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91.
Roger P. Kambour 《Journal of Polymer Science.Polymer Physics》1966,4(1):17-24
Of nine glassy polymers so far investigated, eight yield evidence that fracture propagation involves the formation and breaking of craze material. All eight produce fracture surfaces exhibiting interference colors to one extent or another and even the colorless areas cause low angle x-ray scattering. Ranked in terms of decreasing ease of colored surface formation, these polymers are poly(methyl methacrylate), poly(ethyl methacrylate), polystyrene, acrylonitrile—styrene copolymer, poly-α-methylstyrene, poly(vinyl acetate), a polyhydroxy ether, and polycarbonate. Only rigid poly(vinyl chloride) has failed to show evidence of precrack craze formation. 相似文献
92.
Bickelhaupt FM DeKock RL Baerends EJ 《Journal of the American Chemical Society》2002,124(7):1500-1505
Exceptionally short N [bond] F bond distances of only 1.217 A (crystal) and 1.246 A (gas phase) have been reported for N(2)F(+), making it the shortest N [bond] F bond ever observed. To trace the origin of this structural phenomenon, we have analyzed the model systems N(2)X(+), NF(3)X(+), and NH(3)X(+) (X [double bond] F, H) using generalized gradient approximation density functional theory at BP86/TZ2P. In good agreement with experiment, the computations yield an extremely short N [bond] F bond for N(2)F(+): we find N [bond] F bond distances in N(2)F(+), NF(4)(+), and NH(3)F(+) of 1.245, 1.339, and 1.375 A, respectively. The N [bond] X bonding mechanisms are quantitatively analyzed in the framework of Kohn-Sham MO theory. At variance with the current hypothesis, reduced steric and other Pauli repulsion (of substituents or lone pairs at N with F) rather than the extent of s [bond] p hybridization of N (i.e., sp versus sp(3)) are responsible for the much shorter N [bond] F distance in N(2)F(+) compared to NF(4)(+). The results for our nitrogen compounds are furthermore discussed in the more general context of how bond lengths are determined by both bonding and repulsive orbital interactions. 相似文献
93.
Stopped-flow Fourier transform infrared spectroscopy of nitromethane oxidation by the diiron(IV) intermediate of methane monooxygenase 总被引:1,自引:0,他引:1
Muthusamy M Ambundo EA George SJ Lippard SJ Thorneley RN 《Journal of the American Chemical Society》2003,125(37):11150-11151
The hydroxylase component (MMOH) of soluble methane monooxygenase from Methylococcus capsulatus (Bath) was reduced to the diiron(II) form and then allowed to react with dioxygen to generate the diiron(IV) intermediate Q in the first phase of a double-mixing stopped-flow experiment. CD3NO2 was then introduced in the second phase of the experiment, which was carried out in D2O at 25 degrees C. The kinetics of the reaction of the substrate with Q were monitored by stopped-flow Fourier transform infrared spectroscopy, observing the disappearance of the asymmetric NO2 bending vibration at 1548 cm-1. The data were fit to a single-exponential function, which yielded a kobs of 0.45 +/- 0.07 s-1. This result is in quantitative agreement with a kobs of 0.39 +/- 0.01 s-1 obtained by observing the disappearance of Q by double-mixing stopped-flow optical spectroscopy at its absorption maximum of 420 nm. These results provide for the first time direct monitoring of the hydroxylation of a methane-derived substrate in the MMOH reaction pathway and demonstrate that Q decay occurs concomitantly with substrate consumption. 相似文献
94.
Jacqueline Grewe Adelheid Hagenbach Brigitte Stromburg Roger Alberto Ezequiel Vazquez‐Lopez Ulrich Abram 《无机化学与普通化学杂志》2003,629(2):303-311
Novel rhenium(I) tricarbonyl complexes have been prepared by reactions of (Et4N)2[Re(CO)3Br3] with acetylpyridine benzoylhydrazone, Hapbhyd, di(2‐pyridyl)ketone benzoylhydrazone, Hpy2bhyd, bis(2‐pyridine)ketone, py2CO, and pyridinealdehyde terephtalaldehydebishydrazone, pytehyd. The ligands remain protonated when no supporting base is added and the following complexes have been isolated: [Re(CO)3Br(Hapbhyd)], [Re(CO)3Br(Hpy2bhyd‐py, hyd)], [Re(CO)3Br(Hpy2bhyd‐py1, py2)], [Re(CO)3Br(py2CO‐N, N)] and [Re(CO)3Br(pytehyd)]. Addition of triethyl amine results in deprotonation of Hapbhyd and the formation of [Re(CO)3(OH2)(apbhyd)], whereas Hpy2bhyd is hydrolysed and a rhenium complex with the monoanionic bis(2‐pyridyl)hydroxymethanolato ligand, {py2C(OH)O}‐, is formed. The same compound, [Re(CO)3{py2C(OH)O}], is obtained when triethyl amine and water are added to a mixture of (Et4N)2[Re(CO)3Br3] and py2CO. The air‐stable products have been studied by spectroscopic methods and X‐ray crystallography. 相似文献
95.
