human health benefits, a practical and economical method using pellet techniques was developed. A standard visualizing reagent, 1,1diphenyl-2-picryl-hydrazyl (DPPH), was mixed with a water-miscible polyvinyl alcohol (PVA), serving as a solid phase support for the DPPH reagent. A DPPH pellet was prepared by dropping a small volume of the DPPH solution onto PET film, and drying in an oven. The PVA-based DPPH pellet was dissolved into water, in which the water-miscible PVA plays as a non-ionic surfactant to help the DPPH reagent to be dissolved into the solvent. Using the DPPH assay, the antioxidant capacity of water-soluble extracts of black soybean, barley, green tea, and green gram was examined. Among the natural products tested, green tea showed the highest antioxidant capacity. This PVA-based DPPH antioxidant assay can be further applied in the natural food, raw plant material, and health product inspection field.

The accurate determination of bisphosphonate levels in bone and biological fluids is important in both clinical and pharmacological/toxicological studies; however, the quantitative analysis of the bisphosphonate is difficult because its concentration is quite low in most of biological sample. A novel fluorescent chemosensor (FCS)-based measurement method of bisphosphaonate levels using Naphta-diDPA-$2Zn^{2+}$ (NadDPA-$2Zn^{2+}$, DPA = dipycolylamine), an excellent FCS previously used for detecting PPi, was developed. By the FCS method, the concentration of bisphosphonates having no fluorophores can be determined analyzed with sufficient sensitivity. The results of this study indicate that the FCS-based measurement can be a useful method to analyze bisphosphonates in biological samples.

The orthorhombic $MgB_2C_2$ structure contains well-separated parallel graphite-like $B_2C_2^{2-}$ layers which extend infinitely in two dimensions. Three possible ways to distribute B and C atoms in the hexagonal sublattice sites are adopted. Band structures for the hypothetical distribution patterns are examined to assess the electronic stability of these phases and to account for the observed arrangement by means of extended Huckel tight-binding calculations. The preferred choice is the layer with B and C alternating strictly so that B is nearest neighbor to C and vice versa. A rationale for this is given. Due to the alternation of B and C within the honeycomb layers, $MgB_2C_2$ is a band insulator, which through partial substitution of Mg with Li, is predicted to turn metallic with holes in the $\sigma$ bands at the Fermi level.

We investigate the mechanism of $S_NAr$ fluorination reactions under the influence of protic solvents and ions. We find that counterion or protic solvent alone retards the $S_NAr$ reactions, but together they may promote the reaction. In this mechanism, the protic solvent acts on the counterion as a Lewis base, and the nucleophile reacts as an ion pair. We also show that an anion (mesylate) may exhibit catalytic effects, suggesting the role of ionic liquids for accelerating the $S_NAr$ reactions.

We present a method for chemically reducing silver alkylcarbamate complex with hydrazine to synthesize silver nanocolloids in an organic solvent using polyvinylpyrrolidone (PVP) as the stabilizer. To determine the optimal conditions for preparing stable silver colloids of controlled size and shape, the silver 2-ethylhexylcarbamate (Ag-EHCB) complex, PVP, hydrazine, and 2-propanol solvent concentrations in the reaction mixture were varied. The initial colloid has a mean particle diameter of 5-80 nm, and it exhibits an absorption band with various shapes in the UV region with a maximum near 420 nm. UV-vis spectroscopy, TEM, and X-ray diffraction techniques were used to investigate the formation and growth process of the metallic silver nanocolloids.

Nitration of tyrosine and tryptophan residues is common in cells under nitrative stress. However, physiological consequences of protein nitration are not well characterized on a molecular level due to limited availability of the 3D structures of nitrated proteins. Molecular dynamics (MD) simulation can be an alternative tool to probe the structural perturbations induced by nitration. In this study we developed molecular mechanics parameters for 3-nitrotyrosine (NIY) and 6-nitrotryptophan (NIW) that are compatible with the AMBER-99 force field. Partial atomic charges were derived by using a multi-conformational restrained electrostatic potential (RESP) methodology that included the geometry optimized structures of both $\alpha$- and $\beta$-conformers of a capped tripeptide ACE-NIY-NME or ACE-NIW-NME. Force constants for bonds and angles were adopted from the generalized AMBER force field. Torsional force constants for the proper dihedral C-C-N-O and improper dihedral C-O-N-O of the nitro group in NIY were determined by fitting the torsional energy profiles obtained from quantum mechanical (QM) geometry optimization with those from molecular mechanical (MM) energy minimization. Force field parameters obtained for NIY were transferable to NIW so that they reproduced the QM torsional energy profiles of ACE-NIW-NME accurately. Moreover, the QM optimized structures of the tripeptides containing NIY and NIW were almost identical to the corresponding structures obtained from MM energy minimization, attesting the validity of the current parameter set. Molecular dynamics simulations of thioredoxin nitrated at the single tyrosine and tryptophan yielded well-behaved trajectories suggesting that the parameters are suitable for molecular dynamics simulations of a nitrated protein.

