Headspace micro solid phase extraction using mulberry paper bag (HS-MPB-$\mu$-SPE) has been developed and validated for the analysis of volatile flavor compounds from five spice by gas chromatography-mass spectrometry (GC/MS). HS-MPB-$\mu$-SPE was performed with adsorbent particles enclosed inside a mulberry paper bag. Four different kinds of adsorbents such as Tenax TA, Porapack Q, dimethylpolysiloxane and polyethylene glycol were tested. The extraction solvents compared were petroleum ether, methylene chloride, and chloroform. Better results were obtained when Tenax TA and petroleum ether were used. The limit of detection (LOD) and the limit of quantitation (LOQ) were in the range of 1.3 ng/mL and 4.3 ng/mL, respectively, for o-cymene as a model compound of monoterpene. Proposed method showed good reproducibility (3.3%, RSD) and good recoveries (94.0%). The HS-MPB- μ-SPE is very simple to use, inexpensive, rapid, requires small sample amounts and solvent consumption. Because the solvent for extraction is reduced to only a very small volume (0.6 mL), there is minimal waste or exposure to toxic organic solvent and no further concentration step. This method allows successful characterization of the headspace in contact with the five spice sample. Strong trans-anethole from star anise or fennel is a characteristic flavor of five spice powders. HS-MPB-$\mu$-SPE combined with GC/MS can be a promising technique for the broad spectrum measurement of volatile aroma compounds from solid spices.

The synthesis of coumarin-based natural products and their derivatives is described. In vitro MDR reversal activities of the synthesized compounds were evaluated in P-glycoprotein over-expressing human sarcoma cell line MES-SA/DX5. Some of the coumarin derivatives were found to show potent MDR reversal activity. In particular, pyridyl derivative (15e) exhibited more potency than verapamil.

Single-drop microextraction (SDME) is an extraction methodology where the drop plays an essential role as extracts. It was evaluated for the GC-MS determination of nerve agents, one class of the chemical warfare agents (CWAs). Since these nerve agents are highly toxic, it is important to detect the nerve agents in the environmental samples. Several affecting factors including extraction solvents, stirring rate, extraction time, and amounts of salt were optimized. The limit of detections (LODs) were 0.1 - 10 ng/mL and the relative standard deviations (RSDs%, n=5) were in the range of 6.3% to 9.0% for four nerve agents. Without pretreatment of the environmental samples, 5-103 fold enrichments and 48-100% recovery were accomplished. These results demonstrated the feasibility of this method for on-site and off-site analysis of water sample collected from suspicious CWAs site.

At room-temperature, a facile, seedless, and environmentally benign green route for the synthesis of star like PbS nanoclusters at 7 min in aqueous solution of 1-ethyl-3-methylimidazolium ethyl sulfate, [EMIM] [$EtSO_{4}$], room-temperature ionic liquid (RTIL), via ultrasonic irradiation is proposed. The X-ray diffraction studies display that the products are excellently crystallized in the form of cubic structure. An energy dispersive X-ray spectroscopy (EDX) investigation reveals the products are extremely pure. The absorption spectra of the product exhibit band gap energy of about 4.27 eV which shows an enormous blue shift of 3.86 eV that can be attributed to very small size of PbS nanoparticles produced and quantum confinement effect. A possible formation mechanism of the PbS nanoparticles using ultrasonic irradiation in aqueous solution of the RTIL is presented.

