We performed coupled-cluster calculations to determine the intermolecular interaction energy between two TiAu4 clusters. Our ab initio calculations predict that the binding energy is 2.89 eV, which is somewhat larger than the known binding energy of 2.0 eV for TiH4-TiH4. The intermolecular binding energy is relatively high, despite TiAu4 having all the attributes of a magic cluster. The favorable orbital interaction between occupied Au(6s) and unoccupied Ti(3d) orbitals leads to the strong dimeric interaction for TiAu4-TiAu4.

Two different anode composite materials comprising of Fe, Cu and Si prepared using high energy ball milling (HEBM) were explored for their capacity and cycling behaviors. Prepared powder composites in the ratio Cu:Fe:Si = 1:1:2.5 and 1:1:3.5 were characterized through X-Ray diffraction (XRD) and scanning electron microscope (SEM). Nevertheless, the XRD shows absence of any new alloy/compound formation upon ball milling, the elements present in Cu(1)Fe(1)Si(2.5)/Graphite composite along with insito generated Li2O demonstrate a superior anodic behavior and delivers a reversible capacity of 340 mAh/g with a high coulombic efficiency (98%). The higher silicon content Cu(1)Fe(1)Si(3.5) along with graphite could not sustain capacity with cycling possibly due to ineffective buffer action of the anode constituents.

An enantioselective ring opening of racemic terminal epoxides has been achieved by using heterobimetallic cobalt salen complexes with variety of nucleophiles. They were proven to be highly enantioselective and reactive for the synthesis of valuable chiral building blocks in enantio-riched forms up to 98% ee.

The viability of acetylene addition in each step of aromatic formation initiated by vinyl radical and acetylene also with its competition with structure rearrangement is investigated by determining optimal geometries and barrier and reaction energies using quantum mechanical methods. In principle, the addition reaction has more difficult in term of free energy and enthalpy compared to geometry arrangement. Under combustion conditions, i.e. T = 1200 K, acetylene addition is unfavorable mechanism as the barrier energy values rise much higher than that of geometry arrangement. However, in longer chain hydrocarbon case, e.g. n-CxHx+1 where x ³ 8, C-C bond rotation is rather difficult and requires high energy to form a ring structure, elongation chain is preferable.

A focused library of pyrazole-based compounds was constructed towards novel transcription factor inhibitors. Complementary hydrogen bonding interaction with b-sheet peptide structures was the basis for the design of 5-amino-3-pyrazole carboxamide scaffold. From the preliminary inhibition assay against several transcription factors, compounds 7e and 8g were identified as novel lead compounds against HIF-1a and NF-AT transcription factors, respectively.

The effects of catalyst preparation on the reaction route and the mechanism of biphenol (BP) hydrogenation, which consists of a long series-reaction, were studied. Pd/C catalysts were prepared by incipient wetness method and precipitation and deposition method. The reaction behaviors of the prepared catalysts and a commercial catalyst along with the final product distributions were very different. The choice of the catalyst preparation conditions during precipitation and deposition including the temperature, pH, precursor addition rate, and reducing agent also had significant effects. The reaction behaviors of the catalysts were interpreted in terms of catalyst particle size, metal distribution, and support acidities.

New efficient red emitter having short p?-conjugation length and asymmetric bulky structure, 2-(7-diphenylamino-benzo[1,2,5]thiadiazole-4-ylmethylene)-malononitrile, was synthesized and characterized. Using this material as a dopant, we fabricated electroluminescence device with a structure of ITO/DNTPD/NPD/BTZA (5 wt% in Alq3)/Alq3/LiF/Al. The device exhibited a high brightness of 761 cd/m2 at a driving voltage of 4.8 V, and current efficiency is 0.75 cd/A. The Commission International de IEclairage (CIE) coordinates of the EL device were found to be (0.62, 0.37) at 10 mA/cm2.

