A rapid and inexpensive method was developed for the determination of trace silver in geological samples by using sulfhydryl cotton coupled with ICP-MS. The interferences such as $^{90}Zr$, $^{92}Mo$ and $^{93}Nb$ on silver were investigated in detail. Sulfhydryl cotton was found to be an effective adsorbent for separation of interferences for Ag in the solutions. Excellent agreements with the certified values were obtained for all the certified reference materials. The memory effects of Ag by ICP-MS were examined by using different agents, including water, nitric acid, and HCl-thiourea to all standards/samples. The agents also acted as cleansing solutions. A combination of HCl with thiourea gave the minimum memory effect. For comparison of results, a proposed Chinese Geology Survey procedure DC-ARC-AES and a direct determination pretreatment method of ICP-MS (water bath- auqa regia digestion) were studied. Under optimal conditions, the detection limits of our method for $^{107}Ag$ and $^{109}Ag$ were 1.2 ng/g and 1.3 ng/g, which offered much better accuracy for some difficult analysis geological samples such as GBW07604, GBW07605.

A series of 2,4,6-tripyridyl pyridines were synthesized, and evaluated for their antitumor cytotoxicity, topoisomerase I and II inhibitory activity. From the eighteen prepared compounds, compounds 10-12 have shown better or similar cytotoxicity against several human cancer cell lines as compared to 2,2':6',2"-terpyridine and doxorubicin. Especially, compound 10 exhibited the most potent cytotoxicity better than positive controls. Structure-activity relationship study indicated that 2,2':6',2"-terpyridine skeleton has an important role in displaying significant cytotoxicity against several human cancer cell lines.

Nano-scaled metal oxides have been attractive materials for sensors, photocatalysis, and dye-sensitization for solar cells. We report the controlled synthesis and characterization of single crystalline $TiO_2$ nanowires via a catalyst-assisted vapor-liquid-solid (VLS) and vapor-solid (VS) growth mechanism during TiO powder evaporation. Scanning electron microscope (SEM) and transmission electron microscope (TEM) studies show that as grown $TiO_2$ materials are one-dimensional (1D) nano-structures with a single crystalline rutile phase. Also, energy-dispersive X-ray (EDX) spectroscopy indicates the presence of both Ti and O with a Ti/O atomic ratio of 1 to 2. Various morphologies of single crystalline $TiO_2$ nano-structures are realized by controlling the growth temperature and flow rate of carrier gas. Large amount of reactant evaporated at high temperature and high flow rate is crucial to the morphology change of $TiO_2$ nanowire.

This paper reports a methodology for preparing close-packed two dimensional gold nanoprism films and hexagonal nanoplate films at a hexane/water interface. By controlling the concentration of linker molecules in the hexane layer and the temperature of the colloid solution, highly ordered close-packed nanoplate arrays can be fabricated. These films were investigated to compare their corresponding surface enhanced Raman scattering (SERS) efficiencies. It was demonstrated that the Au nanoprism films resulted in a stronger SERS enhancement than the Au hexagonal nanoplate films. The difference in the SERS enhancement is attributed to the film array difference, demonstrating that Au nanoprism films have a higher line contact density than their Au hexagonal analogues.

Silver nanoparticle (Ag-NPs)-immobilized and amine-functionalized carbon nanotubes (MWCNTs), MWCNT-Ag-$NH_2$, were easily prepared in order to develop an efficient delivery system of biomolecules without complicated processes of manufacture. For this, Ag-NPs-immobilized MWCNTs, MWCNT-Ag, were initially prepared in order to create large surface area to enable more efficient linkage with guest-molecules using pristine MWCNTs. The Ag-NPs on MWCNTs were further positively functionalized with 2-aminoethanthiol to allow ionic linkage with biomolecules. Ultimately, the positively charged delivery system proved to be highly effective for the binding capacity of bovine serum albumin (BSA) as a negatively charged model protein, when compared to that of lysozyme used as a positively charged model protein. The releasing profile of BSA was observed in almost linear pattern for about two weeks in a saline solution. This study demonstrated the potential usefulness of the pristine MWCNTs in conjunction with Ag-NPs for the selective delivery of many (negatively or positively) charged biomolecules including proteins and genes.

