全文获取类型
收费全文 | 72954篇 |
免费 | 16176篇 |
国内免费 | 318篇 |
专业分类
化学 | 75102篇 |
晶体学 | 298篇 |
力学 | 1764篇 |
综合类 | 1篇 |
数学 | 7062篇 |
物理学 | 5221篇 |
出版年
2024年 | 438篇 |
2023年 | 4309篇 |
2022年 | 1652篇 |
2021年 | 2723篇 |
2020年 | 5074篇 |
2019年 | 2720篇 |
2018年 | 2688篇 |
2017年 | 948篇 |
2016年 | 6242篇 |
2015年 | 6096篇 |
2014年 | 5674篇 |
2013年 | 6506篇 |
2012年 | 5064篇 |
2011年 | 3372篇 |
2010年 | 4483篇 |
2009年 | 4259篇 |
2008年 | 3193篇 |
2007年 | 2728篇 |
2006年 | 2210篇 |
2005年 | 2015篇 |
2004年 | 1725篇 |
2003年 | 1421篇 |
2002年 | 1355篇 |
2001年 | 520篇 |
2000年 | 492篇 |
1999年 | 426篇 |
1998年 | 414篇 |
1997年 | 461篇 |
1996年 | 503篇 |
1995年 | 426篇 |
1994年 | 439篇 |
1993年 | 512篇 |
1992年 | 373篇 |
1991年 | 339篇 |
1990年 | 282篇 |
1988年 | 289篇 |
1987年 | 287篇 |
1985年 | 429篇 |
1984年 | 393篇 |
1983年 | 348篇 |
1982年 | 419篇 |
1981年 | 365篇 |
1980年 | 394篇 |
1979年 | 336篇 |
1978年 | 330篇 |
1977年 | 381篇 |
1976年 | 392篇 |
1975年 | 373篇 |
1974年 | 359篇 |
1970年 | 265篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
111.
Michael C. Böhm 《Theoretical chemistry accounts》1983,62(4):351-372
The crystal orbital formalism in the tight-binding approximation is combined with a recently developed CNDO/INDO model for transition metal species of the 3d series in order to allow band structure calculations on the Hartree-Fock (HF) SCF level for one-dimensional (1D) chains with organometallic unit cells. The band structure approach based on the CNDO and INDO approximation can be used for any atom combination up to bromine under the inclusion of the 3d series. The matrix elements for the tight-binding Hamiltonian are derived for an improved CNDO and INDO framework. The total energy of the 1D chain is partitioned into one-center contributions and into two-center increments of the intracell and intercell type. Semiempirical band structure calculations on simple model systems are compared with available ab initio data of high quality. 相似文献
112.
Adarsh Kumar A. K. Bose Prof. S. P. Mushran 《Monatshefte für Chemie / Chemical Monthly》1975,106(4):863-869
The oxidation kinetics of cycloheptanone by chloramine-T in alkaline media has been investigated. A mechanism involving the formation of an intermediate by the interaction between the enolic anion of cycloheptanone and chloramine-T in a slow step followed by its interaction with another molecule of chloramine-T in a fast step leading to products has been proposed. The scheme satisfactorily accords with the observed stoichiometry, negligible influence of ionic strength and a positive dielectric effect. Various rate parameters have been computed and 1.2-cycloheptanedione identified as the end product.With 2 Figures 相似文献
113.
The successive reaction of (CO)6M with Na[NCR21] and [Et3O]BF4 yields (CO)5M[C(NCR21)OEt] (II: M = Cr; III: M = W; CR21 = C(C6H4Br-p)2 (a), CPh2 (b), C(C6H4OMe-p)2 (c), C(C6H4)2O (d), CBu2tt (e)). Hexacarbonyltungsten, (CO)6W, reacts with Na[NCPh2] and MeOSO2F to give (CO)5W[C(NCPh2) OMe] (IV). X-Ray analysis of IIe shows that: (1) the CNC fragment is almost linear (171.7°); (2) the two NC bond lengths are equal within experimental error; and (3) the O,C,Cr,N plane is perpendicular to the C(Me3),C,N,C(Me3) plane (90.0°). Therefore compounds II–IV are best described as 1-alkoxy-2-azaallenyl complexes. 相似文献
114.
We recently reported a beta-peptide foldamer, beta53-1, that folds into a 14-helix in aqueous solution, binds the oncoprotein hDM2 with submicromolar affinity, and potently inhibits the interaction of hDM2 with a peptide derived from the activation domain of p53 (p53AD). Here, we present the solution structure of beta53-1 in methanol. Details of the structure illustrate fundamental and novel elements of beta-peptide folding and recognition. These elements include the detailed arrangement of a complex, 14-helix-stabilizing salt bridge on one helical face, and a unique "wedge into cleft" packing interaction along a second. The structure also reveals how a subtle distortion in the beta53-1 14-helix geometry alters the presentation of its recognition epitope, rendering it particularly well suited for alpha-helix mimicry. The solution structure of beta53-1 demonstrates that well folded beta-peptide oligomers can effectively present an extended, highly variable surface that could be used as a general platform for targeting critical protein-protein interfaces. 相似文献
115.