The potential energy surfaces (PESs) for the primary and secondary dissociations of the phenylarsane molecular ion (1a) were determined from the quantum chemical calculations using the G3(MP2)//B3LYP method. Several pathways for the loss of $H{\cdot}$ were determined and occurred though rearrangements as well as through direct bond cleavages. The kinetic analysis based on the PES for the primary dissociation showed that the loss of $H_2$ was more favored than the loss of $H{\cdot}$, but the $H{\cdot}$. loss competed with the $H_2$ loss at high energies. The bicyclic isomer, 7-arsa-norcaradiene radical cation, was formed through the 1,2 shift of an $\alpha$-H of 1a and played an important role as an intermediate for the further rearrangements in the loss of $H{\cdot}$ and the losses of $As{\cdot}$ and AsH. The reaction pathways for the formation of the major products in the secondary dissociations of $[M-H]^+$ and $[M-H_2]^{+\cdot}$. were examined. The theoretical prediction explained the previous experimental results for the dissociation at high energies but not the dissociation at low energies.

Second-order rate constants ($k_N$) have been measured spectrophotometrically for reactions of 2,4-dinitrophenyl X-substituted benzoates (X = 4-MeO, H and 4-$NO_2$) with a series of Z-substituted pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plots exhibit downward curvature (e.g., $\beta_2$ = 0.89 ~ 0.96 when $pK_a$ < 9.5 while $\beta_1$ = 0.38 ~ 0.46 when $pK_a$ > 9.5), indicating that the reaction proceeds through a stepwise mechanism with a change in rate-determining step (RDS). The ${pK_a}^o$, defined as the $pK_a$ at the center of Br${\o}$nsted curvature, has been analyzed to be 9.5 regardless of the electronic nature of the substituent X in the benzoyl moiety. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio has revealed that $k_1$ is governed by the electronic nature of the substituent X but the $k_2/k_{-1}$ ratio is not. Theoretical calculations also support the argument that the electronic nature of the substituent X in the benzoyl moiety does not influence the $k_2/k_{-1}$ ratio.

Two 3-D zinc framework compounds, $[Zn_6(BTB)_4(4,4'-bipy)_4(H_2O)_4]{\cdot}9H_2O$ (1) and $[Zn_3(BTB)_2(4,4'-bipy)_2(H_2O)_2]{\cdot}5H_2O$ (2) ($H_3BTB$ = 1,2,3-benzenetricarboxylic acid, 4,4'-bipy = 4,4'-bipyridine), are obtained from the diffusion method and hydrothermal reaction respectively. Though 1 and 2 has the same coordination geometries of zinc atoms and coordination mode of $BTB^{3-}$, their 2-D layers are different: mirror symmetric layers in 1; parallel ones in 2, further connecting by 4,4'-bipy into 3-D frameworks. The hydrothermal reaction of 2 results in a more stable 3-D framework than the one in 1, which is supported by the single point energy calculations. 1 and 2 show similar blue fluorescence at 417 nm, which can be assigned to LMCT.

Novel soluble triazoleimide oligomers terminated with arylacetylene terminated were synthesized by the Cu(I)-catalysed 1,3-dipolar cycloaddition polymerization of diazides and imide-containing dialkyne. Several molecular weight triazoleimide oligomers were prepared from diazide and dialkyne monomers with different stoichiometric combinations. The curing behaviors of the oligomers were tested by differential scanning calorimetry (DSC). The thermal properties of the cured products were evaluated by DSC and thermogravimetric analysis (TGA). These cured oligomers showed the glass transition temperature of about $225-235^{\circ}C$ and the decomposition temperature (at 5% weight loss) of about $385-393^{\circ}C$ in nitrogen.

