Indium and gallium have emerged as useful metals in organic synthesis as a result of its intriguing chemical properties of reactivity, selectivity, and low toxicity. Although indium belongs to a main metal in group 13, its first ionization potential energy is very low and stable in H2O and O2. Therefore, indium-mediated organic reactions are of our current interest. On the basis of these properties of indium, many efficient indium-mediated organic reactions have been recently developed, such as the addition reactions of allylindium to carbonyl and iminium groups, the indium-mediated synthesis of 2-(2-hydroxyethyl)homoallenylsilanes, the indiummediated allylation of keto esters with allyl halides, sonochemical Reformatsky reaction using indium, the indium-mediated selective introduction of allenyl and propargyl groups at C-4 position of 2-azetidinones, the indium-mediated Michael addition and Hosomi-Sakurai reactions, the indium-mediated β-allylation, β- propargylation and β-allenylation onto α,β-unsaturated ketones, the highly efficient 1,4-addition of 1,3-diesters to conjugated enones by indium and TMSCl, and the intramolecular carboindation reactions. Also, we found gallium-mediated organic reactions such as addition reactions of propargylgallium to carbonyl group and regioselective allylgallation of terminal alkynes.

We have designed and synthesized three Zn(II)-porphyrin derivatives, such as Zn(II) porphyrin ([G-0]Zn-P1) and aryl ether-typed dendron substituted Zn(II)-porphyrin derivatives ([G-1]Zn-P1 and [G-1]Zn-P-CN1). Their chemical structures were characterized by 1H-NMR, FT-IR, UV-vis absorption, EI-mass, and MALDI-TOF mass spectroscopies. Their electrochemical properties were studied by cyclic voltammetry measurement. These Zn(II)-porphyrin derivatives have been used to fabricate dye-sensitized solar cells (DSSCs) based on solid polymeric electrolytes as dye sensitizers and their device performances were evaluated by comparing with that of a standard Ru(II) complex dye. [G-1]Zn-P-CN1 showed the enhanced power conversion efficiency than those of other porphyrin derivatives, as expected. Short-circuit photocurrent density (Jsc), open-circuit voltage (Voc), fill factor (FF), and power conversion efficiency (η) of solid-typed DSSC for [G-1]Zn-P-CN1 were evaluated to be Jsc = 11.67 mA/cm2, Voc = 0.51 V, FF = 0.46, and η = 2.76%, respectively.

Large colorless single crystals of sodium zeolite X, stoichiometry |Na80 |[Si112Al80O384]-FAU, with diameters up to 200 μm and Si/Al = 1.41 have been synthesized from gels with the composition of 2.40SiO2 : 2.00NaAlO2 : 7.52NaOH : 454H2O : 5.00TEA. One of these, a colorless octahedron about 200 μm in cross-section has been treated with aqueous 0.1 M KNO3 for the preparation of K+-exchanged zeolite X. The crystal structure of |K80|[Si112Al80O384]-FAU per unit cell, a = 24.838(4) A, dehydrated at 673 K and 1 × 10-6 Torr, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd at 294 K. The structure was refined using all intensities to the final error indices (using only the 707 reflections for which Fo > 4σ (Fo)) R1 = 0.075 (based on F) and R2 = 0.236 (based on F2). About 80 K+ ions per unit cell are found at an unusually large number of crystallographically distinct positions, eight. Eleven K+ ions are at the centers of double 6-rings (D6Rs, site I; K-O = 2.492(6) A and O-K-O (octahedral) = 88.45(22)o and 91.55(22)o). Site-I' position (in the sodalite cavities opposite D6Rs) is occupied by five K+ ions per unit cell; these K+ ions are recessed 1.92 A into the sodalite cavities from their 3-oxygen planes (K-O = 2.820(19) A, and O-K-O = 78.6(6)o). Twety-three K+ ions are found at three nonequivalent site II (in the supercage) with occupancies of 5, 9, and 9 ions; these K+ ions are recessed 0.43 A, 0.75 A, and 1.55 A, respectively, into the supercage from the three oxygens to which it is bound (K-O = 2.36(13) A, 2.45(13) A, and 2.710(13) A, O-K-O = 116.5(20)o, 110.1(17)o, and 90.4(6)o, respectively). The remaining sixteen, thirteen, and twelve K+ ions occupy three sites III' near triple 4-rings in the supercage (K-O = 2.64(3) A, 2.94(3) A, 2.73(5) A, 2.96(6) A, 3.06(4) A, and 3.08(3) A).