Alcohol oxidase catalyzes the oxidation of short lines alcohol to aldehyde. In this study, alcohol oxidase from Hansenula polymorpha (HpAOD) was induced by addition of 0.5% methanol as the carbon source and purified to electrophoretic homogeneity by column chromatographies. The purified HpAOD was immobilized with DEAE-cellulose particles and its biochemical properties were compared with those of free enzyme. The substrate specificity and the optimum pH of immobilized enzyme were similar to those of free enzyme. On the other hand, the Km values of free and immobilized enzymes for ethanol were 6.66 and 14.65 mM, respectively. The optimum temperature for free enzyme was ${50^{\circ}C}$, whereas that for immobilized enzyme was ${65^{\circ}C}$. Immobilized enzyme showed high stability against long storage. Immobilized enzyme was also tested for the enzymatic determination of ethanol by the colorimetric method. We detected 1 mg/liter ethanol ($1{\times}10^{-4}$% ethanol) by 2,6- dichloroindophenol system. Therefore, the present study demonstrated that immobilized HpAOD has high substrate specificity toward ethanol and storage stability, which may be of considerable interest for alcohol biosensor and industrial application.

An analytical method based on solid-phase extraction and gas chromatography / mass spectrometry has been developed for measurement of acaricides (amitraz, bromopropylate, coumaphos, cymiazole, and tetradifon) in honey sample. In the stability test of acaricides in honey, amitraz underwent a rapid degradation into 2,4-dimethylaniline (DMA), 2,4-dimethylphenylformamide (DMPF), and N-(2,4-dimethylphenyl)-N'-methylformamidine (DMPMF), whileas other acaricides were found to be stable even for over three months. Extraction of five acaricides from 5g of honey sample was carried out by liquid-liquid extraction using 20mL of ethylacetate. For purification, Florisil-SPE cartridge with elution of 5mL of n-hexane/ acetone (55:45, v/v) was found to remove interferences effectively. 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 values from honey spiked at 0.02 and 0.20 ${\mu}g/g$ levels, respectively, were found to be greater than 75% for all acaricides. The method detection limits for acaricides were ranged from 0.1 to 3 ppb. The developed method in this study was applied for the monitoring of acaricides in honey products collected from urban markets in Korea.

The development of a variety of methods like AM1, PM3, PM5 and DFT now allows the calculation of atomic and molecular properties with high precision as well as the treatment of large molecules with predictive power. In this paper, these methods have been used to calculate a number of quantum chemical descriptors (like Klopman atomic softness in terms of $E_n^{\ddag}\;and\;E_m^{\ddag}$, chemical hardness, global softness, electronegativity, chemical potential, electrophilicity index, heat of formation, total energy etc.) for 75 alkanes to predict their boiling point values. The 3D modeling, geometry optimization and semiempirical & DFT calculations of all the alkanes have been made with the help of CAChe software. The calculated quantum chemical descriptors have been correlated with observed boiling point by using multiple linear regression (MLR) analysis. The predicted values of boiling point are very close to the observed values. The values of correlation coefficient ($r^2$) and cross validation coefficient ($r_{cv}^2$) also indicates the generated QSPR models are valuable and the comparison of all the methods indicate that the DFT method is most reliable while the addition of Klopman atomic softness $E_n^{\ddag}$ in DFT method improves the result and provides best correlation.

Thrombin activatable fibrinolysis inhibitor (TAFI) also known as plasma procarboxypeptidase B or U is a 60 kD glycoprotein, which is the major modulator of fibrinolysis in plasma. TAFI is a proenzyme, which is activated by proteolytic cleavage to an active carboxypeptidase B-like enzyme (TAFIa, 35.8 kD) by thrombin/thrombomodulin and plasmin. Modulation of fibrinolysis occurs when TAFIa enzymatically removes C-terminal lysine residues of partially degraded fibrin, thereby inhibiting the stimulation of tissue plasminogen activator (t-PA) modulated plasminogen activation. TAFIa undergoes a rapid conformational change at $37{^{\circ}C}$ to an inactive isoform called TAFIai. Potato tuber carboxypetidase inhibitor (PTCI) was shown to specifically bind to TAFIa as well as TAFIai. In this study, a novel immunoassay TAFIa/ai ELISA was used for quantitation of the two TAFI activation isoforms TAFIa and TAFIai. The ELISA utilizes PTCI as the capture agent and a double antibody sandwich technique for the detection. Low levels of TAFIa/ai antigen levels were detected in normal plasma and elevated levels were found in hemophilia A plasmas. TAFIa/ai antigen represents a novel marker to monitor fibrinolysis and TAFIa/ai ELISA may be a valuable assay for studying the role of TAFI in normal hemostasis and in pathological conditions.

