A new biologically active peptide with structural similarity to neuromedin N (NMN) has been isolated from extracts of visceral tissue of the African lungfish, Protopterus dolloi, using the rectum of the quail as the bioassay system. The primary structure of NMN-related peptide was established as Lys-Ala-Pro-Tyr-Ile-Leu-OH ([$Ala_2$]-NMN) and contained one substitution ($Ala_2\rightarrow$Ile) compared with the porcine NMN. [$Ala_2$]-NMN was found to have an excitatory effect on rectal muscle tissues of quail (Coturnix japonica), newt (Cynops pyrrhogaster) and black bass (Micropterus sulmoides). The threshold concentration of [Ala2]-NMN for contraction of C. japonica muscle was found to be approximately $10^-11$M. [$Ala_2$]-NMN showed contractile activities in the following order: C. japonica > C. pyrrhogaster > M. sulmoides. The identification of [Ala2]-NMN provides evidence that NMN family, hitherto confined to mammals, has a widespread occurrence in lungfish.

The optimized structures and complexation energies of bis(18-crown-6-ether) analogue (2) of Trgers base (1) with a series of primary alkylbisammonium ions have been calculated by DFT B3LYP/6-31G(d,p) method. The calculated complexation efficiency (-142.84 kcal/mol) of 2 for butane-1,4-diylbisammonium guest is better than twice of the value (-61.40 kcal/mol) for butylammonium ion. The multiple hydrogen-bond abilities for the complexes are described as the function of the length of the alkyl substituents of the bisammonium guests with normal-alkyl chain [$-(CH_2)_{n-}$, n = 4-8]. The longer bisammonium guest shows the stronger hydrogen-bonding characterizations (the distance and the quasi-linear angle of the N-H…O) to the host 2 than the shorter bisammonium ions. These calculated results agree with the experimental data of the complexation of 2 with bisammonium salts ([$NH_3(CH_2)_nNH_3$] $Cl_2$).

3D-QSARs on the neuroblocking activities by 1-(6-chloro-3-pyridylmethyl)-2-nitroiminoimidazolidine analogues as agonist at the nicotinic acetylcholine receptor (nAChR) were studied quantitatively using CoMFA and CoMSIA methodologies. The statistical results of CoMFA (A5: $r^2\;_{cv.}\;=\;0.707\;&\;r^2\;_{ncv.}$= 0.986) and CoMSIA model (A3: $r^2\;_{cv.}$ = 0.715 & $r^2\;_{ncv.}$ = 0.961) showed the best predictability and fitness for neuroblocking activity based on the cross-validated value and non-cross validated value. The steric and H-bond acceptor nature of a compound were essential for high activity. The study on 3D-QSARs between substrate molecules and their neuroblocking activities appears to be an useful approach for designing better neuroblocking drug development.

The dinuclear tetraazadiphenol macrocyclic nickel(II) complexes [$Ni_2$([20]-DCHDC)]$Cl_2$ (I), [$Ni_2$([20]-DCHDC)]$(ClO_4)_2{\cdot}2CH_3CN $ (II(b)) and [$Ni_2$([20]-DCHDC)$(NCS)_2$] (III) {$H_2$[20]-DCHDC = 14,29-dimethyl-3,10,18,25-tetraazapentacyclo-[25,3,1,$0^{4,9}$,$1^{12,16}$,$0^{19,24}$]ditriacontane-2,10,12,14,16(32),17,27(31), 28,30-decane-31,32-diol} have been synthesized by self-assembly and characterized by elemental analyses, conductances, FT-IR and FAB-MS spectra, and single crystal X-ray diffraction. The crystal structure of II(b) is determined. It crystallizes in the monoclinic space group P2(1)/c. The coordination geometries around Ni(II) ions in I and II(b) are identical and square planes. In complex III each Ni(II) ion is coordinated to $N_2O_2$ plane from the macrocycle and N atoms of NCS- ions occupying the axial positions, forming a square pyramidal geometry. The nonbonded Ni…Ni intermetallic separation in the complex II(b) is 2.8078(10) $\AA$. The FAB mass spectra of I, II and III display major fragments at m/z 635.1, 699.4 and 662.4 corresponding to [$Ni_2$([20]-DCHDC)(Cl + 2H)]$^+$, [$Ni_2$([20]-DCHDC)$(ClO_4\;+\;2H)]^+$ and [$Ni_2$([20]-DCHDC)(NCS) + 6H]$^+$, respectively.