Prodigiosin (1) is the parent member of a class of polypyrrole natural products that exhibit promising anticancer activities. They can facilitate copper-promoted oxidative DNA damage by binding to copper ions, and this activity is thought to represent their mechanism of cytotoxicity in the dark. They also possess photoinduced cytotoxicity, although 1 is too toxic in the dark to be used effectively for the treatment of cancer by photodynamic therapies. To circumvent dark toxicity by prodigiosins, the semi-synthetic analogue 2, in which the N-pyrrolic atoms of 1 are methylated to block copper coordination, and the synthetic phenyl analogues 3 and 4, which lack the copper-coordinating A-pyrrole ring of 1, were tested for their ability to inhibit colony formation of HL-60 cancer cells in the absence and presence of visible light (λ > 495 nm). Our results show that 2-4 lack cytotoxicity in the dark, but are able to inhibit colony formation of HL-60 cells following irradiation for 30 min. The synthetic derivative 4 exhibits photo-induced cytotoxicity similar to that of the natural product 1, demonstrating the potential use of prodigiosin-based compounds for treatment of cancers following irradiation with visible light.

In the dehydrogenation of ethylbenzene to styrene, CO2 could play a role as an oxidant to increase conversion of ethylbenzene and stability as well over TiO2-ZrO2 mixed oxide catalysts. TiO2-ZrO2 catalysts were prepared by co-precipitation method and were characterized by BET surface area, bulk density, X-ray diffraction, temperature programmed desorption of NH3 and CO2. These catalysts were found to be X-ray amorphous with enhanced surface areas and acid-base properties both in number and strength when compared to the respective oxides (TiO2 and CO2). These catalysts were found to be highly active (> 50% conversion), selective (> 98%) and catalytically stable (10 h of time-on-stream) at 600 oC for the dehydrogenation of ethylbenzene to styrene. However, in the nitrogen stream, both activity and stability were rather lower than those in the stream with CO2. The TiO2-ZrO2 catalysts were catalytically superior to the simple oxide catalysts such as TiO2 and ZrO2. The synergistic effect of CO2 has clearly been observed in directing the product selectivity and prolonging catalytic activity.

A quantitative analysis method of halogen elements in volatile organohalogen compounds was established by the Wickbold combustion pretreatment in an enclosed system and ion chromatography. The sample pretreatment parameters of Wickbold combustion were experimentally optimized, and using the determined optimal pretreatment parameters, the reproducibility was estimated by ion chromatography. As a comparison for real samples, NIST certified reference materials (CRMs) were analyzed for the recovery efficiency and reproducibility.

Biodegradable cationic poly(ester-amide) polymers were synthesized by double-monomer method, that showed excellent solubility in many organic solvents and water. Different degradation patterns were obtained by the regulation of monomer ratios and overall long period of time of DNA protection up to 12 days was shown by PicoGreen reagent assay. Good transfection profiles in the presence of serum and very low toxicity on mammalian cells may allow these polymers to become suitable for long-term gene delivery systems and therapeutic applications.

A new PVC membrane potentiometric sensor that is highly selective to Hg2+ ions was prepared, using bis(2-hydroxybenzophenone) butane-2,3-dihydrazone (HBBD) as an excellent hexadendates neutral carrier. The sensor works satisfactorily in the concentration range of 1.0 × 10-6 to 1.0 × 10-1 mol L-1 (detection limit 4 × 10-7 mol L-1) with a Nernstian slope of 29.7 mV per decade. This electrode showed a fast response time (~8 s) and was used for at least 12 weeks without any divergence. The sensor exhibits good Hg2+ selectivity for a broad range of common alkali, alkaline earth, transition and heavy metal ions (lithium, sodium, potassium, magnesium, calcium, copper, nickel, cobalt, zinc, cadmium, lead and lanthanum). The electrode response is pH independent in the range of 1.5-4.0. Furthermore, the developed sensor was successfully used as an indicator electrode in the potentiometric titration of mercury ions with potassium iodide and the direct determination of mercury in some binary and ternary mixtures.