To develop new anticancer agents, 3-allylthio-6-aminopyridazine derivatives were synthesized from maleic anhydrides or phthalic anhydrides by formation of a pyridazine nucleus, dichlorination, allylthiolation and amination. The pyridazine nuclei were obtained by condensing a hydrazine monohydrate with maleic anhydride. An allylthio group as a pharmacologically active group was introduced into one side of a pyridazine ring. Arylalkylamines with benzene or pyridine moieties or heterocycloalkylamines with heterocycle moieties such as morpholine, piperidine, or pyrrolidine were also introduced into the para-position of allylthio pyridazine. These new compounds showed antiproliferative activities against SK-Hep-1 human liver cancer cells in MTT assays. These compounds are thus promising candidates for chemotherapy of hepatocellular carcinomas. Two compounds, 20c and 22a, showed higher potencies for inhibiting growth of hepatocellular carcinoma cells than did K6 ($ID_50$=1.08 mM). This suggests the potential anticancer activity of these two compounds.

A new precursor [$Zr(acac)_{3}(H_{2}O)_{2}$] was synthesized by Sonochemical technique and used to deposit thin $ZrO_{2}$ film on quartz and ceramic substrate via ultrasonic aerosol assisted chemical vapour deposition (UAACVD) at 300 ${^{\circ}C}$ in oxygen environment followed by annealing of the sample for 2-3 minutes at 500 ${^{\circ}C}$ in nitrogen ambient. The molecular structure of the precursor determined by single crystal X-ray analysis revealed that the molecules are linked through intermolecular hydrogen bonds forming pseudo six and eight membered rings. DSC and TGA/FTIR techniques were used to determine thermal behavior and decomposition temperature of the precursor and nature of evolved gas products. The optical measurement of annealed $ZrO_{2}$ film with tetragonal phase shows optical energy band gap of 5.01 eV. The particle size, morphology, surface structure and composition of deposited films were investigated by XRD, SEM and EDX.

A new approach was applied to examine the charge generation and transport in organic photoconductive devices by Monte‐Carlo simulation utilizing multiple site interactions of carriers with all other charges within Coulomb radius. Stepwise generation frame was considered first by a charge separation process that was counted in two separate transactions, i.e., hopping against physical decay and dissociation against recombination. Thereafter, diffusion/ drifting process of free carriers was counted to follow. This method enables to examine readily the photocurrent generated alongside the charge generation efficiency. The field and temperature dependences of the efficiency and photocurrent were obtained comparable to Onsager’s and experimental data.

A rapid and sensitive chemiluminescence (CL) method using flow-injection (FI) has been developed for the determination of mandelic acid which is based on the enhancement of mandelic acid to the CL intensity of ${Ru(bipy)_{3}}^{2+}$-Ce(IV) system. The enhancement effect was dependent on the concentration of mandelic acid, based on which, CL system was established for the determination of mandelic acid. The concentrations of ${Ru(bipy)_{3}}^{2+}$+, Ce(IV), and $H_2SO_4$ were optimized. Under the optimum experimental conditions, the linear range and detection limit are 1.46-342.0 ${\mu}g/ml$ and 0.072 ${\mu}g/ml$, respectively. The correlation coefficient (R) was 0.99732. The utility of this method was demonstrated by determining mandelic acid in capsules and human urine sample.

