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71.
Heinz Falk Franz Lehner Marianne Rothböck 《Monatshefte für Chemie / Chemical Monthly》1985,116(11):1359-1361
Donors are added regioselectively to position 10 of 2,3-dihydrobilatrienes-abc in a reversible reaction, which is complicated in case of strongly basic donors due to the easy deprotonation of the partially saturated ring. Compared to the bilatrienes-abc the addition equilibrium is retarded by about two orders of magnitude. 相似文献
72.
Gerald Kainz und Franz Scheidl 《Fresenius' Journal of Analytical Chemistry》1964,202(4):251-258
Zusammenfassung In der vorliegenden Arbeit wurde untersucht, wie man die vergaste Probe am besten durch die Verbrennungszone führt, damit man eine vollständige Vermischung mit Sauerstoff erhält; denn bei hohen Temperaturen ist nicht so sehr die Umsatzgeschwindigkeit der Probe mit Sauerstoff bestimmend, sondern die Mischungsgeschwindigkeit mit Sauerstoff. Es wurden zwei Möglichkeiten untersucht. Bei der schnellen Vergasung im geraden Rohr ergab sich, daß sich dabei ein Substanzpfropf bildet, der durch Sauerstoff (im Wege der Diffusion) durchdrungen werden muß. Eine quantitative Oxydation ist nur dann möglich, wenn die Einwaage auf den Durchmesser des Verbrennungsrohres abgestimmt ist. Bei Mikroeinwaagen (3 mg) muß der Durchmesser des Verbrennungsrohres mindestens 20 mm betragen.Eine wesentlich intensivere Vermischung der Substanzdämpfe mit Sauerstoff wird bei der Verbrennung in der Flamme erreicht, die auf Wickbold bzw. Radmacher zurückgeht. Hierbei wird die Probe in einem engen Rohr unter Durchleiten von Sauerstoff oder Stickstoff vergast und durch eine enge Düse in die heiße Verbrennungszone eingeblasen. An der Düse bildet sich eine Flamme, in die Sauerstoff intensiv eindiffundiert. Eine einfache Apparatur, die eine schnelle, bei Mikroeinwaagen von der Geschicklichkeit des Analytikers unabhängige Vergasung und Verbrennung zuläßt, wird beschrieben.
Summary In this paper the problem is investigated how to pass the vaporised sample through the combustion zone in order to attain a complete mixture with oxygen; at high temperatures the completeness of combustion depends not so much on the rate of reaction with oxygen than on the rate of mixing with oxygen. Two experimental procedures have been investigated. High speed vaporisation in straight tubes leads to a plugshaped concentration of the sample, which must be penetrated by oxygen (diffusion). Using this procedure, a quantitative oxidation is only possible, if the sample weight is in a proper relation to the diameter of the tube. In microanalysis (3 mg of sample) the diameter of the combustion tube must be 20 mm or more.A much more intensive mixing of the vaporised sample with oxygen is attained by the combustion in the flame proposed by Wickbold and Radmacher. The vaporised sample is blown out of a small tube through a narrow nozzle into the heated combustion zone. On the nozzle a flame is formed, in which oxygen is diffusing intensively. A simple apparatus is described, which permits a rapid vaporisation and quantitative oxidation. Analysing micro samples the vaporisation was found to be independent of the skill of the analyst.相似文献
73.
Bracher F Eisenreich WJ Mühlbacher J Dreyer M Bringmann G 《The Journal of organic chemistry》2004,69(25):8602-8608
The first biarylic bis-morphinanedienone alkaloids, saludimerines A (3a) and B (3b), isolated from a tree of Croton flavens (Euphorbiaceae) are described. These naturally occurring dimers of the known alkaloid salutaridine are joined together via a rotationally hindered biaryl axis, giving rise to atropo-diastereomers that are configurationally stable at room temperature but slowly interconvert in methanolic solution within several days. Their structures were established by spectroscopic methods and by partial synthesis, which was achieved by a highly atropo-diastereoselective biomimetic oxidative coupling of the monomeric precursor, salutaridine. Their axial configurations were elucidated by circular dichroism (CD) investigations, which succeeded despite the fact that the two atropo-diastereomers exhibit near-identical CD spectra. This remarkable phenomenon was rationalized by quantum chemical CD calculations. The configurational assignment of saludimerines A (3a) as P-axial and B (3b) as M was corroborated by atropisomer-specific NOE interactions between protons of the one molecular half with nuclei in the other. 相似文献
74.
