全文获取类型
收费全文 | 4021篇 |
免费 | 84篇 |
国内免费 | 35篇 |
专业分类
化学 | 3026篇 |
晶体学 | 17篇 |
力学 | 91篇 |
数学 | 470篇 |
物理学 | 536篇 |
出版年
2022年 | 31篇 |
2021年 | 41篇 |
2020年 | 48篇 |
2019年 | 47篇 |
2018年 | 32篇 |
2016年 | 57篇 |
2015年 | 60篇 |
2014年 | 109篇 |
2013年 | 172篇 |
2012年 | 202篇 |
2011年 | 237篇 |
2010年 | 127篇 |
2009年 | 109篇 |
2008年 | 172篇 |
2007年 | 199篇 |
2006年 | 218篇 |
2005年 | 185篇 |
2004年 | 164篇 |
2003年 | 150篇 |
2002年 | 168篇 |
2001年 | 75篇 |
2000年 | 77篇 |
1999年 | 45篇 |
1998年 | 36篇 |
1997年 | 45篇 |
1996年 | 61篇 |
1995年 | 35篇 |
1994年 | 38篇 |
1993年 | 40篇 |
1992年 | 39篇 |
1991年 | 32篇 |
1990年 | 34篇 |
1989年 | 27篇 |
1988年 | 24篇 |
1987年 | 24篇 |
1986年 | 32篇 |
1985年 | 60篇 |
1984年 | 51篇 |
1983年 | 41篇 |
1982年 | 49篇 |
1981年 | 44篇 |
1980年 | 53篇 |
1979年 | 65篇 |
1978年 | 51篇 |
1977年 | 39篇 |
1976年 | 45篇 |
1975年 | 26篇 |
1974年 | 28篇 |
1973年 | 29篇 |
1969年 | 22篇 |
排序方式: 共有4140条查询结果,搜索用时 15 毫秒
71.
Berry JF Cotton FA Daniels LM Murillo CA 《Journal of the American Chemical Society》2002,124(13):3212-3213
The molecule Ni(3)(dpa)(4)Cl(2) (1) can be oxidized by AgPF(6) to give crystalline Ni(3)(dpa)(4)(PF(6))(3) (2) (dpa is the anion of di(2-pyridyl)amine). This reversible oxidation occurs at a potential of 0.908 V vs Ag/AgCl electrochemically. The X-ray structure of 2 shows that the oxidation causes a major structural change (even though it is reversible), namely, a contraction of the Ni-Ni distances from ca. 2.43 A to 2.284[1] A. In addition, the electronic structure changes so that from four unpaired electrons in 1 there is only one in 2. From these remarkable results, it is inferred that while 1, and all higher homologues with 5, 7, 9,... nickel atoms are poor electronic conductors, the cations obtainable from them may be much better ones. This in turn means that by controlling the oxidation state electrochemically, these molecules may be able to function as nanoscale diodes. 相似文献
72.
Albert Lévai Gábor Tóth Áron Szőllősy Tibor Timár 《Monatshefte für Chemie / Chemical Monthly》1990,121(5):403-411
Summary Arylsulfonyloxy-2,2-dimethyl-2H-chromenes (26–35) have been synthesized by reduction of arylsulfonyloxy-2,2-dimethyl-4-chromanones (6–15) followed by dehydration.
Synthese von Benzopyranderviaten. 15. Mitt.: Darstellung von Arylsulfonyloxy-2,2-dimethyl-2H-chromenen
Zusammenfassung Reduktion von Arylsulfonyloxy-2,2-dimethyl-4-chromanonen (6–15) und anschließende Dehydratisierung liefert Arylsulfonyloxy-2,2-dimethyl-2H-chromene (26–35).相似文献
73.