This study explores and interprets in a new way the complex solvent and the temperature dependence of the NMR shifts for the N-$CH_2$ protons in tris(N,N-diethyldithiocarbamato) iron(III) in acetone, benzene, carbon disulfide, chloroform, dimethylformamide and pyridine. The NMR shifts are interpreted in terms of the Fermi contact interaction and the dipolar term from the multipole expansion of the interaction of the electron orbital angular momentum and the electron spin dipolar-nuclear spin angular momentum. This analysis yields a direct measure of the effect of the solvent system on the environment of the transition metal ion. The results are analysed in terms of the crystal field environment of the transition metal ion with contributions from (a) the dithiocarbamate ligand (b) the solvent molecules and (c) the interaction of the effective dipole moment of the polar solvent molecule with the transition metal ion complex.

A solvent sublation using salphen as a ligand was studied and applied for the determination of trace Ni(II), Co(II) and Cu(II) in water samples. The fundamental study was investigated by a solvent extraction process because the solvent sublation was done by extracting the floated analytes into an organic solvent from the aqueous solution. The salphen complexes of Ni(II), Co(II) and Cu(II) ions were formed in an alkaline solution of more than pH 8 and then they were extracted into m-xylene. It was known that the each metallic ion formed 1 : 1 complex with the salphen and the logarithmic values of extraction constants for the complexes were 3.3 5.1 as an average value. Based on the preliminary study, the procedure was fixed for the separation and concentration of the analytes in samples. Various conditions such as the pH of solutions, the influence of $NaClO_4$, the bubbling rate and time of $N_2$ gas, and the type of organic solvent were optimized. The metal-salphen complexes could be extracted into m-xylene from the solution of more than pH 8, but the pH could be shifted to acidic solution of pH 6 by the addition of $NaClO_4$. In addition, the solvent sublation efficiency of the analytes was increased by adding $NaClO_4$. The recovery of 97-115% was obtained in the spiked samples in which given amounts of 0.3 mg/L Ni(II), 0.8 mg/L Co(II) and 0.04 mg/L Cu(II) were added.

The application of poly(Co(II)-(1,8-diaminonaphthalene))(poly(Co-DAN)) and poly(1,8-diaminonaphthalene) (Poly(1,8-DAN)) to the electrocatalytic reduction of molecular oxygen was investigated, which were electrochemically grown by the potential cycling method on the glassy carbon electrodes. The reduction of oxygen at the polymer and its metal complex polymer coated electrodes were irreversible and diffusion controlled. The Poly(1,8-DAN) and Poly(Co-DAN) films revealed the potential shifts for the oxygen reduction to 30 mV and 110 mV, respectively, in an aqueous solution, compared with that of the bare electrode. Hydrodynamic voltammetry with a rotating ring-disk electrode showed that Poly(1,8-DAN) and Poly(Co-DAN) coated electrodes converted respectively 84% and 22% of $O_2$ to $H_2O$ via a four electron reduction pathway.

A new liquid chromatographic chiral stationary phase based on (2S,3S)-O,O'-bis-(10-undecenoyl)-N,N'-bis-(3,5-dinitrobenzoyl)-2,3-diamino-1,4-butandiol was prepared starting from (2R,3R)-1,4-bis(benzyloxy)-2,3-butanediol. The new chiral stationary phase was applied to the resolution of racemic anilide derivatives of N-acetyl-a-amino acids, 1,1'-bi-2-naphthol and 3,3'-diaryl-1,1'-bi-2-naphthols. The CSP was also applied to the resolution of some chiral drugs including a diuretic, bendroflumethiazide, and non-steroidal anti-inflammatory agents such naproxen and alminoprofen. In every case, the chiral recognition efficiency of the new CSP was quite excellent.

A liquid chromatographic chiral stationary phase (CSP) based on (+)-(18-crown-6)-2,3,11,12-tetracarboxilic acid without extra free aminopropyl groups on silica surface has been demonstrated to be quite effective for the resolution of various $\beta$-amino acids. The retention factors ($k_1$) for the resolution of $\beta$-amino acids on the CSP were quite large and the large retention factors might be quite attractive along with the reasonable separation factors ($\alpha$) for preparative scale enantioselective chromatography. The large retention factors on the CSP were found to be reduced effectively by adding ammonium ion to mobile phase without sacrificing the chiral recognition efficiency of the CSP. Consequently, the CSP is also quite applicable for use in analytical enantioselective chromatography.

