Ionic liquids are alternative reaction media of increasing interest and are regarded as an eco-friendly alternatives, of potential use in place of the volatile organic solvents typically used in current chemical processing methods. They are emerging as the smart and excellent solvents, which are made of positive and negative ions that they are liquids near room temperature. The nucleophilic substitution reaction is one of the important method for inserting functional groups into a carbon skeleton. Many nucleophilic substitution reactions have been found with enhanced reactivity and selectivity in ionic liquid. In this review, some recent interesting results of nucleophilic substitution reactions such as hydroxylations, ether cleavages, carbon-X (X= carbon, oxygen, nitrogen, fluorine) bond forming reactions, and ring opening of epoxides in ionic liquids are discussed.

The structure-property relations of ternary copper chalcogenides, $TlCu_{3-x}S_2$ and $\alpha-BaCu_{2-x}S_2$ are examined. The density of states, band dispersions, and Fermi surfaces of these compounds are investigated to verify the reason of the metal-insulator transitions by extended Huckel tight-binding band calculations. The origin of the metalinsulator transitions of non-stoichiometric $TlCu_{3-x}S_2$ and $\alpha-BaCu_{2-x}S_2$ is thought to be the electronic instability induced by their Fermi surface nesting.

The cobalt titanate, $CoTiO_3$ nanoparticles have been prepared by calcinations of precursor obtained from a mixture of $TiO_2$ and $Co(OH)_2$ in aqueous cetyltrimethylammonium bromide (CTAB) solution. The nanoparticles were investigated with X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and thermogravimetric/differential thermal analysis (TGA/DTA) to determine the crystallite size and the phase composition. The spectroscopic characterizations of these nanoparticles were also done with UV-Vis spectroscopy and FT-Raman spectroscopy. XRD patterns show that $CoTiO_3$ phase was formed at calcinations temperature above 600 ${^{\circ}C}$. UV-Vis absorption spectra indicate that the $CoTiO_3$ nanoparticles have significant red shift to the visible region (400-700 nm) with $\lambda_{max}$ = 500 nm compared to pure $TiO_2$ powder ($\lambda_{max}$ = 320 nm). The new absorption peaks (absorption at 696, 604, 520, 478,456, 383, 336, 267, 238, 208 $c m ^{-1}$), which were not appeared in FT-Raman spectra of P-25, also confirm the formation of Ti-O-Co bonds at above 600 ${^{\circ}C}$ and just not the mixtures of titanium dioxide with cobalt oxides.

$CF_4$ gas is one of the most common chemicals used for dry etching in semiconductor manufacturing processes. For application to the etching process and environmental control, the low-pressure inductively coupled plasma (LP-ICP) was employed to obtain the spectrum of $CF_4$ gas. In terms of the analysis of the spectra, trace CF radical by A-X and B-X transitions was detected. The other $CF_x$ radicals, such as $CF_2$ and $CF_3$, were not seen in this experiment whereas strong C and $C_2$ emissions, dissociation products of $CF_4$ gas, were observed.

The semiconductor PbS nanobelts (width 50-120 nm and length over 3 $\mu$m) were self-assembled in a simple reverse micelle solvent system containig the surfactant of polyoxyethylene (9) dodecy ether $(C_{12}E_9)$. The nanobelts synthesized were found to possess cube galena poly-crystal structure with high purity when analyzed by ED and X-ray diffraction. Significant “blue shift” from bulk material was observed on the PbS nanobelts using photoluminescence and UV-Vis spectroscopy. A mechanism involving the possible formation of nanobelts based on surfactant template was also proposed.