The reactions of O,O-diethyl Z-S-aryl phosphorothioates with X-benzylamines are kinetically investigated in dimethyl sulfoxide at $85.0^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}x$) and Br$\ddot{o}$nsted [log $k_2$ vs $pK_a$(X)] plots are biphasic concave downwards for substituent X variations in the nucleophiles with a break point at X = H. The signs of the cross-interaction constants (${\rho}xz$) are positive for both the strongly and weakly basic nucleophiles. Considerably great magnitude of ${\rho}xz$ (= 6.56) value is observed with the weakly basic nucleophiles, while ${\rho}xz$ = 0.91 with the strongly basic nucleophiles. Proposed reaction mechanism is a stepwise process with a rate-limiting leaving group expulsion from the intermediate involving a backside nucleophilic attack with the strongly basic nucleophiles and a frontside attack with the weakly basic nucleophiles. The kinetic results are compared with those of the benzylaminolysis of O,O-diphenyl Z-S-aryl phosphorothioates.

A novel poly(vinylchloride)-based membrane sensor using $N^1$,$N^3$,$N^5$-tris(2-(2,3-dihydroxybenzylamino)-ethyl)cyclohexane-1,3,5-tricarboxamide (CYCOENCAT, L) as ionophore has been prepared and explored as $Fe^{3+}$ selective electrode. The membrane electrode composed of ionophore, poly(vinylchloride) and o-nitropheyloctyl ether in the optimum ratio 4:33:63 gave excellent potentiometric response characteristics, and displayed a linear log[$Fe^{3+}$] versus EMF response over a wide concentration range of $1.0{\times}10^{-5}-1.0{\times}10^{-1}$ M with super nernstian slope of 28.0 mV/decade and the detection limit of $8.0{\times}10^{-6}$ M. The proposed ion selective electrode showed fast response time (< 15 s), wide pH range (3.0-7.0), high non-aqueous tolerance (up to 20%) and adequate long life time (120 days). It also exhibited very good selectivity for $Fe^{3+}$ relative to a wide variety of alkali, alkaline earth, transition and heavy metal ions. Further, the analytical applicability of the sensor was tested as an indicator electrode in the potentiometric titration of $Fe^{3+}$ with EDTA.

A simple and rapid analytical method was developed for the determination of eight isoquinoline alkaloids in Corydalis species. Eight isoquinoline alkaloids, including 2 aporphine alkaloids (isocorydine and glaucine) and 6 protoberberine alkaloids (coptisine, palmatine, berberine, canadine, corydaline, and tetrahydrocoptisine) were used as chemical markers which have a various biological activity and determined for quality control of Corydalis (C.) species (C. ternata, C. yanhusuo, and C. decumbens). To evaluate the quality of these herbal medicines, LC chromatographic separation of alkaloids were preferentially investigated on reversed-phase C18 column with pH variation and composition of mobile phase. In addition, the separation of these alkaloids in herbal extracts was found to be significantly affected on mobile phase composition using gradient elution. Especially for C. yanhusuo extract, berberine was seriously interfered with other alkaloid extracted from sample matrix when mobile phase composition was not optimized. As results, these compounds were successfully separated within 28 min using 10 mM ammonium acetate containing 0.2% triethylamine (adjusted at pH 5.0) as a mobile phase with gradient elution. On the basis of optimized HPLC conditions, 23 different Corydalis species samples were analyzed for the determination of alkaloid levels. In addition, principal component analysis (PCA) combined with the chromatographic data could be successfully classified the different geographic origin samples.