Cloud point extraction was used to extract mefenamic acid (MF) from human urine, and spectrofluorimetry and spectrophotometry were used to analyze extracted MF. The variables affecting extraction and phase separation, i.e. HCl and Triton X-114 concentration, temperature and time of equilibration, were optimized. Under the experimental conditions used the limit of detection for extraction of 25 mL of sample was 0.006 and 0.045 mg $L^{-1}$, with relative standard deviations of 2.52 and 1.45% (n = 5) for spectrofluorimetric or spectrophotometric methods, respectively. Good recoveries in the range of 95-107% were obtained for spiked samples. The proposed methods were applied to the determination of MF in human urine.

A novel kinetic method for determination of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ in ozone decomposition in water is described. In this study, potential interferences of $O_3$ and the hydroxyl radicals, $^{\cdot}OH_{(O3)}$, are suppressed by $HSO_3{^-}/SO_3{^{2-}}$. $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ formed in ozone decomposition reduces $Fe^{3+}$-EDTA into $Fe^{2+}$-EDTA and subsequently the well-known Fenton-like (FL) reaction of $H_2O_2$ and $Fe^{2+}$-EDTA produces the hydroxyl radicals, $^{\cdot}OH_{(FL)}$. Benzoic acid (BA) scavenges $^{\cdot}OH_{(FL)}$ to produce OHBA, which are analyzed by fluorescence detection (${\lambda}_{ex}=320nm$ and ${\lambda}_{ex}=400nm$). The concentration of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ in ozone decomposition has been determined by the novel kinetic method using the experimentally determined half-life ($t_{1/2}$). The steady-state concentration of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ is proportional to the $O_3$ concentration at a given pH. However, the steady-state concentration of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ in ozone decomposition is inversely proportional to pH values. This pH dependence is due to significant loss of $O_2{^{{\cdot}-}}$ by $O_3$ at higher pH conditions. The steady-state concentrations of $HO_2{^{\cdot}}/O_2{^{{\cdot}-}}$ are in the range of $2.49({\pm}0.10){\times}10^{-9}M(pH=4.17){\sim}3.01({\pm}0.07){\times}10^{-10}M(pH=7.59)$ at $[O_3]_o=60{\mu}M$.

We have introduced a new enantioselective receptor 1 by incorporation of chiral building blocks to the previously reported carboxylate selective receptor 2. Binding studies carried out using $^1H$ NMR revealed that the receptor 1 showed moderate enantioselectivity with a general preference for D-amino acids and a highest enantioselectivity for leucine among the amino acids we investigated.

The convergent synthesis of symmetric PAMAM-like dendrimers from azide-functionalized poly(amido- amine) (PAMAM) dendrons and two different multi-alkynes was investigated. The stitching method was based on the click chemistry protocol, i.e., the copper-catalyzed cycloaddition reaction between an alkyne and an azide.

The interaction between whey carrier protein $\beta$-lactoglobulin type A and B (BLG-A and -B) and 2,2'-bipyridin n-hexyl dithiocarbamato Pd(II) nitrate (BPHDC-Pd(II)), a new heavy metal complex designed for anticancer property, was investigated by fluorescence spectroscopy combined with chemometry and circular dichroism (CD) techniques. A strong fluorescence quenching reaction of BPHDC-Pd(II) to BLG-A and -B was observed. Hence, BPHDC-Pd(II) complex can be bound to both BLG-A and -B, and quench the fluorescence spectra of the proteins. The quenching constant was determined using the modified Stern-Volmer equation. The binding parameters were evaluated by fluorescence quenching method. The results of binding study provided evidences presence of two and three sets of binding sites on the BLG-B and -A, respectively, for BPHDC-Pd(II) complex. Using fluorescence spectroscopy and chemometry, the ability of BLG-A and -B to form an intermediate upon interaction with BPHDC-Pd(II) complex was assessed. CD studies displayed that under influence of different concentrations of BPHDC-Pd(II) complex, the regular secondary structure of BLG-B had no significant changes, whereas for BLG-A a transition from $\alpha$-helix to $\beta$-structure was appeared. The results for both of BLG-A and -B displayed that BPHDC-Pd(II) complex can induce a conformational transition from the native form to an intermediate state with a slightly opened conformation, which is detectable with chemometry analyses.