Catalytic trimerization of isobutene to produce triisobutenes has been performed over cation-exchange resin and zeolite catalysts. Resin catalysts have the advantage of long lifetime and high trimers selectivity even though the regeneration of an aged catalyst is not satisfactory. On the contrary, zeolite catalysts can be regenerated facilely by simple calcination in air even though the lifetime is short and trimers selectivity is low probably due to small pore size and strong acidity, respectively. It is, therefore highly desirable to develop an inorganic acid catalyst with macro- or meso-pores to show catalytic performances similar or superior to those of macroporous resin catalysts.

Aurintricarboxylic acid (ATA) prevents apoptosis in a wide range of cell types, including PC12 cells. ATA is known to increase the phosphorylation level of IGF-1 receptor (IGF-1R) and downstream signaling proteins. ATA can translocate across the plasma membrane of PC12 cells and inhibit protein tyrosine phosphatases (PTPs) and, therefore, it is not clear whether ATA exerted its antiapoptotic effect through activation of IGF-1R or by inhibition of cytosolic PTPs. When PC12 cells, deprived of serum, were treated with Fab fragment of anti-IGF-1R antibody to prevent the binding of ATA to the extracellular domain of IGF-1R, ATA was found to penetrate into the cytosolic space of the cells. Under these conditions, the survival-promoting effects of ATA were abolished, and the increase of phosphorylation and characteristic cleavage of IGF-1R were not observed. These results indicate that the antiapoptotic effect of ATA in PC12 cells is due to the binding of ATA to the extracellular domain of IGF-1R and subsequent activation of the IGF-1R, not inhibition of cytosolic PTP(s).

Acetyl-CoA carboxylase (ACC) is an excellent candidate for antibiotics drug target, which mediates malonyl-CoA synthesis from acetyl-CoA through acetylation process. It is also involved in the committed step of fatty acid synthesis which is essential for living organisms. We have determined the three dimensional structure of C terminal domain of HP0371, biotin-carboxyl carrier protein of H. pyroli, in solution state using heteronuclear multi-dimensional NMR spectroscopy. The structure of HP0371 shows a flatten b-sheet fold which is similar with that of E. coli. However, the sequence and structure of protruding thumb are different with that of E. coli and the thumb shows different basis of structural rigidity based on backbone dynamics data.

An analytical method has been developed for measuring chlorostyrenes in fish tissue sample. Extraction of chlorostyrenes from fish tissue was carried out by ultrasonication using acetone/n-hexane (5:2, v/v) mixture. Most of the lipids in the extract were eliminated by freezing-lipid filtration, prior to solid-phase extraction (SPE) cleanup. During freezing-lipid filtration, about 90% of the lipids extracted from the fish samples were easily removed without any significant losses of chlorostyrenes. For purification, SPE using Florisil was used for the rapid and effective cleanup. Quantification was performed using gas chromatography-mass spectrometry in the selected ion monitoring mode. Spiking experiments were carried out to determine the recovery, precision, and limits of detection (LODs) of the method. The overall recovery was above 80% in the spiked fish tissue sample at 10 and 100 ng/g levels, respectively. The detection limits for chlorostyrenes were ranged from 0.05 to 0.1 ng/g. This developed method is demonstrated to give efficient recoveries and LODs for detecting chlorostyrenes spiked into fish tissue with high lipid content.

A method for synthesizing o-carborane substituted tetrahydroisoquinolines containing a polar functional group such as sulfamide, sulfonic, or phosphoric acid on the nitrogen atom of the piperidine ring, starting from arylethylamine, N-(2-arylethyl)sulfamide, N-(2-arylethyl)sulfamic acid or 2-arylethylamidophosphate, is described. In vitro studies showed the desired compounds 10, 15, 19, and 25 synthesized accumulate to high levels in B-16 melanoma cells with low cytotoxicity.