This study investigated the decomposition activities of toluene on 10 mol% Al-W-incorporated mesoporous titano (15 mol %) silicates. The mesopore sizes observed in the transmission electron microscopy images ranged from 2.0 to 5.0 nm, and the pores were irregular on the addition of 10 mol% Al or W ions, but changed to regular hexagonal forms with the simultaneous additions of Al and W. The X-ray photon spectroscopy results showed a shift of the special peak for Ti2p in Al-incorporated mesoporous titanosilicates to a stronger binding energy compared to those of mesoporous titanosilicates and Al-incorporated mesoporous titanosilicates. Three O1s peaks in the spectra of the Al and W coexisted samples were observed at 530.5 and 531.7, 533, and 533.7eV, which were assigned to $Ti-Os\;in\;TiO_2\;and\;Ti_2O_3,\;Si-O\;in\;SiO_2\;and\;Al-O\;in\;Al_2O_3$, respectively. The toluene molecules desorbed at lower temperatures over W-incorporated mesoporous titanosilicates, and the amounts of toluene desorbed were also small; however, Al-incorporated mesoporous titanosilicates adsorbed much more toluene, particular over $Al_7.5-W_2.5-Ti_15-Si_75$. The photocatalytic decomposition of toluene was more enhanced over $Al_7.5-W_2.5-Ti_15-Si_75$ than over Al- or W-incorporated mesoporous titanosilicates only.

A new Zn/O single source precursor, TMEDA-Zn$(eacac)_2$, has been synthesized by using N, N, N’, N’-tetramethylethylendiamine (TMEDA), sodium ethyl-acetoacetate, and $ZnCl_2$. From this organometallic precursor, ZnO thin films have been successfully grown on Si (100) substrates through the metal organic chemical vapor deposition (MOCVD) method at relatively mild conditions in the temperature range of 390~430 ${^{\circ}C}$. The synthesized ZnO films have been found to possess average grain sizes of about 70 nm with an orientation along the c-axis. The precursor and ZnO films are characterized through infrared spectroscopy, nuclear magnetic resonance spectroscopy, EI-FAB-spectroscopy, elemental analyses, thermal analysis, X-ray diffraction, and field emission scanning electron microscopic analyses.

Structural modifications were performed on the C-3 and C-28 positions of ursolic acid and oleanolic acid and the NO production inhibitory activities of the resulting derivatives were evaluated. The SAR revealed that the ursolic acid and oleanolic acid derivatives 3a and 4a, which possessing methoxy group at C-3 position exhibit improved NO production inhibitory activity on LPS-induced RAW247 cells while showing less cytotoxicity than the parent compounds.

In this study, the effect of multi-step purification or functionalization on physicochemical properties of multi-walled carbon nanotubes (MWNTs)/epoxy (EP) nanocomposites was investigated. The nanocomposites containing multi-step purified MWNTs showed a stronger influence on $T_g$ and increased in mechanical properties in comparison to nanocomposites containing the same amount of only purified MWNTs. Consequently, the multi-step purification of MWNTs led to an improvement of thermomechanical properties of nanocomposites, resulting from improving the intermolecular interaction of MWNTs in epoxy matrix resins.

Monodisperse ZnS colloidal particles with precisely specified diameters over a broad size range were synthesized by controlled aggregation. Sub-10nm ZnS seed crystals were first nucleated at ambient temperature and then grown at an elevated temperature, which produced large polydisperse colloidal particles. Subsequent rapid thermal quenching and heating processes induced a number of secondary nucleations in addition to growing the large polydisperse microparticles which were finally removed by centrifugation and discarded at the completion of the reaction. The secondary nuclei were then aggregated further at elevated temperatures, resulting in colloidal particles which exhibited a nearly monodisperse size distribution. Particle diameters were controlled over a wide size range from 50 nm to 1 μm. Mie simulations of the experiment extinction spectra determined that the volume fraction of the ZnS is 0.66 in an aggregated colloidal particle and the colloidal particle effective refractive index is approximately 2.0 at 590 nm in water. The surface of the colloidal particles was subsequently coated with silica to produce ZnS@silica core-shell particles.

