Alkyliron(Ⅲ) porphyrins, n-butyliron(Ⅲ) tetraphenylporphyrin, (TPP)Fe-Bu and n-butyliron(Ⅲ) tetrakis-(pentafluorophenyl)porphyrin, $(F_{20}TPP)Fe-Bu$ have been evaluated as suitable for olefin free-radical polymerization. Butyl radicals dissociated from n-butyliron(Ⅲ) porphyrin initiated the polymerization reaction, but the ratio of the propagation was low. The GCMS analysis of the reaction mixture of nbutyliron(Ⅲ) porphyrin and styrene has revealed several products containing two butyl groups, while traces of b-hydrogen-abstracted products were observed. The crystal structure of (TPP)Fe-Bu has been determined. The structure of the n-butyliron(Ⅲ) porphyrin reveals the compound containing five-coordinated iron with the average Fe-N distance of 1.973(1) Å and Fe-C of 2.030(2) Å. The iron atom is displaced by 0.137Å from a four nitrogen mean plane. Crystal system is triclinic, and space group is P-1.

The present work is focused on the preconcentration of nickel and its determination by means of diffuse reflection spectroscopy. The preconcentration of nickel was carried out by sorption on macroporous aminocarboxylic amphoteric resin ANKB-35. Based on this collector, a method to determine nickel in wastes of heat power industry was worked out using solid-phase spectroscopy. The colored surface compound to be determined was obtained by a preceding nickel sorption on the resin and by subsequent treatment of the concentrate obtained with definite amounts of 1-(2-pyridilazo)-2-naphtol (PAN). The Ni calibration curve is linear in the concentration range of 0.5-20.0 mg/L (sample volume is 200.0 mL) and the detection limit is 0.05 mg/L. The presence of $Cu^{2+},\;Fe^{3+},\;Co^{2+}$ ions as well as macrocomponents of natural water $(Na^+,\;K^+,\;Ca^{2+},\;Mg^{2+})$ do not hinder the solid-phase spectroscopy determination of nickel. The nickel determination by diffuse reflection spectroscopy was carried out in model solutions as well as in solutions obtained after the dissolution of wastes of heat power industry.

The stress and the heat-flux auto-correlation functions in the Green-Kubo formulas for shear viscosity and thermal conductivity have non-decaying long-time tails. This problem can be overcome by improving the statistical accuracy by N (number of particles) times, considering the stress and the heat-flux of the system as properties of each particle. The mean square stress and the heat-flux displacements in the Einstein formulas for shear viscosity and thermal conductivity are non linear functions of time since the quantities in the mean square stress and the heat-flux displacements are not continuous under periodic boundary conditions. An alternative to these quantities is to integrate the stress and the heat-flux with respect to time, but the resulting mean square stress and heat-flux displacements are still not linear versus time. This problem can be also overcome by improving the statistical accuracy. The results for transport coefficients of liquid argon obtained are discussed.

The micro-patterning of multi-layered thin films containing CdS and $Ta_2O_5$ layers on ITO substrate with various structures was successfully obtained by combining three different techniques: chemical solution depositions, sol-gel, and microcontact printing (μCP) methods using octadecyltrichlorosilane (OTS) as the organic thin layer template. $Ta_2O_5$ layer was prepared by sol-gel casting and CdS one obtained by chemical solution deposition, respectively. Parallel and cross patterns of multi-layers with $Ta_2O_5$ and CdS films were fabricated additively by successive removal of OTS layer pre-formed. This study presents the designed architectures consisting of the two types of feature having horizontal dimensions of 170 ㎛ and 340 ㎛ with constant thickness ca. 150 nm of each deposited materials. The thin film lay-out of the cross-patterning is composed of four regions with chemically different layer compositions, which are confirmed by Auger electron microanalysis.

The reaction of 4-(2-methylaziridin-1-yl)-3-ureidobenzotrifluorides 4 with triphenylphosphine, carbon tetrachloride, and triethylamine (Appel's condition) led to the corresponding carbodiimides 5, which underwent intramolecular cycloaddition reaction with aziridine under the reaction condition to give the benzimidazolefused heterocycles, 2,3-dihydro-1H-imidazo[1,2-a]benzimidazoles 8 and 12,13-dihydro-5H-benzimidazo[2,3-b] [1,3]benzodiazepines 9.

Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)$ to benzylidene Meldrum's acids (BMA; $YC_6H_4CH=C(COO)_2C(CH_3)_2$) have been investigated in acetonitrile at 20.0 ℃. The rates of addition are greatly enhanced due to the abnormally high acidity of Meldrum's acid. The magnitudes of the Hammett $({\rho}_X\;and\;{\rho}_Y)$ and Bronsted $({\rho}_X$)$ coefficients are rather small suggesting an early transition state. The sign and magnitude of the cross-interaction constant, ${\rho}_{XY}$ (= -0.33), and kinetic isotope effects $(k_H/k_D\;{\stackrel}{~}{=}\;1.5-1.7)$ involving deuterated benzylamine nucleophilies $(XC_6H_4CH_2ND_2)$ are indicative of hydrogen-bonded cyclic transition state. The activation parameters, ${\Delta}H^{\neq}\;{\stackrel}{~}{=}\;4\;kcal\;mol^{-1}\;and\;{\Delta}S^{\neq}\;{\stackrel}{~}{=}\;-37\;e.u.$, are also in line with the proposed mechanism.

The intracluster ion-molecule reactions of $Ti^+(H_2O)_n,\;Ti^+(CH_3OCH_3)_n,\;and\;Ti^+(CH_3OD)_n$ complexes produced by the mixing of the laser-vaporized plasma and the pulsed supersonic beam were studied using a reflectron time-of-flight mass spectrometer. The reactions of $Ti^+$ with water clusters were dominated by the dehydrogenation reaction, which produces $TiO^+(H_2O)_n$ clusters. The mass spectra resulting from the reactions of $Ti^+\;with\;CH_3OCH_3$ clusters exhibit a major sequence of $Ti^+(OCH_3)_m(CH_3OCH_3)_n$ cluster ions, which is attributed to the insertion of $Ti^+$ ion into C-O bond of $CH_3OCH_3$ followed by $CH_3$ elimination. The prevalence of $Ti^+(OCH_3)_m(CH_3OD)_n$ ions in the reaction of $Ti^+\;with\;CH_3OD$ clusters suggests that D elimination via O-D bond insertion is the preferred decomposition pathway. In addition, the results indicate that consecutive insertion reactions by the $Ti^+$ ion occur for up to three precursor molecules. Thus, examination of $Ti^+$ insertion into three different molecules establishes the reactivity order: O-H > C-O > C-H. The experiments additionally show that the chemical reactivity of heterocluster ions is greatly influenced by cluster size and argon stagnation pressure. The reaction energetics and formation mechanisms of the observed heterocluster ions are also discussed.

Laser-induced Raman spectroscopy has been utilized to demonstrate its feasibility for studying the kinetics of imine formation in chloroform solvent. The imine formation, by the nucleophilic addition of primary amine to the carbonyl group of ketone, has been monitored at ten minute intervals for eight hours. The intensity of the C=O stretching mode at 1684 $cm^{-1}$ was measured to determine the rate constant of the reaction. In order to correct the sample-to-sample fluctuations in Raman peak area, this peak was normalized to the C-Cl bending peak at 666 $cm^{-1}$. By the peak area change during the course of reaction, the second order rates at three different temperatures have been determined. The substituent effects on the π conjugations of imine product have also been investigated. On the basis of Raman frequency shifts, the delocalization properties of the aromatic system modified by substitution of a hydrogen atom with -Cl and $-CH_3O$ groups could be clearly understood.

Ecosystems in the Keweenaw Peninsula region of Lake Superior, USA, were disturbed by over 500 million tons of copper-rich mine tailings during the period 1850-1968. Metals leaching from these mine residues have had dramatic effects on the ecosystems. Vast acreages of exposed tailings that are over 100 years old remain unvegetated because of the combination of metal toxicity, absence of nutrients, and temperature and water stress. Therefore, it is important to characterize and fractionate solid copper phases for assessing labile forms of copper in soils and sediments contaminated by the mining wastes. X-ray diffraction analyses indicate that calcite, quartz, hematite, orthoclase, and sanidine minerals are present as major minerals, whereas cuprite,tenorite, malachite, and chalcopyrite might be present as copper minerals in the mining wastes. Sequential extraction technique revealed that carbonate and oxide fractions were the largest pools of copper (ca. 50-80%) in lakeshore and wetland stamp sands whereas the organic matter fraction was the largest reservoir (ca. 32%) in the lake sediments. The concentrations of iron and copper were inversely correlated in the oxide fraction suggesting that copper may occur as a surface coating on iron oxides. As particle size and water contents decrease, the percent of the copper bound to the labile carbonate fraction increases.

Rabi oscillation between bound states of a single potential is well known. However the corresponding formula between the states of two different potentials has not been obtained yet. In this work, we derive Rabi formula between the states of a coupled harmonic oscillator which may be used as a simple model for the electron transfer. The expression is similar to typical Rabi formula for a single potential. This result may be used to describe transitions between coupled diabatic potential curves.