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101.
Phillips J. R. Klasson K. T. Clausen E. C. Gaddy J. L. 《Applied biochemistry and biotechnology》1993,(1):559-571
The anaerobic bacteriaClostridium ljungdahlii produces ethanol and acetate from CO, CO2, and H2 in synthesis gas. Early studies with the bacterium showed that relatively high concentrations of ethanol could be produced
by lowering the fermentation pH and eliminating yeast extract from the medium in favor of a defined medium. This article presents
the results from a medium development study based on the aerobic bacteriumEscherichia coli. The results of continuous-reactor studies in a continuously stirred tank reactor (CSTR) with and without cell recycle are
shown to demonstrate the utility of this improved medium. 相似文献
102.
Compounds of general formulatrans-ArNi(PR3)2OAr' (R = Et, cyclohexyl; Ar = 2-MeC6H4, 2-FC6H4; Ar' = 4-FC6H4, 4-NO2C6H4) were synthesized by the reaction of Ar'OK with cationic nickel complexes generated by treatment of ArNi(PR3)2Cl with TlBF4. Syntheses of 4-fluorophenoxide complexes, ArNi(PR3)2OC6H4F-4, additionally give some quantities oftrans-[ArNi(PR3)2OC6H4F-4][HOC6H4F-4] adducts. Exchange reactions MeC6H4Ni(PEt3)2OC6H4F-4 + XC6H4OH 2-MeC6H4Ni(PEt3)2OC6H4X + 4-FC6H4OH were studied in THF. The equilibrium is shifted to the right as the acidity of ArOH increases. A linear relationship between lgK
eq and pK
a of XC6H4OH in DMSO was found. A conclusion concerning the strong polarization of the Ni-O bond was made on the basis of an analysis of the chemical shifts of fluorine atoms in 2-MeC6H4Ni(PEt3)2OC6H4F-4.Translated fromIvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2266–2271, November, 1995. 相似文献
103.
K. A. Lyssenko D. V. Lyubetsky M. Yu. Antipin I. L. Odinets 《Russian Chemical Bulletin》2005,54(11):2484-2491
The nature of the intramolecular O—H...O bond was studied and its energy was estimated by X-ray diffraction analysis and quantum-chemical
calculations (B3LYP/6-311G**) of (diphenylphosphoryl)acylacetonitriles. The influence of the nature of the substituents at
the double bond in the H-bonded ring and the crystal packing effects on the hydrogen bond were investigated.
Dedicated to Corresponding Member of the Russian Academy of Sciences T. A. Mastryukova.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2406–2413, November, 2005. 相似文献
104.
Th. Emmler S. Gieschler H. H. Limbach G. Buntkowsky 《Journal of Molecular Structure》2004,700(1-3):29-38
A set of OHO hydrogen bonded systems with known neutron diffraction structure has been studied by fast 1H-MAS echo spectroscopy. It is shown that the application of a simple rotor synchronized echo sequence combined with fast MAS allows a faithful determination of the chemical shift of the proton in the hydrogen bond. Employing the empirical valence bond order model, the experimental 1H chemical shifts of the hydrogen bonded protons are correlated to the hydrogen bond geometries. The resulting correlation between the proton chemical shift and the deviation of the proton from the center of the hydrogen bond covers a broad range of substances. Deviations from the correlation curve, which are observed in certain systems with strong hydrogen bonds, are explained in terms of proton tautomerism or delocalization in low-barrier hydrogen bonds. These deviations are a highly diagnostic tool to select potential candidates for further experimental and theoretical studies. Thus, the combination of the 1H-MAS echo sequence with the correlation curve yields a simple and versatile tool for the structural analysis of OHO hydrogen bonds. 相似文献
105.