A newly designed Ag/$Ag^+$ reference electrode in a quartz tube with a tungsten tip junction (W-tip-Quartz- REF) was fabricated and its electrochemical performance was compared with a conventional Pyrex tube-based Ag/$Ag^+$ reference electrode (Py-REF). The results of the electrochemical potential measurements with the W-tip-Quartz- REF and the Py-REF in the LiCl-KCl eutectic melts for a wide temperature range proved that the oxide layer on the surface of the tungsten metal tip provided a high ionic conduction. Stability of our newly designed W-tip- Quartz-REF was tested by measuring a junction potential for 12 hours at 700${^{\circ}C}$. The results of the cyclic voltammetric measurement indicated that the Ag/$Ag^+$ reference electrode in the quartz tube with a tungsten tip junction can provide a good performance for a wide temperature range.

In this study, quantitative and pattern recognition analyses for the quality evaluation of Herba Epimedii using HPLC was developed. For quantitative analysis, five major bioactive constituents, hyperin, epimedin A, epimedin B, epimedin C, and icariin were determined. Analysis was carried out on Capcell pak $C_{18}$ column ($250{\time}4.6$ mm, 5 ${\mu}m$) with a mobile phase of mixture of acetonitrile and 0.1% formic acid, using UV detection at 270 nm. The linear behavior was observed over the investigated concentration range (2-50 ${\mu}g/mL;\;r_2\;>$ 0.99) for all analytes. The intraand inter-day precisions were lower than 4.3% (as a relative standard deviation, RSD) and accuracies between 95.1% and 104.4%. The HPLC analytical method for pattern recognition analysis was validated by repeated analysis of one reference sample. The RSD of intra- and inter-day variation of relative retention time (RRT) and relative peak area (RPA) of the 12 selected common peaks were below 0.8% and 4.7%, respectively. The developed methods were applied to analysis of twenty Herba Epimedii extract samples. Contents of hyperin, epimedin A, epimedin B, epimedin C, and icariin were calculated to be 0$\sim$0.79, 0.69$\sim$1.91, 0.93$\sim$9.58, 0.65$\sim$3.05, and 2.43$\sim$11.8 mg/g dried plant. Principal component analysis (PCA) showed that most samples were clustered together with the reference samples but several apart from the main cluster in the PC score plot, indicating differences in overall chemical composition between two clusters. The present study suggests that quantitative determination of marker compounds combined with pattern-recognition method can provide a comprehensive approach for the quality assessment of herbal medicines.

Nucleotides are the building blocks of nucleic acids and essential for many cellular functions. In this study, ultrasonic absorption spectra of $\beta$-cyclodextrin ($\beta$-CD) and adenosine 5'-monophosphate (AMP) in aqueous solution were measured over the broad frequency range 0.1-40 MHz with emphasis on the low-frequency range below 1 MHz. Here we show that the interaction of $\beta$-CD and AMP complies with a typical spectrum of a single relaxation process. We determined reliable rate (kb) and equilibrium (K) constants and a standard volume change ($\Delta$V) of the reaction. They are $k_b=2.3{\times}{{10^{-6}}_s}^{-1},\;K=89M^{-1},\;and\;{\Delta}V=13.8(10^{-6}m^3mol^{-1})$, respectively.

Hydrotalcites are anionic clays that are quite prevalent in nature and their importance is growing more and more because of their very wide range of potential applications and uses. Understanding the structural and compositional changes that occur on the molecular scale during the thermal decomposition of hydrotalcite compounds is essential for the basic prediction and comprehensive understanding of the behavior and technical application of these materials. In this study, several hydrotalcite compounds calcined at different temperatures for applications in a chlorine resistant textile were prepared and 27-Aluminm solid-state nuclear magnetic resonance (NMR) spectroscopy was used as a tool to study their local structure and behavior. The changes in the Al coordination of the hydrotalcite compounds were investigated with one dimensional (1D) solid-state magic angle spinning (MAS) NMR spectroscopy. The two broad resonances arising from the structurally different Al coordinations of these compounds were clearly resolved by two dimensional (2D) triple quantum magic angle spinning (3QMAS) NMR spectroscopy.