Prunioside A, isolated from the methanol extract of Spiraea prunifolia var. Simpliciflora's root, is composed of coumaroyl, monoterpene-type, and glucosyl units. The esterase activity of tannase was used to remove the p-coumaroyl and glucopyranosyl groups. The enzymatically hydrolyzed compound was reacted with various acyl chlorides to synthesize its ester derivatives, which showed the inhibitory effects on NO production in murine machrophage?like RAW 264.7 cells stimulated with lipopolysaccharide and interferon-γ.

As neurofilament proteins are major cytoskeletal components of neuron, abnormality of neurofilament is proposed in brain with neurodegenerative disorders such as Parkinson's disease (PD). Since oxidative stress might play a critical role in altering normal brain proteins, we investigated the oxidative modification of neurofilament-L (NF-L) induced by the reaction of cytochrome c with H2O2. When NF-L was incubated with cytochrome c and H2O2, the protein aggregation was increased in cytochrome c and H2O2 concentrationsdependent manner. Radical scavengers, azide, formate and N-acetyl cysteine, prevented the aggregation of NFL induced by the cytochrome c/H2O2 system. The formations of carbonyl group and dityrosine were obtained in cytochrome c/H2O2-mediated NF-L aggregates. Iron specific chelator, desferoxamine, prevented the cytochrome c/H2O2 system-mediated NF-L aggregation. These results suggest that the cytochrome c/H2O2 system may be related to abnormal aggregation of NF-L which may be involved in the pathogenesis of PD and related disorders.

Ab initio periodic Hartree-Fock calculations with the full potential and minimum basis set are applied to interpretation of scanning tunneling microscope (STM) and atomic force microscope (AFM) images on 1TVTe2. Our results show that the simulated STM image shows asymmetry while the simulated AFM image shows the circular electron densities at the bright spots without asymmetry of electron density to agree with the experimental AFM image. The bright spots of both the STM and AFM images of VTe2 are associated with the surface Te atoms, while the patterns of bright spots of STM and AFM images are different.

Ab initio periodic Hartree-Fock calculations with the full potential and minimum basis set are applied to interpretation of scanning tunneling microscope (STM) and atomic force microscope (AFM) images on 1TVTe2. Our results show that the simulated STM image shows asymmetry while the simulated AFM image shows the circular electron densities at the bright spots without asymmetry of electron density to agree with the experimental AFM image. The bright spots of both the STM and AFM images of VTe2 are associated with the surface Te atoms, while the patterns of bright spots of STM and AFM images are different.

The new pinane derivative containing unique multifused ring system was synthesized. The crystal, molecular and electronic structure of the title compound has been determined. Both pinane ring systems have the same conformation. The five-membered oxazolidine ring exists in twisted chair conformation. The structure is expanded through O-H…O hydrogen bond to semiinfinite hydrogen-bonded chain. The bond lengths and angles in the optimised structure are similar to the experimental ones. The CH3 and CH2 groups (except this of oxazolidine ring) are negatively charged whereas the CH groups are positively charged. The largest negative potential is on the oxygen atoms. The C-N natural bond orbitals are polarised towards the nitrogen atom (ca. 61% at N) whereas the C-O bond orbitals are polarised towards the oxygen atom (ca. 67% at O). It is consistent with the charges on the nitrogen and oxygen atom of oxazolidine ring and the direction of the dipole moment vector (3.08 Debye).