K.D. Franz H. Tom Dieck U. Krynitz I.W. Renk 《Journal of organometallic chemistry》1973,64(3):361-366
Glyoxal- and diacetyl-bis(imine)metal tetracarbonyls (RNCR′CR′NR)M(CO)4 (M = Cr, Mo, W) are reduced with potassium in DME to give paramagnetic mono-anions. Their high-resolutior, ESR spectra show the hyperfine splittings of the magnetically active ligand atoms as well as the satellites of the metal isotopes 53Cr,95,97Mo and 183W. The coupling constants are discussed with respect to π-bonding mechanisms. 相似文献
75.
Warren DB Grieser F Perera JM Stevens GW 《Langmuir : the ACS journal of surfaces and colloids》2005,21(7):2822-2826
A model to calculate the interfacial concentration of competing surface active species in a two-phase oil/water system was developed. To enable the calculation of the surface excess of 2-hydroxy-5-nonylacetophenone oxime (HNAPO, active ingredient of LIX 84) in the presence of surfactants competing for interfacial area, an interfacial adsorption competition model was derived for noninteracting surface active species in a n-heptane/aqueous system, assuming ideal enthalpy and entropy of mixing. The model was found to be valid for HNAPO in the presence of sodium dodecyl sulfate (SDS) or dodecyldimethyl(3-sulfopropyl)ammonium (DDSA). In the case of dodecyltrimethylammonium chloride (DTAC) or octa(ethylene glycol) mono-n-dodecyl ether (C12E8) as the competing surfactants with HNAPO, the predicted surface excess values from the model fit less favorably. The difference was shown to not be due to nonideal entropy of mixing. 相似文献
76.
Zbigniew Gregorowicz und Franz Buhl 《Fresenius' Journal of Analytical Chemistry》1960,173(2):115-121
Zusammenfassung Es wird eine volumetrische Methode zur Bestimmung von Cyanid- und Quecksilber(II)-ionen mit titrierter Quecksilber(II)-nitratlösung gegen Variaminblau als Indicator beschrieben. Das Verfahren liefert genaue, wenig streuende Werte.Vorgetragen auf der III. Arbeitstagung für analytische Chemie in Prag am 1. September 1959. 相似文献
77.
W. Franz A. Grießel F. Steglich D. Wohlleben 《Zeitschrift für Physik B Condensed Matter》1978,31(1):7-17
We report measurements of the electrical resistivity, the thermal conductivityk and the thermoelectric powerS between 1.5K and 300K on the anomalous CeCu2Si2 compound and on LaCu2Si2 as reference compound. For LaCu2Si2 the temperature dependences of andS are in accord with those found in otherd band metals. For CeCu2Si2 the observed resistivity (220 µ cm at 200K) leads to a very short electronic mean free path which is of the order of the Ce-Ce spacing. Correspondingly,k is almost identical with the phonon contributionk
p
. Below 20K, resistivity and thermoelectric power strongly suggest Fermi liquid behavior with a degeneracy temperature between 20K and 40K. Above 200K, both andS decrease proportionally to –ln(T/1 K).Work performed within the research program of the Sonderforschungsbereich 125 Aachen/Jülich/KölnPart of this work will be presented at the Int. Conf. on Rare Earths in the Metallic State, St. Pierre de Chartreuse, Sept. 1978 相似文献
78.
Franz Pertlik 《Monatshefte für Chemie / Chemical Monthly》1990,121(2-3):129-139
Summary 2-Hydroxy-benzamide, C7H7NO2; monoclinic; I2/a-C
2h
6
;a=12.901 (2),b=4.982 (1),c=20.987 (3) Å; =91.50 (2)°;Z=8. 2-Hydroxy-thiobenzamide, C7H7NOS; monoclinic; P21/n-C
2h
5
;a=13.508 (5),b=6.780 (2),c=15.878 (6) Å; =93.74 (5)°;Z=8. 2-Hydroxy-N,N-dimethyl-benzamide, C9H11NO2; orthorhombic; Pbca-D
2h
15
;a=11.752 (2),b=16.680 (3),c=9.079 (2) Å;Z=8. 2-Hydroxy-N,N-dimethyl-thiobenzamide, C9H11NOS; monoclinic; P21/c-C
2h
5
;a=6.983 (1),b=11.652 (3),c=11.704 (3) Å; =100.02 (2)°;Z=4. The crystal structures of these four compounds were determined (respectively refined: 2-hydroxy-benzamide) by single crystal X-ray data. The refinements of the structure parameters by least squares methods yielded in all casesR<0.056. The hydrogen atoms were located by means of difference Fourier summations. The O-H ... O distances are 2.513 (1) Å in 2-hydroxy-benzamide (intramolecular) and 2.625 (1) Å in 2-hydroxy-N,N-dimethyl-benzamide (intermolecular). The two O-H ... S distances in 2-hydroxy-thiobenzamide are 2.904 (2) Å and 2.918 (2) Å (intramolecular, two molecules in the asymmetric unit) and 3.228 (2) Å in 2-hydroxy-N,N-dimethyl-thiobenzamide (intermolecular). Clear N-H ... O hydrogen bonds with 2.926 (1) Å and 3.006 (1) Å occur only in the structure of 2-hydroxy-benzamide (intermolecular).