Low temperature methane steam reforming to produce $H_2$ for fuel cells has been calculated thermodynamically considering both heat loss of the reformer and unreacted $H_2$ in fuel cell stack. According to the thermodynamic equilibrium analysis, it is possible to operate methane steam reforming at low temperatures. A scheme for the low temperature methane steam reforming to produce $H_2$ for fuel cells by burning both unconverted $CH_4$ and $H_2$ to supply the heat for steam methane reforming has been proposed. The calculated value of the heat balance temperature is strongly dependent upon the amount of unreacted $H_2$ and heat loss of the reformer. If unreacted $H_2$ increases, less methane is required because unreacted $H_2$ can be burned to supply the heat. As a consequence, it is suitable to increase the reaction temperature for getting higher $CH_4$ conversion and more $H_2$ for fuel cell stack. If heat loss increases from the reformer, it is necessary to supply more heat for the endothermic methane steam reforming reaction from burning unconverted $CH_4$, resulting in decreasing the reforming temperature. Experimentally, it has been confirmed that low temperature methane steam reforming is possible with stable activity.

General, fast, and efficient methods for the synthesis of Fréchet-type dendrimers having core diversities were elaborated. Two core building blocks, 4,4'-(3,5-bis(propargyloxy)benzyloxy)bisphenyl and N,N,N',N'-tetra(prop-2- ynyloxycarbonylethyl)-1,2-diaminoethane, were designed to serve as the alkyne functionalities for dendrimer growth via click reactions with the azide-dendrons. The synthetic strategy involved an 1,3-dipolar cycloaddition reaction between an alkyne and an azide- functionalized Fréchet-type dendrons in the presence of Cu(I) species which is known as the best example of click chemistry.

Few $\alpha$-Hydroxy-$\beta$-amino acids were synthesized via various nucleophilic addition of the epoxide and followed by stereoselective nucleophilic substitution reaction and eliminative cleavage of the acetal selectively in diacetal compound. One of the synthesized $\alpha$-Hydroxy-$\beta$-amino acid reacted with L-leucine methylester to give corresponding dipeptide in good yields.

The nature and morphology of titanium dioxide films play a significant role in determining the overall efficiency of dye-sensitized solar cell (DSSCs). In this work, the preparation of nanostructured titania particles by sol-gel method (SG-$TiO_2$) and its characterization were investigated for the application of DSSCs. The samples were characterized by XRD, XPS, FE-SEM, BET and FT-IR analysis. The energy conversion efficiency of SG-$TiO_2$ was approximately 8.3 % under illumination with AM 1.5 (100 mW/$cm^2$) simulated sunlight. DSSCs made of SG-$TiO_2$ nanocrystalline films as photoanodes achieved better energy conversion efficiency compared to those prepared using commercially available Degussa P25.

We present the geminate rebinding kinetics measurements of CO to 2-methylimidazole (2-MeIm) bound ferrous protoporphyrin- IX (FePPIX) in alkaline glycerol/water mixtures at 293 K after photolysis. The kinetics was probed by monitoring the CO stretching mode using femtosecond vibrational spectroscopy. When 2-MeIm is used in excess, heme dimers that typically form in low viscosity solutions disappear as the viscosity of the solvent increases. Heme aggregates formed in low viscosity solutions turn monomeric as more 2-MeIm is added, suggesting that 6-coordinated heme, including a strong proximal histidine tends to be in the monomeric form. The vibrational band of CO in the 2-MeIM-FePPIX-CO is well described by a single Gaussian function centered at 1958 $cm^-1$ and 28 $cm^-1$ full width at half maximum. The efficiency and rate of the geminate rebinding of CO to the heme increase with viscosity of the solvent, suggesting that retention of the dissociated CO near the heme, for a longer period by the viscous solvent media, accelerates rebinding.