Human tissue-type plasminogen activator (tPA) is a valuable thrombolytic agent used to successfully treat acute myocardial infarction, thromboembolic stroke, peripheral arterial occlusion, and venous thromboembolism. Recombinant tPA is accumulated as an inactive form in inclusion bodies of E. coli and is refolded in vitro, which is accompanied by extensive aggregation. In the present study, a tPA protease domain was expressed in an active soluble form in the cytosol of E. coli Rosetta-gami cells, which allowed disulfide bond formation and supplied the tRNA molecules required for six rarely used codons in E. coli. This strategy increased the amount of soluble protease domain protein and avoided the cumbersome refolding process. The purified protease domain not only degraded tPA substrate peptides but also formed a covalently bound complex with plasminogen activator inhibitor-1, as does full-length tPA. Soluble expression and purification of tPA domains may aid in functional analyses of this multi-domain protein, which has been implicated in many physiological and pathological processes.

Chloroprene is a chlorine substituent of 1,3-butadiene. Butadiene rubber (BR) and chloroprene rubber (CR) composites were thermally aged at 60, 70, 80, and $90^{\circ}C$ for 2 - 185 days in a convection oven and changes of the crosslink densities by the accelerated thermal aging were investigated. The crosslink densities increased as the aging time elapsed and as the aging temperature became higher. Degrees of the crosslink density changes of the BR composite were on the whole larger than those of the CR one except the short-term thermal aging at 60 and $70^{\circ}C$. The crosslink densities abnormally increased after themal aging at high temperatures for a long time. Activation energies for the crosslink density changes of the rubber composites tended to increase with increase of the aging time and the variation showed a local minimum. The activation energies of the CR composite were lower than those of the BR one. The experimental results were explained with a role of ligand of chlorine atom of CR in a zinc complex, steric hindrance by chlorine atom of CR, and oxidation of rubber chain.

In this paper poly (4-methyl vinylpyridinium hydroxide)/SBA-15 composite was prepared as a highly efficient heterogeneous basic catalyst by in situ polymerization method for the first time. It was characterized by XRD, FT-IR, BET, TGA, SEM and back titration using NaOH. This catalyst exhibited the excellent catalytic activities for the Knoevenagel condensation of various aldehydes with ethyl cyanoacetate. Over this catalyst, ${\alpha},{\beta}$-unsaturated carbonyl compounds were obtained in the reasonable yield at $95^{\circ}C$ in 10 - 30 min in $H_2O$ as a solvent with a 100% selectivity to the condensation products. Catalyst could be easily recycled after the reaction and it could be reused without the significant loss of activity/selectivity performance. No by-product formation, high yields, short reaction times, mild reaction conditions and operational simplicity with reusability of the catalyst were the salient features of the present synthetic protocol. Presence of $H_2O$ as a solvent was also recognized as a "green method".

Hormone sensitive lipase (HSL) plays a major role in energy homeostasis and lipid metabolism. Several crystal structures of HSL-homolog proteins have been identified, which has led to a better understanding of its molecular function. HSL-homolog proteins exit as both monomer and dimer, but the biochemical and structural basis for such oligomeric states has not been successfully elucidated. Therefore, we determined the crystal structure of HSL-homolog protein EstE7 from a metagenome library at $2.2\;{\AA}$ resolution and characterized the oligomeric states of EstE7 both structurally and biochemically. EstE7 protein prefers the dimeric state in solution, which is supported by its higher enzymatic activity in the dimeric state. In the crystal form, EstE7 protein shows two-types of dimeric interface. Specifically, dimerization via the external ${beta}8$-strand occurred through tight association between two pseudosymmetric folds via salt bridges, hydrogen bonds and van der Waals interactions. This dimer formation was similar to that of other HSL-homolog protein structures such as AFEST, BEFA, and EstE1. We anticipate that our results will provide insight into the oligomeric state of HSL-homolog proteins.

3-Acetyl-5-benzoyl-6-methyl-2-phenyl-4H-pyran-4-one has been subjected to condensation with a series of primary amines (ethylamine - octylamine) to clarify the proposed mechanism in our previous study. The reactions of the shorter amines of the series (ethylamine - butylamine) yielded unsymmetric pyridinone products, whereas the other amines (pentylamine - octylamine) yielded symmetrical pyridinones. The starting material and the products as well as the intermediates have been subjected to theoretical analysis by quantum chemical calculations at B3LYP/6-31G(d,p) level, which provided supporting data for the experimental findings.

