This work assesses the potential of natural Analcime Zeolite as an adsorbent for preconcentration of lead (II) traces. Lead is quantitatively retained on 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol by column method with Analcime in the pH range of 5-6.5 and 2 mL $min^{?1}$ flow rate. Lead was removed from the column with 10.0 mL of 4 M hydrochloric acid and was determined by anodic stripping differential pulse voltammetry. 0.5ppb detection limit was obtained and linear dynamic range was 3 to $1.2{\times}10^5$ ppb in final solution with correlation coefficient of 0.999 and relative standard deviation of ${\pm}$ 1.2% (for eight replicate determination of 2.5 ${\mu}g\;mL^{?1}$ of lead). Various parameters such as the effect of pH, flow rate, instrumental conditions and interferences of some ions on the determination of lead have been studied in detail for optimization of conditions. The method was successfully applied for determination of lead in various samples.

Photodissociation dynamics of tert-butyl isocyanide at 193 nm has been investigated by measuring rotationally resolved laser induced fluorescence spectra of CN fragments that were exclusively produced in the ground electronic state. From the spectra, internal energies of CN and translational energy releases in the products were obtained. The dissociation takes place in the excited triplet states which are strongly repulsive along the dissociation coordinate via curve crossing from the initially prepared state.

The need for highly reliable methods for the determination of trace metals is recognized in analytical chemistry and environmental science. A method based on the cloud-point extraction (CPE) technique for the trace analysis of Pb and Cu in water samples is described in this study. The analytes in the initial aqueous solution are complexed with pyrogallol, and 0.1%(w/v) Triton X-114 is added as surfactant. Following phase separation at $50^{\circ}C$, based on the cloud point of the mixture and dilution of the surfactant-rich phase with acidified methanolic solution, the enriched analytes are determined by flame atomic absorption spectrometry. After optimization of the complexation and extraction conditions, the enrichment factors of Pb and Cu were found to be 72 and 85, respectively. Under optimum conditions, the preconcentration of 60 mL of samples in the presence of 0.1%(w/v) Triton X-114 permitted the detection of 0.4 ${\mu}gL^{?1}$ of Pb and 0.05 ${\mu}gL^{?1}$ of Cu. The proposed method was applied successfully to the determination of Pb and Cu in water samples.

A spectrophotometric and first derivative spectrophotometric method was developed in aquatic Tween 80 micellar solutions for selective determination of nickel without using any pre-separation step. 1-(2-Pyridylazo)-2-naphthol (PAN), as a sensitive chromogenic complexing agent formed a red-colored Ni(II)-PAN complex in Tween 80 media with satisfactory solubility and stability. Conditions such as pH, PAN concentration, type and concentration of micellizing agent were optimized. Molar absorptivity of Ni-PAN complex was found $4.62\;{\times}\;10^4L\;cm^{?1}\;mol^{?1}$ at 569 nm, under the optimum condition. Calibration graphs were derived by zero, first and second derivative spectrophotometry at maximum wavelengths of 569, 578 and 571 nm with linear ranges of 30-1800, 20-2500 and 30-2000 ng $mL^{?1}$ , respectively. Precision as standard deviation as well as accuracy as recovery percent were in the range of 1-20 ng $mL^{?1}$, and 93.3-103.3%, respectively, for the entire of the linear ranges. Spectrophotometric detection limit was 3 ng $mL^{?1}$ and effects of diverse ions on the first derivative determination of nickel were studied to investigate selectivity of the method. Interferences of cobalt and copper on the nickel determination were prevented using o-phenanthroline as masking agent. The recommended procedures were applied to the various synthetic and stainless steel alloys, tea leaves and human hair, with satisfactory results.

A simple and effective procedure for conversion of primary, secondary, allylic and benzylic alcohols into the corresponding iodides is described using $CeCl_3{\cdot}7H_2O/NaI\;over\;SiO_2$ under microwave irradiation. Benzylic alcohols are selectively converted in the presence of saturated alcohols into their corresponding benzylic iodides under these conditions.