The structure of nano-crystalline $MnFe_2O_4$ was determined and refined with electron powder diffraction data employing the Rietveld refinement technique. A nano-crystalline sample (with average crystal size of about 10.9 nm) was characterized by selected area electron diffraction in an energy-filtering transmission electron microscope operated at 120 kV. All reflection intensities were extracted from a digitized image plate using the program ELD and then used in the course of structure refinements employing the program FULLPROF for the Rietveld analysis. The final structure was refined in space group Fd-3m (# 227) with lattice parameters a=8.3413(7) $\AA$. The reliability factors of the refinement are $R_F$=7.98% and $R_B$=3.55%. Comparison of crystallographic data between electron powder diffraction data and reference data resulted in better agreement with ICSD-56121 rather than with ICSD-28517 which assumes an initial structure model.

New $\alpha$-pyrones (1 and 2) and cyclohexenones (13 and 14) were isolated along with known analogues (3, 5−12) from the ethyl acetate extract of the whole broth of the fungus Paecilomyces lilacinus, a strain derived from a marine sponge Petrosia sp. Their structures were established by interpretation of 1D and 2D NMR, and FABMS data. It is interesting to isolate cyclohexenone derivatives from the genus Paecilomyces (family Trichocomaceae, order Eurotiales), since these cyclohexenones were previously reported only from far distinct genera, Phoma and Alternaria (family Pleosporaceae, order Pleosporales). Compounds 6, 7, and 9 were evaluated for cytotoxicity against a small panel of human solid tumor cell lines. Their cytotoxicity was insignificant upto a concentration of 30 ${\mu}g/mL$.

Mesoporous $TiO_2$ material was synthesized from diblock copolymers with ethylene oxide chains via a sol-gel process in aqueous solution. The properties of these materials were characterized with several analytical techniques including field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), wide angle X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) analysis, and Barrett-Joyner-Halenda (BJH) analysis. The mesoporous $TiO_2$ materials calcined at 400${^{\circ}C}$ were found to have specific surface areas 212 $m^2g^-1$, average pore sizes 6.2 nm, and their average crystal sizes were found to be 8.2 nm. The photocatalytic activity of mesoporous $TiO_2$ was characterized with UV-Vis spectroscopy, and it was found to be 5.8 times higher than that of Degussa P25 $TiO_2$ (P25). For deactivation of Escherichia coli, mesoporous $TiO_2$ also has high photocatalytic inactivity than that of P25. Such a high photocatalytic activity is explained with large surface area and small crystal size with wormhole-like mesoporous structure.

A simple dye having phenol and indole moieties was synthesized and its chromogenic signaling behaviors for the determination of water content in organic solvents were investigated. The compound revealed a pronounced chromogenic behavior in response to the variation of water content in water miscible aprotic organic solvents of acetone, acetonitrile, THF, and dioxane. Significant red shifts and changes in absorption spectra allowed a ratiometric analysis of the signaling behavior. The chemosensing behaviors were particularly pronounced in water content in less than 10% that is suitable for the application of the compound as a probe for the determination of water content in binary aqueous organic solutions having lower water content.

$BaTiO_3/SrTiO_3$ and $PbTiO_3/PbZrO_3$ superlattice thin films were fabricated on $Pt/Ti/SiO_2/Si$ substrate by the pulsed laser deposition process. The morphologies and physical properties of deposited films were characterized by using X-ray diffractometer, HR-SEM, and Impedance Analyzer. XRD data and SEM images of the films indicate that each layer was well deposited alternatively in the superlattice structure. The dielectric constant of $BaTiO_3/SrTiO_3$ superlattice thin film was higher than that of individual $BaTiO_3$ or $SrTiO_3$ film. Same result was obtained in the $PbTiO_3/PbZrO_3$system. The dielectric constant of a superlattice film was getting higher as the number of layer is increased.