As a computational method for the discovery of the effective agonists for PPARd, we address the usefulness of molecular dynamics free energy (MDFE) simulation with explicit solvent in terms of the accuracy and the computing cost. For this purpose, we establish an efficient computational protocol of thermodynamic integration (TI) that is superior to free energy perturbation (FEP) method in parallel computing environment. Using this protocol, the relative binding affinities of GW501516 and its derivatives for PPARd are calculated. The accuracy of our protocol was evaluated in two steps. First, we devise a thermodynamic cycle to calculate the absolute and relative hydration free energies of test molecules. This allows a self-consistent check for the accuracy of the calculation protocol. Second, the calculated relative binding affinities of the selected ligands are compared with experimental IC50 values. The average deviation of the calculated binding free energies from the experimental results amounts at the most to 1 kcal/mol. The computational efficiency of current protocol is also assessed by comparing its execution times with those of the sequential version of the TI protocol. The results show that the calculation can be accelerated by 4 times when compared to the sequential run. Based on the calculations with the parallel computational protocol, a new potential agonist of GW501516 derivative is proposed.

The hydrolysis of gallium(III) has been studied using potentiometric techniques under physiological conditions of temperature 37 C and ionic strength 0.15 moldm-3 NaCl and at different metal ion concentrations. Changes in pH were monitored with a glass electrode calibrated daily in hydrogen ions concentrations. The titration data within the pH range of 2.5-9.99 were analyzed to determine stability constants of hydroxide species using the SUPERQUAD program. Several different species were considered during the calculation procedure and the following hydroxides have been characterized: Ga(OH)3, Ga(OH)4- Ga3(OH)112-, Ga4(OH)11+ and Ga6(OH)153+. Speciation calculations based on the determined constants were then used to simulate the species distribution.

Ground state structures and ring flipping transition states of eight- and seven-membered silicon containing heterocyclic compounds such as dithienodisilacyclooctatriene and oxadithienodisilacycloheptadiene derivatives, respectively have theoretically been investigated. Although the bithienylene moiety of the derivatives does not change the ground state structures, they significantly increase the ring flipping barrier by 13-17 kcal/mol in the case of the eight-membered rings (2, 3, and 4) in comparison with that of silicon containing heterocyclic compound 6, chosen as a model. The same moiety increases the flipping barrier of seven-membered ring (5) is only slightly (3.3 kcal/mol) in comparison with that of model compound 7. Hence, it has been concluded that not only the existing ring strain of eight-membered ring but also the bithienylene moiety collectively increases the ring flipping barrier so as to prevent such conformational changes explaining anomalous NMR behaviour of dithienodisilacyclooctatriene derivatives (2-4). In contrast, the effect of substituents R1 and R2 at the olefinic carbons of the eight-membered ring on the flipping barrier turned out to be mild.

An X-linked skeletal disorder, SEDT (spondyloepiphyseal dysplasia tarda) is a genetic disease characterized by a disproportionately short trunk and short stature caused by mutations in the SEDL gene. This gene is evolutionarily conserved from yeast to human. The yeast SEDL protein ortholog, Trs20p, has been isolated as a member of a large multi-protein complex called the transport protein particle (TRAPP), which is involved in endoplasmic reticulum (ER)-to-Golgi transport. The interaction between SEDL and partner proteins is important in order to understand the molecular mechanism of SEDL functions. We isolated several SEDL-binding proteins derived from rat cells by an immobilized GST-fusion method. Furthermore, the SEDL-homologue proteins were identified using motif based methods. Common motifs between SEDL-binding proteins and SEDL-homologue proteins were classified into seven types and 78 common motifs were revealed. Sequence similarities were contracted to seven types using phylogenetic trees. In general, types I-III and VI were classified as having the function of acetyl-CoA carboxylase, glycogen phosphorylase, isocitrate dehydrogenase, and enolase, respectively, and type IV was found to be functionally related to the GST protein. Types V and VII were found to contribute to TRAPP vesicle trafficking.

High purity carbon nano fibers/tubes (CNF/Ts) which contain 97% pure graphitic carbon are prepared by a new catalytic method. These carbon nano fibers/tubes are ready to use without any further purification. The striking feature of this method is the production of carbon nano fibers/tubes of narrow distribution range. The developed catalytic method also produces pure hydrogen. An additional advantage of this catalytic method is that catalyst can be reused without reactivation. Ni:Cu catalyst system is embodied into SCHOTT-DURAN filter disc of large pore size (40-100 mm). Due to the production of hydrogen in the reaction catalyst stability is enhanced and deactivation process is considerably slowed down.