Hypericin (1,3,4,6,8,13-hexahydroxy-10,11-dimethylphenanthro[1,10,9,8-opqra]perylene-7,14-dione), an antidepressant which is also known to be a potent protein kinase C (PKC) inhibitor was synthesized as a precursor for radioiodine labeling via two step reactions. Malignant glioma cells express higher PKC activity compared to untransformed glial cell. Here we report the synthesis and radioiodine labeling of hypericin as a potential brain tumor imaging radiopharmaceutical. The reference compound, 2-iodohypericin, and its radiolabelled analogues, 2-[$^{123}I$]iodohypericin and 2-[$^{124}I$]iodohypericin have been prepared by the reaction of hypericin with NaI or [$^{123}I$]NaI or [$^{124}I$]NaI. The labeling yield was 60-65% for each analogue and the optimal reaction time was 10 min. The purification and isolation of the labelled products were achieved by a reversed-phase HPLC.

The chemosenssor that consists of [$Zn_2$(1,3-bis[bis(2-pyridylmethyl)aminomethyl]benzene)]$^{4+}$ (receptor) and pyrecatechol violet (signaling unit) detects with naked eyes di- and tri-phosphates conjugated to nucleosides or in free forms. The blue color of the aqueous solution (pH 7.0) of the sensor turns to yellow upon exposing to the analytes.

The technique of an on-line preconcentration by the direct sulfide precipitation has been developed. Sn was homogeneously precipitated by sulfide, which was generated in situ from the hydrolysis of thioaceteamide. Precipitate was collected on a filter in the line and dissolved out instantaneously by KOH to be sent to an ICP. The enrichment factor was 4 with the sampling speed of 15/hr for 1.0 mL of sample. It was increased to more than 40 times when the sampling volume was increased to 10 mL with the sampling speed of 5/hr. $Sn^{2+}/Sn^{4+}$ could be separately determined with the on-line precipitation technique. The method was applied to the analysis of NIST SRM 1566 Oyster sample and yielded good agreement with the certified value.

Calculations are presented for phenol ?acetonitrile - $(water)_n$ (n = 1-3) clusters. We examine the nature of interactions in the mixed clusters by calculating and comparing the structures, relative energies and harmonic frequencies of isomers with different type of hydrogen bonding. The conformers exhibit quite different patterns in the shifts of the CN and OH stretching frequencies, depending on the type of hydrogen bonding. Cyclic hydrogen bonding among the water molecule(s), acetonitrile and phenolic OH proves very important in determining the relative stability. It is also shown that acetonitrile tends to bind to the OH group of phenol in low energy conformers.

The applicability of the combined nearly ideal binary solvent/Redlich-Kister (CNIBS/R-K) equation for correlation of various solvatochromic parameters (SP) with composition is shown employing 84 experimental data sets for aqueous and organic binary solvent systems at temperatures ranging 15 to $75^{\circ}C$. The model provides a simple computational model to correlate/predict different SP values in various binary solvent systems. In proposed equations, $MPD_s$ (mean percentage deviations) are between 0.0500% and 6.9591% in mixtures of dimethyl sulfoxide with 2-methylpropan-2-ol and benzene with 2-methylpropan-2-ol, respectively. Correlation of the calculated and experimental values of various SP give an equation with an overall mean percentage deviation (OMPD) of 1.1900, $R^2$ = 0.99692, s.e = 0.01223 and F = 341925.51. Approximately 70% of the calculated SP values have IPD (individual percentage deviation) lower than one and it is possible to predict unmeasured SP values by using only eight experimental data.

Three banana-shaped achiral compounds, 4-chloro-1,3-phenylene bis [4-{4-(undecenyloxy)phenyl imino-methyl} benzoate] derivatives, were synthesized with variation of a substituent (x=H, F, Cl); their antiferro-electric properties are described. The smectic mesophases, including a switchable chiral smectic C(Sm $C^{\ast}$) phase, were characterized by differential scanning calorimetry, polarizing optical microscopy, triangular wave method, and X-ray diffractometry. The presence of vinyl groups at the terminals of linear side wings in the banana-shaped achiral molecules induced a decrease in melting temperature and formation of the switchable Sm $C^{\ast}$ phase in the melt. The smectic phase having a lateral fluorine-substituent at 3-position of the Schiff's base moiety showed antiferroelctric switching, and the value of spontaneous polarization on reversal of an applied electric field was 250 nC/$cm^2$ .