Die Kristallstrukturen und Wasserstoffbrücken-Bindungsschemata in vier Benzamid-Derivaten
Zusammenfassung 2-Hydroxy-benzamid, C7H7NO2; monoklin; I2/a-C 2h 6 ;a=12.901 (2),b=4.982 (1),c=20.987 (3) Å; =91.50 (2)°;Z=8. 2-Hydroxy-thiobenzamid, C7H7NOS; monoklin; P21/n-C 2h 5 ;a=13.508 (5),b=6.780 (2),c=15.878 (6) Å; =93.74 (5)°;Z=8. 2-Hydroxy-N,N-dimethyl-benzamid, C9H11NO2; orthorhombisch; Pbca-D 2h 15 ;a=11.752 (2),b=16.680 (3),c=9.079 (2) Å;Z=8. 2-Hydroxy-N,N-dimethyl-thiobenzamid, C9H11NOS; monoklin; P21/c-C 2h 5 ;a=6.983 (1),b=11.652 (3),c=11.704 (3) Å; =100.02 (2)°;Z=4. Die Kristallstrukturen dieser vier Verbindungen wurden mittels Röntgen-Einkristalldaten bestimmt (bzw. verfeinert: 2-Hydroxy-benzamid). Die Verfeinerungen der Strukturparameter nach der Methode der kleinsten Quadrate ergab in allen FällenR<0.056. Die Wasserstoffatome konnten anhand von Differenz-Fourier-Summationen belegt werden. Die O-H ... O-Abstände haben folgende Werte: 2.513(1)Å in 2-Hydroxy-benzamid (intramolekular) und 2.625(1) Å in 2-Hydroxy-N,N-dimethyl-benzamid (intermolekular). Die zwei O-H ... S-Abstände sind in 2-Hydroxy-thiobenzamid 2.904(2)Å und 2.918(2)Å (intramolekular, zwei moleküle in der asymmetrischen Einheit) und 3.228(2)Å in 2-Hydroxy-N,N-dimethyl-thiobenzamid(intermollekular). Klar zuzuordnende N-H ... O-Wasserstoffbrücken mit 2.926(1)Å und 3.006(1)Å treten lediglich in der Struktur des 2-Hydroxy-benzamid auf (intermolekular).相似文献
79.
A mixed ligand 12 complex of copper(II) azide with 3,5-lutidine, namely di-(1,1)-azido-di(0,0)-nitrato)tetrakis(3,5-lutidine)dicopper(II) has been prepared and characterized by X-ray crystallographic and spectroscopic methods. The dimeric molecule, which possesses a crystallographic inversion center, contains two(1,1) bridging azido ligands. Each copper(II) atom in the cyclic Cu2N2 unit is further coordinated by two oxygen atoms from two(0,0-nitrato) bridges at Cu-O distances of 2.465(3) and 2.568(3) Å and two nitrogen atoms from the lutidine molecules [Cu-N=2.003(3) and 2.012(3) Å] to give a distorted tetragonal bipyramid. Both azido ligands are linear [N-N-N angle=179.0(4) and asymmetric N-N=1.207(4) and N-N=1.135(5) Å]. The azido bridges produce a rather short Cu Cu distance of 3.013(2) Å. Infrared and electronic data are presented and discussed. 相似文献
80.
Dietger Leyendecker Dagmar Leyendecker Franz P. Schmitz Ernst Klesper 《Chromatographia》1987,23(1):38-42
Summary In supercritical fluid chromatography (SFC), the elution behavior of styrene oligomers in pentane depends greatly on the degree of oligomerization, n. The influence of capacity ratio, k, on the lower oligomers up to about n=11 resembles the behavior of other substrates of low molecular weight, like aromatic hydrocarbons. Thus, with pentane of 100 bar and below, minima are found in plots of k versus temperature. In contrast, the k of oligomers of higher molecular weight (n>11) increase monotonously with increasing temperature. The studies were performed using oligostyrene fractions obtained by semipreparative SFC fractionation. 相似文献