Revised mechanism and improved methodology for the Perkin condensation. Resuscitation of the mechanism involving benzal acetate and the improbability of the enolate of acetic anhydride

The Perkin condensation most likely occurs via the initial formation of a gem-diacetate from the aromatic aldehyde and acetic anhydride reactants. The key reactive nucleophile appears to be the enolate of the gem-diacetate rather than of acetic anhydride. The diacetate from PhCHO may be converted to cinnamic acid under a variety of (relatively) mild basic conditions.     

Influence of boric acid on the electrochemical deposition of Ni

The electrolytic deposition of Ni onto a paraffin-impregnated graphite electrode from supporting chloride electrolyte (0.5 mol dm⁻³ NaCl) adjusted to the required pH using dilute HCl is investigated. The effect of electrolyte composition on the Ni electrodeposition is studied using linear sweep voltammetry in the cathodic region. An elimination voltammetry procedure was applied to evaluate the polarization curves. The aim of this work was to deduce the mechanism of Ni reduction in the chloride bath as well as the influence of boric acid on this. Positively-charged NiCl⁺ ions were found to be the electroactive particles in the Ni reduction mechanism. The strong competition between the NiCl⁺, Cl⁻ and H⁺ ions for active sites at the electrode is discussed. Kinetically-controlled adsorption/desorption processes of various species were also confirmed using elimination voltammetry with a linear scan. The evolution of gaseous hydrogen, catalyzed by the freshly-deposited Ni, accompanies the electrodeposition process. The presence of boric acid at a sufficiently high concentration inhibits the deposition of Ni and, at the same time, improves the morphology and brightness, as well as the adhesion of the deposited Ni. Elimination voltammetry with a linear scan is an efficient way to evaluate current–potential curves that reflect the electrodeposition of one-component Ni coatings. By eliminating selected currents, additional interesting and useful information can be obtained from voltammetric data.     

Synthesis and properties of poly(amic acid)s and polyimides based on 2,2′,6,6′‐biphenyltetracarboxylic dianhydride

Poly(amic acid)s (PAAs) having the high solution stability and transmittance at 365 nm for photosensitive polyimides have been developed. PAAs with a twisted conformation in the main chains were prepared from 2,2′,6,6′‐biphenyltetracarboxylic dianhydride (2,2′,6,6′‐BPDA) and aromatic diamines. Imidization of PAAs was achieved by chemical treatment using trifluoroacetic anhydride. Among them, the PAA derived from 2,2′,6,6′‐BPDA and 4,4′‐(1,3‐phenylenedioxy)dianiline was converted to the polyimide by thermal treatment. The heating at 300 °C under nitrogen did not complete thermal imidization of PAAs having glass‐transition temperatures (T_g)s higher than 300 °C to the corresponding PIs. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6385–6393, 2006     

Glycopolymeric inhibitors of β‐glucuronidase. III. Configurational effects of hydroxy groups in pendant glyco‐units in polymers upon inhibition of β‐glucuronidase

Two kinds of new glycopolymers, (P(VB‐1‐GlcaH‐co‐AAm), 9 ) and (P(VB‐1‐Glco‐co‐AAm), 10 ), were synthesized through the radical copolymerization of styrene derivatives bearing pendant D ‐glucaric and D ‐gluconic moieties, N‐(p‐vinylbenzyl)‐1‐D ‐glucaramide (VB‐1‐GlcaH, 7 ), and N‐(p‐vinylbenzyl)‐D ‐gluconamide (VB‐1‐Glco, 8 ), with acrylamide (AAm). Glycopolymer 9 bearing the pendant glucaric moiety at the first position inhibited the hydrolysis of a model compound for xenobiotics‐β‐glucuronide conjugates, p‐nitrophenyl β‐D ‐glucuronide, uncompetitively, in contrast to the competitive inhibition in the presence of the corresponding isomeric glycopolymer bearing the pendant D ‐glucaric unit at the sixth position (P(VB‐6‐GlcaH‐co‐AAm), 3 ) reported in our previous article. On the other hand, another copolymer 10 bearing the gluconic moiety was found not to inhibit the hydrolysis as well as the corresponding copolymer bearing pendant gulonic unit (P(VB‐6‐Glco‐co‐AAm), 4 ). These results indicate that the hydrolysis is influenced not only by existence of pendant carboxyl units but also by the direction on the linkage of the glyco‐units to the polymer frame. Therefore the configurational position of hydroxy groups in pendant glyco‐units in macromolecular inhibitors may be essential for the interaction with β‐glucuronidase. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4895–4903, 2006     

Reinforcement effect of MAA on nano‐CaCo3‐filled EPDM vulcanizates and possible mechanism

