Vinyl‐type polymerization of norbornene by nickel(II) bisbenzimidazole catalysts

Novel nickel(II) bisbenzimidazole complexes were prepared via a three‐step synthetic procedure consisting of aniline/diacid condensation, ligand N‐alkylation, and metal complexation. The complexes were characterized by X‐ray crystallography and found to possess a pseudotetrahedral geometry. Upon activation with methylaluminoxane, these nickel bisbenzimidazoles did not polymerize simple olefins (e.g., ethylene, propylene, and 1‐butene) but were found to carry out the rapid and efficient polymerization of norbornene. The polynorbornene products were characterized by gel permeation chromatography/light scattering, ¹³C NMR, and IR, and their Mark–Houwink and dn/dc parameters were determined. The molecular weights of the polynorbornenes were very high (weight‐average molecular weight = 587,000–797,000 g/mol). ¹³C NMR suggested that the polymerization occurred via vinyl addition (i.e., a 2,3‐linked polymer); no ring‐opened product was observed. Thermogravimetric analysis indicated that the polynorbornenes were stable up to 400 °C under nitrogen. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2095–2106, 2003     

Superconvergence of recovered gradients of discrete time/piecewise linear Galerkin approximations for linear and nonlinear parabolic problems

Superconvergent error estimates in l₂(H¹) and l∞(H¹) norms are derived for recovered gradients of finite difference in time/piecewise linear Galerkin approximations in space for linear and quasinonlinear parabolic problems in two space dimensions. The analysis extends previous results for elliptic problems to the parabolic context, and covers problems in regions with nonsmooth boundaries under certain assumptions on the regularity of the solutions. © 1994 John Wiley & Sons, Inc.     

Molecular sieving of lambda phage DNA in polyacrylamide solutions as a function of the molecular weight of the polymer.

Electrophoresis of lambda phage DNA was carried out in solutions at various concentrations of uncrosslinked polyacrylamide of 0.6, 1, 5 and 9 x 10(6) molecular weight (Mw) with narrow Mw distribution. By inspection of mobilities in the various concentration ranges, it appears that mobilities decrease, and retardation increases, with increasing Mw. The relation between electrophoretic retardation and the Mw of the polymer was also interpreted (i) in the manner previously applied to nonlinear Ferguson plots and compatible with the Ogston model; and (ii) empirically, on the basis of the first derivatives of the functions describing the Ferguson plots at the polymer concentrations used. Interpretation (i) shows that the retardation increases linearly in the order of 0.6, 1, 5 and 9 x 10(6) Mw of polyacrylamide. Interpretation (ii) shows a nonlinear increase of retardation in the Mw range 5 to 9 x 10(6), and a decrease in retardation as Mw is raised from 0.6 to 5.0 x 10(6). Hypothetically, interpretation (ii) can be explained mechanistically by a progressive change, as the polymer size is increased, from a collision with the surface of the polymer fiber to one occurring after permeation in the interior of a random-coiled fiber. Interpretation (i) may fail to detect that change due to the large difference between DNA mobility in solutions of the smallest polymer and the free mobility. DNA peak detection in all of the four size classes of polyacrylamide in solution is limited to relatively narrow ranges of polymer concentration.(ABSTRACT TRUNCATED AT 250 WORDS)     

Information on DNA conformation derived from transverse pore gradient gel electrophoresis in conjunction with an advanced data analysis applied to capillary electrophoresis in polymer media.

Abnormally slow migration of DNA is conventionally viewed as being due to an abnormal conformation relative to "linear" standards. The evidence for this rests on a few instances where nonlinear DNA structures have been established by independent methods and yield low mobilities relative to standards. Transverse pore gradient gel electrophoresis of authentically bent kinetoplast DNA and of an upstream activator sequence (UAS) of an E. coli operon promoter shows in addition that curves of migration distance vs. gel concentration ("Ferguson curves") of such abnormally conformed DNA differ from those of "linear" standards. Since Ferguson curves are interpretable with regard to molecular size in concordance with a mathematical model (Ogston model), transverse pore gradient gel electrophoresis provides a simple means of correlating abnormally slow migration of DNA with molecular size. In addition, transverse pore gradient gel electrophoresis is able to distinguish between DNA banding which exhibits a steeper dependence on gel concentration than "linear" standards from one which shows the same dependence. The former appears characteristic of circularly bent DNA and gives rise to a substantial retardation, the latter of bending across a knot or kink in the DNA chain associated with a relatively minor retardation relative to standards. Circularly bent restriction fragments formed from kinetoplast DNA retain the characteristic intersecting Ferguson curves on the transverse pore gradient gel. Another authentically "abnormal" DNA structure recognizable on transverse pore gradient gels is supercoiled DNA derived from the reaction of topoisomerase with a plasmid. Different lengths of supercoiled sequences give rise to parallel Ferguson curves clearly intersecting with those of linear standards.(ABSTRACT TRUNCATED AT 250 WORDS)     

