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321.
P. Schuster A. Stephen O. E. Polansky F. Wessely 《Monatshefte für Chemie / Chemical Monthly》1968,99(3):1246-1276
Zusammenfassung Die Acidität von insgesamt 43 verschiedenartigen organischenLewissäuren wurde in 99 Vol.-proz. Methanol durch potentiometrische Titration bestimmt. Einige ausgewählte Vertreter wurden auch in anderen Methanol/Wasser-Mischungen und in absol. Methanol mit potentiometrischen und optischen Methoden untersucht; in zwei Fällen wird der pK
L
-Wert auf Wasser extrapoliert. Bei allen Messungen in wasserhaltigen Lösungsmitteln muß die Hydrolyse derLewissäuren als Fehlerquelle der pK
L
-Bestimmung untersucht und ausgeschaltet werden.
Mit 10 Abbildungen
Herrn Prof. Dr.J. W. Breitenbach zum 60. Geburtstag gewidmet.
Teile der DissertationenP. Schuster (Univ. Wien, 1966) undA. Stephen (Univ. Wien, 1966).
20. Mitt.:H. Peham, O. E. Polansky undF. Wessely, Mh. Chem.98, 1665 (1967).
8. Mitt.:P. Schuster undO. E. Polansky, Mh. Chem.99, 1234 (1968). 相似文献
The acidity of 43 different organicLewis acids in 99% (v/v) methanol was determined by potentiometric titration. A few compounds were investigated at different methanol/water ratios or in anhydrous methanol using potentiometric and optical methods; in two cases the pK L -values were extrapolated to water. For all measurements in water containing solvents hydrolysis of theLewis acids has to be taken into consideration and eliminated as a source of error for the determination of pK L -values.
Mit 10 Abbildungen
Herrn Prof. Dr.J. W. Breitenbach zum 60. Geburtstag gewidmet.
Teile der DissertationenP. Schuster (Univ. Wien, 1966) undA. Stephen (Univ. Wien, 1966).
20. Mitt.:H. Peham, O. E. Polansky undF. Wessely, Mh. Chem.98, 1665 (1967).
8. Mitt.:P. Schuster undO. E. Polansky, Mh. Chem.99, 1234 (1968). 相似文献
322.
Easton CJ Lincoln SF Barr L Onagi H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(13):3120-3128
Molecular reactors are miniature vessels for the assembly of reactants at the molecular level, in order to change the nature of chemical transformations. It seems probable that those that will find most immediate applications are those that change product ratios or give products which would not readily form in the absence of the reactors, and thereby afford easy access to materials that are otherwise difficult to obtain. Molecular machines consist of interrelated parts with separate functions and perform some kind of work, at the molecular level. Practical examples are likely to be relatively uncomplicated and not based on individual functions of single-molecule devices. Instead they will probably rely on extensive redundancy of the molecular components and their interactions and reactions, as well as of the machines themselves. 相似文献
323.
At least one Holy Grail for many academic researchers and pharmaceutical research divisions alike has been to identify therapeutically useful selective PI3K inhibitors. There are several different but closely related PI3Ks which are thought to have distinct biological roles. Until now, however, researchers have been frustrated by poor selectivity of the available pharmacological inhibitors, which are unable to distinguish the different isoforms of PI3K adequately. Fortunately, recently published work gives cause for optimism; there are now several patent specifications published that describe new PI3K inhibitors, including some that are more selective for the delta isoform of PI3K. Given the involvement of PI3Ks in a plethora of biological settings, such isoform-selective inhibitors may have immense potential use for the treatment of patients with inflammatory and autoimmune disorders as well as cancer and cardiovascular diseases. 相似文献
324.
Thomas JM Walker NR Cooke SA Gerry MC 《Journal of the American Chemical Society》2004,126(4):1235-1246
Microwave spectra of the complexes KrAuF and KrAgBr have been measured for the first time using a cavity pulsed jet Fourier transform microwave spectrometer. The samples were prepared by laser ablation of the metal from its solid and allowing the resulting plasma to react with an appropriate precursor (Kr, plus SF6 or Br2) contained in the backing gas of the jet (usually Ar). Rotational constants; geometries; centrifugal distortion constants; vibration frequencies; and 197Au, 79Br, and 81Br nuclear quadrupole coupling constants have all been evaluated. The complexes are unusually rigid and have short Kr-Au and Kr-Ag bonds. The 197Au nuclear quadrupole coupling constant differs radically from its value in an AuF monomer. In addition 83Kr hyperfine structure has been measured for KrAuF and the previously reported complex KrAgF. The geometry of the latter has been reevaluated. Large values for the 83Kr nuclear quadrupole coupling constants have been found for both complexes. Both the 197Au and 83Kr hyperfine constants indicate a large reorganization of the electron distribution on complex formation. A thorough assessment of the nature of the noble gas-noble metal bonding in these and related complexes (NgMX; Ng is a noble gas, M is a noble metal, and X is a halogen) has been carried out. The bond lengths are compared with sums of standard atomic and ionic radii. Ab initio calculations have produced dissociation energies along with Mulliken populations and other data on the electron distributions in the complexes. The origins of the rigidity, dissociation energies, and nuclear quadrupole coupling constants are considered. It is concluded that there is strong evidence for weak noble gas-noble metal chemical bonding in the complexes. 相似文献
325.