Methacrylic acid (MAA) was used as in situ surface modifier to improve the interface interaction between nano‐CaCO₃ particle and ethylene–propylene–diene monomer (EPDM) matrix, and hence the mechanical properties of nano‐CaCO₃‐filled EPDM vulcanizates. The results showed that the incorporation of MAA improved the filler–matrix interaction, which was proved by Fourier transformation infrared spectrometer (FTIR), Kraus equation, crosslink density determination, and scanning electron microscope (SEM). The formation of carboxylate and the participation of MAA in the crosslinking of EPDM indicated the strong filler–matrix interaction from the aspect of chemical reaction. The results of Kraus equation showed that the presence of MAA enhanced the reinforcement extent of nano‐CaCO₃ on EPDM vulcanizates. Crosslink density determination proved the formation of the ionic crosslinks in EPDM vulcanizates with the existence of MAA. The filler particles on tensile fracture were embedded in the matrix and could not be observed obviously, indicating that a strong interfacial interaction between the filler and the matrix had been achieved with the incorporation of MAA. Meanwhile, the presence of MAA remarkably increased the modulus and tensile strength of the vulcanizates, without negative effect on the high elongation at break. Furthermore, the ionic bond was thought to be formed only on filler surface because of the absolute deficiency of MAA, which resulted in the possible structure where filler particles were considered as crosslink points. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1226–1236, 2006     

Synergistic effect between 4-(2-pyridylazo) resorcin and chloride ion on the corrosion of cold rolled steel in 0.5 M sulfuric acid

The corrosion inhibition of 1-(2-pyridylazo)-2-naphthol (PAR) on the corrosion of cold rolled steel in 0.5 M sulfuric acid (H₂SO₄) was studied using weight loss method and potentiodynamic polarization method. Results obtained revealed that together with chloride ion, PAR is an effective corrosion inhibitor for steel corrosion in sulfuric acid. It was found that for steel corrosion inhibition in the presence of single PAR in sulfuric acid the Temkin adsorption isotherm may be used to explain the adsorption phenomenon. For the mixture of PAR and NaCl used as corrosion inhibitor, however, the Langmuir adsorption isotherm can be used to satisfactorily elucidate the adsorption of mixture of PAR and NaCl. Potentiodynamic polarization studies showed that single PAR mainly acts as a cathodic inhibitor for the corrosion of steel in 0.5 M sulfuric acid. The mixture of PAR and chloride ion, however, acts as a mixed type inhibitor that mainly inhibits cathodic reaction of the steel corrosion in sulfuric acid. By means of electrochemical polarization tests, a desorption potential at ca. −370 mV was observed for the adsorption of mixture of PAR and chloride ion, when potential reaches this value, adsorbed inhibitor molecule heavily departs from the steel surface. For the mixture of PAR and chloride ion, thermodynamic parameters such as adsorption heat, adsorption entropy and adsorption free energy were obtained from experimental data of the temperature studies of the inhibition process at four temperatures ranging from 30 to 45 °C, the kinetic data such as apparent activation energies and pre-exponential factors at different concentrations of the inhibitor were calculated, and the effect of the apparent activation energies and pre-exponential factors on the corrosion rates of cold rolled steel was discussed. The most suitable range of inhibitor concentration was discussed. The inhibitive action was satisfactorily explained by using both thermodynamic and kinetic models. Synergism between chloride ion and PAR was proposed. The results obtained from weight loss and potentiodynamic polarization were in good agreement.     

乌骨鸡磷脂侧链脂肪酸的GC-MS分析

用氯仿:甲醇(2:1)超声提取乌骨鸡总磷脂,丙酮脱油精制后,经皂化、甲酯化处理,应用GC-MS联用技术对其侧链脂肪酸组成进行分析,并以面积归一法,计算各脂肪酸的相对百分含量.结果显示,乌骨鸡总磷脂中含有硬脂酸27.46%、花生四烯酸21.39%、油酸18.22%、亚油酸16.67%、棕榈酸12.13%、二十二碳六烯酸(DHA) 2.26%、二十碳三烯酸1.71%、棕榈油酸0.16%.不饱和脂肪酸和多不饱和脂肪酸的含量分别为60.41%和42.03%.乌骨鸡磷脂侧链脂肪酸中高比例的多不饱和脂肪酸和花生四烯酸含量是乌骨鸡磷脂的显著特征.     

Moisture sorption, transport, and hydrolytic degradation in polylactide

Management of moisture penetration and hydrolytic degradation of polylactide (PLA) is extremely important during the manufacturing, shipping, storage, and end-use of PLA products. Moisture transport, crystallization, and degradation, in PLA have been measured through a variety of experimental techniques including size-exclusion chromatography, differential scanning calorimetry, and X-ray diffraction. Quartz crystal microbalance and dynamic vapor sorption experiments have also been used to measure moisture sorption isotherms in PLA films with varying crystallinity. A surprising result is that, within the accuracy of the experiments, crystalline and amorphous PLA films exhibit identical sorption isotherms.