The temperature dependence on the electron transfer rate constant $(k_{app})$ for hydroquinone redox center in $H_2Q(CH_2)_n$SH-SAMs (n = 1, 4, 6, 8, 10, and 12) on gold electrode was investigated to obtain reorganization energy $(\lambda)$ using Laviron’s formalism and Arrhenius plot of ln $[k_{app}/T^{1/2}]$ vs. T^{-1} based on the Marcus densityof-states model. All the symmetry factors measured for the SAMs were relatively close to unity and rarely varied to temperature change as expected. The electron tunneling constant $(\beta)$ determined from the dependence of the $k_{app}$ on the distance between the redox center and the electrode surface gives almost the same $\beta$ values which are quite insensitive to temperature change. Good linear relationship of Arrhenius plot for all $H_2Q(CH_2)_n$SH-SAMs on gold electrode was obtained in the temperature range from 273 to 328 K. The slopes n Arrhenius plot deduced that $\lambda$ of hydroquinone moiety is ca. 1.3-1.4 eV irrespectively of alkyl chain length of the electroactive SAM.

Membrane proteins in highly oriented lipid bilayer samples are useful for membrane protein structure determination. We used in the past planar lipid bilayers which were aligned and supported on the glass slide. These samples were mechanically aligned in a magnetic field. However, these stacks of glass slides with planar lipid bilayers are not well suited for use with a commercial solid-state NMR probe with a round coil. Therefore, a homebuilt solid-state NMR probe was built and used with a stack of thin glass plates wherein the RF coil was wrapped directly around the flat square sample. Recently, we began to use magnetically aligned bicelles that are suitable for the structure determination of membrane proteins by solid-state NMR spectroscopy without any effort to build a flat square coil probe. These bicelle samples are well suited for use with a commercial solidstate NMR probe with a round coil, are very easy to prepare and are very stable, so that they can be kept for more than a year. In this paper, we present the solid-state NMR spectra of optimized and magnetically oriented bicelle samples of membrane proteins.

Fragmentation efficiencies of various ‘activated-ion’ electron capture dissociation (AI-ECD) methods are compared for a model system of bovine ubiquitin 7+ cations. In AI-ECD studies, sufficient internal energy was given to protein cations prior to ECD application using IR laser radiation, collisions, blackbody radiation, or in-beam collisions, in turn. The added energy was utilized in increasing the population of the precursor ions with less intra-molecular noncovalent bonds or enhancing thermal fluctuations of the protein cations. Removal of noncovalent bonds resulted in extended structures, which are ECD friendly. Under their best conditions, a variety of activation methods showed a similar effectiveness in ECD fragmentation. In terms of the number of fragmented inter-residue bonds, IR laser/blackbody infrared radiation and ‘in-beam’ activation were almost equally efficient with ~70% sequence coverage, while collisions were less productive. In particular, ‘in-beam’ activation showed an excellent effectiveness in characterizing a pre-fractionated single kind of protein species. However, its inherent procedure did not allow for isolation of the protein cations of interest.

Nerve agents (sarin, tabun, soman and VX) are class of military important substances able to cause many severe intoxications during few minutes. Currently, the threat of misuse of these agents is daily discussed. Unfortunately, there is no single antidote able to treat intoxication caused by all of these agents. Owing to this fact, new generation of antidotes, especially acetylcholinesterase (AChE; EC 3.1.1.7) reactivators, is still developed. In this study, we have tested four newly developed AChE reactivators: 1-(4-hydroxyiminomethylpyridinium)- 5-(4-carbamoylpyridinium)-3-oxa-pentane dibromide (1), 1-(3-hydroxyiminomethylpyridinium)-5-(4-carbamoylpyridinium)-3-oxa-pentane dibromide (2), 1,5-bis(2-hydroxyiminomethylpyridinium)-3-oxa-pentane dichloride (3) and 1,5-bis(4-hydroxyiminomethylpyridinium)-3-oxa-pentane dibromide (4) for their potency to reactivate in vitro tabun and cyclosarin-inhibited AChE. Their reactivation efficacy was compared with currently the most promising oxime HI-6 (1-(2-hydroxyiminomethylpyridinium)-3-(4-carbamoylpyridinium)-2-oxa-propane dichloride). According to obtained results, two AChE reactivators 1 and 4 were able to reactivate tabun-inhibited AChE. On the contrary, there was no better AChE reactivator than HI-6 able to reactivate cyclosarin-inhibited AChE.