In order to develop a new line injection system for spin draw yarn (FD SDY) fibers, the effect of various parameters in extrusion and melt line conditions on the dispersion and distribution of $TiO_2$ particles within FD PET fibers was investigated. As a result, the dispersibility of $TiO_2$ particles in a PET matrix is found to depend on the particle size and its surface characteristics. Surface modification of $TiO_2$ by dimethyl polysiloxane resulted in the improved dispersibility and affinity of $TiO_2$ particles in the PET matrix. Especially, residence time, mixing temperature, and mixing shear rate in the new line injection system under the SDY spinning process were very important parameters to minimize the agglomeration of $TiO_2$ particles. The FD SDY prepared by the new line injection system was superior to those using the polymerization process and the conventional masterbatch chip dosing process in the color-L and color-b values of the fibers.

Catalytic conversion of structurally different epoxides to the corresponding 1,2-diacetoxy esters was carried out readily with phosphomolybdic acid alone or its supported on $SiO_2$. The reactions were carried out under solvolytic or solvent free conditions within 5-15 min at room temperature. The product 1,2-diacetates were obtained in high to excellent yields. Supporting of phosphomolybdic acid on $SiO_2$ showed the better catalytic activity than $Al_2O_3$. Conversion of optically pure R-(+)-styrene oxide to S-(+)-1,2-diacetoxy-1-phenylethane was carried with phosphomolybdic acid in high yield and stereospecificity.

$PKC{\delta}$-catalytic V5 Heptapeptide (FEQFLDI, FP7) interacts with heat shock protein 27 (HSP27) and inhibits HSP27-mediated resistance to cell death against various stimuli including radiation therapy. Here, we prepared radio-iodinated heptapeptide and further investigated its uptake properties in HSP27 expression cells. Peptide sequence of FP7 and a negative control peptide (WSLLEKR, QP7) was modified by substituting their C-terminus residue to tyrosine (FP6Y and QP6Y) to label radio-iodine. Iodinated peptides were confirmed by LC mass analysis with cold iodine reaction mixture. Accumulation of [$^{125}I$]iodo-FP6Y and [$^{125}I$]iodo-QP6Y in NCI-H1299 cell line, with higher level of HSP27, and NCI-H460 cell line, with lower level of HSP27, was measured by NaI(Tl) scintillation counter. The modification of substituting C-terminus residue of FP7 to tyrosine (FP6Y) did not affect its interaction with HSP27. Accumulation of [$^{125}I$]iodo-FP6Y in NCI-H1299 cells was 3 fold higher than in NCI-H460 cells. The novel radio-iodinated FP6Y would be used as a tracer for targeting HSP27 protein.

We have synthesized a series of push-pull porphyrins containing both donor and acceptor substituents at the mesopositions and have examined their spectral and biological properties. The push-pull porphyrins containing both strong donor $NH_2$ and acceptor $NO_2$ at meso-positions, in which donor group condensed with the ligand, (2,6-bis(4-methylpiperazine-1-yl-methyl)-4-formlyphenol (L) to form imine linkages with porphyrin. The Schiff base ligand 5-[4-(2,6-bis(4-methylpiperazine-1-yl-methyl)-4-iminomethylphenol)phenyl]-10,15,20-tris(4-nitrophenyl) porphyrin [$an_3$(TPP)L] can be synthesized from 2,6-bis(4-methylpiperazine-1-yl-methyl)-4-formylphenol (L) and 5-(4-aminophenyl)-10, 15,20-tris(4-nitrophenyl)porphyrin. The push-pull porphyrin [$an_3$(TPP)L] was metallated to get copper, nickel and zinc complexes. The spectral, electrochemical, antibacterial, antifungal and cytotoxicity properties of all the donor- acceptor push-pull porphyrins and their complexes were characterized and studied.

This work shows that both L2 and L3 bearing two and four N-$(CH_2)_2OCH_3$ groups, respectively, can be prepared selectively by the reaction of $L^1$ with 1-bromo-2-methoxyethane. The di-N-substituted macrocycle $L^2$ readily forms its copper(II) and nickel(II) complexes. The N-$(CH_2)_2OCH_3$ groups in $[CuL^2]^{2+}$ are coordinated to the metal ion, whereas those in $[NiL^2]^{2+}$ are not involved in coordination. Interestingly, $L^3$ reacts with $Cu^{2+}$ ion to form $[Cu(HL^3)]^{3+}$, in which one tertiary amino group is not involved in coordination.