Metal complexation of crosslinked polyacrylamide-supported dithiocarbamates: Effect of the molecular character and extent of crosslinking on complexation

Dithiocarbamate functions were incorporated into different polyacrylamide matrices crosslinked with a flexible and hydrophilic crosslinking agent, tetraethyleneglycol diacrylate (TEGDA), and their complexation behaviours were investigated. Crosslinked polyacrylamides with varying extents of the tetrafunctional TEGDA crosslinks were prepared by free radical solution polymerization at 60°C using potassium persulphate as initiator in ethanol. The dithiocarbamate functionality was incorporated into these polyacrylamides by a two-step polymer-analogous reaction involving (i)trans-amidation with ethylenediamine and (ii) dithiocarbamylation of the aminopolyacrylamide with carbon disulphide and alkali. The complexations of dithiocarbamate with Cu(II), Ni(II), Zn(II), Co(II) and Hg(II) ions were followed under different conditions. The metal ion intake varied with the extent of the crosslinking agent and the observed trend in complexation is Hg(II) > Cu(II)> Zn(II)> Co(II)> Ni (II). The time-course of complexation, the possibility of recycling, swelling characteristics, and spectral and thermal analyses were carried out. The thermal stability increases upon complexation with metal ions.     

X-ray evidence for the absence of 90°-domains in polycrystalline PbTiO3 thin films with grains below a critical size

3 thin films is systematically studied by using X-ray diffraction (XRD). The PbTiO₃ thin films with different average grain sizes were prepared on various substrates by a sol-gel process. The films on NaCl and fused glass are randomly grain-oriented, while those on (111)Pt/Ti/SiO₂/Si are highly {100} cubic index grain-oriented . It is found from the XRD patterns of the films on NaCl that with decreasing average grain size from 230 to 80 nm, the intensities of high h index (h>l) peaks (hkl), such as (100), (110), (200), (201), (210), (211), etc., decrease rapidly and ultimately disappear, whereas another set of peaks (lkh), including (001), (002), (102), (112), etc., are still intense. This interesting result suggests that at grain size below a certain critical size an increasing number of grains no longer show 90°-domains, which is confirmed by TEM observations. Meanwhile, X-ray evidence of such a grain-size-related absence of 90°-domains is also found for PbTiO₃ films on Pt(111) and fused-glass substrates. The volume fractions of single-domain grains (without 90°-domains) in the films are estimated from their XRD patterns. By combining SEM and TEM investigations, the critical grain size for the formation of 90°-domains is further determined to be near 200 nm. Received: 19 December 1996/Accepted: 24 March 1997     

Inhomogeneities in silicon p-n-junctions

Latent macroscopic defects in silicon are detected by electrical and electron microscope measurements. They lead to anomalous temperature dependence of the Fermi level position and growth in the hole capture coefficient. A level with energy of 0.55 eV measured from the conduction zone controls the recombination process. It is proposed that macroscopic defects develop upon association of oxygen-silicon vacancy complexes. Action of an electron beam leads to reversible changes which increase upon multiple scanning, affecting the value of the diffusion length.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 71–75, April, 1991.     

Variational perturbation theory. Anharmonic oscillator

A nonperturbative method is suggested for calculating functional integrals. Its efficiency is demonstrated for the quantum-mechanical anharmonic oscillator. A quantity we are interested in is represented by a series, a finite number of terms of which describes not only the region of small coupling constants but well reproduces the strong coupling limit. The method is formulated only in terms of the Gaussian functional quadratures and diagrams are used of the conventional perturbation theory.     