A novel sampling method of the headspace poly(dimethylsiloxane) (PDMS) mini-disk extraction (HS-PDE) was developed, optimized, validated and applied for the GC/MS analysis of spices flavors. A prototype PDMS mini-disk (8 mm outer diameter, 0.157 mm thickness, 9.4 mg weight) has been designed and fabricated as a sorption device. The technique uses a small PDMS mini-disk and very small volume of organic solvent and less sample size than the solvent extraction. This new HS-PDE method is very simple to use, inexpensive, rapid, requires less labor. Linearities of calibration curves for ${\alpha}$-pinene, ${\beta}$-pinene, limonene and ${\gamma}$-terpinene by HS-PDE combined with GC/MS were excellent having $r^2$ values greater than 0.99 at the dynamic range of 6.06~3500 ng/mL. The limit of detection (LOD) and the limit of quantitation (LOQ) showed very low values. This method exhibited good precision and accuracy. The overall extraction efficiency of this method was evaluated by using partition coefficients ($K_p$) and concentration factors (CF) for several characteristic components from nutmeg and mace. Partition coefficients were in the range from $2.04{\times}10^4$ to $4.42{\times}10^5$, while CF values were 0.88-15.03. HS-PDE was applied successfully for the analysis of flavors compositions from nutmeg, mace and cumin. The HS-PDE method is a very promising sampling technique for the characterization of volatile flavors.

CdS nanoparticles (NPs) were synthesized in an aqueous phase in order to investigate their spectral behaviors as efficient fluorescence resonance energy transfer (FRET) donors for various organic dye acceptors. Our prepared CdS NPs exhibiting strong and broad emission spectra between 480-520 nm were able to transfer energy in a wide wavelength region from green to red fluorescence dyes. Rhodamine 6G (Rh6G), rhodamine B (RhB), and sulforhodamine 101 acid (Texas red) were tested as acceptors of the energy transfer from the CdS NPs. The three dyes and synthesized CdS NPs exhibited good FRET behaviors as acceptors and donors, respectively. Energy transfers from the CdS NPs and organic Cy3 dye were compared to the same acceptor Texas red dye at different concentrations. Our prepared CdS NPs appeared to exhibit better FRET behaviors comparable to those of the Cy3 dye. These CdS NPs in an aqueous solution may be efficient FRET donors for various organic dyes in a wide wavelength range between green and red colors.

A density functional theory method with the local basis set was employed to perform slab calculations to study thiolate-induced surface reconstruction structures of butylthiolates (ButS) with c($4{\times}2$) superlattice of the Au(111) surface. The slab calculations indicate that the most stable adsorption structure is the ButS-Au (adatom)-SBut complex form, which is in good agreement with the reported experiments and theoretical results for thiolates with shorter alkyl chains. The cis form of ButS-Au (adatom)-SBut motifs is preferred by 0.11 eV with respect to the trans form, and by 0.15 eV over the mixed cis-trans configurations due to the steric hindrance between adjacent butyl groups. It appears that the motif of Au adatom on the Au(111) surface is favored even for butylthiolate.

This paper presents a stable isotope chemistry of bone collagen and carbonate. Bone carbonate has the potential to provide additional isotopic information. However, it remains controversial as to whether archaeological bone carbonate retains its original biogenic signature. I used a novel application of bone density fractionation and checked the integrity of ${\delta}^{13}C_{apa}$ values using radiocarbon dating. Diagenesis in archaeological bone carbonate still remains to be resolved in extracting biogenic information. The combined use of bone density fractionation and differential dissolution method shows a large shift in the ${\delta}^{13}C_{apa}$ values. Although ${\delta}^{13}C_{apa}$ values are improved in lighter density fractions, a large percentage of contamination in bone carbonate was reported via $^{14}C$ dating compared to that noted with bone collagen.

Fr$\acute{e}$chet-type dendritic benzaldehydes were efficiently synthesized using 3,5-dihydroxybenzaldehyde as an aldehyde focal point functionalized unit by adding a generation to the existing dendron or direct oxidation of Fr$\acute{e}$chet-type dendritic benzyl alcohols. These dendritic benzaldehydes were applied for the construction of dendrimers containing secondary amines as connectors via Staudinger/aza-Wittig Reactions with ${\alpha}$,${\alpha}'$,-diazidop-xylene core.