Electrostatic influence on rotational mobilities of sol-gel-encapsulated solutes by NMR and EPR spectroscopies

The rotational mobilities of small solute molecules encapsulated in tetramethyl orthosilicate (TMOS) sol-gels have been investigated by EPR spectroscopy of encapsulated nitroxide probes and by high-resolution NMR spectroscopic measurements of transferred NOE's (trNOE's), of T(1)'s, and of T(1)'s in the rotating frame (T(1)rho). The two spectroscopic methods are sensitive to motions on different time scales and hence, are nicely complementary. Suites of neutral, positively, and negatively charged nitroxide probes (EPR) and of simple diamagnetic small molecules (NMR) were selected to disclose influences of electrostatic interactions with the sol-gel walls and to probe the presence of multiple populations of molecules in distinct regions of the sol-gel pores. For neutral and negatively charged solute probes, both techniques disclose a single population with a significantly increased average rotational correlation time, which we interpret at least in part as resulting from exchange between free-volume and transiently immobilized surface populations. The electrostatic attraction between cationic probes and the negatively charged sol-gel walls causes the positively charged probes to be more effectively immobilized and/or causes a greater percentage of probes to undergo this transient immobilization. The EPR spectra directly disclose a population of cationic probes which are immobilized on the X-band EPR time scale: tau(c) greater than or approximately equal 10(-7) s. However, NMR measurements of trNOE's and of T(1)rho demonstrate that this population does exchange with the free-volume probes on the slower time scale of NMR. This approach is equally applicable to the study of solutes within other types of confined spaces, as well.     

Pre-irradiation treatments for CR-39 detectors

The production of track-spots in CR-39 detectors for alpha particles and the subsequent optical counting of the detectors are often influenced by foreign substances deposited on the surface of the detectors. The removal of these substances can be achieved using chemicals for pre-irradiation treatment. Two methods of pre-irradiation treatment were studied in the present experiments. One of them involves the dipping of the detectors in ethanol. In the other method, the detectors were treated in 6N KOH etchant prior to exposure. It was found that prolonged treatment could only produce a reduction in the track density of less than 20%.     

Solid-Phase Extraction and Capillary Gas Chromatographic Determination of Triazine Herbicides in Water

Abstract

A facile and efficient method is described for the determination of trace quantities of triazine herbicides, terbutryn, prometryn and ametryn in water. The procedure involved preconcentration of water samples by sorption on chromatographic grade silica gel particles with chemically modified surface, being covalently bonded with a nonofunctional C₈H₁₇ group. This was followed by solvent desorption with 2-propanol. The determinative step was achieved by capillary gas chromatography on Supelcowax-10 fused silica column using a nitrogen-phosphorus detector. The limit of detection was 0.1 μg-10 μgL^?1.     

Spontaneous macroscopic spin polarization in independent spinor Bose-Einstein condensates

We present experimental evidence for the spontaneous formation of a macroscopic spin polarization in overlapping regions of two independent Bose-Einstein condensates produced in different hyperfine states of 87Rb. The condensates are independent in the sense that we do not explicitly introduce a relative phase between them. A single "spin-tip" pulse maps the transverse spin polarization into longitudinal spin polarization, and the atomic density distributions are measured with a Stern-Gerlach imaging method. The resulting matter-wave interference patterns are anticorrelated.     

Backward-wave propagation and discrete solitons in a left-handed electrical lattice

We study experimentally, analytically and numerically the backward-wave propagation, and formation of discrete bright and dark solitons in a nonlinear electrical lattice. We observe experimentally that a focusing (defocusing) effect occurs above (below) a certain carrier frequency threshold, and backward-propagating bright (dark) discrete solitons are formed. We develop a discrete model emulating the relevant circuit and benchmark its linear properties against the experimental dispersion relation. Using a perturbation method, we derive a nonlinear Schrödinger equation, that predicts accurately the carrier frequency threshold. Finally, we use numerical simulations to corroborate our findings and monitor the space-time evolution of the discrete solitons.