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991.
David J. Morris Charles V. Manville Gary Woodward Martin Wills 《Tetrahedron letters》2010,51(1):209-12310
The highly enantioselective addition of acetone to 2-nitrostyrene, using N-diphenylphosphinyl-trans-1,2-diphenylethane-1,2-diamine (PODPEN) as a catalyst, is described. 相似文献
992.
Non-extractable photoinitiators based on thiol-functionalized benzophenones and thioxanthones 总被引:1,自引:0,他引:1
Hironori Matsushima Qin Li Masamitsu Shirai Charles E. Hoyle 《European Polymer Journal》2010,46(6):1278-1287
Non-extractable photoinitiators could be advantageous for use in biological, electronic, and food packaging applications. Therefore, thioxanthone and benzophenone derivatives were synthesized from 1,6-hexane dithiol and chlorinated benzophenone or thioxanthone. The efficiency of thiol-functionalized photoinitiators in combination with amine co-initiators was compared to benzophenone and isopropylthioxanthone with amine co-initiators, and the cleavage of photoinitiator 2,2-dimethoxy-1,2-diphenylethan-1-one in acrylic resins. The reaction kinetics were analyzed using photo-differential scanning calorimetry and real-time FTIR. Coating physical properties were evaluated by pendulum and pencil hardness, steel-wool scratch and mandrel bend tests. The non-extractable photoinitiators had higher absorbance than their benzophenone or isopropylthioxanthone counterparts due to the sulfide substitution on the phenyl ring, and the free thiol groups reacted with the acrylate by either an amine catalyzed Michael addition or a free-radical chain process. The combination of thiol-functionalized photoinitiators with secondary amines provides an efficient photoinitiator system that is locked into the photopolymerized network and cannot be extracted with typical solvents. 相似文献
993.
McIntosh JA Robertson CR Agarwal V Nair SK Bulaj GW Schmidt EW 《Journal of the American Chemical Society》2010,132(44):15499-15501
A protease from ribosomal peptide biosynthesis macrocyclizes diverse substrates, including those resembling nonribosomal peptide and hybrid polyketide-peptide products. The proposed mechanism is analogous to thioesterase-catalyzed chemistry, but the substrates are amide bonds rather than thioesters. 相似文献
994.
Alexander Samokhvalov Eduardus C. Duin Sachin Nair Bruce J. Tatarchuk 《Surface and interface analysis : SIA》2010,42(9):1476-1482
The Ag/titania sorbent for the ultradeep desulfurization of liquid fuels was characterized by electron spin resonance and was found to contain nearly the stoichiometric titania, without significant concentration of Ti3+ or the reactive oxygen species. The surface chemical reactions of thiophene adsorbed on the Ag/titania were studied by temperature‐programmed XPS from 25 to 525 °C upon in situ thermal annealing in high vacuum and in situ oxidation by oxygen gas. The titania support is not chemically reactive under those conditions. Silver oxide in the Ag/titania sorbent is converted to Ag2 S without formation of the transient surface sulfates or sulfites and is further oxidized by molecular oxygen. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
995.
Guoliang Li Ioan Silaghi-Dumitrescu R. Bruce King Henry F. Schaefer III 《Journal of organometallic chemistry》2010,695(6):804-808
Density functional theory studies on a series of Cp2Co2E2 derivatives (E = S and PX; X = H, Cl, OH, OMe, NH2, NMe2) predict global minimum butterfly structures with one Co-Co bond for the “body” of the butterfly and four Co-E bonds at the edges of the “wings” of the butterfly. Tetrahedrane structures with both Co-Co and E-E bonds are higher in energy for Cp2Co2S2 and Cp2Co2(PH)2 and are not found in the other systems. This differs from the corresponding Fe2(CO)6S2 and Fe2(CO)6(PX)2 derivatives where tetrahedrane structures are predicted to be the lowest energy structures for all cases except X = NR2 and OH and such a tetrahedrane structure is found experimentally for Fe2(CO)6S2. The butterfly structures for the Cp2Co2E2 derivatives are of two types. For Cp2Co2(PX)2 (X = H, OH, OMe, NH2, NMe2) the lowest energy structures are unsymmetrical butterflies Cp2Co2(P)(PX2) with two X groups on one phosphorus atom and a lone pair on the other (naked) phosphorus atom. Related low-energy unsymmetrical butterfly Fe2(CO)6(P)(PX2) structures, not observed in previous theoretical studies, are now found for the corresponding Fe2(CO)6(PX)2 derivatives. Symmetrical butterfly singlet diradical structures with one X group on each phosphorus atom in relative cis or trans positions are also found for the Cp2Co2(PX)2 derivatives and are the global minima for Cp2Co2(PCl)2 as well as Cp2Co2S2. In all cases the cis structures are of lower energy than the corresponding trans structures. Rhombus structures having neither Co-Co nor E-E bonds are also found for all of the Cp2Co2(PX)2 derivatives but always at higher energies than the butterfly structures, ranging from 17 to 29 kcal/mol above the global minima. 相似文献
996.