The determination of uric acid in urine samples was studied by a chemiluminescence measurement using tris (2,2'-bipyridine)ruthenium(II)-octylphenylpolyglycolether [Ru$(bpy)_3^{2+}$ -OPE] system. The oxidized uric acid by Ce(IV) excited Ru$(bpy)_3^{2+}$ to emit a chemiluminescence in this system so that the intensity was stoichio-metrically dependent upon the concentration of uric acid. In a reaction cell, a luminescent reagent, oxidant, surfactant and sulfuric acid were flowed into and mixed with a taken sample. Experimental conditions were optimized to obtain the maximum intensity of chemiluminescence. Each reactant solution of more than the following concentration gave a good result: $2\;{\times}\;10^{?4}$ M Ru$(bpy)_3^{2+}$ , 0.01 M Ce(IV), 6% OPE, and 0.33 M $H_2SO_4$. Any interferences were not shown in this process by the investigation of concomitant constitutes such as albumin, creatine, lactic acid, glucose, urea, $Cl^?,\; Mg^{2+},\;Ca^{2+}$ and so on. The linearity of a calibration curve was good with r = 0.998, the relative standard deviation of the slope was 3.3% and the detection limit was 5.6ng/mL. The recoveries of 80 to 91% were obtained from the standard spiked samples. The values were little bit low, but this procedure could be considered to be reliable for the determination of trace uric acid in urine samples.

Polydisperse oligo(PO-b-EO) allyl ether siloxane surfactants were synthesized by the hydrosilylation reaction of OMTS with Allyl-oligo(PO-b-EO) series. The surface tension of siloxane surfactants increased with increasing the EO chain length while it decreased with increasing the PO ratio. However, the sedimentation time of the aqueous solution showed opposite trend to the surface tension data. Both the surface tension and sedimentation time of the aqueous solution containing inorganic electrolyte gradually decreased as the content of inorganic electrolyte increased because of the surface arrangement of surfactant molecules. However, they increased with an increase of pH values due to the hydrolysis of the siloxane backbone. The $C_p$ values tended to increase with the increase in the EO chain length and decrease of the PO ratio. It seems that intermolecular interaction between PO/EO block copolymer and water affects the variation of transition temperature.

The adsorption isotherms of N2 onto the metallic silver treated activated carbon fiber samples after acid treatment are Type I with a small amount of capillary condensation hysteresis. Increasing amount of acid treatment leads to a decrease in SBETs and external surface area. But, micropore volume and average pore diameter are presented in constant regular values with increasing amount of sulfuric acid treatment. SEM observes the surface morphology and crystal grown state of metal on the fiber surface. The results of EDX of Ag-activated carbon fiber pre-treated with acid show the spectra corresponding to almost all samples rich in silver with increasing the amount of acid treated. The FT-IR spectra of Ag-activated carbon fiber show that the acid pre-treatment is consequently associated with the homogeneous dispersion of metal with the increased surface acidity of the activated carbon fiber. The type and quality of oxygen groups are determined with Boehm titration method. From the those results, a positive influence of the acidic groups on the carbon fiber surface by acid treatment is also demonstrated by an increase in the contents of metallic silver with increasing of acidic groups.

Tyrosinase was covalently immobilized on platinum electrode according to the method we developed for laccase (Bull. Korean Chem. Soc. 2002, 23(7), 385) and p-chlorophenol, p-cresol, and phenol could be detected with sensitivities of 334, 139 and 122 nA/ ${\mu}M$ and the detection limits of 1.0, 2.0, and 2.5 ${\mu}M$, respectively. The response time ($t_{90\%}$) is 3 seconds for p-chlorophenol, and 5 seconds for p-cresol and phenol. The optimal pHs of the sensor are in the range of 5.0- 6.0. This sensor can tolerate at least 500 times repeated injections of p-chlorophenol with retaining 80% of initial activity. In case of tyrosinase and laccase co immobilized platinum electrode, the sensitivities are 560 nA/ ${\mu}M$ for p-phenylenediamine (PPD) and 195 nA/ ${\mu}M$ for p-chlorophenol, respectively. The sensitivity of the bi-enzyme sensor for PPD increases 70% compared to that of only laccase immobilized one, but the sensitivity for p-chlorophenol decreases 40% compared to that of only tyrosinase immobilized one. The sensitivity increase for the bi-enzyme sensor for PPD can be ascribed to the additional catalytic function of the co-immobilized tyrosinase. The sensitivity decrease for p-chlorophenol can be explained by the “blocking effect” of the co-immobilized laccase, which hinders the mass transport through the immobilized layer. If PPD was detected with the electrode that had been used for p-chlorophenol, the sensitivity decreased 20% compared to that of the electrode that had been used only for PPD. Similarly, if p-chlorophenol was detected with PPD detected electrode, the sensitivity also decreased 20%. The substrate-induced conformation changes of the enzymes in a confined layer may be responsible for the phenomena.

