Elimination reactions of $XC_6H_4CH_2CO_2C_6H_3-2-Y-4-NO_2$ have been studied under various conditions. When X was moderately electron-withdrawing, Y = H, and base-solvent was $R_2$NH-MeCN, the reaction proceeded by the E2 mechanism via an E1cb-like transition state. Concave downward curve was noted in the Hammett plots. When X = 4-$NO_2$, Y = Cl, $CF_3,\;NO_2$, and the base-solvent was ${R_2NH/R_2NH_2}^+$ in 70 mol % MeCN(aq), the reaction proceeded by the E2 mechanism. The mechanism changed to a competing E2 and E1cb when X = 4-$NO_2$ and Y = H, MeO, and to the E1cb when X = 2,4-($NO_2)_2$, and Y = $NO_2$. From these results, a plausible pathway of the change of the mechanism from E2 to the E1cb extreme is proposed.

Kinetic study on the cleavage of N-methylphthalamic acid (NMPA) in mixed acidic aqueous-acetonitrile solvent reveals the formation of both phthalic anhydride (PAn) (through O-cyclization) and N-methylphthalimide (NMPT) (through N-cyclization). The formation of NMPT varies from $\sim$20% to $\sim$3% with the increase in the content of acetonitrile from 2 to 70% v/v. Pseudo first-order rate constants for the formation of PAn are more than 4-fold larger than those for the formation of NMPT at 2% v/v $CH_3CN$ in mixed aqueous solvents. Pseudo first-order rate constants for alkaline hydrolysis of NMPT reveal a nonlinear decrease with increase in the content of $CH_3CN$ in mixed aqueous solvents.

The reaction of cis-[Cr([14]-decane)($OH_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = isothiocyanate ($NCS^-$), azide ($N3^-$) or chloroacetate(caa)} leads to a new cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ (1), cis-[Cr([14]-decane)($N_3)_2]ClO_4$ (2) or cis-[Cr([14]-decane)($caa)_2]ClO_4$ (3). These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two $NCS^-$anions are bonded to the chromium(III) ion via the Ndonor atom in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by 13$^{\circ}$ from the ideal value of 180$^{\circ}$ for a perfect octahedron. The bond angle N-Cr-N between the Cr(III) ion and the two nitrogen atoms of the isothiocyanate ligands is close to 90$^{\circ}$. The bond lengths of Cr-N between the chromium and $NCS^-$groups are 1.964(5) and 2.000(5) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 2073, 1344 and 1684 $cm^{-1}$ attributed to the $NCS^-$, ${N_3}^-$ and caa groups stretching vibrations, respectively.

The interaction of bovine carbonic anhydrase II with copper ions was studied by isothermal titration microcalorimetry, circular dichroism, UV spectrophotometry and temperature scanning spectrophotometry methods at 27 ${^{\circ}C}$ in Tris buffer solution at pH = 7.5. It was indicated that there are three non-identical different binding sites on carbonic anhydrase for $Cu^{2+}$. The binding of copper ions is exothermic and can induce some minor changes in the secondary and tertiary structure of the enzyme, which does not unfold it, but can result in a decrease in both activity and stability of the enzyme.

Photoluminescence (PL) spectra of Eu(III) and Tb(III) complexes with mixed oxydiacetate (ODA) and 1,10-phenanthroline (phen) ligands and with homoleptic ODA reveal characteristic line-splitting at 10 K, depending on the site-symmetry of the lanthanide ion in the complex. The energy-level schemes of the $^7F_J$ states and the emitting levels for Eu(III) and Tb(III) ions have been proposed by simulating the line splitting in the framework of crystal-field Hamiltonian. The sets of refined crystal-field parameters for the experimentally determined sitesymmetry satisfactorily reproduce the experimental energy-level schemes. In addition, the PL quantum yield and the decay time were determined at room temperature. The PL quantum yields of [$Eu(ODA){\cdot}(phen){\cdot}4H_2O]^+$ and [Tb$(ODA){\cdot}(phen){\cdot}4H_2O]^+$ in the crystalline state (Q = 17.7 and Q = 56.6%, respectively) are much greater than those of [Eu($ODA)_3]^{3-}and\;[Tb(ODA)_3]^{3-}$(Q = 1.1 and Q = 1.3, respectively), due to the energy transfer from phen to the lanthanide ion. In the aqueous state, the relaxation of the phen moiety due to the solvent results in the reduction of the quantum yield and the shortening of the lifetime.

$[Mn_{12}O_{12}(O_2CPh-4-SMe)_{16}(H_2O)_4]{\cdot}7CH_2Cl_2$ (1), a new single-molecule magnet complex has been successfully synthesized by substitution of acetate ligand of Mn12ac with 4-(methylthio)benzoic acid. Complex 1 crystallizes into triclinic P$\overline{1}$ with a = 18.321(3) $\AA$, b = 19.011(3) $\AA$, c = 27.230(4) $\AA$, $\alpha$ = 86.973(3)$^{\circ}$, $\beta$ = 76.919(3)$^{\circ}$, $\gamma$ = 87.613(3)$^{\circ}$, and Z = 2. In complex 1, one Mn(III) ion has an abnormal Jahn-Teller elongation axis oriented at an oxide ion. Complex 1 has two out-of-phase ac susceptibility peaks in the 2-4 K and 4-7 K regions. Effective anisotropy energy barrier and pre-exponential factor are $U_{eff}$ = 45.95 K, 1/$\tau$0 = 8.6 ${\times}\;10^9s^{-1}\;for\;{\chi}_M$'' peaks in the lower temperature region and $U_{eff}$ = 59.45 K, 1/$\tau_0$ = 2.2 ${\times}\;10^8\;s^{-1}$ for $\chi_M$'' peaks in the higher temperature region. The parameters of S = 10, g = 1.87, D = -0.40 $cm^{-1}$, and E = 0.00034 $cm^{-1}$ were obtained from the M/N${\mu}_B$ vs. H/T plot of complex 1.

