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811.
Gundula Voss Michael Gradzielski Jürgen Heinze Helmut Reinke Carlo Unverzagt 《Helvetica chimica acta》2003,86(6):1982-2004
Two new types of 4,4′,7,7′‐tetraalkoxyindigotins, 1a – f and 2a – f along with the new N‐substituted indigotins 4e – f , were synthesized from dinitrobenzaldehydes 5a – f , which were prepared from 2‐hydroxy‐5‐methoxybenzaldehyde ( 7 ) via dialkoxybenzaldehydes 6a – f (Scheme). The new dialkoxyindigotin 3g was obtained from dialkoxybenzaldehyde 6g via nitrobenzaldehyde 8g . The 1,4‐dialkoxy‐2,3‐dinitrobenzenes 9 were isolated as by‐products. The 4,4′,7,7′‐tetraalkoxy‐5,5′‐diaminoindigotins 1 are soluble in organic solvents, and their solutions are green, which is highly uncommon for indigotins and is primarily caused by electronic effects of substituents, steric effects playing a minor role. The indigotins 1 produce a strong red shift of the longest‐wavelength absorption and negative solvatochromism indicating the predominance of polar resonance structures in the ground state. Tautomeric structures were excluded. These indigotins are valuable compounds for technical applications, for synthetic purposes, and for analytical studies. SANS (Small‐angle neutron scattering) experiments showed that certain 4,4′,7,7′‐tetraalkoxy‐5,5′‐diaminoindigotins 1 form rod‐like aggregates in solution. The similarly substituted 4,4′,7,7′‐tetraalkoxy‐5,5′‐dinitroindigotins 2 are far less soluble. They produce red monoanions (preferably dimers) and bluish‐purple dianions in organic solvents. 相似文献
812.
Switching between three different adsorbed states was achieved using potential control to separately induce electrochemical behaviour associated with changes in binding and orientation of the thiophene and pyridine moieties of 2-(2'-thienyl)pyridine adsorbed to Au(111) in neutral and basic solution. 相似文献
813.
John J. Fenske Andrew Hashimoto Michael H. Penner 《Applied biochemistry and biotechnology》1998,73(2-3):145-157
The relative toxicity of the combined nonxylose components in prehydrolysates derived from three different lignocellulosic
biomass feedstocks was determined. One woody (poplar) and two herbaceous (corn stover and switchgrass) feedstocks were dilute-acid
pretreated under temperature and acid conditions chosen to optimize xylose recovery in the liquid prehydrolysate; xylose yields
averaged 96,89,and 87% of theoretical for switchgrass,corn stover,and poplar,respectively. Prehydrolysates from each feedstock
were neutralized,adjusted to equivalent xylose concentrations,and bioassayed for toxicity,using a standardized fermentation
protocol withPichia stipitis NRRL 11545. Full time-courses for ethanol production (30-60 h) clearly illustrate the distinct inhibitory effects of prehydrolysates
from different feedstocks. The relative toxicity of the prehydrolysates,ranked in order of decreasing toxicity,is poplar-derived
prehydrolysates > switchgrass-derived prehydrolysates > corn stover-derived prehydrolysates. The inhibition of ethanol production
appeared to be the result of a general slowdown of yeast metabolism,rather than the result of the production of alternative,
nonethanol end products. Ethanol yields averaged 74,83,and 88% of control values for poplar,switchgrass,and corn stover prehydrolysates,
respectively. Volumetric ethanol productivities (g ethanol L/h) averaged 32,70,and 102% of control values for poplar,switchgrass,and
corn stover prehydrolysates,respectively. Ethanol productivities correlated closely with acetate concentrations in the prehydrolysates;
however, regression lines correlating acetate concentrations and ethanol productivities were found to be feedstock-dependent.
Oregon State University Agricultural Experiment Station Technical Publication Number 11114 相似文献
814.
Michael Ptzel Andreas Schulz Jürgen Liebscher Wolfgang Richter Monika Richter 《Journal of heterocyclic chemistry》1992,29(5):1209-1211
Cyclic N-cyanocarbonimidodithioesters 4 or N-aroylcarbonimidothioic acid esters 10 react regioselectively with arylhydrazines and methylhydrazine by a ring chain transformation reaction forming ω-functionalized 3-alkylthio-1,2,4-triazoles 8 and 11 or 5-alkylthio-1,2,4-triazoles 9 . 相似文献
815.
Silvia Dorn Peter Eggenberg Michael R. C. Gerstenberger Alois Haas Ulrich Niemann Peter Zobrist 《Helvetica chimica acta》1979,62(5):1442-1450
(Perhalomethylthio)heterocycles. X 1 IX. Mitt.: s. [1]. . Acid-catalyzed substitutions on (perchlorofluoromethylthio)pyrroles and their agro-biological activities In the presence of C4F9SO3H the (perhalomethylthio)pyrroles 1a–c react with Cl3?nFnCSCl (n = 1–3) to give mixtures of the 2,5- and 2,4-disubstituted pyrroles 2a–f and 3a–h . 2a and 3a react with CF3SCl (catalyst CF3SO3H) yielding 2,3,5-tris (trifloromethylthio)pyrrole ( 4a ), which under similar conditions reacts further to give 2,3,4,5-tetrakis (trifluoromethylthio)pyrrole ( 5 ). As a by-product during the conversion of 3a to 4a 2,3,4-tris (trifluoromethylthio)pyrrole ( 4b ) is formed. The pyrroles 2a , 4a and 5 form the mercury salts 6a–c ; compound 5 yields also a silver salt 7 . The 1H- and 19F-NMR. spectra are discussed and the agro-biological properties of the compounds investigated. 相似文献
816.
