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11.
Prof. Dr. Heinz Falk Alfred Leodolter Georg Schade 《Monatshefte für Chemie / Chemical Monthly》1978,109(1):183-192
The electrochemical oxidation of arylmethylene-pyrrolinones, pyrromethenones and pyrromethenes as representative bile pigment partial structure models was investigated by means of a rotating disc platinum electrode using acetonitrile as the solvent. Two different oxidation reactions were found. The first reaction being a reversible one-electron oxidation with compounds of the arylmethylene-pyrrolinone series and pyrromethenones which are unsubstituted in position 5 of the pyrrole ring. A two step reaction (the first one reversible, the second irreversible) on the other hand was found to be typical for pyrromethenones bearing a methyl group in this position.Through protonation the first step is at a higher potential, whereas the second one is lowered and becomes reversible. The resulting oxidation pattern can be interpreted analogous to the oxidation of hydroquinones in aprotic solvents.The geometrical isomers of a pyrromethenone were oxidized at appr. the same potential, but there is a strong dependence of the potential of the first oxidation step on the substitution: a higher degree of alkylation favours oxidation by lowering the oxidation potential.
Mit 1 Abbildung 相似文献
Mit 1 Abbildung 相似文献
12.
Heinz Falk Gabriele Streßler Norbert Müller 《Monatshefte für Chemie / Chemical Monthly》1988,119(4):505-508
Using a specific force field model, relative stabilities of 2,2-bipyrrole and 2,2-furylpyrrole conformers as well as of prodigiosene tautomers, configurations, and conformations, are studied. 2,2-Bipyrrole adopts anantiperiplanar conformation in accord with other theoretical calculations and experimental findings. Its rotational barrier calculated by this method compares favourably to the one derived by other means. For the parent prodigiosene the (Z)sp,sp arrangement is found to be the most stable one. The two possible tautomers within its dipyrrin fragment do not show a significant energy difference. 相似文献
13.
Beate Hager Bettina Schwarzinger Heinz Falk 《Monatshefte für Chemie / Chemical Monthly》2006,137(2):163-168
Summary. Two model compounds for the green fluorescent protein chromophore were prepared. One of them incorporates the natural 4-hydroxybenzylidene
group of the natural tyrosin derived chromophore, the other one bears a methyl group instead of the hydroxy group. Whereas
the photochemically prepared (E)-diastereomer of the first compound very effectively reverted thermally (room temperature) to the thermodynamically stable
(Z)-diastereomer, the (E)-diastereomer of the second derivative proved to be stable even at elevated temperatures for more than a day. This finding
can be rationalized by constructing the appropriate resonance structures showing that only in the first case an effective
delocalization enables partial single bond character of the benzylidene double bond. From the standpoint of chemical etiology,
only Nature’s choice of the tyrosin derived chromophore of the green fluorescent protein provides an efficient radiationless
thermal relaxation channel for the unwanted photo-diastereomerization product formed after excitation besides the dominating
fluorescence channel of its chromophore. 相似文献
14.
15.
C. Etzlstorfer H. Falk N. Müller W. Schmitzberger Ulrike G. Wagner 《Monatshefte für Chemie / Chemical Monthly》1993,124(6-7):751-761
Summary Stereochemistry and tautomerism of hypericin, pseudohypericin, and several of their partial structure models were investigated using an MM2 derived force field method. Besides the propeller type conformer, which was also found by the X-ray crystallographic study, the complicated energy hypersurface was shown to contain a novel double-butterfly conformer of similar stability. The upper limit interconversion barrier between these conformers and their enantiomers was found to be in the order of 115 kJ/mol.1H-NMR experiments suggested a lower limit interconversion barrier of at least 80 kJ/mol. From the ten tautomers possible in principle, the 7,14-species was derived to be the most stable one by at least 48 kJ/mol.
Tautomerie und Stereochemie von Hypericin: Untersuchungen mit Hilfe der Kraftfeld-Methodik, NMR-Spektroskopie und Röntgenstrukturanalyse
Zusammenfassung Die Stereochemie von Hypericin, Pseudohypericin und einigen seiner Partialstrukturmodelle wurde mit Hilfe einer von MM2 abgeleiteten Kraftfeldmethodik untersucht. In der komplizierten Energiehyperfläche wurde neben dem auch durch Röntgenstrukturanalyse gefundenen Propeller-Konformeren ein neues Doppelschmetterling-Konformer ähnlicher Stabilität aufgefunden. Die obere Grenze für die Interkonversionsbarrieren zwischen diesen Konformeren und ihren Enantiomeren sind in der Größenordnung von 115 kJ/mol. Aus1H-NMR-Experimenten konnte eine untere Grenze von wenigstens 80 kJ/mol abgeleitet werden. Es wurde gefunden, daß von den zehn prinzipiell möglichen Tautomeren die 7,14-Spezies die um wenigstens 48 kJ/mol stabilste ist.相似文献
16.
By spectrophotometric measurements in the systemDMSO/H2O/Me
4NOH pK
a-values for several model compounds representing bile pigment partial structures were established. The acidic protons of pyrrole and lactame type nitrogen atoms are removed by bases governed by the electronic properties of the substituents on these ring systems. The pK
a-values for both types lie in the same region. In the pyrromethenones the lower one corresponds to the lactame type NH as was deduced by comparison with specifically methylated derivatives.The complexation of these ligands is determined by the possibility of removing an acidic proton and achieving a chelate structure by means of an adjacent pyrrolinone type nitrogen atom. Complexes are favoured in the series pyrromethenes > lactim ethers > pyrromethenones. With the latter there are two possibilities: one observed with BF2-chelation where the lactime form becomes stabilized, the other one with zink where both acidic centers are involved in the bonding.