Porous organic-inorganic hybrids have been prepared from tetraethylorthosilicate (TEOS) and organosilane precursors by sol-gel method. Two organosilanes, 3-(2,4-dinitrophenylamino)propyltriethoxysilane (DNPTES) and N-[[(2-nitrophenyl)methoxy]carbonyl]-3-triethoxysilylpropylamine (NPTES) were used to incorporate electron-accepting (di)nitrophenyl groups into the hybrids. The hybrids were characterized by FT-IR spectroscopy and elemental analysis, and their pore characteristics were studied by nitrogen sorption porosimetry. Surface area of the hybrids ranged from 563 to 770 $m^2$/g, pore volume, 0.23-0.30 $cm^3$/g, and porosity, 35-41%. It was demonstrated by UV-vis spectroscopy that aniline, ethylenediamine, and 1-aminonaphthalene could be removed from their hexane solutions in the presence of the hybrid powders. The removal of amines is attributable to donor-acceptor interaction between the electron-donating amines and electron-accepting (di)nitrophenyl moiety.

The surface structure and electrochemical behavior of self-assembled monolayers (SAMs) formed by aromatic thiols on Au(111) were investigated by scanning tunneling microscopy (STM) and cyclic voltammetry. Benzenethiol (BT) forms disordered phases on Au(111) which are composed of many bright domains, while benzyl mercaptan (BM), with a methylene unit between the aromatic group and sulfur atom, forms twodimensional ordered SAMs on Au(111). In addition, two phase-separated domains consisting of disordered and ordered phases were observed in binary SAMs formed from a 1 : 1 mixed ethanol solution of BT and BM. From STM and CV measurements, we found that the blocking efficiency of aromatic thiol SAMs coated on an Au(111) electrode for an electron transfer reaction decreases as the structural order of the SAMs increases. Molecular-scale STM and CV results obtained here will be very useful in designing functional SAMs for further applications, such as the improvement of corrosion passivation of Au(111) on an aromatic thiolmodified Au(111) surface.

Bioluminescence single-site immunometric assay for methamphetamine (MA) using the native aequorin, a photoprotein, as a signal generator was developed for the first time. MA is a potent sympathomimetic amine with stimulant effects on the central nervous system. MA abuse induces hallucinations and, thus, may cause a serious social problem. The single-site immunometric MA assay was optimized and its dose-response behavior was examined. The dose-response curve shows that the detection limit is 1.1 ${\times}$ $10^{-10}$ M and a dynamic range is four orders of magnitude with 15 $\mu$g/mL BSA-MA conjugate and 1.0 ${\times}$ $10^{-8}$ M anti-MA antibody-biotin conjugate. In order to evaluate this assay, the structurally similar compounds, amphetamine, ephedrine, norephedrine, benzphetamine and N-4-(aminobutyl)methamphetamine were examined for their crossreactivity. None of these five compounds showed any cross-reactivity. Additionally, an artificial urine solution spiked with MA was analyzed by the MA assay, and the result of the analysis demonstrated the usefulness of the present assay for the determination of MA in urine.

Sodium hyaluronate (NaHA), water soluble polymer having ultra-high molecular weight, is characterized by using on-line frit inlet asymmetrical flow field-flow fractionation (FI-AFlFFF) and multiangle light scattering (MALS). This study demonstrates the capability of power programming FI-AFlFFF for the separation of NaHA and the applicability of FI-AFlFFF with MALS for the characterization of molecular weight distribution and their structural information. Since sample injection and relaxation in FI-AFlFFF are achieved by using hydrodynamic relaxation, separation of high molecular weight polymers can be achieved smoothly without halting the separation flow. Experiments are carried out with the two different NaHA products (a raw NaHA sample and a thermally degraded NaHA product) and molecular weight distribution and conformations in solution are determined. Influence of sample filtration on the change of molecular weight distribution is also discussed.