The effect of a dense $TiO_2$ blocking layer prepared using the sol-gel method on the performance of dye-sensitized solar cells was studied. The blocking layer formed directly on the working electrode, separated it from the electrolyte, and prevented the back transfer of electrons from the electrode to the electrolyte. The dyesensitized solar cells were prepared with a working electrode of fluorine-doped tin oxide glass coated with a blocking layer of dense $TiO_2$, a dye-attached mesoporous $TiO_2$ film, and a nano-gel electrolyte, and a counter electrode of Pt-deposited FTO glass. The gel processing conditions and heat treatment temperature for blocking layer formation affected the morphology and performance of the cells, and their optimal values were determined. The introduction of the blocking layer increased the conversion efficiency of the cell by 7.37% for the cell without a blocking layer to 8.55% for the cell with a dense $TiO_2$ blocking layer, under standard illumination conditions. The short-circuit current density ($J_{sc}$) and open-circuit voltage ($V_{oc}$) also were increased by the addition of a dense $TiO_2$ blocking layer.

We have performed quantum mechanical calculations to study the geometries and binding energies of biologically important, cyclic hydrogen-bonded complexes, such as formic acid + $H_2O$, formamidine + $H_2O$, formamide + $H_2O$, formic acid dimer, formamidine dimer, formamide dimer, formic acid + formamide, formic acid + formamidine, formamide + formamidine, and barrier heights for the double proton transfer in these complexes. Various ab initio, density functional theory, multilevel methods have been used. Geometries and energies depend very much on the level of theory. In particular, the transition state symmetry of the proton transfer in formamidine dimer varies greatly depending on the level of theory, so very high level of theory must be used to get any reasonable results.

Multiconfigurational wavefunctions were adopted to study structural isomers, their isomerization reactions and excited states of $HN_3$. In addition to the known linear isomer, two new structural isomers were found. The three isomers can be classified as sp, $sp^2$ and $sp^3$ hybridized species, respectively. The sp3 hybridized species turned out to be the second most stable. Large reaction barriers among these species prevent thermal isomerizations. A low-lying $^3A'$ exists with a relative energy of 13.5 kcal/mol. Dramatic re-hybridization and bond elongation was found in the first excited $^1A"$.

Multinuclear solid-state nuclear magnetic resonance (NMR) experiments were performed to investigate the local structure changes of nanoporous silica during hydrothermal treatment and surface modification with 3-aminopropyltriethoxysilane (3-APTES). The nanoporous silica was prepared by sol-gel polymerization using inexpensive sodium silicate as a silica precursor. Using $^1H$ magic angle spinning (MAS) NMR spectra, the hydroxyl groups, which play an important role in surface reactions, were probed. Various silicon sites such as $Q^2$, $Q^3$, $Q^4$, $T^2$, and $T^3$ were identified with $^{29}Si$ cross polarization (CP) MAS NMR spectra and quantified with $^{29}Si$ MAS NMR spectra. The results indicated that about 25% of the silica surface was modified. $^1H$ and $^{29}Si$ NMR data proved that the hydrothermal treatment induced dehydration and dehyroxylation. The $^{13}C$ CP MAS and $^1H$ MAS NMR spectra of 3-APTES attached on the surface of nanoporous silica revealed that the amines of the 3-aminopropyl groups were in the chemical state of ${NH_3}^+$ rather than $NH_2$.

Two new unusual soyasaponins named 6"-O-methyldehydrosoyasaponin I(7) and desglucosylsoyasaponin $A_1$ (10) along with eight known saponins, dehydrosoyasaponin IV (1), dehydrosoyasaponin III (= impatienoside A) (2), soyasaponin III (3), dehydrosoyasaponin II (= soyasaponin Bg) (4), soyasaponin II (5), dehydrosoyasaponin I (= soyasaponin Be) (6), soyasaponin I (8), and kudzusaponin $SA_3$ (9), were isolated as their methyl esters and identified from the liquid culture of G. applanatum. Their structures were determined by chemical and spectroscopic analyses including 1D- and 2D-NMR as well as by comparison of their spectroscopic data with those of the reported in literatures. Although dehydrosoyasaponin IV was identified by LC-MS/MS method from soy protein isolate, this is the first report of the isolation of this compound. Dehydrosoyasaponin III (2) and kudzusaponin $SA_3$ (9) were also isolated for the first time from soybean. The presence of soyasaponins in Ganoderma species seems to be unusual feature. Thus, we presumed that compounds 1-10 might all be derived from the defatted soybean flour which was added to the culture medium as a nitrogen source.

