Chemistry of biureas—I: Cyclisation of ethoxycarbonyl derivatives of thiobiureas and bithioureas

The interaction of ethoxycarbonyl isothiocyanate with semicarbazides or thiosemicarbazides produces 1-ethoxycarbonyl-2-thiobiureas or bithioureas, respectively. The former are cyclisable to 2-ethoxycarbonamido-5-hydroxy-l,3,4-thiadiazole in acid, or to 2(H)-carbamoyl-3-hydroxy-5-alkylthio-1,2,4-triazoles, and thence to 3-hydroxy-5-mercapto-1,2,4-triazole in alkaline media. The ring-closure of the 1-ethoxycarbonylbithioureas proceeds similarly affording, under the influence of acids, 5-amino (or mercapto)-2-ethoxycarbonamido-1,3,4-thiadiazoles. The action of alkali produces compounds derived from 3-hydroxy-5-mercapto-1,2,4-triazole; the isolation, in a selected example, of the 2(H)-phenylthiocarbamoyl-derivative, elucidates the course of this reaction. Hydrazinolysis of 1-ethoxycarbonylbithiourea yields 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole.     

Effect of the amine group on relative bond strengths in cubane and azacubanes

We have carried out an ab initio self-consistent-field molecular orbital study of the structures and relative bond strengths of some monoamine derivatives of cubane, azacubane, and 1,3-diazacubane. Our focus has been on the effect of the NH₂ group on the strengths of the endocyclic strained bonds in these molecules, and, in particular, on the conformation dependence of this effect. Our results show a consistent bond-weakening observed in one [and only one] C-C or C-N bond adjacent to the site of NH₂ substitution. We find that the particular bond that is weakened is in all cases essentially coplanar with the C-NH₂ bond and the position of the most negative electrostatic potential of the amine nitrogen. This direction-specific bond-weakening is viewed as an example of the anomeric effect.     

Composting and biodegradation of thermally processed feather keratin polymer

Proteins obtained from agricultural sources represent a unique feedstock from which to prepare thermally processable polymers. In this study, thermally processed feather keratin films were composted with three-month-old compost inoculum in self-heating laboratory composters for 30 days and temperature and carbon dioxide development monitored. About 24% of the available carbon in the feather keratin polymer (FKP) was metabolized in this time and this may not be high enough for some applications. Degradation of the feather keratin polymers was observed within 10 days with concurrent molecular weight reduction measured using FT-IR. Visual inspection of the polymers also showed destruction of the films. A change in crystallinity was observed in DSC analysis and some degradation processes could be inferred from this as well.     

Formation of tetra(ethylene oxide) terminated Si-C linked monolayers and their derivatization with glycine: an example of a generic strategy for the immobilization of biomolecules on silicon

Surface modification with oligo(ethylene oxide) functionalized monolayers terminated with reactive headgroups constitutes a powerful strategy to provide specific coupling of biomolecules with simultaneous protection from nonspecific adsorption on surfaces for the preparation of biorecognition interfaces. To date, oligo(ethylene oxide) functionalized monolayer-forming molecules which can be activated for attachment of biomolecules but which can selectively form monolayers onto hydrogen terminated silicon have yet to be developed. Here, self-assembled monolayers (SAMs) containing tetra(ethylene oxide) moieties protected with tert-butyl dimethylsilyl groups were formed by thermal hydrosilylation of alkenes with single-crystal Si(111)-H. The protection group was used to avoid side reactions with the hydride terminated silicon surface. Monolayer formation was carried out using solutions of the alkene in the high-boiling-point solvent 1,3,5-triethylbenzene. The protecting group was removed under very mild acidic conditions to yield a free hydroxyl functionality, a convenient surface moiety for coupling of biological entities via carbamate bond formation. The chemical composition and structure of the monolayers before and after deprotection were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray reflectometry. To demonstrate the utility of this surface for covalent modification, two reagents were compared and contrasted for their ability to activate the surface hydroxyl groups for coupling of free amines, carbonyl diimidazole (CDI), and disuccinimidyl carbonate (DSC). Analysis of XP spectra before and after activation by CDI or DSC, and after subsequent reaction with glycine, provided quantitative information on the extent of activation and overall coupling efficiencies. CDI activated surfaces gave poor coupling yields under various conditions, whereas DSC mediated activation followed by aminolysis at neutral pH was found to be an efficient method for the immobilization of amines on tetra(ethylene oxide) modified surfaces.     

