Reductive monoalkylation of aromatic and aliphatic nitro compounds and the corresponding amines with nitriles

[reaction: see text] A simple, selective, rapid, and efficient procedure for the synthesis of secondary amines from the reductive alkylation of either aliphatic or aromatic nitro compounds and the corresponding amines is reported. Ammonium formate is used as the hydrogen source and Pd/C as the hydrogen transfer catalyst. The reaction is carried out at room temperature. The rate differences for the preferential formation of secondary over tertiary products are due to both steric and electronic factors.     

Rapid crack growth in a thermoelastic solid under mixed-mode thermomechanical loading

A two-dimensional steady-sate analysis of semi-infinite brittlecrack growth at a constant subcritical rate in an unboundedfully-coupled thermoelastic solid under mixed-mode thermomechanicalloading is made. The loading consists of normal and shear tractionsand heat fluxes applied as point sources (line loads in theout-of-plane direction). A related problem is solved exactly in an integral transformspace, and robust asymptotic forms used to reduce the originalproblem to a set of integral equations. The equations are partiallycoupled and exhibit operators of both Cauchy and Abel types,yet can be solved analytically. The temperature change field at a distance from the moving crackedge is then constructed, and its dominant term is found tobe controlled by the imposed heat fluxes. The role of this termis, indeed, enhanced if the heat fluxes serve to render thecrack as a net heat source/sink for the solid, as opposed tobeing a transmitter of heat across its plane. More generally,the influence of the thermoelastic coupling on this field, aswell as other functions, is found to increase with crack speed.     

Determination of traces of heavy metals in positively charged inorganic colloids in fresh waters

Summary Determination of Traces of Heavy Metals in Positively Charged Inorganic Colloids in Fresh Waters After removal of suspended particulate matter by centrifugation followed by filtration through 0.4-m membrane filters, humic substances and other negatively charged species are sorbed on a small column of macroreticular weak-base anion exchanger DEAE-Sephadex A-25 at fast flow rates. Positively charged inorganic colloids pass through the column and are collected on a 0.015-m membrane filter, which is then ultrasonically treated with 1M nitric acid for the determination of copper, lead and cadmium by differential pulse anodic stripping voltammetry with a static mercury drop electrode. Up to O.2g 1^–1 of the heavy metals are found in positively charged inorganic colloids in river, pond and tap waters.     

Synthesis of imidazolo analogues of the oxidation-reduction cofactor pyrroloquinoline quinone (PQQ)

Parallel syntheses of 2-hydro-, 2-methyl-, and 2-methoxycarbonylimidazo-7,9-dimethoxycarbonyl analogues of the oxidation-reduction cofactor pyrroloquinoline quinone [4,5-dihydro-4,5-dioxo-1H-pyrrolo[2,3-f]quinoline-2,7,9-tricarboxylic acid] have been developed. The properties of the imidazolo analogues in relation to the corresponding pyrrole analogues will be important in assessing the origins of catalysis and biological activity in the cofactor, which has recently been shown to be a vitamin.     

Design, total synthesis, and evaluation of novel open-chain epothilone analogues

[structure: see text] The design, total synthesis, and biological evaluation of two open-chain analogues of epothilone incorporating the critical C1-C8 fragment and the aromatic side chain held together by a small molecular scaffold have been achieved. Biological evaluation revealed that further restraint between the flexible C1-C8 region and the molecular scaffold may be necessary for potent inhibition of cell proliferation.     

Synthetic magnetic opals

We present studies of novel nanocomposites of BiNi impregnated into the structure of opals as well as inverse opals. Atomic force microscopy and high resolution elemental analyses show a highly ordered structure and uniform distribution of the BiNi filler in the matrix. These BiNi-based nanocomposites are found to exhibit distinct ferromagnetic-like ordering with transition temperature of about 675 K. As far as we know there exists no report in literature on any BiNi compound which is magnetic.     

Mechanism of the photo-initiation process in polyethylene

It is shown that, during the processing of low density polyethylene, the hydroperoxide content increases rapidly to a very sharp maximum and then declines. Vinylidene groups initially present in the polymer, decrease to zero after an induction period and the rate of destruction is related to hydroperoxide concentration.Carbonyl concentration increases in an auto-accelerating mode in a process which follows the formation and decay of hydroperoxide; when the carbonyl concentration is low, hydroperoxide and vinylidene are the main source of the photo-initiation step. In the later stages of the reaction, Norrish II photolysis of carbonyl is the most important process.     

Electrochemical and Electrocatalytic Properties of Imidazole Analogues of the Redox Cofactor Pyrroloquinoline Quinone

The electrochemical and electrocatalytic properties of two synthetic imidazole analogues of the redox cofactor pyrroloquinoline quinone (PQQ) were evaluated. Cyclic voltammetry measurements as a function of pH indicated that both 4,5‐dihydro‐4,5‐dioxo‐1H‐imidazolo[5,4‐f]quinoline‐7,9‐dicarboxylic acid ( 1 ) and 4,5‐dihydro‐4,5‐dioxo‐2‐methyl‐1H‐imidazolo[5,4‐f]quinoline‐7,9‐dicarboxylic acid ( 2 ) undergo a reversible reduction of the o‐quinone moiety below pH 8 with potentials slightly more positive than those observed for PQQ. Upon incorporation into a polypyrrole membrane on the tip of a glassy carbon electrode, 1 and 2 exhibited electrocatalytic properties sufficient for the indirect amperometric detection of cysteine. The response for cysteine was linear up to 1 mM over a wide pH range. Detection limits (S/N=3) were in the μM range and dependent on the solution pH. Interference from redox active species such as dopamine and uric acid were minimized by the pH‐dependent redox potentials of 1 and 2 and thus the ability to tune the detection potential.     

Separation and determination of traces of heavy metals complexed with humic substances in fresh waters by sorption on diethylaminoethyl-sephadex a-25

Copper(II), lead and cadmium complexed with humic and fulvic acids in filtered 1-l samples of fresh water are sorbed on a column containing 0.5 ml of the macroreticular weak-base anion exchanger, diethylaminoethyl-Sephadex A-25 at a flow rate of 20 ml min^?1. Simple metal cations are not sorbed at all. The sorbed trace metals are quantitatively desorbed with 4 M nitric acid batchwise and determined by graphite-furnace atomic absorption spectrometry. For synthetic aqueous solutions containing traces of heavy metals and humic acid, the results are in conformity with those obtained by cationexchange separation. About 80% of the sorbed humic substances are eluted with 0.5 M sodium hydroxide solution from the A-25 column and its quantity is estimated spectrophotometrically at 400 nm.