The hydrogenolysis of polymer-bound arenesulfonates by 2-propylmagnesium chloride was performed through reductive cleavage of the C-S bond in the presence of a nickel catalyst. The reaction underwent in the highest efficiency by adding 15 equiv of the nucleophile in two additions with $dppfNiCl_2$ in THF. Various unfunctionalized naphthalene, biphenyl, and stilbene derivatives were produced in good yields by the traceless sulfonate linker system at room temperature.

CO-tolerant PtMo/C alloy electrocatalyst was prepared by a colloidal method, and its electrocatalytic activity toward CO oxidation was investigated. Electrochemical study revealed that the alloy catalyst significantly enhanced catalytic activity toward the electro-oxidation of CO compared to Pt/C counterpart. Cyclic voltammetry suggested that Mo plays an important role in promoting CO electro-oxidation by facilitating the formation of active oxygen species. The effect of Mo on the electronic structure of Pt was investigated using X-ray absorption spectroscopy to elucidate the synergetic effect of alloying. Our in-depth spectroscopic analysis revealed that CO is less strongly adsorbed on PtMo/C catalyst than on Pt/C catalyst due to the modulation of the electronic structure of Pt d-band. Our investigation shows that the enhanced CO electrooxidation in PtMo alloy electrocatalyst is originated from two factors; one comes from the facile formation of active oxygen species, and the other from the weak interaction between Pt and CO.

Overexpression of P-glycoprotein (Pgp) is associated with multidrug resistance (MDR) of tumor cells to a number of chemotherapeutic drugs. Pgp inhibitors have been shown to effectively reverse Pgp-mediated MDR. We prepared a series of phenoxy-N-phenylacetamide derivatives and tested for their ability to inhibit Pgp as potential MDR reversing agents, using a Pgp over-expressing MCF-7/ADR cell line. Some of the synthesized compounds exhibited moderate to potent reversal activity. Of note, compound 4o showed a 3.0-fold increased inhibition compared with verapamil, a well-known Pgp inhibitor. In addition, co-treatment of the representative compound 4o and a substrate anticancer agent doxorubicin resulted in a remarkable increase in doxorubicin's antitumor effect and inhibition of DNA synthesis in the MCF-7/ADR cell line. Taken together, these findings suggest that compound 4o could be a useful lead for development of a novel Pgp inhibitor for treatment of MDR.

Fusarium oxysporum, an important pathogen that mainly causes vascular or fusarium wilt disease which leads to economic loss. Disruption of gene encoding a heterotrimeric G-protein-${\beta}$-subunit (FGB1), led to decreased intracellular cAMP levels, reduced pathogenicity, colony morphology, and germination. The plant defense protein, Nicotiana alata defensin (NaD1) displays potent antifungal activity against a variety of agronomically important filamentous fungi. In this paper, we performed a molecular modeling and docking studies to find vital amino acids which can interact with various antifungal compounds using Discovery Studio v2.5 and GRAMMX, respectively. The docking results from FGB1-NaD1 and FGB1-antifungal complexes, revealed the vital amino acids such as His64, Trp65, Ser194, Leu195, Gln237, Phe238, Val324 and Asn326, and suggested that the anidulafungin is a the good antifungal compound.The predicted interaction can greatly assist in understanding structural insights for studying the pathogen and host-component interactions.