AUTOMATED WIND TUNNEL MEASUREMENTS

It is common practice in power transmission to use bundled overhead electrical conductors because the lower rate of corona discharge, compared with single conductors, makes the bundle attractive for high voltages. However, secondary problems may arise from the vibrations induced by the aerodynamic forces which act on the leeward conductors as a result of their immersion in the wake of a windward conductor. Thus, in addition to possible aeolian and galloping oscillations observed for a single conductor, bundle conductors may also be subjected to wake-induced oscillations. ^1,2 Although extensive research has been done on the aeroelastic behavior of single and bundled conductors which are bare, little is known about the galloping or wake oscillation characteristics of given bundle conductors which, depending upon the environmental conditions during the formation of ice, may have five or so representative shaped cross-sections. One important task involves the aerodynamic quasi-static force and moment measurements in a wind tunnel using full scale conductor cross-sections each of which must be rotated through many angles at different spacings. Such measurements are repetitive as well as tediously time consuming and, hence, are beneficially automated. A reliable, accurate and inexpensive automated apparatus is described in this paper which permits the aerodynamic measurements to be performed efficiently and without intervention. Most importantly, it relieves the operator of the usual responsibility for manually controlling the separation and orientation of the sections as well as the need to manually compensate fluctuations in the free stream air speed. For simplicity, the apparatus is detailed in the context of a twin bundle conductor.     

The binding of manganese(II) and zinc(II) to the synthetic oligonucleotide d(C-G-C-G-A-A-T-T-C-G-C-G)2. A 1H NMR study

The interaction of the synthetic oligonucleotide d(C-G-C-G-A-A-T-T-C-G-C-G)2 with two different transition-metal ions has been investigated in aqueous solution by means of 1H NMR spectroscopy. The effects on the DNA due to the presence of manganese(II) or zinc(II) have been monitored by observing the paramagnetic broadening and diamagnetic shifts of the non-exchangeable proton resonance lines, respectively. The 1H NMR spectra acquired during the course of the manganese(II) titration show very distinct broadening effects on certain DNA resonance lines. Primarily, the H8 resonance of G4 is affected, but also the H5 and H6 resonances of C3 are clearly affected by the metal. The results imply that the binding of manganese(II) to DNA is sequence specific. The 1H spectra obtained during the zinc(II) titration reveal diamagnetic shift effects which largely conform with the paramagnetic broadening effects due to the presence of manganese(II), although this picture is somewhat more complex. The H8 resonance of G4 displays a clearly visible high-field shift, while for the other guanosine H8 protons this effect is absent. The H1' and H2' protons of C3 show an effect of similar strength, although in the opposite direction, while H5 and H6 of C3 are only slightly affected. Local differences in the structure of the DNA and the basicities of potential binding sites on different base steps in the sequence might account for the observed sequence selectivity.     

The oxidation of 3,3′-dimethoxy benzidine with potassium bromate in acidic solutions

The kinetics and mechanism of the oxidation of 3,3′-dimethoxybenzidine (oda, o-dianisidine) by potassium bromate in aqueous acidic medium were studied by monitoring the formation rate of the reaction product, 3,3′-dimethoxy 4,4′-diphenoquinone at 447 nm. The reaction is, first order with respect to both the substrate and oxidant, and second order with respect to H⁺. The oda: bromate stoichiometric ratio is 1:1. Plausible mechanism and rate laws are proposed accounting the experimental findings. Computer simulations were done using the proposed mechanism.     

Synthesis of dimethylditritiogermane Me<Subscript>2</Subscript>GeT<Subscript>2</Subscript>

A microsynthetic procedure for preparing tritium-labeled alkyl-substituted germanes is developed. The resulting dimethylditritiogermane can be used as a source of dimethylgermylium ions. The synthesis was performed by the reduction of dibromodimethylgermane with lithium tritide in presence of AlBr₃.     

Low-energy ion-assisted control of interfacial structures in metallic multilayers

A molecular dynamics method has been used to simulate the argon ion-assisted deposition of Cu/Co/Cu multilayers and to explore ion beam assistance strategies that can be used during or after the growth of each layer to control interfacial structures. A low-argon ion energy of 5–10 eV was found to minimize a combination of interfacial roughness and interlayer mixing (alloying) during the ion-assisted deposition of multilayers. However, complete flattening with simultaneous ion assistance could not be achieved without some mixing between the layers when a constant ion energy approach was used. It was found that multilayers with lower interfacial roughness and intermixing could be grown either by modulating the ion energy during the growth of each metal layer or by utilizing ion assistance only after the completion of each layers deposition. In these latter approaches, relatively high-energy ions could be used since the interface is buried and less susceptible to intermixing. The interlayer mixing dependence upon the thickness of the over layer has been determined as a function of ion energy.