A variable-low temperature scanning tunneling microscope (VT-STM), which operates from 77 to 350 K in ultrahigh vacuum, was built and used to study imaging and manipulation of benzene molecules on Si surfaces. Four types of benzene adsorption structures were first imaged on the Si(5 5 12)-2x1 surface. Desorption process of benzene molecules by tunneling electrons was studied on the Si(001)-2xn surface.

Hydrogen adsorption on various porous materials have been studied with a volumetric method at low temperature in the pressure of 0-760 torr. Their hydrogen uptakes depend at least partly on microporosity rather than total porosity. However, it is also necessary to consider other parameters such as pore size and pore architecture to explain the adsorption capacity. The heat of adsorption and adsorption-desorption-readsorption experiments show that the hydrogen adsorption over the porous materials are composed of physisorption with negligible contribution of chemisorption. Among the porous materials studied in this work, SAPO-34 has the highest adsorption capacity of 160 mL/g at 77 K and 1 atm probably due to high micropore surface area, micropore volume and narrow pore diameter.

The purpose of this study was to develop a method for increasing the solubility of paclitaxel in water to reduce its toxicity and make the drug more feasible for chemotherapy. A series of highly water soluble paclitaxel polyethylene glycol (PEG) esters were synthesized and evaluated for their anti-tumor activity and toxicity. The solubility of 7-polyethylene glycol paclitaxel carbonate 5 was 840 mg/mL and the acute toxicity ($LD_{50}$) was 286 mg/kg. Because of its reduced toxicity, compound 5 showed a dramatic reduction of tumor volume without any loss of animals in long-term treatment (daily consecutive injections for 15 days).

Most experimental studies available in the literature on filtration are based on observed average zeta potential of particles (usually 10 measurements). However, analyses of data using the average zeta potential alone can lead to misleading and erroneous conclusions about the attachment behavior because of the variation of particle zeta potentials and the heterogeneous distribution of the collector surface charge. To study characteristics of zeta potential, zeta potential distributions (ZPDs) of silica particles under 9 different chemical conditions were investigated. Contrary to many researchers’ assumptions, most of the ZPDs of silica particles were broad. The solids concentration removal was better near the isoelectric point (IEP) as many researchers have noticed, thus proper destabilization of particles is very important to achieve better particle removal in particle separation processes. While, the mean zeta potential of silica particles at a given coagulant dose was a function of particle concentration; the amount of needed coagulant for particle destabilization was proportional to the total surface charge area of particles in the suspension.

$Ag_4Br_4$ nanoclusters have been synthesized in about 75% of the sodalite cavities of fully $K^+$-exchanged zeolite A (LTA). An additional KBr molecule is retained in each large cavity as part of a near square-planar $K_4Br^{3+}$ cation. A single crystal of $Ag_{12}$-A, prepared by the dynamic ion-exchange of $Na_{12}$-A with aqueous 0.05 M $AgNO_3$ and washed with $CH_3OH$, was placed in a stream of flowing 0.05 M KBr in $CH_3OH$ for two days. The crystal structure of the product ($K_9(K_4Br)Si_{12}Al_{12}O_{48}{\cdot}0.75Ag_4Br_4$, a = 12.186(1) $\AA$) was determined at 294 K by single-crystal X-ray diffraction in the space group Pm m. It was refined with all measured reflections to the final error index $R_1$ = 0.080 for the 99 reflections for which $F_o\;{\gt}\;4_{\sigma}\;(F_o)$. The thirteen $K^+$ ions per unit cell are found at three crystallographically distinct positions: eight $K^+$ ions in the large cavity fill the six-ring site, three $K^+$ ions fill the eight-rings, and two $K^+$ ions are opposite four-rings in the large cavity. One bromide ion per unit cell lies opposite a four-ring in the large cavity, held there by two eight-ring and two six-ring $K^+$ ions ($K_4Br^{3+}$). Three $Ag^+$ and three $Br^-$ions per unit cell are found on 3-fold axes in the sodalite unit, indicating the formation of nano-sized $Ag_4Br_4$ clusters (interpenetrating tetrahedra; symmetry $T_d$; diameter ca. 7.9 $\AA$) in 75% of the sodalite units. Each cluster (Ag-Br = 2.93(3) $\AA$) is held in place by the coordination of its four $Ag^+$ ions to the zeolite framework (each $Ag^+$ cation is 2.52(3) $\AA$ from three six-ring oxygens) and by the coordination of its four $Br^-$ ions to $K^+$ ions through six-rings (Br-K = 3.00(4) $\AA$).