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51.
Charlotte Froese Fischer 《International journal of quantum chemistry》1975,9(2):273-285
Results are reported for multiconfiguration Hartree–Fock studies of correlation in the lithium ground state, which maintain orthogonality of orbitals within a configuration. It is shown that when the 1s- and 2s-orbitals are fixed at their Hartree–Fock value, configurations for which Brillouin's theorem holds may be important, particularly for atomic properties other than energy. The Fermi contact term is considered as an example. 相似文献
52.
W. K. Fischer 《Fresenius' Journal of Analytical Chemistry》1967,227(2):116-120
Zusammenfassung Es wird auf eine bisher nicht beachtete Fehlermöglichkeit bei der analytischen Untersuchung und Weiterverwendung von membranfiltrierten Lösungen hingewiesen. Die üblichen Membranfilter enthalten zur Hydrophilisierung bestimmte Mengen anionaktiver Tenside, die sich nur in wechselndem Ausma\e vor dem Gebrauch eluieren lassen. Bei der Untersuchung von membranfiltrierten Flu\-, Grund- und Trinkwasserproben findet man dadurch zu hohe Tensidkonzentrationen und bei der Austestung und Verwendung sterilfiltrierter Wirkstofflösungen u. a. können betrÄchtliche Störungen eintreten. Von Fall zu Fall ist darum eine sorgfÄltige Versuchskontrolle hinsichtlich einer spezifischen Tensidwirkung nötig.
Summary Reference is made to a source of error so far unknown in analytical examinations of aqueous membrane-filtered solutions. Membrane filters usually contain a certain amount of anionic surface-active substances for hydrophilizing purposes. These substances are only partly eliminated before the use of the filter. Therefore, in samples of membrane-filtered river, underground and tap water concentrations are found higher than the actual detergent content. There may also be interferences with the testing of bio-active substances, for instance of antibiotics. Advice is given to control carefully the possible specific effect of surface-active substances during these experiments.相似文献
53.
Absolute rate constants are reported for the addition of the 1‐[(tert‐butoxy)carbonyl]ethyl (= 2‐(1,1‐dimethylethoxy)‐1‐methyl‐2‐oxoethyl) radical .CHMeCO2(t‐Bu) to several cyclic and monosubstituted alkenes in MeCN as obtained by time‐resolved electron paramagnetic resonance (EPR). The activation energies for the addition of this alkyl radical are mainly governed by the addition enthalpy but are also substantially lowered by the ambiphilic effect and by relief of cyclic strain. 相似文献
54.
Axel Fischer Peter G. Jones Ion Neda Reinhard Schmutzler Igor V. Shevchenko 《无机化学与普通化学杂志》1994,620(5):908-913
Synthesis and Molecular Structure of new Ring Systems from 1,1,3,3-Tetrachloro-1,3-diphosphapropane 1,1,3,3-Tetrachloro-1,3-diphosphapropane 1 reacts in two different ways to form new heterocycles. Partial oxidation of 1 with tetrachloroorthobenzoquinone furnishes the methylene-bridged λ3P, λ5P species 3 . Subsequent reactions with di- and triethylamine lead to the condensed ring system 6 with the P?C bonds connected to a central four-membered ring. Compound 6 displays crystallographic inversion symmetry, a short transannular P? P distance and an extremely distorted tetrahedral coordination geometry at the four-membered ring phosphorus atoms. 1 reacts with 7 to give the heterocycle 8 with a central eight-membered ring involving four phosphorus atoms. The eight – membered ring shows a ?bent”? crown conformation, the condensed five – membered rings display envelope conformation. 相似文献
55.
The mass spectrometric behaviour of 1-aryl-5-(2-dialkylaminovinyI)-lH-tetrazoles was studied, especially 1-phenyl-5-(2-dimethylaminovinyl)-l H-tetrazole as a typical example of D- and 15N-labelled derivatives revealed a rearrangement via a carbodiimide-like intermediate ion. 相似文献
56.
57.
Jochen Münchenberg Jens R. Goerlich Axel K. Fischer Peter G. Jones Reinhard Schmutzler 《无机化学与普通化学杂志》1996,622(2):348-354
Synthesis, Structure, and some Reactions of N-(N′,N′,N″,N″-tetramethyl)guanidinyl-substituted Phosphoryl Compounds The tetramethylguanidinyl-substituted phosphoryl compounds 1 – 10 were prepared in the reaction of the appropriate chlorophosphoryl compounds with either N′,N′,N″,N″-tetramethylguanidine (HTMG) or N-trimethylsilyl-(N′,N′,N″,N″-tetramethyl)guanidine (TMSTMG). With methyl iodide 1 reacted with N-alkylation to give the ammonium salt 11. 1 reacted with BF3 · Et2O at both imino nitrogen atoms with formation of the bis-BF3-adduct 12 . The X-ray structure determination of phenylphosphonic acid-bis(N′,N′,N″,N″-tetramethylguanidinide) 3 shows shortened PN-bonds and widened PNC-angles, consistent with the partial double bond character of the PN-bond. 相似文献
58.
When crystallized from appropriate solvents, the complex aqua-bis(dimethylglyoximato)nitrocobalt (III) may incorporate solvent molecules, thus forming a variety of mixed crystals. In the resulting host-guest crystals, the space groupP2l/m and the packing motif of the pure host compound are retained. Lattice constantsa andb remain essentially unaltered upon intercalation, whereasc and the monoclinic angle depend largely on the clathrated guest. Space filling and intermolecular contacts are discussed.Dedicated to Professor Peter Paetzold at the occasion of his 60th birthday. A preliminary account of this work has been given at the Spring Meeting of the British Crystallographic Association, Newcastle upon Tyne, 1994. 相似文献
59.
Chen Wang Amit Fischer Avner Ehrlich Yaakov Nahmias Itamar Willner 《Chemical science》2020,11(17):4516
The enzymes glucose oxidase (GOx), acetylcholine esterase (AchE) and urease that drive biocatalytic transformations to alter pH, are integrated into pH-responsive DNA-based hydrogels. A two-enzyme-loaded hydrogel composed of GOx/urease or AchE/urease and a three-enzyme-loaded hydrogel composed of GOx/AchE/urease are presented. The biocatalytic transformations within the hydrogels lead to the dictated reconfiguration of nucleic acid bridges and the switchable control over the stiffness of the respective hydrogels. The switchable stiffness features are used to develop biocatalytically guided shape-memory and self-healing matrices. In addition, loading of GOx/insulin in a pH-responsive DNA-based hydrogel yields a glucose-triggered matrix for the controlled release of insulin, acting as an artificial pancreas. The release of insulin is controlled by the concentrations of glucose, hence, the biocatalytic insulin-loaded hydrogel provides an interesting sense-and-treat carrier for controlling diabetes.Biocatalytic control over the stiffness of pH-responsive hydrogels is applied to develop shape-memory, self-healing and controlled release matrices. 相似文献
60.
The enol of acetone, formed by disproportionation reactions of 1-hydroxy-1-methylethyl radicals, is detected by NMR, spectroscopy during photoreactions of 3-hydroxy-3-methyl-2-butanone in acetonitrile and of acetone in 2-propanol and slowly tautomerizes to acetone. The photolysis of 3-hydroxy-3-methyl-2-butanone is shown to proceed via Type I cleavage, predominantly from an excited triplet state. 相似文献