Triton-B Catalyzed, Efficient, One-Pot Synthesis of Carbamate Esters from Alcoholic Tosylates

A novel process for the one-step chemoselective conversion of a variety of alcoholic tosylates into carbamates serving as protected amines was developed using benzyltrimethylammonium hydroxide (Triton-B) in the presence of gaseous carbon dioxide. Thus carbamate esters of different amines were prepared in very good to excellent yields.     

Chromium(VI) Accumulation and Tolerance by Tradescantia pallida: Biochemical and Antioxidant Study

Tradescantia pallida (Wandering jew)—a succulent perennial herb—was screened to be a potent chromium (Cr) accumulator. Its ability to grow under Cr stress was examined by studying biochemical changes and physiological response of the plant in presence of 5–20 mg L^?1 Cr(VI) concentration in hydroponic environment for up to ca. 90 days. Average Cr(VI) bioaccumulation in plant roots reached about 408 μg g^?1 dry weight (dw) after 30 days and up to 536 μg g^?1dw after 60 days of culture. Biochemical changes in the plant exposed to Cr(VI) indicated a reduction in the total carbohydrate and protein content. Furthermore, lipid peroxidation, catalase, peroxidase and ascorbate peroxidase activity were measured in different parts of the plant exposed to Cr(VI). Increased activities of these enzymes showed their important role in overcoming the Cr-induced oxidative stress on the plant.     

Synthesis,Spectroscopic Studies,and Antifungal Activity of Tris(O-Alkyl or O-Aryltrithiophosphato) Aluminum(III)

Abstract

Aluminum(III) derivatives of O-alkyl or O-aryl trithiophosphate of the type Al[S₂P(SH)OR]₃ (R = Me, Et, Prⁱ, Buⁱ, Ph, CH₂Ph) have been synthesized. The products were obtained as white powdery solids. The monomers are soluble in common organic solvents and were characterized by elemental analyses, molecular weight determinations, and IR and (¹H, ²⁷Al, and ³¹P) NMR spectroscopic studies, which are consistent with six coordinated aluminum and bidentate behavior of the trithiophosphate moiety. The products also exhibit antifungal effectiveness against powdery mildew disease.     

Spin-parity measurements in the neutron-rich N ∼ 20 34P and 36S nuclei

Yrast and near-yrast energy levels in the neutron-rich N ∼ 20 nuclei ³⁴P, ³⁶S were populated using transfer/deep-inelastic processes following the ³⁴S + ¹¹⁵In reaction at an incident energy of 140MeV. The use of a multi-clover array has facilitated polarization measurements of the observed γ-rays and necessitated some changes in the previously known level scheme. The observation of the negative-parity levels in these nuclei on the periphery of the “island of inversion” is indicative of the influence of the intruder orbitals on the level structure at low spins. Shell-model calculations indicate that the inclusion of the orbitals from the upper pf shell is important even for the low-lying positive-parity states.     

Modeling of an EMP simulator using a 3-D FDTD code

Performed self-consistent, three-dimensional (3-D), time-domain calculations for a bounded-wave electromagnetic pulse simulator. The simulator consists of a constant-impedance transverse electromagnetic structure driven by a charged capacitor, discharging through a fast closing switch. These simulations yield the detailed 3-D electromagnetic field structure in the vicinity of the simulator. The prepulse seen in these simulations can be explained quantitatively in terms of capacitive coupling across the switch and the known charging waveform across the capacitor. Placement of a test object within the simulator significantly modifies the electric fields within the test volume, in terms of field strength as well as the frequency spectrum. This means that, for a given simulator, larger objects would be subjected to somewhat lower frequencies. The E-field waveform experienced by a small test object is reasonably close to that for free-space illumination, but the mismatch increases with object size. The use of a resistive sheet as a matching termination significantly reduces radiation leakage as compared to two parallel resistive rods. For a given termination, larger test objects marginally reduce leakage. A physical interpretation of these conclusions is also included. This work is a first step toward full-fledged optimization of such simulators using 3-D modeling.     

Facile synthesis of non-ionic dimeric molecular resonance imaging contrast agent: its relaxation and luminescence studies

A bis-polyazamacrocycle, 10'-bis(acetamido)ethane-bis[1,4,7-tri(carboxymethane)-1,4,7,10-tetraazacyclododecane] (DO3A-AME-DO3A) was synthesized for application in magnetic resonance imaging. The efficacy of DO3A-AME-DO3A as non ionic magnetic contrast agent was tested by performing relaxometric studies on its gadolinium complex. The longitudinal relaxivity, r(1) and transverse relaxivity, r(2) values were found to be 5.84 mM(-1)s(-1) and 6.82 mM(-1)s(-1), per Gd(III) at pH 7.0, 37 °C. The luminescence properties of europium complex of DO3A-AME-DO3A were investigated in aqueous medium. The lifetime of Eu(2)-DO3A-AME-DO3A in water was found to be 0.786 ms. Emission and luminescence lifetime measurements on the europium complex of DO3A-AME-DO3A gives a hydration number of q = 1.9. The reaction enthalpy and entropy were found to be, ΔH(0) = -(6.2 ± 2) kJ mol(-1), ΔS(0) = - (1.8 ± 0.4) kJ mol(-1)K(-1), and K(Eu)(298) = (1.8 ± 0.1).     