meso-Tetraphenylporphyrin (and its derivatives), in the reaction with fuming yellow nitric acid (d=1.53), form either 5-(4-nitroaryl)-10,15,20-triarylporphyrin, 5,10-bis(4-nitroaryl)-15,20-diarylporphyrin, or 5,10,15-tris(4-nitroaryl)-20-arylporphyrin, depending on the reaction temperature (0-20 °C), amounts of the acid used, and reaction time. The above nitroporphyrins react, in the presence of a base (t-BuOK) at 0 °C, with carbanions (which bear nucleophugal groups at the carbanionic center: −CH(Cl)SO2Tol, −CH(Br)SO2Tol, and −CH(Cl)SO2NMe2), leading to the nucleophilic substitution of hydrogen in one or more of the meso-nitroaryl rings. By this route, the preparation of the highly substituted ‘synthetic’ porphyrins (bearing up to ten O-, N-, Cl-, or C-substituents) was demonstrated. 相似文献
106.
Grzegorz WojciechowskiMa?gorzata Ratajczak-Sitarz Andrzej KatrusiakBogumil Brzezinski 《Journal of Molecular Structure》2002,612(1):59-64
The crystals of 5,5′-dibromo-3-diethylaminomethyl-2,2′-biphenol N-oxide were studied by X-ray and FT-IR spectroscopy. Within this molecule two short OHO intramolecular hydrogen bonds are formed. The NO?H+?O− bond between the OH and the N-oxide groups is very strong, of 2.419(7) Å between the oxygen atoms. The proton potential of this hydrogen bond is flat, broad and has probably no barrier—consequently it could not be located from X-ray diffraction data. The other hydrogen bond formed between two hydroxyl groups appears asymmetrical from FT-IR spectra, and shows also relatively limited proton polarizability. The molecular conformation is non-planar, due to strong overcrowding effect between the oxygen atoms involved in the hydrogen bonds. 相似文献
107.
V. M. Tapilin 《Journal of Structural Chemistry》2005,46(1):9-15
Electronic structure calculations have been performed for flat graphite sheets and periodically distorted sheets with different values of deformation angle and hydrogen adsorption. These characteristics do not all behave monotonically with increasing deformation angle. At small deformation angles, the electrons pass from the atoms of terraces to those of edges, while at larger angles the reverse pattern is observed. The position of the Fermi level also varies nonmonotonically. The binding energy of hydrogen depends significantly on the adsorption site, and the difference can be doubled. Based on the ata obtained, it was concluded that a priori statements derived from the “general concepts” on the difference in the physicochemical properties of, for example, terrace and edge atoms on high-index facets are unreliable. 相似文献
108.
Rong-Bin Huang Nan-Feng Zheng Su-Yuan Xie Lan-Sun Zheng 《Journal of inclusion phenomena and macrocyclic chemistry》2001,40(1-2):121-124
Crystal structure analysis shows that the p-tert-butylcalix[8]arene host and its four pyridine guests sit around an inversion center in the P21/c crystal lattice. The monoclinic cell parameters and its volume are: a = 19.617(4), b = 9.912(2), c = 25.178(5) , = 101.03(3)°, V =4805.27(17) 3. For Z = 2 and Mw = 1614.18, the calculated density Dcalc = 1.116 g/cm3. A host calixarene molecule includes four pyridine guests in two different ways: by hydrogen bonding and by possible C–H· interaction between the molecules. The hydrogen bonding drives the host macrocycle into a chair-like conformation. 相似文献
109.
110.
Rosenberg Edward Freeman William Carlos Zinnia Hardcastle Kenneth Yong Jin Yoo Milone Luciano Gobetto Roberto 《Journal of Cluster Science》1992,3(4):439-457
The general relationships between trinuclear cluster reactivity and the ligand dynamical processes in these systems are explored. Three specific mechanistic studies are presented: (1) the rate and stereochemistry of ligand addition to 3-imidoyl complexes, (2) the factors influencing the rate of carbon-hydrogen bond activation in 3-alkyne complexes, and (3) the origin of anomalously large kinetic deuterium isotope effect in metal to ligand and ligand to metal hydrogen transfer in trinuclear and binuclear complexes. In all three cases, the current state of the mechanistic studies are summarized and the possible rate of specific ligand dynamical processes in controlling the mechanism are put forth. 相似文献