Inductively coupled plasma atomic emission spectrometry (ICP-AES) was used to determine the presence of germanium and phosphorus in a pure gold bonding wire. The samples were dissolved with hydrobromic acid and nitric acid at room temperature. The quantitation limits were 0.012 mg L-1 at 265.118 nm for Ge and 0.009 mg L-1 at 177.495 nm for P. Using the mixed acid digestion formula of DIW+HBr+HNO3, the recoveries were in the range of 98-100% and the relative standard deviation was within 1.1-2.3%. On the other hand, the amount of Ge decreased by about 16.2% using DIW+HCl+HNO3, due to the formation of a volatile compound. The Ge contents determined using the external method and the standard addition method were 9.45 mg kg-1 and 9.24 mg kg-1, respectively, and the P contents, using the same methods, were 22.49 mg kg-1 and 23.09 mg kg-1, respectively. Both methods were successfully used to determine the trace amounts of P and Ge in the pure gold bonding wire samples.

A new solvent polymeric membrane electrode, based on N,N'-bis(salicylidene)-2,2-dimethylpropane-1,3-diamine Ni(II) as the ionophore, was designed. The oxalate-selective electrode has the dynamic range between 1.0 10-6 M and 1.0 10-1 M with a Nernstian slope of -28.7 1.0 mV per decade. The detection limit was 6.3 10-7 M. The proposed electrode revealed good selectivities for oxalate over a variety of other anions and could be used in a pH range of 2.0-7.8. The electrode can be used for at least two months without any considerable divergence in potential. The designed electrode was applied as an indicator electrode in the potentiometric determination of oxalate in real samples.

Functionalized SAB-15 samples by octadecyltrimethoxysilane (OTC) were studied by 13C magic angle spinning (MAS) cross polarization (CP) nuclear magnetic resonance (NMR) spectroscopy. In the SBA-15 sample fully functionalized by 3-aminopropyltrimethoxysilane (APS) and OTC in 1:1 molar ratio, octadecyl chains were observed to have, on average, more trans conformation than those in the SBA-15 samples fully modified by OTC only. Our results confirm that long chain molecules tend to organize themselves better in the co-presence of short chain molecules on the surface of mesoporous materials by packing of the different length chains in an interdigitized fashion even when the short chains are long enough to have three carbons and a functional group at the ends. In addition, our results indicate that solid-state 13C CP MAS NMR spectroscopy is a simple and non-destructive method to probe the molecular structures of the domains composed of long alkyl chains.

FLOWERING LOCUS T (FT) and TERMINAL FLOWER 1 (TFL1) in Arabidopsis are homologous proteins that perform opposite functions: FT is an activator of flowering, and TFL1 is a repressor. It was shown before that change of a single amino acid (His88) of TFL1 to the corresponding amino acid (Tyr) of FT is enough to convert the floral repressor to an activator. However, structural basis of the functional conversion has not been understood. In our molecular dynamics simulations on modified TFL1 proteins, a hydrogen bond present in native TFL1 between the His88 residue and a residue (Asp144) in a neighboring external loop became broken by change of His88 to Tyr. This breakage induced conformational change of the external loop whose structure was previously reported to be another key functional determinant. These findings reveal that the two important factors determining the functional specificities of the floral regulators, the key amino acid (His88) and the external loop, are correlated, and the key amino acid determines the functional specificity indirectly by affecting the conformation of the external loop.