A method is described for the direct determination of cadmium in undiluted sea water by graphite-furnace atomic absorption spectrometry. The addition of EDTA ( 1 mg ml-1) reduces the temperature of atomization of cadmium to far below that of volatilization of other matrix components. The need for very careful temperature control and accurate background compensation is thus minimized. Sea water was analyzed by the method of standard additions. A detection limit of 0.01 μg l-1, a sensitivity of 0.034 μg l-1 and a precision of ±10% at the 0.05 μg l-1 level were obtained for 20-μl injections. 相似文献
96.
The oxidation of [PtCl3(C2H4)]- by Cl2 in aqueous solution, to yield CH2ClCH2OH and [PtCl4]2-, has been shown to proceed through the following sequence of steps: [PtCl3(C2H4)] Cl2Cl [PtCl5(CH2CH2Cl)]2- [PtCl5(CH2CH2OH)]2- → [PtCl42- + CH2ClCH2OHEach of the steps and intermediates in this mechanistic sequence has been identified and characterized. 相似文献
97.
New optically active polyamides were synthesized according to two ways: using a microwave-assisted polycondensation of an optically active isosorbide-derived diacylchloride with different aromatic diamines in NMP and using interfacial polymerization from an isosorbide-derived diamine with different diacylchlorides. The polymers are obtained with inherent viscosities in the range from 0.11 to 1.05 dL/g. The DSC and TGA measurements clearly demonstrate the high thermal stability of these polymers when considering the range of the melting points from 200 °C to 300 °C and the absence of decomposition till 350 °C. 相似文献
98.
Christian Bellec Daniel Bertin Roger Colau StPhane Deswarte Pierre Maitte Claude Viel 《Journal of heterocyclic chemistry》1979,16(8):1657-1659
Nitration of α-acylstilbenes with dinitrogen tetroxide leads to corresponding Z-α-acyl-β-nitrostilbenes. By chemical or electochemical reduction of these compounds, trisubstituted isoxazoles were prepared in good yields. 相似文献
99.
Watzke A Brunsveld L Durek T Alexandrov K Rak A Goody RS Waldmann H 《Organic & biomolecular chemistry》2005,3(7):1157-1164
Rab/Ypt guanosine triphosphatases (GTPases) represent a family of key membrane traffic regulators in eukaryotic cells. For their function Rab/Ypt proteins require double modification with two covalently bound geranylgeranyl lipid moieties at the C-terminus. Generally, prenylated proteins are very difficult to obtain by recombinant or enzymatic methods. We generated prenylated RabGTPases using a combination of chemical synthesis and protein engineering. This semi-synthesis depends largely on the availability of functionalized prenylated peptides corresponding to the proteins' native structure or modifications. We developed solution phase and solid phase strategies for the generation of peptides corresponding to the prenylated C-terminus of Rab7 GTPase in preparative amounts enabling us to crystallize the mono-prenylated Ypt1:RabGDI complex. The structure of the complex provides a structural basis for the ability of RabGDI to inhibit the release of nucleotide by Rab proteins and a molecular basis for understanding a RabGDI mutant that causes mental retardation in humans. 相似文献
100.
Fei Yu Yuhuan Liu Xuejun Pan Xiangyang Lin Chengmei Liu Paul Chen Roger Ruan 《Applied biochemistry and biotechnology》2006,130(1-3):574-585
This research investigated a novel process to prepare polyester from corn stover through liquefaction and crosslinking processes.
First, corn stover was liquefied in organic solvents (90 wt% ethylene glycol and 10 wt% ethylene carbonate) with catalysts
at moderate temperature under atmospheric pressure. The effect of liquefaction temperature, biomass content, and type of catalyst,
such H2SO4, HCl, H3PO4, and ZnCl2, was evaluated. Higher liquefaction yield was achieved in 2 wt% sulfuric acid, 1/4 (w/w) stover to liquefying reagent ratio;
160°C temperature, in 2h. The liquefied corn stover was rich in polyols, which can be directly used as feedstock for making
polymers without further separation or purification. Second, polyester was made from the liquefied corn stover by crosslinking
with multifunctional carboxylic acids and/or cyclic acid anhydrides. The tensile strength of polyester is about 5 MPa and
the elongation is around 35%. The polyester is stable in cold water and organic solvents and readily biodegradable as indicated
by 82% weight loss when buried in damp soil for 10 mo. The results indicate that this novel polyester could be used for the
biodegradable garden mulch film production. 相似文献