Polyethylenimine (PEI) has been widely investigated for delivery of DNA into cells. It was previously reported that there were at least two types of cytotoxicity in PEI-mediated gene delivery, immediate and delayed toxicities. PEI-mediated gene delivery protocols use net cationic complexes with an excess of PEI to maintain equilibrium between the complexed and dissociated forms in solution. In this study, toxicity of free PEI or PEI/ DNA complex was investigated. Human embryonic kidney 293 cells were incubated with free PEI or PEI/DNA complex for 4 hrs. Then, the cells were analyzed at 6, 24, 48, and 96 hrs after the incubation. In MTT assay, the viability of the cells incubated with PEI/DNA complex was continuously decreased with time, while that of the cells incubated with free PEI was not. On the contrary, the expression level of the luciferase gene increased gradually along with time. Release of DNAs from the complexes for transcription produces free PEIs in the cells. This process may proceed slowly due to high charge density of PEI and may be related to delayed toxicity. In addition, apoptotic cells were observed only in the cells incubated with the PEI/DNA complex from 24 hrs after the incubation. The results suggest that PEI/DNA complex contributes to the delayed toxicity by inducing apoptosis and that the delayed toxicity may be related to decomplexation of the complexes in the cells.

To prepare freeze-dried ascorbyl palmitate (AsP)-containing liposome which can protect the drug from moisture attack and be used instantly by mixing with water for anti-aging and skin whitening therapy, AsP was encapsulated into liposomes and freeze-dried with trehalose. The freeze-dried liposome formulations were characterized by measuring water contents, particle size, time required for complete reconstitution. With the freeze-dried liposomes, we performed the stability test under accelerated conditions, skin permeation and localization test. The measurement of the time to perfect reconstitution showed that the freeze-dried liposomes can be changed to their initial state rapidly and short term stability test of AsP in reconstituted liposomes under accelerated conditions confirmed that the stability of AsP was considerably enhanced as compared to freshly prepared liposomes. The skin permeation and localization properties of AsP in reconstituted liposomes were not significantly different, indicating that the liposomal structures were maintained before and after freezedrying. In conclusion, the freeze-drying method provided a possible way to overcome the instability issue of AsP induced by the moisture and reproduced similar skin permeation and localization properties as shown by freshly prepared liposomes.

A mild, chemoselective and convenient method for the formation and deprotection of tetrahydropyranyl ethers is described. With 1-5 mol% of acetyl chloride and slightly excess dihydropyran in methylene chloride or in neat dihydropyran, the formation of THP ethers from the corresponding alcohols was accomplished in the presence of many acid-sensitive functional groups. Efficient cleavage of THP ethers was also accomplished with the same reagent by switching the solvent to methanol.

The lyotropic behaviors to form the structure of distearoylphosphatidylcholine (DSPC)-based liquid crystal (LC) hydrated by only propylene glycol (PG) without water were examined by differential scanning calorimetry (DSC), X-ray diffractions (XRD), polarized microscope (PM) and transmission electron microscope (TEM). By increasing the amount of PG instead of water, it showed the phase transition to be gradually changed from anisotropic structures to other structures more close to isotropic ones and their appearance to be changed from solid-like states to liquid-like ones with more fluidity. Below 50% w/w PG, the mixtures of DSPC and PG resulted in no direct observation of LC structure through PM because they were very close to solid-states. From 55% w/w to 90% w/w of PG, the dense lamella crystalline structures were observed through PM, and their thickness and area decreased as the content of PG increased. Measured by DSC with heating process, the main phase transition from α -lamella phase to isotropic phase appeared from 52.89 °C to 47.41 °C to show linearly decreasing behaviors because PG affects the hydrophobic region of DSPC-based lamella phase. The repeating distance of the lamella phase and the interlayer distance between bilayers were calculated with XRDs and the average number of bilayers related to the thickness in LC structure was approximately estimated by combining with TEM results. The WAXS and DSC measurements showed that all of PG molecules contributed to swelling both the lipid layer in the edge region of lamella phase close to phosphate groups and the interlayer between bilayers below 90% w/w of PG. The phase and thermal behaviors were found to depend on the amount of PG used by means of dissolving DSPC as a phospholipid and rearranging its structure. Instead of water, the inducement of PG as a polar solvent in solid-lamella phase is discussed in terms of the swelling effect of PG for DSPC-based lamella membrane.