Novel naphthyl-containing biphenyl analogues were prepared by Suzki reaction for the chemiluminescent blue fluorophores. UV-Vis absorption, photoluminescence, chemiluminescence and CIE chromaticities were measured. The fluorophores displayed blue photoluminescence in solution with a maximum intensity around 378-415 nm. Sodium salicylate-catalyzed reaction of them with bis(2 carbopentyloxy-3,5,6-trichlorophenyl)-oxalate with hydrogen peroxide provided a strong chemiluminescent red light emission with wavelengths of 398-427 nm; these were similar to the photoluminescent spectra. The chemiluminescent intensity decayed exponentially and the glow of chemiluminescence, which was visible with naked eyes, was maintained for more than 4 h.

Holmium $\beta$ -diketonate complexes, Ho(hfa)$_3$(tme), has been prepared and characterized by IR, TGA, MS, and single-crystal X-ray analyses. This complex is air- and moisture-stable and most importantly has good volatility and thermal stability. Holmium atom binds to nine oxygen atoms, contributed by six oxygen atoms of three hfa ligands and three oxygen atoms of the tme ligand. The coordination polyhedron of Ho can be described as a distorted tricapped trigonal prism. Crystal data for $Ho(hfa)_3(tme)$; orthorhombic $P2_12_12_1$, a = 15.415(4), b = 13.17(2), c = 17.291(3) $\AA$, V = 3496(1) ${\AA}^3$.

The interaction of the antitumour agent doxorubicin with calf thymus DNA is investigated in an aqueous solution at a pH level of 6-7 with molar ratios of 1/10. A UV-resonance Raman spectroscopy and surface enhanced Raman spectroscopy are used to determine the doxorubicin binding sites and the structural variations of doxorubicin-DNA complexes in an aqueous solution. Doxorubicin intercalates with adenine and guanine via a hydrogen bond formation between the N7 positions of purine bases and the hydroxyl group of doxorubicin.

We have calculated the probability of HBr formation and energy disposal of the reaction exothermicity in HBr produced from the reaction of gas-phase bromine with highly covered chemisorbed hydrogen atoms on a Si (001)-(2 ${\times}$1) surface. The reaction probability is about 0.20 at gas temperature 1500 K and surface temperature 300 K. Raising the initial vibrational state of the adsorbate(H)-surface(Si) bond from the ground to v = 1, 2 and 3 states causes the vibrational, translational and rotational energies of the product HBr to increase equally. However, the vibrational and translational motions of product HBr share most of the reaction energy. Vibrational population of the HBr molecules produced from the ground state adsorbate-surface bond ($v_{HSi}$ =0) follows the Boltzmann distribution, but it deviates seriously from the Boltzmann distribution when the initial vibrational energy of the adsorbate-surface bond increases. When the vibration of the adsorbate-surface bond is in the ground state, the amount of energy dissipated into the surface is negative, while it becomes positive as vHSi increases. The energy distributions among the various modes weakly depends on surface temperature in the range of 0-600 K, regardless of the initial vibrational state of H(ad)-Si(s) bond.

The stability of fluoroalkyl groups as a pendent on the phenyl ring was measured in vitro using rat hepatic microsomes and human serum to predict their in vivo stabilities. We have prepared three [$^{18}F$]fluoroalkyl-biphenyls as the model compounds of fluoroalkyl aromatic compounds to compare the in vitro stabilities. In addition, in vitro stabilities were measured separately using rat hepatic microsomes and human serum at $37^{\circ}C$. Fluoroethylbiphenyl had similar or slightly superior stability to fluoropropylbiphenyl and these two compounds were much more stable than fluoromethylbiphenyl in vitro.

Rate constants for photolytic reactions of p-substituted 2-diazopropiophenones were determined in acetonitrile. The reactions show a comparatively low value of activation energy and activation enthalpy to alkylcarbenes or other arylcarbenes. The transition state corresponds to the step of a new carbonyl bond formation. The high negative ρ -values are shown in Hammett plots. The kinetics results and EPR spectrum are in accord with a phenomenon that occurs in interconversion between singlet and triplet carbenes.