Four new stationary phases for HPLC were prepared by modifying silica gel with a trifrnctional aminoalkyl silane. A conjugated π-electron system was linked to the amino group either directly or with a carboxylic anhydride as a spacer in between. Characterization and dynamic measurements of the new stationary phases were performed by solid state NMR spectroscopy. The results of the 29si and 13C CP/MAS techniques were compared with the recently developed 1H MAS-only technique. Despite strong homonuclear dipole-dipole interactions it was possible to obtain well resolved 1H MAS spectra of those stationaru phases with a high degree of crosslinking. Limited mobility of the aromatic ligand fragments is common for all examined stationaryu phases. The chromatographic properties of the new phases were tested by their ability tio sepatate a mixture of eight PAHS. It could be shown that the π-π interaction mechanism is responsible for the separation of the eight PAHs, because the elution order of the PAHs did not changem despite the use of both a nonpolar mobile phase (n-heptane) and a polar mobile phase (methanol/ water mixture). 相似文献
74.
Contribution to the study of the behaviour of catechin in alkaline medium When catechin ( 1 ) is warmed with aqueous alkali it first undergoes rapid epimerisation. After some time a novel bridged carbocyclic enol, catechinic acid ( 3 ) separates out and may be isolated in excellent yield. Eventually catechinic acid isomerises to 2-(3′,4′-dihydroxyphenyl)-3,9-epoxy-6-oxo-bicyclo[3,3,1]-non-7-en-8,9-diol ( 4 ) via an open chain anion ( 5 ) which is also involved in the epimerisation of catechin. Assignments of structure are given and the equilibria observed are discussed. 相似文献
75.
Heinz Albert Flocke 《Colloid and polymer science》1962,180(2):118-126
Zusammenfassung Mit der Torsionsschwingungsmethode nachSchmieder undWolf wurde das Relaxationsverhalten von Polyäthylen, Polypropylen verschiedener Taktizität, Gemischen aus diesen beiden Polymerisaten, sowie Mischpolymerisaten aus Propylen und äthylen in einem Temperaturbereich von –180 C bis 160 C untersucht.Während sich bei Polymerisatgemischen einfache Mischungsregeln für den Gleitmodul und die Dämpfung ergeben, zeigen Mischpolymerisate gleicher chemischer Zusammensetzung ein komplizierteres Verhalten, welches an Hand der gemessenen Kurven diskutiert wird. Außerdem wird das Relaxationsverhalten einer langsam abgekühlten Niederdruckpolyäthylen-Probe mit demjenigen einer abgeschreckten Probe verglichen. Bei Polypropylen konnte eine zeitabhängige Nachkristallisation nachgewiesen werden.Herrn Dr.Knappe vom Deutschen Kunststoffinstitut, Darmstadt, sei für Diskussionen und wertvolle Ratschläge, den Firmen Stickstoffwerk Hibernia A. G., Wanne-Eickel, und C. Freudenberg, Weinheim/Bergstraße, für die Erlaubnis zur Veröffentlichung dieser Arbeit und meinen Mitarbeitern H. Becker,W. Hering undU. Wenster für die Durchführung der Messungen gedankt. 相似文献
76.
Christian Lehmann Bernd Schweizer Christian Leumann Albert Eschenmoser 《Helvetica chimica acta》1997,80(5):1421-1442
Chemistry of α-Aminonitriles. Regioselective Synthesis and Crystal Structure of Uroporphyrinogen (Type I) Octanitrile A regioselective synthesis of uroporphyrinogen-octanitrile (type I) based on the strategy of multiple use of (dimethylmethylidene)ammonium iodide for stepwise regioselective functionalization of the pyrrole nucleus is described. This uroporphyrinogen derivative is remarkably stable and beautifully crystallizes in space group P1 with one molecule per unit cell. The crystal structure of the compound shows interesting conformational characteristics which are interpreted to be caused by subtle stereoelectronic effects. The English Footnotes to Schemes 1-3 and Figs. 1-12 provide an extension of this summary. 相似文献
77.