Joan E. Roberts Stephen J. Atherton James Dillon 《Photochemistry and photobiology》1990,52(4):845-848
Previous studies have shown that mesotetra(p-sulfonatophenyl)porphine (TPPS) binds to lens proteins. This characteristic should increase the residence time of the sensitizer in the lens and therefore enhance the probability of inducing photooxidative damage to that tissue in vivo. Subsequent in vivo studies have verified that contention. The present studies were performed to determine the effect of such binding on the spectroscopy and photophysics of the porphyrins. It was found that the binding of TPPS (1) quenches the fluorescence of lens proteins, (2) causes a shift in the ground state absorption spectra, fluorescence excitation spectra and the triplet excited state spectrum of TPPS to longer wavelengths and (3) results in an increase in the triplet state lifetime of TPPS. In the presence of the isolated crystallins the average triplet lifetime increases in the following order: gamma less than beta less than alpha. 相似文献
326.
The total synthesis of 6,7-dideoxysqualestatin H5 (3) has been completed by a concise approach that features the stereoselective intramolecular vinylogous aldol reaction of the furoic ester 25a to give 30 or its trimethylsilyl ether derivative 34, which possess the requisite absolute stereochemistry at C(3)-C(5) of 3. Compound 34 was reduced to the saturated bislactone 39, and the C(1) side chain subunit 47 was introduced leading to a mixture of the hemiacetals 48 and the corresponding ketone 49. When this mixture was stirred with methanolic acid, transketalization occurred to give a mixture of 50 and the spirocyclic methyl acetals 51a,b. Oxidation of the primary alcohol group in 50 followed by saponification of the two remaining ester groups gave 3. The longest linear sequence in the synthesis commences with commercially available erythronolactone (26) and requires 17 chemical steps with only 10 isolated intermediates. 相似文献
327.
Jones SC Coropceanu V Barlow S Kinnibrugh T Timofeeva T Brédas JL Marder SR 《Journal of the American Chemical Society》2004,126(38):11782-11783
A complex featuring two triarylamine redox centers bridged by Pt, trans-bis(triethylphosphine)-bis{4-[bis(4-methoxyphenyl)amino]phenylethynyl} platinum(II), has been synthesized as a model system for pi-conjugated Pt-containing polymers. Analysis of the intervalence charge-transfer band displayed by its mixed-valence monocation affords a quantitative assessment of electronic delocalization through the Pt bridge; this is found to be only slightly smaller than that determined for a benzene-bridged analogue. These results are supported by density functional theory calculations, which show that the active orbitals involved in the electron-transfer process in both cases have similar delocalization through the bridging unit. 相似文献
328.
Schmidt Sherry L. Myers Michele D. Kelley Stephen S. McMillan James D. Padukone Nandan 《Applied biochemistry and biotechnology》1997,(1):469-482
The use of membrane processes for the recovery of fermentation products has been gaining increased acceptance in recent years.
Pervaporation has been studied in the past as a process for simultaneous fermentation and recovery of volatile products such
as ethanol and butanol. However, membrane fouling and low permeate fluxes have imposed limitations on the effectiveness of
the process. In this study, we characterize the performance of a substituted polyacetylene membrane, poly[(l-trimethylsilyl)-l-propyne]
(PTMSP), in the recovery of ethanol from aqueous mixtures and fermentation broths. Pervaporation using PTMSP membranes shows
a distinct advantage over conventional poly(dimethyl siloxane) (PDMS) membranes in ethanol removal. The flux with PTMSP is
about threefold higher and the concentration factor is about twofold higher than the corresponding performance achieved with
PDMS under similar conditions. The performance of PTMSP with fermentation broths shows a reduction in both flux and concentration
factor relative to ethanol-water mixtures. However, the PTMSP membranes indicate initial promise of increased fouling resistance
in operation with cell-containing fermentation broths. 相似文献
329.
The folate analogue, 9‐thia‐5,10‐dideazafolic acid ( 3b ), was obtained in an efficient two‐step procedure in an overall yield of 60%. The previously unknown intermediate dimethyl‐thiocarbamic acid S‐(2‐amino‐3,4‐dihydo‐4‐oxo‐pyrido[2,3‐d]pyrimidin‐6‐yl) ester ( 5 ) was prepared via the condensation of 2,6‐diamino‐3H‐pyrimidin‐4‐one and S‐(2‐malonaldehyde)‐1,1,3,3‐tetramethylthiouronium bromide ( 4 ). Compound 5 , in a one pot procedure, was deprotected using sodium hydroxide and then coupled to diethyl N‐[(4‐chloromethyl)benzoyl]‐L‐glutamate, followed by saponification of the ethyl esters to give the 9‐thia‐5,10‐dideazafolic acid ( 3b ). Compound 3b was a potent inhibitor of human 5‐aminoimidazole‐4‐carboxamide ribonucleotide transformylase (Ki of 8 ± 5 μM) and showed no inhibition of human glycinamide ribonu‐cleotide transformylase at concentrations as high as 50 μM. Compound 3b was screened by the National Cancer Institute Developmental Therapeutics Program against 60 human tumors and was found to be active against a leukemia RPMI‐8226 cell line where the LC50 was 1 μM. 相似文献
330.
Charles W. Bauschlicher Stephen P. Walch Harry Partridge 《Chemical physics letters》1984,103(4):291-295
The electron affinity (EA) of the Cu atom is computed using large STO and GTO basis sets at several levels of correlation. The best computed value is 1 相似文献