The L-Valinate anion coordinating zinc complex, [$Zn(val)_2(H-2O)$], was isolated and structurally characterized by single crystal X-ray crystallography. The crystal possess orthorhombic symmetry with a space group $P2_12_12_1$, Z = 4, and a = 7.4279(2)$\AA$, b = 9.4342(2)$\AA$, c =20.5862(7)$\AA$ respectively. The compound features a penta-coordinate zinc ion in which the two valine anion molecules are directly coordinating the central zinc metal ion via their N (amine) and O (carboxylate) atoms, and an additional coordination to zinc is made by water molecule (solvent) to form a distorted square pyramidal structure. In addition, further synthesis of the valine capped ZnS:Mn nanocrystal from the reaction of [$Zn(val)_2(H-2O)$] precursor with $Na_2S$ and 1.95 weight % of $Mn^{2+}$ dopant is described. Obtained valine capped nanocrystal was water dispersible and was optically characterized by UV-vis and solution PL spectroscopy. The solution PL spectrum for the valine capped ZnS:Mn nanocrystal showed an excitation peak at 280 nm and a very narrow emission peak at 558 nm respectively. The measured and calculated PL efficiency of the nanocrystal in water was 15.8%. The obtained powders were characterized by XRD, HR-TEM, and EDXS analyses. The particle size of the nanocrystal was also measured via a TEM image. The measured average particle size was 3.3 nm.

Imogolite which has chemical composition, $(HO)_3Al_2O_3SiOH$, was synthesized with orthosilicate acid and aluminium chloride at low pH solution. It has extremely large aspect ratio with an external diameter of 2nm and the length of a few micrometers. The high aspect ratio of the imogolite could make the material as the filler for the high strength fiber and as the wire for the electronic applications. Here, Imogolite that derives considerable microporosity from a nanometer-sized tubular structure has been modified with a conducting polymer, polypyrrole. Its bonding and wiring structure were confirmed by IR and TEM. The measured conductivity after modification with polypyrrole increased with polypyrrole thickness at various voltage conditions.

The general objective of the present study was to investigate the potential application of the UV spectroscopic method for determination of the polymeric additives present in papermaking fibrous stock solutions. The study also intended to establish the surface-chemical retention model associated with the adsorption kinetics of additives on fiber surfaces. Polyamide epichlorohydrin (PAE) wet strength resin and imidazolinium quaternary (IZQ) softening agents were selected to evaluate the analytical method. Concentrations of PAE and IZQ in solution were proportional to the UV absorption at 314 and 400 nm, respectively. The time-dependent behavior of polymeric additives obeyed a mono-molecular layer adsorption as characterized in Langmuir-type expression. The kinetic modeling for polymeric adsorption on fiber surfaces was based on a concept that polymeric adsorption on fiber surfaces has two distinguishable stages including initial dynamic adsorption phase and the final near-equilibrium state. The simulation model predicted not only the real-time additive adsorption behavior for polymeric additives at high accuracy once the kinetic parameters were determined, but showed a good agreement with the experimental data. The spectroscopic method examined on the PAE and IZQ adsorption study could potentially be considered as an effective tool for the wet-end retention control as applied to the paper industry.

The influence of solvent viscosity on conformational dynamics of the heme-pocket, a small vacant site near the binding site of myoglobin (Mb) and hemoglobin (Hb), and playing a functionally important role by serving as a station in ligand binding and escape, was studied by probing time-resolved vibrational spectra of CO photodissociated from MbCO and HbCO in $D_2O$, 75 wt% glycerol/$D_2O$, and trehalose at 283 K. Two absorption bands ($B_1$ and $B_2$) of the sample in viscous solvents, arising from CO in the heme pocket, are very similar to those in $D_2O$. Two bands in Mb and Hb under all three solvents exhibit very similar nonexponential spectral evolution ($B_1$ band; blue shifting and broadening, $B_2$ band; narrowing with a negligible shifting), suggesting that in the present experimental time window of 100 ps, the extents of the spectral shift and narrowing is much influenced neither by the viscosity of solvent nor by the quaternary contact of Hb. Spectral evolution can be described by a biexponential function with a fast universal time constant of 0.52 ps and a slow time constant ranging from 13 to 32 ps. For both proteins in all three solvents majority of spectral evolution occurs with the fast universal time constant. The magnitude of the slow rate in the spectral shift of B1 band decreases with increasing solvent viscosity, indicating that it is influenced by global conformational change which is retarded in viscous solvent, thereby serve as a reporter of global conformational change of heme proteins after deligation.