Dieter Seebach Thomas Weller Gerd Protschuk Albert K. Beck Marvin S. Hoekstra 《Helvetica chimica acta》1981,64(3):716-735
Preparation of 1,3-Diketones and of Nitro-diketones by (1:1)-Acylation of Lithium Enolates with Acyl Chlorides Slow addition of precooled solutions of lithium enolates in THF (Fig. 1) to solutions of equimolar amounts of acyl chlorides in the same solvent at temperatures between ? 80 and ? 100° furnishes 1, 3-diketones in acceptable to good yields (Tables 1?3). Even 3-nitropropionyl and 4-nitrobutyryl chloride can be employed for the (1:1)-acylation of enolates to give the synthetically useful 5- and 6-nitro-1, 3-diketones 13 and 25 , respectively. The scope and the limitations of this method of preparing 1, 3-diketones are given and are compared with alternative methods. 相似文献
78.
Jacques Piette Claire-M. Calberg-Bacq Albert van de Vorst 《Photochemistry and photobiology》1977,26(4):377-382
Abstract. Thiols and disulfides protect both φX174 phage and its isolated DNA from the lethal action of proflavine plus light. The protective ability of these compounds appears to be attributed to the -SH or the -S-S- group and the property to interact with the proflavine-phage DNA complex. The phage inactivation efficiency per proflavine bound to DNA is reduced by 50 to 30% upon addition of cysteine or cystamine. Substances that affect the lifetime of singlet oxygen modify the rate of phage photoinactivation in the presence of proflavine; the inactivation rate is decreased by N- 3 and increased by D2 O. Irradiation under N2 atmosphere markedly decreases the phage photosensitization by proflavine. Irradiation with monochromatic light of 440 nm is less efficient than irradiation with light of 440 nm plus 360 nm, and the difference is more pronounced in N2 than in air. These results are discussed in relation to various possible photochemical pathways. 相似文献
79.
Frank J. Quaeyhaegens Herman O. Desseyn Spiros P. Perlepes John C. Plakatouras Ben Bracke Albert T. H. Lenstra 《Transition Metal Chemistry》1991,16(1):92-101
Summary The synthesis of the NiII, PdII and CuII complexes of N, N-bis(aminoalkyl)oxamides (LH2) is described and structures are proposed on the basis of their physical and spectroscopic properties. With NiII and PdII only one complex is formed with general formula NiL or PdL, characterised by coordination through two deprotonated amide N-atoms and two terminal NH2 groups. With CuII it proved possible to obtain three structurally different compounds, depending on the pH, with general formulae Cu(LH2)X2, Cu2(L)X2 and CuL in which X=Cl, Br or NO3. The structure of [Cu2(C8O2N4H16](NO3)2 was solved by means ofx-ray diffraction; Mr=451.33, monoclinic, space group P21/n, a=9.503(4), b=7.614(1), c=10.407(3) Å, =98.43(3)°, V=744.3(7)Å3, Z=2, Dx=1.202 g cm–3, =1.33 cm–1, (MoK)=0.71073 Å, F(000)=520, room temperature, R=0.043, wR=0.047 for 1080 observed [I>-3(I)] not systematically absent reflections out of 1423 measurements and 137 variables. The compound has a conformational chair/boat disorder with 82% in the more stable chair form. 相似文献
80.
Ze'ev V. I. Zaretskii Albert Avraham Ben-Bassat David Lavie 《Journal of heterocyclic chemistry》1975,12(5):837-840
The mass spectra of α-, β- and γ-pyridine aldoximes and the respective O-methyl ethers were studied. The mass spectral behaviour of α-pyridine aldoxime is characterized by the elimination of NO, while the molecular ion of the γ-isomer expels H2 CN. In the case of the β-isomer the formation of the m/e 67 ion (C4H5N) in a concerted process is the main feature. In the α-pyridine aldoxime methyl ether, in sharp contrast to the hydroxy analog, the M-30 peak was found to be due to the elimination of CH2O, the expulsion of NO being absent. The mechanism of the fragmentation reactions is discussed, the conclusion drawn being based on the high resolution measurements as well as on the spectra of the respective deuterioanalogs and on the metastable transitions. 相似文献