A new solid-phase polymerization—metal phthalocyanine sheet polymers

The thermal reactions of pure metal(11) 4,4′,4″,4′″-phthalocyanine-tetracarboxylic acids of copper, cobalt, and nickel at 350–400°C in vacuum have been studied using Fourier transform infrared spectrometry, gas chromatography, and mass spectrometry. Based on these observations, novel in situ reactions for the synthesis of heat-resistant phthalocyanine “sheet” polymers are described. The poly(metal phthalocyanine) polymers of copper, cobalt, and nickel so synthesized have been characterized by elemental analysis, infrared spectroscopy, and dynamic thermogravimetric analysis. The most noteworthy property of these polymers is their extreme resistance to heat in an anaerobic atmosphere and their high char yields (89–93%) at 800°C in a nitrogen atmosphere.     

Mass transfer of oxygen in poly(2-hydroxyethyl methacrylate)

The diffusion coefficient of oxygen in poly(2-hydroxyethyl methacrylate) has been explicitly measured using an optical technique based on fluorescence quenching. This measurement represents the first explicit determination of D in PHEMA. A diffusion coefficient of oxygen in PHEMA of 1.36 × 10^?7 cm²/s at 20°C was obtained from this measurement. This value is shown to agree well with permeability data for PHEMA, the free volume theory of diffusion, and with values of D that have been explicitly measured in other methacrylate hydrogels.     

Preparation and properties of some α-aza-amino-acid derivatives,their possible use in peptide synthesis

Some derivatives of azaglycine and azaphenylalanine are described. Esters of acetyl- and benzoyl-aza-amino-acids rapidly cyclise to stable oxadiazolones and it is concluded that similar derivatives would be unsuitable for aza-peptide synthesis. t-Butyloxycarbonyl-azaglycine azide was too unreactive for use in peptide synthesis. Benzoyl-azaglycylphenylalanine ethyl ester and acetyl-azaphenylalanylphenylalanine ethyl ester were prepared by coupling benzoyl hydrazide and N-acetyl-N'-benzylhydrazide respectively with 2,4-dinitrophenyloxycarbonyl-phenylalanine ethyl ester.     

Synthesis and thermal characteristics of bisimides. I

Ten structurally different bisimide resins were prepared by reacting maleic anhydride/citraconic anhydride and benzophenone tetracarboxylic dianhydride with aromatic diamines and fused aromatic structures or heterocyclic groups. The amines included were 1,5-diaminonaphthalene, 2,5-bis(p-aminophenyl)1,3,4-oxadiazole, 3,3-bis(p-aminophenyl)phthalide, 9,9-bis(p-aminophenyl)fluorene. and 10,10-bis(p-aminophenyl)anthrone. These monomers were characterized by infrared (IR). ¹H-NMR, mass spectroscopy, and elemental analysis. Thermal polymerization of these monomers was investigated by differential scanning calorimetry. Broad exothermic peaks were observed for a temperature range of 225–380°C. Temperature of exothermic peak position was influenced by the presence of substituents at the olefinic bond, and in biscitraconimides it was 40–50°C lower than in the corresponding bismaleimides. Anaerobic char yields of cured bisimide resins ranged from 44 to 64%. Oxadiazole-containing bisimides had low thermal stability. Increase in formula weight between the imide groups did not influence the char yields in a systematic manner. Graphite cloth laminates with two of these bisimide resins were fabricated and tested for a number of physical properties. Their limiting oxygen index was 70–72%.     

Facile synthesis of novel functionalized bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) derivatives

An improved and efficient synthetic route to four functionalized bis(ethylenedithio)-tetrathiafulvalene (BEDT-TTF) derivatives 2-5 is reported. Tetrathiolate 1 was readily prepared from 2,2'-bis(1,3,4,6-tetrathiapentalen-5-one) under carefully controlled conditions. Subsequent reaction of 1 with selected primary alkyl halides affords new functionalized BEDT-TTF derivatives in good yields.     

Comment: 2004's fastest organic and biomolecular chemistry!

