Molecular architecture and conformation of macromolecules of novel polysilanes

Molecular-weight parameters of new silane homo- and copolymers were analyzed. For all polymers, theM _w values are close ((6.0–8.6)·10⁴), the curves of molecular weight distribution are unimodal, andM _w/M _n=2−2.5. Cyclic fragments or those containing the −C=C− groups make the major contribution to the polysilane chain rigidity. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2430–2433, December, 1998.     

Controlled assembly of carbon nanotubes by designed amphiphilic Peptide helices

Carbon nanotubes have properties potentially useful in diverse electrical and mechanical nanoscale devices and for making strong, light materials. However, carbon nanotubes are difficult to solubilize and organize into architectures necessary for many applications. In the present paper, we describe an amphiphilic alpha-helical peptide specifically designed not only to coat and solubilize carbon nanotubes, but also to control the assembly of the peptide-coated nanotubes into macromolecular structures through peptide-peptide interactions between adjacent peptide-wrapped nanotubes. The data presented herein show that the peptide folds into an amphiphilic alpha-helix in the presence of carbon nanotubes and disperses them in aqueous solution by noncovalent interactions with the nanotube surface. Electron microscopy and polarized Raman studies reveal that the peptide-coated nanotubes assemble into fibers with the nanotubes aligned along the fiber axis. Most importantly, the size and morphology of the fibers can be controlled by manipulating solution conditions that affect peptide-peptide interactions.     

Influence of swelling in supercritical carbon dioxide of Ultem and polyhexafluoropropylene thin films on their gas separation properties: comparative analysis

Thin films of polyetherimide Ultem and polyhexafluoropropylene serially underwent different treatments: drying to a constant weight, annealing at temperature slightly higher than glass transition temperature, and swelling in supercritical carbon dioxide and their gas transport properties were investigated.     

Effect of supercritical carbon dioxide on nanoporous polyhexafluoropropylene

The effect of supercritical CO₂ (sc-CO₂) on the size distribution of free volume holes (nanopores) in a polyhexafluoropropylene (PHFP) polymer matrix has been studied. Residual (after CO₂ release) swelling improves gas transport properties of the material. Relaxation of these properties over time has been compared with changes in permeability and nanoporosity. For PHFP samples with different histories, the data on nanoporosity have been obtained using positron annihilation lifetime spectroscopy (micropores) and the lowtemperature gas sorption technique (mesopores and part of micropores). Matching of the data is intended to reveal the role of pores of different sizes in permeability of membrane materials to different gases and determine the specifics of application of the positron annihilation technique to studying sc-CO₂-modified objects.     

Sorption-Catalytic Determination of Imazapyr on a Copper-Containing Sorbent

 Sorption of copper on filter-paper with chemically attached hexamethylenediamino-groups (HMDA-filter) allows to obtain the sorbent (Cu/HMDA-filter) stable in respect to desorption of copper. A nitrogen-containing herbicide imazapyr (imaz) is retained on Cu/HMDA-filters at pH 5.5–7.0 forming a relatively stable complex. Imazapyr is determined directly on the sorbent by its activating effect in the oxidation of hydroquinone with H₂O₂ catalyzed by Cu(II) with the formation of a product absorbing at 490 nm. The copper ions serve both to preconcentrate imazapyr and to catalyze the indicator reaction. The use of 1-μL sample aliquots pipetted onto the Cu/HMDA-filters allows to determine 1 × 10⁻³–0.03 μmol of imazapyr, whereas preconcentration of the analyte by pumping of its solution through the same sorbent expands the linear range to 1 × 10⁻⁴–1 × 10⁻¹ μmol of imazapyr. When the indicator reaction is carried out in solution, the range of activating action of imazapyr is narrower (0.06–0.1 μmol a for a solution volume of 10 mL). The determination is selective: 5–100-fold amounts of amines, aminoacids, carboxylic acid derivatives and other model compounds do not interfere. Soil extracts and carrot juice samples spiked with imazapyr have been analyzed. Received January 10, 2000. Revision July 28, 2000.     

Correlation between the transport behavior of polyimides and the conformational rigidity of their chains

For a number of polyimides, Kuhn segment lengths have been calculated by the Monte Carlo method under the free-rotation approximation and the energies of cohesion have been estimated by the group-contribution method. It has been shown that, in the case of isomeric polyimides characterized by close energies of interchain interactions, a decrease in the rigidity of chains always leads to reductions in the free volume and gas permeability. For polyimides of allied structures, the simultaneous (and frequently oppositely directed) effects of chain rigidity and the energy of interchain interactions ambiguously influence gas permeability. Both factors should be taken into account during estimation of the influence of chain rigidity on the transport characteristics of polymers. Small-scale effects of packing and mobility of chain fragments exert the decisive effect on the transport characteristics of polyimides possessing a decreased mobility of chains.     

Fabrication and characterization of homogeneous surface-enhanced Raman scattering substrates by single pulse UV-laser treatment of gold and silver films

The fabrication of SERS-active substrates, which offer high enhancement factors as well as spatially homogeneous distribution of the enhancement, plays an important role in the expansion of surface-enhanced Raman scattering (SERS) spectroscopy to a powerful, quantitative, and noninvasive measurement technique for analytical applications. In this paper, a novel method for the fabrication of SERS-active substrates by laser treatment of 20, 40, and 60 nm thick gold and of 40 nm thick silver films supported on quartz glass is presented. Single 308 nm UV-laser pulses were applied to melt the thin gold and silver films. During the cooling process of the noble metal, particles were formed. The particle size and density were imaged by atomic force microscopy. By varying the fluence, the size of the particles can be controlled. The enhancement factors of the nanostructures were determined by recording self-assembled monolayers of benzenethiol. The intensity of the SERS signal from benzenethiol is correlated to the mean particle size and thus to the fluence. Enhancement factors up to 10(6) with a high reproducibility were reached. Finally we have analyzed the temperature dependence of the SERS effect by recording the intensity of benzenethiol vibrations from 300 to 120 K. The temperature dependence of the SERS effect is discussed with regard to the metal properties.     

Citric acid traps to replace sulphuric acid in the ammonia diffusion of dilute water samples for 15N analysis

The analysis of 15N in aqueous samples requires the concentration of dissolved nitrogen (N) into a small volume that can be analysed by mass spectrometry. This is conveniently achieved by the NH3 diffusion technique, where NH4+ is captured on small acidified filters enclosed in PTFE. NO3- can be analysed the same way by reducing it to NH4+ with Devarda's alloy. H2SO4 is commonly used for the acidification of the filters. During combustion, however, this acid leads to the production of SO2 and elemental sulphur, which both have detrimental effects on the mass spectrometer. We propose here to replace H2SO4 with citric acid because it is combusted completely to CO2 and H2O in the elemental analyser before entering the mass spectrometer. Citric acid was found to give comparable results in terms of N recovery and 15N values, both for NH4+ and for NO3- samples. Blank samples revealed that N contamination was slightly lower using citric instead of sulphuric acid as acidifier of the glass filters. NH4+ samples first concentrated over cation-exchange columns were strongly acidic and several methods were tested to raise the pH for the subsequent diffusion. These samples gave incomplete N recoveries, but this problem was independent of the acid used on the filters and of the final pH of the sample. Complete recovery was achieved only by increasing the volume of the eluate from the columns. Citric acid can thus generally be recommended instead of H2SO4 for ammonia diffusion.