A synthesis route to ordered mesoporous carbons with controllable nitrogen content has been developed for high-performance EDLC electrodes. Nitrogen-doped ordered mesoporous carbons (denoted as NMC) were prepared by carbonizing a mixture of two different carbon sources within the mesoporous silica designated by KIT-6. Furfuryl alcohol was used as a primary carbon precursor, and melamine as a nitrogen dopant. This synthesis procedure gave cubic Ia3d mesoporous carbons containing nitrogen as much as 13%. The carbon exhibited a narrow pore size distribution centered at 3-4 nm with large pore volume (0.6-1 cm3 g-1) and high specific BET surface area (700-1000 m2 g-1). Electrochemical behaviors of the NMC samples with various N-contents were investigated by a two-electrode measurement system at aqueous solutions. At low current density, the NMC exhibited markedly increasing capacitance due to the increase in the nitrogen content. This result could be attributed to the enhanced surface affinity between carbon electrode and electrolyte ions due to the hydrophilic nitrogen functional groups. At high current density conditions, the NMC samples exhibited decreasing specific capacitance against the increase in the nitrogen content. The loss of the capacitance with the N-content may be explained by high electric resistance which causes a significant IR drop at high current densities. The present results indicate that the optimal nitrogen content is required for achieving high power and high energy density simultaneously.

The efficient synthesis of four mesitylene-based receptors 1-4 and their potentiometric response characteristics to alkali metal, alkaline earth metal, and transition metal ions, under various pH conditions are outlined. Receptor 1-based electrode exhibited more sensitive response to Ag+ ion (49 mV/decade of range from 10-6 to 10-2 M) than the 2-based electrode (47 mV/decade of range from 3 ´ 10-5 to 10-2 M), while the 3- and 4-based ones revealed sub-Nernstian below 40 mV/pAg+. All electrodes showed substantial responses to Ag+ ion under acidic condition, but there was almost nil-response to other transition metal ions (Fe2+, Co2+, Zn2+, Ni2+, Pb2+, Cd2+, Cu2+ and Hg2+). The association constant of receptor 1 toward Ag+ ion, measured by 1H NMR titration, showed the largest value (200 M-1) among the tested receptors. The results were interpreted with semi empirically-modeled structures.

Hemodialysis graft coated with paclitaxel prevents stenosis; however, large initial burst release of paclitaxel causes many negative effects such as drug toxicity and inefficient drug loss. Therefore we developed and tested a novel coating method, double dipping, to provide controlled and sustained release of paclitaxel locally. Expanded polytetrafluoroethylene (ePTFE) grafts were dipped twice into a solution of several different paclitaxel concentrations. In vitro release tests of the double dipping method showed that early burst release could be somewhat retarded and followed by sustained release for a long time. We observed the effect of paclitaxel coating by double dipping in porcine model of arterio-venous (AV) grafts between the common carotid artery and the external jugular vein. 12 weeks after constructing AV grafts, cross sections of the graft venous anastomosis were obtained and analyzed. Paclitaxel coated ePTFE grafts by double dipping were observed to prevent neointimal hyperplasia and therefore reduced stenosis of the arteriovenous hemodialysis grafts, especially at the graft venous anastomosis sites. Our results demonstrate that second dipping of ePTFE graft, which was already coated once with paclitaxel, washes off the drug on a surface of the graft and affects the ratio of paclitaxel on the surface to that of the inner space, possibly by diffusion: thus the early burst of drug can be somewhat reduced.

BaTiO3 and SrTiO3 thin films were fabricated on Pt/Ti/SiO2/Si substrate by the pulsed laser deposition process. The dependence of the deposited film quality upon the partial oxygen pressure during the deposition process was importantly examined. Regardless of the oxygen pressure, the as-deposited films were not fully crystallized. However, the film deposited at low oxygen pressure became well crystallized after the annealing process. It was concluded, therefore, that the partial oxygen pressure is reduced as low as possible during the deposition process and then anneal the as-deposited samples at ambient pressure to fabricate the well crystallized SrTiO3 and BaTiO3 films by laser ablation.