19. Mitt.:H. Falk, A. Leodolter undG. Schade, Mh. Chem.109, 183 (1978). 相似文献
19. Mitt.:H. Falk, A. Leodolter undG. Schade, Mh. Chem.109, 183 (1978). 相似文献
17.
Summary Fringelite D was synthesized from 1,3,6,8-tetramethoxyanthracen-9-olvia two different efficient routes. The first one involved demethylation and subsequent dimerization. The other one started with dimerization to yield octamethylfringelite D and subsequent demethylation. The starting material was prepared in four steps from commercially available educts, the key step being a benzamideortho-lithiation. The spectroscopic properties of fringelite D were measured and are discussed. The dissociation, deprotonation, and protonation equilibria of fringelite D were characterized by their respectivepK values in ground and excited states and compared with those of hypericin. Homo- and heteroassociation properties of fringelite D were found to be similar to those of hypericin.
Synthese und Eigenschaften von Fringelit D (1,3,4,6,8,10,11,13-Octahydroxy-phenanthro[1,10,9,8,o,p,q,r,a]perylen-7,14-dion)
Zusammenfassung Fringelit D wurde auf zwei effizienten Routen aus 1,3,6,8-Tetramethoxyanthracen-9-ol synthetisiert. Die erste umfaßt Demethylierung und anschließende Dimerisierung. Die andere beginnt mit der Dimerisierung zu Octamethylfringelit D und endet mit einer Demethylierung. Das Ausgangsmaterial wurde in vier Stufen aus kommerziell zugänglichen Edukten dargestellt; der Schlüsselschritt ist eineortho-Lithiierung eines Benzamids. Die spektroskopischen Eigenschaften von Fringelit D wurden gemessen und werden diskutiert. Die Dissoziations-, Deprotonierungs- und Protonierungsgleichgewichte wurden durch ihrepK-Werte in Grundzustand und angeregtem Zustand charakterisiert und mit jenen des Hypericins verglichen. Die Homo- und Hetero-assoziationseigenschaften von Fringelit D sind jenen des Hypericins ähnlich.相似文献
18.
Josef Edinger Heinz Falk Norbert Müller 《Monatshefte für Chemie / Chemical Monthly》1984,115(6-7):837-852
The diastereomeric 2,3-Dihydrobilatrienes-abc derivatives (4Z, 9Z, 15Z)-7 and (4Z, 9Z, 15E)-7 bearing a cholesterylacetate moiety in position 3 of the chromophore are prepared. The reaction sequence contains an isomerisation step providing quantitative enantioselective formation of the chiral center in position 3. Configurations and conformations of the diastereomers are elucidated using1H- and13C-NMR spectra, NOE-difference spectra, 2D-NMR experiments (NOESY) and arguments from UV-VIS and CD data. It is concluded that the hydrophobic interactions between chromophore and cholesteryl-fragment yield a compact conformation where the two substructures are in close contact with each other. On the other hand these interactions seem to be too weak to induce significant changes in the chemistry, absorption spectra and conformational characterics of the bile pigment chromophore. Therefore hydrophobic interactions between chromophor and apolar amino acid residues of the protein in phytochrome should be of minor relevance for determining spectroscopic shifts. 相似文献
19.
Three-dimensional model binary glasses produced by quenching from a range of liquid temperatures were tested in shear over a range of strain rates using molecular-dynamics techniques. Tests were performed under constant volume and constant pressure constraints. The simulations revealed a systematic change in short-range order as a function of the thermal and strain history of the glass. While subtle signs of differences in short-range order were evident in the pair distribution function, three-body correlations were observed to be markedly more sensitive to the changes in structure. One particular structural parameter, the number of aligned three-atom clusters, was analyzed as a function of the degree of supercooling, the strain and the strain rate. The glasses quenched from the supercooled liquid regime were observed to contain an initially higher number of such clusters, and this number decreased under shear. Those quenched from high-temperature equilibrium liquids contained lower numbers of such clusters and these increased or remained constant under shear. The glasses quenched from the supercooled liquid regime showed higher strength, more marked shear softening, and an increased propensity toward shear localization. The evolution of this structural parameter depended both on its initial value and on the imposed shear rate. These results were observed to hold for simulations performed under both constant density and constant pressure boundary conditions. 相似文献
20.
Summary The base catalyzed oxidative dimerization of emodin anthrone exclusively yields hypericin. However, on oxidative dimerization of trimethylemodinanthrone a mixture of hexamethylhypericin and hexamethylisohypericin was obtained. Chromatographic separation of the hexabenzoyl derivatives was achieved, and by saponification about equal amounts of hypericin and isohypericrin were produced. Isohypericin could be characterized for the first time by its spectroscopic data and its protonation and deprotonationpK
a
andpK
a
*
values.
Zur Synthese von Hypericin durch oxidative Dimerisierung von Trimethylemodinanthron und Emodinanthron: Isohypericin
Zusammenfassung Die basenkatalysierte oxidative Dimerisierung von Emodinanthron liefert ausschließlich Hypericin. Oxidative Dimerisierung von Trimethylemodinanthron ergibt jedoch ein Gemisch von Hexamethylhypericin und Hexamethylisohypericin. Die Hexabenzoylderivate wurden chromatographisch getrennt, und Hypericin und Isohypericin konnten aus diesen Derivaten durch Verseifung freigesetzt werden. Isohypercin konnte erstmals durch seine spektroskopischen Daten und seine Protonierungs- und Deprotonierungs-pK aundpK a * -Werte charakterisiert werden.相似文献