C?H Bond dissociation of acetylene: Local density functional calculations

The C? H bond dissociation energy of acetylene was computed by both ab initio approaches and density functional theory in a local density approximation (DFT–LDA ). Structures and energies for acetylene and its dissociation products (the ethynyl and hydrogen radicals) are presented and compared. Using directly computed HCCH and HCC· energies and the exact H· value, the DFT–LDA calculations are found to yield C? H dissociation energies ranging from 129 to 131 kcal/mol, in good agreement with recent experimental and the highest level theoretical results. The DFT–LDA results show little dependence upon the computational procedure used to obtain geometries.     

High-performance liquid chromatographic analysis of basic drugs on silica columns using non-aqueous ionic eluents. II. Application of UV, fluorescence and electrochemical oxidation detection

Unmodified silica columns together with non-aqueous ionic eluents give stable yet flexible systems for the analysis of basic drugs by high-performance liquid chromatography. Low-wavelength UV and fluorescence detection may be used, and fluorescence may be optimised by, for example, post-column pH change or derivatisation of some primary aliphatic amines with o-phthaldialdehyde. A novel feature is that electrochemical oxidation can be used for the detection of most analytes and this detection mode is thus discussed in detail. Retention and relative response data (UV, 254 nm and electrochemical, +1.2 V) have been generated for 462 compounds using a 125-mm Spherisorb S5W silica column and methanolic ammonium perchlorate (10 mM, pH 6.7) as eluent. This system can be used isocratically in qualitative analyses and also for quantitative work, when either the wavelength or the applied potential can be adjusted to optimise the response.     

Temperature dependence of development of slip bands and of strain hardening in AgCl crystals

The dependence of the flow stress and the slip band density on the plastic strain has been measured at 201 K, 293 K and 363 K. The growth of deformation concentrated in an average slip band has been stated. The types of obstacles acting against the rise and development of a slip band and the temperature dependence of the strain hardening in AgCl crystals are discussed. An equation stating the dependence of the flow stress on the slip band density is presented. The hardening in AgCl crystals is classified as the stage III — hardening.     

Effect of added alpha-lactalbumin protein on the phase behavior of AOT-brine-isooctane systems

We have found that the presence of <1 wt% of the globular protein alpha-lactalbumin has a significant impact on the equilibrium phase behavior of dilute sodium bis(ethylhexyl) sulfosuccinate (AOT)/brine/isooctane systems. Nuclear magnetic resonance (NMR), Karl Fischer titration, and ultraviolet spectroscopy were used to determine the surfactant, oil, water, and protein content of the organic and aqueous phases as a function of the total surfactant and protein present. As a small amount of alpha-lactalbumin is added to the mixture, there is a substantial increase (up to 80%) in the maximum water solubility in the water-in-oil microemulsion phase. Dynamic light scattering measurements indicate that this increase is due to a decrease in the magnitude of the (negative) spontaneous curvature of the surfactant monolayer, as droplets swell in size. As the molar ratio of alpha-lactalbumin to AOT surpasses approximately 1:300, the partitioning of water, protein, and surfactant shifts to the excess aqueous phase, where soluble assemblies with positive curvature are detected by dynamic light scattering. Significant amounts of isooctane are solubilized in these aggregates, consistent with the formation of oil-in-water microemulsion droplets. Circular dichroism studies showed that the tertiary structure of the protein in the microemulsion is disrupted while the secondary structure is increased. In light of these findings, the protein most likely expands to a molten-globule type conformation in the AOT interfacial environment, but does not substantially unfold to become an extended chain.     

Dendritic nanowire ultraviolet laser array

Self-organized dendritic crystal growth is explored to assemble uniform semiconductor nanowires into highly ordered one-dimensional microscale arrays that resemble comb structures. The individual ZnO nanowires have uniform diameters ranging from 10 to 300 nm. They are evenly spaced on a stem with a regular periodicity of 0.1-2 micrometer. Under optical excitation, each individual ZnO nanowire serves as a Fabry-Perot optical cavity, and together they form a highly ordered nanowire ultraviolet laser array.