The electrochemical properties of lithium-sulfur batteries with binary electrolytes based on DME and DOL, TEGDME and DOL mixed solvent containing $LiClO_4$, LiTFSI, and LiTF salts were investigated. The ionic conductivity of 1M LiTFSI and $LiClO_4$ electrolytes based on TEGDME and DOL increased as the volume ratio of DOL solvent increased, because DOL effectively reduces the viscosity of the above electrolytes medium under the same salts concentration. The first discharge capacity of lithium-sulfur batteries in the DME and DOL-based electrolyte followed this order: LiTFSI (1,000 mAh/g) > LiTF (850 mAh/g) > $LiClO_4$ (750 mAh/g). In case of the electrolyte based on TEGDME and DOL, the first discharge capacity of batteries followed this order: $LiClO_4$ (1,030 mAh/g) > LiTF (770 mAh/g) > LiTFSI (750 mAh/g). The cyclic efficiency of lithium-sulfur batteries at 1M $LiClO_4$ electrolytes is higher than that of batteries at other lithium salts-based electrolytes. Lithium-sulfur battery showed discharge capacity of 550 mAh/g until 20 cycles at all electrolytes based on DME and DOL solvent. By contrast, the discharge capacity of batteries was about 450 mAh/g at 1M LiTFSI and LiTF electrolytes based on TEGDME and DOL solvent after 20 cycles.

Ion exchange experiments of molybdenum(VI) from strong HCl and $H_2SO_4$ solution have been done to investigate the existence of anionic complexes. The concentration of HCl and $H_2SO_4$was changed from 1 to 9 M. From the data on the complex formation of molybdenum in aqueous solution, a new distribution diagram of Mo(VI) was constructed in the pH range from zero to 10. AG 1 X-8, an anion exchange resin, and Diphonix, a cation exchange resin were used in the loading experiments. Ion exchange results indicate that anionic complexes of Mo(VI) begins to form from 3 M HCl and 1 M $H_2SO_4$ solution and the tendency to form anionic complexes is stronger in HCl than in $H_2SO_4$ solution. Our results can be utilized in the analysis of Mo(VI) in strong acid solution and in the design of a process to separate Mo(VI).

Poly(N,N'-Dichloro-N-ethyl-benzene-1,3-disulfonamide) (PCBS) and N,N,N',N'-Tetrachlorobenzene-1,3-disulfonamide (TCBDA) were found to be a mild and efficient reagent for the direct oxidative conversion of sulfur compounds to the corresponding arenesulfonyl chlorides in good to excellent yields through the oxidative chlorination. The overall process is simple, practical, and it provides convenient access to a variety of aryl or heteroarylsulfonyl chlorides. The mild reaction conditions and the broad substrate scope render this method attractive, and complementary to existing syntheses of aryl or heteroarylsulfonyl chlorides.

The single-crystal structure of partially dehydrated partially $Mg^{2+}$-exchanged zeolite Y, ${\mid}Mg{30.5}Na_{14}(H_2O)_{2.5}{\mid}$ [$Si_{117}Al_{75}O_{384}$]-FAU per unit cell, ${\alpha}$ = 25.5060(1) ${\AA}$, dehydrated at 723 K and $1{\times}10^{-4}$ Pa, has been determined by single-crystal X-ray diffraction techniques in the cubic space group Fd$\bar{3}$ m at 100(1) K. The structure was refined using all intensities to the final error indices (using only the 561 reflections with $F_{\circ}$ > $4{\sigma}(F_{\circ})$) $R_1$ = 0.0377 (Based on F) and $R_2$ = 0.1032 (Based on $F^2$). About 30.5 $Mg^{2+}$ ions per unit cell are found at four different crystallographic sites. The 14 $Mg^{2+}$ ions occupy at site I at the center of double 6-ring (Mg-O = 2.231(3) ${\AA}$, O-Mg-O = $89.15(11)^{\circ}$ and $90.85(11)^{\circ}$). Four $Mg^{2+}$ ions are found at site I' in the sodalite cavity; the $Mg^{2+}$ ions are recessed 1.22 ${\AA}$ into the sodalite cavity from their 3-oxygen plane (Mg-O = 2.20(3) ${\AA}$ and O-Mg-O = $92.3(14)^{\circ}$). Site II' positions (opposite single 6-rings in the sodalite cage) are occupied by 2.5 $Mg^{2+}$ ions, each coordinated to an $H_2O$ molecule (Mg-O = 2.187(20) ${\AA}$ and O-Mg-O = $114.2(16)^{\circ}$). The 10 $Mg^{2+}$ ions are nearly three-quarters filled at site II in the supercage, being recessed 0.12 ${\AA}$ into the supercage (Mg-O = 2.123(4) A and O-Mg-O = $119.70(19)^{\circ}$). About 14 $Na^+$ ions per unit cell are found at one crystallographic site; the $Na^+$ ions are located at site II in the supercage (Na-O = 2.234(7) ${\AA}$ and O-Mg-O = $110.5(4)^{\circ}$).