Nonenzymatic assembly of natural polyubiquitin chains of any linkage composition and isotopic labeling scheme

Polymeric chains made of a small protein ubiquitin act as molecular signals regulating a variety of cellular processes controlling essentially all aspects of eukaryotic biology. Uncovering the mechanisms that allow differently linked polyubiquitin chains to serve as distinct molecular signals requires the ability to make these chains with the native connectivity, defined length, linkage composition, and in sufficient quantities. This, however, has been a major impediment in the ubiquitin field. Here, we present a robust, efficient, and widely accessible method for controlled iterative nonenzymatic assembly of polyubiquitin chains using recombinant ubiquitin monomers as the primary building blocks. This method uses silver-mediated condensation reaction between the C-terminal thioester of one ubiquitin and the ε-amine of a specific lysine on the other ubiquitin. We augment the nonenzymatic approaches developed recently by using removable orthogonal amine-protecting groups, Alloc and Boc. The use of bacterially expressed ubiquitins allows cost-effective isotopic enrichment of any individual monomer in the chain. We demonstrate that our method yields completely natural polyubiquitin chains (free of mutations and linked through native isopeptide bonds) of essentially any desired length, linkage composition, and isotopic labeling scheme, and in milligram quantities. Specifically, we successfully made Lys11-linked di-, tri-, and tetra-ubiquitins, Lys33-linked diubiquitin, and a mixed-linkage Lys33,Lys11-linked triubiquitin. We also demonstrate the ability to obtain, by high-resolution NMR, residue-specific information on ubiquitin units at any desired position in such chains. This method opens up essentially endless possibilities for rigorous structural and functional studies of polyubiquitin signals.     

The chemistry of cadmium-thiocarboxylate derivatives: synthesis, structural features, and application as single source precursors for ternary sulfides

Novel heterobimetallic complexes [(PPh(3))(2)Cu(μ-SCOPh)(2)Cd(SCOPh)] (2a), [(PPh(3))(2)Cu(μ-SCOth)(2)Cd(SCOth)] (2b), [(PPh(3))(2)Ag(μ-SCOth)(2)Cd(SCOth)] (3a), [(PPh(3))(2)Ag(μ-SCOth)(2)Cd(H(2)O)(SCOth)] (3b), [(PPh(3))(2)Ag(μ-SCOPh)(2)Cd(SCOPh)] (3c), and a bimetallic complex [PPh(3)Cd(μ-SCOth)SCOth](2)·CH(2)Cl(2) (5) (th = thiophene) were prepared and characterized by single crystal X-ray diffraction analysis. A coordination polymer [Cd(SCOPh)(2)](n) (4) has also been characterized structurally that exhibited metal-like electrical conductivity. The heterobimetallic complexes on pyrolyzing under controlled conditions yielded ternary sulfides of composition CuCd(7)S(8), CuCd(10)S(11), Ag(2)Cd(8)S(9), and Ag(2)Cd(5)S(6), which have been characterized by SEM-EDX and X-ray diffractometry. Photophysical properties and electrical conductivities of the sulfides have also been studied.     

On the development of a new pre-weld thermal treatment procedure for preventing heat-affected zone (HAZ) liquation cracking in nickel-base IN 738 superalloy

Hot cracking in the heat-affected zone (HAZ) of precipitation strengthened nickel-base superalloys, such as IN 738, during fusion welding remains a major factor limiting reparability of nickel-base gas turbine components. The problem of HAZ intergranular cracking can be addressed by modifying the microstructure of the pre-weld material through thermal treatment, which requires significant understanding of the critical factors controlling cracking behaviour. The decomposition of Mo-Cr-W-and Cr-rich borides in the alloy, among other factors, has been observed to contribute significantly to non-equilibrium intergranular liquation and, hence, intergranular liquation cracking during welding. Gleeble physical simulation of HAZ microstructure has also shown that non-equilibrium liquation is more severe in the vicinity of decomposed borides in the alloy and can occur at temperatures as low as 1,150 °C. Although currently existing pre-weld heat treatments for IN 738 superalloy minimize the contributions of dissolution of second phases, including borides, to HAZ intergranular liquation, these heat treatments are not industrially feasible due to process-related difficulties. Therefore, a new industrially feasible and effective pre-weld thermal treatment process, designated as FUMT, was developed during the present research by controlling both the formation of borides and the segregation of boron at the grain boundaries in the pre-weld heat-treated material. This thermal treatment was observed to very significantly reduce intergranular HAZ cracking in welded IN 738 superalloy. The details of the development process and developed procedure are presented in this paper.