The present paper is focused on sorption concentration of silver (I) on some complex-forming ion exchangers in the initial thiocyanate form and subsequent determination of Ag(I) in the phase of anion exchanger AN-25 by diffuse reflectance spectroscopy. The sorption and kinetic characteristics of the sorbents were investigated. The apparent stability constants of thiocyanate silver complexes in the ion exchanger phase were calculated. The sorption-spectroscopic method is proposed for Ag(I) determination in aqueous solutions. The calibration curve is linear in the concentration range of 10-200 mg/L (sample volume is 10.0 mL) and the detection limit is 2 $\mu$g/mL. The presence of $Na^+,\;K^+,\;Mg^{2+}$ (macrocomponents) as well as of Ni (II), Co (II), Cu (II) do not hinder the determination of silver (I).

Hydrothermal reactions of $Ln(NO_3)_3{\cdot}5H_2O $ (Ln = Eu (1), Sm (2), Ho (3), Dy (4)) with 3,5-pyridinedicarboxylic acid (3,5-pdcH2) in the presence of 4,4'-bipyridine led to the formation of the 3-D Ln(III)-coordination polymers with a formula unit of $[Ln_2(3,5-pdc)_2(C_2O_4)(H_2O)_4]{\cdot}2H_2O$. These polymers contain a bridging oxalate ligand ($C_2O_4\;^2$). On the basis of GCMS study of the mother liquor remaining after the reaction, we proposed that the $C_2O_4\;^2$ formation proceeds in three steps: (1) Ln(III)-mediated decarboxylation of $3,5-pdcH_2$ to give $CO_2$, (2) the reduction of $CO_2$ to $CO_2\;^{\cdot}$ by the Ln(II) species, and (3) the reductive coupling of the two $CO_2\;^{\cdot}$ radicals to the oxalate ($C_2O_4\;^2$) ion. All polymers were structurally characterized by X-ray diffraction.

Two types of catalyst samples were prepared, one sulfated zirconia and the other silica doped sulfated zirconia. The acidity tests indicate that sulfated zirconia doped with silica has higher concentration and strength of acidic catalyst sites than undoped sulfated zirconia. The acidic surface sites have been characterized using FTIR, NMR, pyridine adsorption, TPD, XRD and nitrogen adsorption. Doping with silica increased the concentration of surface Lewis and Brfnsted acid sites and resulted in generation of proximate acid sites.The activity test indicates that doping sulfated zirconia with silica increases both the acidity and catalytic activity for liquid phase dehydration of methanol at 413-453 K. Methanol is sequentially dehydrated to dimethyl ether and ethylene over both catalysts. Significant amounts of propylene are also formed over the silica-doped catalyst, but not over the undoped catalyst.

We herein report a new analytical application of XPS to the identification of organic molecules in room temperature ionic liquid for the first time. An organic compound, propargylamine (1), produced in 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][$PF_6$]), which is one of the room temperature ionic liquids (RTILs), via $A^3$ coupling reaction, is characterized by means of x-ray photoelectron spectroscopy (XPS) rather than using conventional organic compound analysis techniques. There are four non-equivalent carbons in RTILs and 1 each. The ratios of normalized integrated areas of the deconvoluted binding energy of core electron of carbon (C1s) peaks are well matched to the number of carbons in those compounds. The binding energies of C1s of the featured carbons in 1, C4 (sp carbons in acetylene group) and C5 ($sp^2$ carbons in benzene ring), are assigned 286.2 and 285.4 eV, respectively. These results will be able to provide an important tool and a new strategy for the analysis of organic molecules

Electrochemical behaviors of acetaminophen at a muti-wall carbon nano-tube composite film modified glassy carbon electrode were investigated by cyclic voltammetry, linear sweep voltammetry and chronocoulometry. Compared with that obtained at the unmodified electrode, the peak currents were enhanced significantly, and the oxidation peak shifted towards more negative potential with the reduction peak shifted positively. The peak-to-peak separation turned narrow, and suggested that the reversibility was improved greatly. Experimental parameters, such as scan rate, pH and accumulation conditions were optimized. It was found that a maximum current response can be obtained at pH = 5.0 after accumulation at -0.50 V for 80 s. The oxidation peak current was found to be linearly related to acetaminophen concentration over the range of $5.0{\times}10^{-7}\;\sim\;1.0{\times}10^{-4}$ mol $L^{-1}$ with a detection limit of $5.0{\times}10^{-8} $mol $L^{-1}$. A convenient and sensitive electrochemical method was developed for the determination of acetaminophen in a commercial paracetamol oral solution. Its practical application demonstrated that it has good selectivity and high sensitivity.