The conformation of a neuropeptide, substance P (SP), in isotropic (q = 0.5) acidic bicelles was investigated using two-dimensional NMR techniques. By the nuclear Overhauser effect (NOE) cross peaks between SP and long-chain lipid molecules SP was probed to bind on the flat surface of the disc-like bicelles. Structural analysis of NMR data indicated that the helical conformation of SP extended to the C-terminal region of Leu10 as well as in the mid-region from Pro4 to Phe8. As compared with the conformations of SP bound on the sodium dodecylsulfate (SDS) or the dodecylphosphocholine (DPC) micelles with curved surfaces, the surface curvature of the membrane mimics was found to be one of the major factors inducing the biologically relevant conformation of SP. The negative surface charge of the membrane is also a key factor inducing both the binding of SP on the membrane and its biologically active structure.

Silver nanoparticles coated with silica can be obtained by the reduction of $AgNO_3$ with hydrazine in the presence of NaOH-stabilized, active silicic acid (polysilicic acid). The size of the silver nanoparticles and the silica shell thicknesses were affected by varying the hydrazine content, the active silicic acid content and the experimental method (e.g. hydrothermal method). Typically, silver nanoparticles sized around 40 nm were aggregated, connected by silica. The presence of peaks centered around 400 nm in UV-vis spectra corresponds to the surface plasmon resonance of silver nanoparticles. The size of the aggregated silver nanoparticles increased with increasing hydrazine concentration. Under hydrothermal conditions at $150^{\circ}C$ the formation of individual silica particles was observed and the sizes of the silver nanoparticles were reduced. The hydrothermal treatment of silver nanoparticles at $180^{\circ}C$ gives a well-defined Ag@$SiO_2$ core-shell in aggregated silica sol particles. The absorption band observed at around 412 nm were red-shifted with respect to the uncoated silver nanoparticles (${\lambda}_{max}$ = 399 nm) due to the larger refractive index of silica compared to that of water. The formation of silver nanoparticles coated with silica is confirmed by UV-visible absorption spectra, transmission electron microscopy (TEM) and energy-dispersive spectroscopy (EDS) data.

Confined Pt and $CoFe_2O_4$ nanoparticles (NPs) in a mesoporous core/shell silica microsphere, Pt-$CoFe_2O_4$@meso-$SiO_2$, were prepared using a bi-functional linker molecule. A large number of Pt NPs in Pt-$CoFe_2O_4$@meso-$SiO_2$, ranging from 5 to 8 nm, are embedded into the shell and some of them are in close contact with $CoFe_2O_4$ NPs. The hydrogenation of cyclohexene over the Pt-$CoFe_2O_4$@meso-$SiO_2$ microsphere at $25^{\circ}C$ and 1 atm of $H_2$ yields cyclohexane as a major product. In addition, it gives oxygenated products. Control experiments with $^{18}O$-labelled water and acetone suggest that surface-bound oxygen atoms in $CoFe_2O_4$ are associated with the formation of the oxygenated products. This oxidation reaction is operative only if $CoFe_2O_4$ and Pt NPs are in close contact. The Pt-$CoFe_2O_4$@meso-$SiO_2$ catalyst is separated simply by a magnet, which can be re-used without affecting the catalytic efficiency.

$TiO_2$ nanoparticles were synthesized and characterized by SEM and XRD techniques. The $TiO_2$ nanoparticles were employed as a recyclable, inexpensive and efficient catalyst for the synthesis of substituted quinoxalines in high to excellent yields and in relatively short duration.