This study reports on the geometry optimizations and electronic structure calculations for methyl pyropheophorbide (MPPa), tropolonyl methyl pyropheophorbides (TMPPa, ITMPPa), and cationic tropolonyl methyl pyropheophorbides ($TMPPa^+{{\cdot}BF_4}^-,\;ITMPPa^+{{\cdot}BF_4}^-,\;TMPPa^+,\;and\;ITMPPa^+$) using Local Spin Density Approximation (LSDA/ 6-31G*) and the Restricted Hatree-Fock (RHF/6-31G*) level theory. From the calculated results, we found that substituted cationic tropolonyl groups have larger structural effects than those of substituted neutral tropolonyl groups. The order of structural change effects is $ITMPPa^+ > ITMPPa^+{{\cdot}BF_4}^-$ > ITMPPa, as a result of the isopropyl group. Because it is an electron-releasing group, the substituted isopropyl group electronic effect on a 3-position tropolone increases the Highest Occupied Molecular Orbital and Lowest Unoccupied Molecular Orbital (HOMO-LUMO) energy gap. It was constituted that the larger the cationic characters of these photosensitizers, the smaller the HOMOLUMO band gaps are. The orbital energies of the cationic systems and the ions are stronger than those of a neutral system because of a strong electrostatic interaction. However, this stabilization of orbital energies are counteracted by the distortion of chlorin macrocycle, which results in a large destabilization of chlorin-based compound HOMOs and smaller destabilization of LUMOs as shown in TMPPa (ITMPPa), $TMPPa^+{{\cdot}BF_4}^- (ITMPPa^+{{\cdot}BF_4}^-),\;and\;TMPPa^+\;(ITMPPa^+)$ of Figure 6 and Table 6-7. These results are in reasonable agreement with normal-coordinate structural decomposition (NSD) results. The HOMO-LUMO gap is an important factor to consider in the development of photodynamic therapy (PDT).

Second-order rate constants ($k_N$) have been measured for nucleophilic substitution reactions of S-4-nitrophenyl thiobenzoate with a series of alicyclic secondary amines in $H_2O$ containing 20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The Br$\phi$nsted-type plot exhibits a downward curvature, i.e., $\beta_{nuc}$ decreases from 0.94 to 0.34 as the amine basicity increases. The reactions in the aqueous DMSO have also been suggested to proceed through a zwitterionic tetrahedral intermediate (T${\pm}$) with change in the RDS on the basis of the curved Br$\phi$nsted-type plot. The reactions in the aqueous DMSO exhibit larger $k_N$ values than those in the aqueous EtOH. The macroscopic rate constants ($k_N$) for the reactions in the two solvent systems have been dissected into the microscopic rate constants ($k_1\;and\;k_2/k_{-1}$ ratio) to investigate effect of medium on reactivity in the microscopic level. It has been found that the $k_2/k_{-1}$ ratios are similar for the reactions in the two solvent systems, while $k_1$ values are larger for the reactions in 20 mol % DMSO than for those in 44 wt % EtOH, indicating that the larger $k_1$ is mainly responsible for the larger $k_N$. It has been suggested that the transition state is more stabilized in 20 mol % DMSO through mutual polarizability interaction than in 44 wt % EtOH through H-bonding interaction.

$TiO_2$ doped with $Er^{3+\;and\;Yb^{3+}$ was used for fabricating a scattering layer and a nano-crystalline $TiO_2$ electrode layer to be used in dye-sensitized solar cells. The material was prepared using a new sol-gel combustion hybrid method with acetylene black as fuel. The $Er^{3+}$-$Yb^{3+}$ co-doped titanium oxide powder synthesized at 700oC had embossed structure morphology with a size between 27 to 54 nm that agglomerated to produce micron size particles, as observed by the scanning electron micrographs. The XRD patterns showed that the $Er^{3+}$-$Yb^{3+}$ co-doped titanium oxide had an amorphous structure, while using the same method without doping $Er^{3+}\;or\;Yb^{3+},\;TiO_2$ was obtained in the crystallite form with thea dominance of rutile phase. Fabricating a bilayer structure consisting of nano-crystalline $TiO_2$ and the synthesized $Er^{3+}$-$Yb^{3+}$ co-doped titanium oxide showed better scattering property, with an overall increase of 15.6% in efficiency of the solar cell with respect to a single nano-crystalline $TiO_2$ layer.