Dabkowska I Rak J Gutowski M Nilles JM Stokes ST Bowen KH 《The Journal of chemical physics》2004,120(13):6064-6071
The photoelectron spectrum of the uracil-alanine anionic complex (UA)(-) has been recorded with 2.540 eV photons. This spectrum reveals a broad feature with a maximum between 1.6 and 2.1 eV. The vertical electron detachment energy is too large to be attributed to an (UA)(-) anionic complex in which an intact uracil anion is solvated by alanine, or vice versa. The neutral and anionic complexes of uracil and alanine were studied at the B3LYP and second-order M?ller-Plesset level of theory with 6-31++G(*) (*) basis sets. The neutral complexes form cyclic hydrogen bonds and the three most stable neutral complexes are bound by 0.72, 0.61, and 0.57 eV. The electron hole in complexes of uracil with alanine is localized on uracil, but the formation of a complex with alanine strongly modulates the vertical ionization energy of uracil. The theoretical results indicate that the excess electron in (UA)(-) occupies a pi(*) orbital localized on uracil. The excess electron attachment to the complex can induce a barrier-free proton transfer (BFPT) from the carboxylic group of alanine to the O8 atom of uracil. As a result, the four most stable structures of the uracil-alanine anionic complex can be characterized as a neutral radical of hydrogenated uracil solvated by a deprotonated alanine. Our current results for the anionic complex of uracil with alanine are similar to our previous results for the anion of uracil with glycine, and together they indicate that the BFPT process is not very sensitive to the nature of the amino acid's hydrophobic residual group. The BFPT to the O8 atom of uracil may be relevant to the damage suffered by nucleic acid bases due to exposure to low energy electrons. 相似文献
817.
Napper AM Head NJ Oliver AM Shephard MJ Paddon-Row MN Read I Waldeck DH 《Journal of the American Chemical Society》2002,124(34):10171-10181
A systematic determination of electronic coupling matrix elements in U-shaped molecules is demonstrated. The unique architecture of these systems allows for the determination of the electronic coupling through a pendant molecular moiety that resides between the donor and acceptor groups; this moiety quantifies the efficiency of electron tunneling through nonbonded contacts. Experimental electron-transfer rate constants and reaction free energies are used to calibrate a molecular-based model that describes the solvation energy. This approach makes it possible to experimentally determine electronic couplings and compare them with computational values. 相似文献
818.
Jebanathirajah JA Pittman JL Thomson BA Budnik BA Kaur P Rape M Kirschner M Costello CE O'Connor PB 《Journal of the American Society for Mass Spectrometry》2005,16(12):1985-1999
The use of a new electrospray qQq Fourier transform ion cyclotron mass spectrometer (qQq-FTICR MS) instrument for biologic applications is described. This qQq-FTICR mass spectrometer was designed for the study of post-translationally modified proteins and for top-down analysis of biologically relevant protein samples. The utility of the instrument for the analysis of phosphorylation, a common and important post-translational modification, was investigated. Phosphorylation was chosen as an example because it is ubiquitous and challenging to analyze. In addition, the use of the instrument for top-down sequencing of proteins was explored since this instrument offers particular advantages to this approach. Top-down sequencing was performed on different proteins, including commercially available proteins and biologically derived samples such as the human E2 ubiquitin conjugating enzyme, UbCH10. A good sequence tag was obtained for the human UbCH10, allowing the unambiguous identification of the protein. The instrument was built with a commercially produced front end: a focusing rf-only quadrupole (Q0), followed by a resolving quadrupole (Q1), and a LINAC quadrupole collision cell (Q2), in combination with an FTICR mass analyzer. It has utility in the analysis of samples found in substoichiometric concentrations, as ions can be isolated in the mass resolving Q1 and accumulated in Q2 before analysis in the ICR cell. The speed and efficacy of the Q2 cooling and fragmentation was demonstrated on an LCMS-compatible time scale, and detection limits for phosphopeptides in the 10 amol/muL range (pM) were demonstrated. The instrument was designed to make several fragmentation methods available, including nozzle-skimmer fragmentation, Q2 collisionally activated dissociation (Q2 CAD), multipole storage assisted dissociation (MSAD), electron capture dissociation (ECD), infrared multiphoton induced dissociation (IRMPD), and sustained off resonance irradiation (SORI) CAD, thus allowing a variety of MS(n) experiments. A particularly useful aspect of the system was the use of Q1 to isolate ions from complex mixtures with narrow windows of isolation less than 1 m/z. These features enable top-down protein analysis experiments as well structural characterization of minor components of complex mixtures. 相似文献
819.
Farwell JD Hitchcock PB Lappert MF Protchenko AV 《Chemical communications (Cambridge, England)》2005,(17):2271-2273
The crystalline compounds [Mg(Br)(L)(thf)].0.5Et2O [L = {N(R)C(C6H3Me2-2,6)}2SiR, R = SiMe3] (1), [Mg(L){N=C=C(C(Me)=CH)2CH2}(D)2] [D = NCC6H3Me2-2,6 (2), thf (3)] and [{Mg(L)}2{mu-OSO(CF3)O-[mu}2] (4) were prepared from (a) Si(Br)(R){C(C6H3Me2-2,6)=NR}2 and Mg for (1), (b) [Mg(SiR3)2(thf)2] and 2,6-Me2C6H3CN (5 mol for (2), 3 mol for (3)), and (c) (2) + Me3SiOS(O)2CF3 for (4); a coproduct from (c) is believed to have been the trimethylsilyl ketenimide Me3SiN=C=C{C(Me)=CH}2CH2 (5). 相似文献
820.