Sub-micron sized airborne particulate matter (PM) is not collected well on regular quartz or glass fiber filter papers. We used a micro-orifice uniform deposit impactor (MOUDI) to fractionate PM into six size fractions and deposit it on specially designed high purity thin aluminum disks. The MOUDI separated PM into fractions 56-100 nm, 100-180 nm, 180-320 nm, 320-560 nm, 560-1000 nm, and 1000-1800 nm. Since the MOUDI has a low flow rate (30 L/min), it takes several days to collect sufficient carbon on 47 mm foil disks. The small carbon mass (20-200 microgram C) and large aluminum substrate (~25 mg Al) present several challenges to production of graphite targets for accelerator mass spectrometry (AMS) analysis. The Al foil consumes large amounts of oxygen as it is heated and tends to melt into quartz combustion tubes, causing gas leaks. We describe sample processing techniques to reliably produce graphitic targets for (14)C-AMS analysis of PM deposited on Al impact foils. 相似文献
997.
Dunne JF Fulton DB Ellern A Sadow AD 《Journal of the American Chemical Society》2010,132(50):17680-17683
Coordinatively saturated To(M)MgMe (1; To(M) = tris(4,4-dimethyl-2-oxazolinyl)phenylborate) is an active precatalyst for intramolecular hydroamination/cyclization at 50 °C. The empirical rate law of -d[substrate]/dt = k'(obs)[Mg](1)[substrate](1) and Michaelis-Menten-type kinetics are consistent with a mechanism involving reversible catalyst-substrate association prior to cyclization. The resting state of the catalyst, To(M)MgNHCH(2)CR(2)CH(2)CH═CH(2) [R = Ph, Me, -(CH(2))(5)-], is isolable, but isolated magnesium amidoalkene does not undergo unimolecular cyclization at 50 °C. However, addition of trace amounts of substrate allows cyclization to occur. Therefore, we propose a two-substrate, six-center transition state involving concerted C-N bond formation and N-H bond cleavage as the turnover-limiting step of the catalytic cycle. 相似文献
998.
Plínio C. Sathler Charles S. Craik Toshihiko Takeuchi Russolina B. Zingali Helena C. Castro 《Applied biochemistry and biotechnology》2010,160(8):2355-2365
Ecotin is a bidentate, fold-specific inhibitor of mammalian serine-proteases produced by Escherichia coli. This molecule may be engineered to increase and/or change its affinity and specificity providing significant biotechnological
potential. Since ecotin binds tightly to serine proteases of the trypsin fold, it may help to identify the role of these enzymes
in different biological processes. In this work, we tested ecotin variants as an affinity purification reagent for identifying
enzymes in samples of tumor progression and mammary gland involution. Initially, we used a commercial source of urokinase-type
plasminogen activator (u-PA) that remained fully active after elution from an affinity column of the ecotin variant (M84R,
M85R). We then successfully identified u-PA from more complex mixtures including lysates from a prostate cancer cell line
and involuting mouse mammary glands. Interestingly, a membrane-type serine protease 1 was isolated from the Triton X-100-solubilized
PC-3 cell lysates, and surprisingly, haptoglobin, a serine-protease homolog protein, was also identified in mammary gland
lysates and in blood. Haptoglobin does not prevent ecotin inhibition of u-PA, but it may act as a carrier within blood when
ecotin is used in vivo. Finally, this affinity purification matrix was also able to identify a thrombin-like enzyme from snake venom using an ecotin
variant directed against thrombin. Overall, the ecotin variants acted as robust tools for the isolation and characterization
of proteins with a trypsin fold. Thus, they may assist in the understanding of the role of these serine proteases and homologous
proteins in different biological processes. 相似文献
999.
Ming J. Lau Ming W. Lau Christa Gunawan Bruce E. Dale 《Applied biochemistry and biotechnology》2010,162(7):1847-1857
Empty palm fruit bunch fiber (EPFBF), a readily available cellulosic biomass from palm processing facilities, is investigated
as a potential carbohydrate source for cellulosic ethanol production. This feedstock was pretreated using ammonia fiber expansion
(AFEX) and enzymatically hydrolyzed. The best tested AFEX conditions were at 135 °C, 45 min retention time, water to dry biomass
loading of 1:1 (weight ratio), and ammonia to dry biomass loading of 1:1 (weight ratio). The particle size of the pretreated
biomass was reduced post-AFEX. The optimized enzyme formulation consists of Accellerase (84 μL/g biomass), Multifect Xylanase
(31 μL/g biomass), and Multifect Pectinase (24 μL/g biomass). This mixture achieved close to 90% of the total maximum yield
within 72 h of enzymatic hydrolysis. Fermentation on the water extract of this biomass affirms that nutrients solely from
the pretreated EPFBF can support yeast growth for complete glucose fermentation. These results suggest that AFEX-treated EPFBF
can be used for cellulosic biofuels production because biomass recalcitrance has been overcome without reducing the fermentability
of the pretreated materials. 相似文献
1000.