The solvent effects on the relative free energies of binding of K+ and Na+ ions to 12-crown-4 and Dlog Ks (the difference of stability constant of binding) have been investigated by a Monte Carlo simulation of statistical perturbation theory (SPT) in several solvents. Comparing the relative free energies of binding of K+ and Na+ ions to 12-crown-4, in CH3OH of this study with experimental works, there is a good agreement among the studies. We have reported here the quantitative solvent-polarity relationships (QSPR) studied on the solvent effects the relative free energies of binding of K+ and Na+ ions to 12-crown-4. We noted that DN(donor number) dominates the differences in relative solvation Gibbs free energies of K+ and Na+ ions and DN dominates the negative values in differences in the stability constant (Dlog Ks) as well as the relative free energies of binding of K+ and Na+ ions to 12-crown-4 and p* (Kamlet-Tafts solvatochromic parameters) dominates the positive values in differences in the stability constant (Dlog Ks) as well as the relative free energies of binding of K+ and Na+ ions to 12-crown-4.

A self-assembled monolayer of 2,2'-bipyridine (22BPY) molecules on Au(111) underwent a structural phase transition when the polarity of a bias voltage was switched in scanning tunneling microscopy (STM) experiments. The nature of two bright spots representing each 22BPY molecule on Au(111) in the high-resolution STM images was identified by calculating the partial density plots for a monolayer of 22BPY molecules adsorbed on Au(111) using tight-binding electronic structure calculations. The stacking pattern of the chains of 22BPY molecules on Au(111) was explained by examining the intermolecular interactions between the 22BPY molecules based on first principles electronic structure calculations for a 22BPY dimer, (22BPY)2. The structural instability of the 22BPY molecule arrangement caused by a change in the bias voltage switch was investigated by estimating the adsorbate-surface interaction energy using a point-charge approximation for Au(111).

Micrometer-sized copper (mCu) powders are weakly surface-enhanced Raman scattering (SERS) active by the excitation at 632.8 nm, but nearly ineffective as a SERS substrate at 514.5 nm excitation. The SERS activity of mCu powders at both excitation wavelengths can be increased dramatically by a simple method of the galvanic exchange reaction with AgNO3 in aqueous medium. In this work, the SERS activity of the Ag-exchanged Cu powders (mCu@Ag) has been evaluated by taking a series of Raman spectra using benzenethiol (BT) as the probe molecule. It is clearly confirmed by field emission scanning electron microscopy and X-ray diffractometry that the SERS activity of mCu@Ag powders is, in fact, highly dependent on the extent of galvanic reaction.

The physical chemistry (PC) articles published in the Bulletin of the Korean Chemical Society (BKCS) from 2003 to 2007 are surveyed, and in-depth content analysis was conducted to classify the PC articles into 12 topics used in The Journal of Physical Chemistry (JPC). The PC articles published in the Journal of the American Chemical Society (JACS) in 2007 are also surveyed. The extensive summary of all PC articles in BKCS for the last five years reveals the current trend of physical chemistry research in Korea. The comparison study with the JACS shows that the proportion of PC articles among all articles published in BKCS (16%) is slightly higher than that of JACS (11%), and the non-Korean authorship ratio of BKCS (12%) is very low compared with the non-US authorship of JACS (52%). From the comparison study with articles published in JPC in 2007, it is found that BKCS disseminates various topics of physical chemistry researches adequately. In particular, BKCS most frequently published PC articles in molecular structure and spectroscopy topics, whereas JPC published surface chemistry and nano-chemistry articles most frequently. It is concluded that BKCS should publish more articles to be a leading journal, and it is suggested that the SCI impact factor of BKCS must be increased by improving the electronic version of BKCS.

We report a method to increase the surface area of the titania films used as the anodes of dye-sensitized solar cells (DSSCs) by applying additional titania-coating. The modification was achieved by spin-coating a coating solution that contained a surfactant with a titania source onto the titania electrodes, followed by calcination. Previous similar attempts without a surfactant all reported decreased surface areas. We fabricated DSSCs by using the modified titania films as the anode and measured their performances. The increased surface area increased the amount of adsorbed dyes, which resulted in increased current densities. At the same time, the titania-coating increased both the open-circuit voltage and the current density by reducing the charge-recombination rates of the injected electrons, similar to the results of literatures. Therefore, our method shows an additional mechanism to increase the current density of DSSCs in addition to the other mechanisms of surface modifications with titania-coatings.