Phospha-Michael additions to activated internal alkenes: steric and electronic effects

The addition of P(O)-H bonds to internal alkenes has been accomplished under solvent-free conditions without the addition of a catalyst or radical initiator. Using a prototypical secondary phosphine oxide, a range of substrates including cinnamates, crotonates, coumarins, sulfones, and chalcones were successfully functionalized. Highly activated acceptors such as isopropylidenemalononitrile and ethyl 2-cyano-3-methyl-2-butenoate underwent the phospha-Michael reaction upon simple trituration of the reagents at room temperature, whereas less activated substrates such as ethyl cinnamate and methyl crotonate required heating (>150 °C) in a microwave reactor to achieve significant consumption of the starting alkenes. For the latter alkenes, a competing reaction involving disproportionation of the ditolylphosphine oxide into ditolylphosphinic acid and ditolylphosphine was observed at the high temperatures needed to promote the addition reaction.     

Self-reinforced cellulose nanocomposites

A self-reinforced cellulosic material was produced exclusively from regenerated cellulose microcrystals. The level of reinforcement was controlled by tailoring the crystallinity of cellulose by controlling the dissolution of microcrystalline cellulose (MCC) before its regeneration process. After the cellulose regeneration a self-reinforced material was obtained in which cellulose crystals reinforced amorphous cellulose. This structure was produced by dissolution of MCC in a non-derivatising cosolvent N,N-dimethylacetamide/LiCl followed by subsequent cellulose regeneration in distilled H₂O. The reduction of the overall crystallinity of self-reinforced regenerated cellulose was dependent on the dissolution time of the cellulose precursor. The crystallinity of regenerated cellulose was determined by wide angle X-ray diffraction. A reduction in crystal size from microcrystalline cellulose to regenerated cellulose was observed with increasing dissolution time in DMAc/LiCl cosolvent. The reduction in degree of crystallinity of regenerated cellulose led to a decrease in the tensile mechanical performance and thermal stability of the regenerated cellulose. The controlled dissolution of microcrystalline cellulose resulted in the modification of structural, physical, thermal properties and moisture uptake behaviour of regenerated cellulose.     

Determination of hydrazine in maleic hydrazide technical and pesticide formulations by gas chromatography: collaborative study

Twelve collaborating laboratories assayed hydrazine in technical maleic hydrazide (MH), 6-hydroxy-2H-pyridazin-3-one, and 2 formulated products, a liquid concentrate and a soluble granule, using gas chromatography (GC) with electron capture detection. The hydrazine content in the samples ranged from 0.03 ppm, in the liquid concentrate, to 0.26 ppm, in MH technical. Hydrazine and MH are dissolved in an aqueous solution. The MH is then precipitated out of solution by acidification. The solution containing hydrazine is treated with excess pentafluorobenzaldehyde (PFB) to form pentafluorobenzaldehyde azine (PFBA). The PFBA is extracted with hexane for analysis by GC using an electron capture detector. Peak area responses of PFBA are measured and quantified by external standardization. Hydrazine concentration is calculated from the PFBA determination. The laboratories weighed each test sample in duplicate with duplicate analysis for each weighing. Data from these laboratories were statistically analyzed. The average relative repeatability was determined to be 5.34% and the average relative reproducibility was 27.99%.     

Optimisation and characterisation of biosensors based on polyaniline

With lower limits of detection and increased stability constantly being demanded of biosensor devices, characterisation of the constituent layers that make up the sensor has become unavoidable, since this is inextricably linked with its performance. This work describe the optimisation and characterisation of two aspects of sensor performance: a conductive polymer layer (polyaniline) and the immobilised protein layer. The influence of the thickness of polyaniline films deposited electrochemically onto screen-printed electrode surfaces is described in this work in terms of its influence on a variety of amperometric sensor performance characteristics: time to reach steady state, charging current, catalytic current, background current and signal/background ratios. The influence of polymer film thickness on the conductivity and morphology of finished films is also presented.