In January 2004, the Royal Society of Chemistry launched Organic & Biomolecular Chemistry (OBC) - a journal promising to provide high quality research from all aspects of synthetic, physical and biomolecular organic chemistry. The journal was set to build upon the foundations laid down by its predecessor publications (J. Chem. Soc., Perkin Trans. 1 and J. Chem. Soc., Perkin Trans. 2) as well as complement the subject coverage already published in prestigious general chemistry journals such as Chemical Communications and Chemical Society Reviews. Nearly two years on, just how is the programme developing and what can the community expect to see from the Royal Society of Chemistry (RSC)?     

Photofragmentation of dichloromethanol Cl2CHOH along C-O and C-Cl cleavages: a theoretical study

Multireference configuration interaction calculations are carried out for ground and excited states of dichloromethanol, Cl2CHOH, to investigate two important photofragmentation processes relevant to atmospheric chemistry. Five low-lying excited states (1(1)A", 2(1)A', 1(3)A", 2(3)A" and 1(3)A') in the energy range between 6.4 and 7.5 eV are found to be highly repulsive for C-Cl elongation, leading to ClCHOH (X2A) and Cl (X2P). Photodissociation along the C-O bond resulting in CHCl2 (X2A') and OH (X2II) has to overcome a barrier of about 0.5 eV because the low-lying excited states 1(1)A", 1(3)A' and 1(3)A" become repulsive only after the C-O bond is elongated by about 0.3 A.     

Neutron spectroscopic study of hydrogen bonding dynamics in L-serine

Inelastic incoherent neutron scattering (IINS) spectra were obtained at 10 K for normal and deuterated L-serine. The geometry of L-serine molecule was optimized for the zwitterion form using ab initio HF, MP2 and DFT (B3LYP) levels with 6-31G* and 6-311 + +G4** basis sets. The theoretical frequencies of normal and d4-L-serine were compared with IINS spectra. Normal coordinate analysis and band assignments based on ab initio calculations and experimental data were presented. IINS frequencies due to the out-of-plane gamma(N-H...O) hydrogen bond motions were observed and identified.     

The Early Stages of Native Enamel Dissolution Studied with Atomic Force Microscopy

Food-induced demineralization (erosion) is one of the key factors in surface structural changes of tooth enamel, with soft drinks being a significant etiological agent. The objective of this study was to measure early stages of enamel loss with high accuracy on native enamel surfaces combined with qualitative observations of changes in the surface morphology using the atomic force microscope (AFM). Native unerupted third molar surfaces were partly covered with a gold reference layer. Samples were imaged with the AFM before dissolution (at baseline) and after exposure to three different drinks (mineral water, a "toothkind" blackcurrant drink, and a lemon and lime juice drink) at five different exposure times (15 min, 30 min, 1 h, 2 h, and 3 h). The changes in the surface morphology were investigated qualitatively as well as quantitatively. This study showed that the maximum material loss occurred at the aprismatic parts of the enamel close to the perikymata. The maximum enamel loss was greatest for the lemon and lime juice drink and lowest for water. A two-way ANOVA of the transformed data, employing the natural logarithm, showed a statistically significant difference between both the drinks and the exposure time at a 95% confidence level (P=0.000). This demonstrates that the AFM is a suitable tool for measuring early stages of enamel demineralization. Copyright 2000 Academic Press.     

193 NM LIGHT INDUCES SINGLE STRAND BREAKAGE OF DNA PREDOMINANTLY AT GUANINE

Irradiation of DNA with 193 nm light results in monophotonic photoionization, with the formation of a base radical cation and a hydrated electron (φ_P1 = 0.048–0.065). Although >50% of the photoionization events initially occur at guanine in DNA, migration of the “hole” from the other bases to guanine occurs to yield predominantly its radical cation or its deprotonated form. From sequence analysis, the data reveal that 193 nm light induces single strand breaks (ssb) in double-stranded DNA preferential 3’ to a guanine residue. However, it has previously been reported that 193 nm light yields very low yields of ssb (<2% of the yield of eaq). The distribution of these ssb at guanine is nonrandom, showing a dependence on the neighboring base moiety. The efficiency of ssb formation at nonguanine sites is estimated to be at least one order of magnitude lower. The preferred cleavage at guanine is consistent with migration and localization of the electron loss center at guanine. It is argued that singlet oxygen and the photoionized phosphate group of the sugar moiety are not major precursors to ssb. At present, the mechanisms of strand breakage are not known although a guanine radical or one of its products remain potential precursors.