Biofilm formation is inevitable in a bioelectrochemical system in which microorganisms act as a sole biocatalyst. Cathodic biofilm (CBF) works as a double-edged sword in the performance of the air-cathode microbial fuel cells (MFCs). Proton and oxygen crossover through the CBF are limited by the robust structure of extracellular polymeric substances, composition of available constituents and environmental condition from which the biofilm is formed. The MFC performance in terms of power, current and coulombic efficiency is influenced by the nature and origin of CBF. Development of CBF from different ecological environment while keeping the same anode inoculums, contributes additional charge transfer resistance to the total internal resistance, with increase in coulombic efficiency at the expense of power reduction. This study demonstrates that MFC operation conditions need to be optimized on the choice of initial inoculum medium that leads to the biofilm formation on the air cathode.

The degree of self-assembly and the size variation of nanotubular structures in anodic titanium oxide prepared by the anodization of titanium in ethylene glycol containing 0.25 wt % $NH_4F$ at 40 V were investigated as a function of anodization time. We found that the degree of self-assembly and the size of the nanotubes were strongly dependent on thickness deviation and thus indirectly on anodization time, as the thickness deviation was caused by the dissolution of the topmost tubular structures at local areas during long anodization. A large deviation in thickness led to a large deviation in the size and number of nanotubes per unit area. The dissolution primarily occurred at the bottoms of the nanotubes ($D_{bottom}$) in the initial stage of anodization (up to 6 h), which led to the growth of nanotubes. Dissolution at the tops ($D_{top}$) was accompanied by $D_{bottom}$ after the formed structures contacted the electrolyte after 12 h, generating the thickness deviation. After extremely long anodization (here, 70 h), $D_{top}$ was the dominant mode due to increase in pH, meaning that there was insufficient driving force to overcome the size distribution of nanotubes at the bottom. Thus, the nanotube array became disorder in this regime.

We report a simple method for fabricating ZnO gas sensors via a sonochemical route and their $H_2$ gas sensing properties. Vertically aligned ZnO nanorod arrays as a sensing material were synthesized on a Pt-electrode patterned alumina substrate under ambient conditions. The advantage of the proposed method is a high speed of processing. The gas sensor based on ZnO nanorod arrays with large specific surface area showed a high response to $H_2$ and a detection limit of 70 ppm at $250^{\circ}C$. Also, their response and recovery time were relatively short and a complete regeneration was observed. A mechanism for sensing $H_2$ gas on the surface of ZnO nanorods is proposed.

Bismuth tribromide ($BiBr_3$) catalyzed Mannich-type reactions of N-acyliminium ions which generated in situ from N-benzyloxycarbonylamino p-tolylsulfones have been developed. In the presence of catalytic amount of $BiBr_3$, N-benzyloxycarbonylamino p-tolylsulfones prepared from aromatic and aliphatic aldehydes reacted with silyl enol ether and silyl enol ester under mild reaction conditions to afford N-Cbz-protected ${\beta}$-amino ketones and N-Cbz-protected ${\beta}$-amino esters in moderate to good yield, respectively.

Kinetic studies on the reactions of Y-S-aryl phenyl phosphonochloridothioates with X-pyridines have been carried out in MeCN at $55.0^{\circ}C$. The Hammett and Bronsted plots for substituent X variations in the nucleophiles are biphasic concave upwards with a break point at X = H. The Hammett plots for substituent Y variations in the substrates are biphasic concave upwards with a break point at Y = H, and the sign of ${\rho}_Y$ is changed from unusual negative (${\rho}_Y$ < 0) with the weaker electrophiles to positive (${\rho}_Y$ > 0) with the stronger electrophiles. The stepwise mechanism is proposed on the basis of the ${\rho}_X$, ${\beta}_X$, and ${\rho}_{XY}$ values as follows: a ratelimiting leaving group departure from the intermediate involving a frontside attack and product-like TS for the stronger nucleophiles and weaker electrophiles; a rate-limiting leaving group departure from the intermediate involving a backside attack and product-like TS for the weaker nucleophiles and electrophiles; a rate-limiting bond formation involving a frontside attack for the stronger nucleophiles and electrophiles; a rate-limiting bond formation involving a backside attack for the weaker nucleophiles and stronger electrophiles. The substituent effects of X and Y on the pyridinolysis mechanisms of $R_1R_2P$(=S)Cl-type substrates are discussed.