An electrostatic method of protein immobilisation is used in this work and scanning electron microscopy in conjunction with gold-labelled antibodies and back-scattered electron detection has enabled the direct visualisation of individual groups of proteins on the sensor surface. Such information can provide an insight into the performance of sensors under influence of increasing protein concentrations.     

Zur Hochdruck-Flüssigkeits-Chromatographie von polycyclischen aromatischen Kohlenwasserstoffen

Two aspects of high-pressure liquid chromatography (HPLC) of polycyclic aromatic hydrocarbons (PAH) have been studied: The application of HPLC to the analysis of very highly condensed PAH, that cannot be analyzed by gas chromatography, and the application of u.v. spectroscopy to the identification of PAH, that have been separated by HPLC. A device, that allows the rapid scanning of u.v. spectra within the HPLC apparatus, is described.     

Ferromagnetic resonance investigation of dispersed Ni catalysts: epitaxial and textural effects from the support

Catalysts consisting of dispersed Ni particles supported on silica and alumina, with sizes ranging from 6 to 20 nm, have been studied by ferromagnetic resonance. For the Ni on Al₂O₃ catalyst, a textural promotion effect is shown to be present and it is attributed to the possible presence of NiAl₂O₄. The FMR data confirm the epitaxial growth of Ni on SiO₂ when Ni antigorite is reduced and show that some anisotropy is still present after sintering of the catalyst at about 1200K.     

Templated synthesis of the novel layered silver-antimony sulfides [H3NCH2CH2NH2][Ag2SbS3 and [H3NCH2CH2NH2]2[Ag5Sb3S8

Two new silver-antimony sulfides, [C(2)H(9)N(2)][Ag(2)SbS(3)] (1) and [C(2)H(9)N(2)](2)[Ag(5)Sb(3)S(8)] (2), have been prepared solvothermally in the presence of ethylenediamine and characterized by single-crystal X-ray diffraction, thermogravimetry, and elemental analysis. Compound 1 crystallizes in the space group Pn (a = 6.1781(1) A, b =11.9491(3) A, c = 6.9239(2) A, beta =111.164(1) degrees ) and 2 in the space group Pm (a = 6.2215(2) A, b = 15.7707(7) A, c = 11.6478(5) A, beta = 92.645(2) degrees ). The structure of 1 consists of chains of fused five-membered Ag(2)SbS(2) rings linked to form layers, between which the template molecules reside. Compound 2 contains honeycomb-like sheets of fused silver-antimony-sulfide six-membered rings linked to form double layers. The idealized structure can be considered to be an ordered defect derivative of that of lithium bismuthide, Li(3)Bi, and represents a new solid-state structure type.     

Electron delocalization in cross-conjugated p-phenylenevinylidene oligomers

The synthesis, structure, and electronic properties of a series of cross-conjugated p-phenylenevinylidene oligomers with one to four double bonds are reported. The X-ray crystal structure of the compound with two double bonds reveals a nonplanar conformation with torsion angles about the C(phenylene)-C(vinylidene) and C(phenyl)-C(vinylidene) formal single bonds of 39.5(2) degrees and 30.5(2) degrees, respectively. Admixture of quinoid character in the ground state is observed. Infrared and Raman spectroscopy do not provide a clear picture of the degree of electron delocalization in the series, since the C=C stretching mode does not adequately reflect the C=C bond order and has a local nature. In contrast, electronic spectra and electrochemical data, as well as AM1 and PPP/SCF calculations, reveal that the cross-conjugated compounds basically behave as linearly pi-conjugated systems in the sense that molecular orbitals are delocalized over the entire structure and systematically change in energy. The electronic interaction between the repeating units is, however, not very strong, which has the consequence that spatial extension of the molecular orbitals does not lead to a red shift of the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) electronic transition. This is related to the feature that the modest narrowing of the HOMO-LUMO gap with the chain length is accompanied by a relatively large reduction of electron repulsion. This finding implies that care should be taken in the use of electronic spectra for the evaluation of conjugation phenomena.