L. Mandelkern J. Michael Price M. Gopalan J. G. Fatou 《Journal of Polymer Science.Polymer Physics》1966,4(3):385-400
Replicas of fracture surfaces of fractions of linear polyethylene, which were crystallized at elevated temperatures for extended time periods, were examined by electron microscopy. Striated. lamella-type crystallites were observed for all molecular weights over the range 3.2 × 103?5.7 × 105. In agreement with Anderson's previous report, for molecular weights of 12,000 or less, the crystallite thicknesses were comparable to the extended chain length. As the molecular weight increased above this level, however, the crystallite sizes increased only slightly and hence at high molecular weights were very much smaller than the extended chain length. From the measured melting temperatures, crystallite interfacial free energies were calculated from the theory for the melting of finite size crystals comprised of chains of finite length. The crystallite interfacial free energy was found to increase with molecular weight. Based on these results, a crystallization process is outlined which allows for the formation of either extended chain crystallites, or crystallites whose size is much smaller than the extended chain length without any change in nucleation mechanism or arbitrary adjustment in growth mechanism with molecular weight. 相似文献
116.
Burford N Ragogna PJ McDonald R Ferguson MJ 《Chemical communications (Cambridge, England)》2003,(16):2066-2067
Polyphosphorus dications have been synthesised and comprehensively characterised as diphosphine (dppe, dmpe and dpph) linked Ar2P+ Lewis acids (Ar = C6H5); this application of unique homoatomic coordination chemistry provides important building blocks for extended systems. 相似文献
117.
Zusammenfassung Mit bekannten mikroanalytischen Arbeitsmethoden — Oberflächenreaktionen, Abstrichuntersuchungen mit dem Korundstäbchen, Schutzschichtreaktionen sowie dem Abdruckverfahren — lassen sich archaeometrische Probleme einer Lösung näherbringen. Die Art der Korrosion kupferhaltiger Oberflächen wurde diskutiert.
Vortrag anläßlich der Tagung Chemische Analysen — Kunst- und Kulturwissenschaften im Reiß-Museum in Mannheim, 19.–21. September 1974. 相似文献
Application of microanalytical methods to the solution of artistic- and cultural historical problems
Summary Archeometrical problems are brought closer to a solution by means of known microanalytical procedures-surface reactions, surface scraping studies with the corundum rod, protective layer reactions as well as the imprint method. A discussion of the corrosion of copper-bearing surfaces is included.
Vortrag anläßlich der Tagung Chemische Analysen — Kunst- und Kulturwissenschaften im Reiß-Museum in Mannheim, 19.–21. September 1974. 相似文献
118.
[reaction: see text] The enediamine tautomer of a variety of substituted amidine free bases reacts with nitric oxide (NO) to produce compounds containing a carbon-bound diazeniumdiolate [R1R2R3C-N(O)=NO-] functional group (previously called "nitrosohydroxylamines"). The new reaction has been shown to be quite general, although the nature of the products does vary. Amidines containing more than one replaceable hydrogen produce polydiazeniumdiolates as intermolecular salts, while those in which only one diazeniumdiolation can occur provide zwitterionic salts. These diazeniumdiolated amidines are shown to be useful NO donor compounds which undergo very slow spontaneous dissociation on dissolution in pH 7.4 phosphate buffer to produce mixtures of NO and nitrous oxide containing mostly NO. The most advantageous manifestation of the new discovery is the preparation of the monodiazeniumdiolated amidine zwitterions. Reaction of the medically relevant alpha-adrenergic agonists tetrahydrozoline and idazoxan produced monodiazeniumdiolated amidine zwitterions from which NO release was observed for up to 28 days and showed little sign of ending. The reaction should be applicable to a variety of pharmaceutical agents, including NO synthase inhibitors, antitumor agents, and antibacterials. 相似文献
119.
Summary A new technique is described for the identification of the chloride ion through the formation of chromyl chloride, based on the extraction of the latter with carbon tetrachloride. The identification limit is 2g of chloride. It is possible to carry out the test in the presence of many other anions, including fluoride, which cannot be present when the traditional distillation technique is employed.
Zusammenfassung Vorgeschlagen wird eine neue Technik zum Chloridnachweis durch Bildung von Chromylchlorid. Dieser Nachweis beruht auf der Extraktion des Chromylchlorids mit Tetrachlorkohlenstoff. Die Nachweisgrenze liegt bei 2g Chlorid, wobei die Möglichkeit besteht, den Test auch in Gegenwart von Fluorid durchzuführen, das bei Anwendung der üblichen Destillationsmethoden nicht anwesend sein darf.相似文献
120.
Michael Laing 《Structural chemistry》1995,6(6):397-402
A new qualitative treatment of the bonding in ozone is presented. It is based upon a combination of several simple concepts: the nonparticipation of the pairs of electrons tightly held in the atomic 2s orbitals; simple overlap of the 2p orbitals to form sigma bonds; interaction of three 2p orbitals to yield bonding and nonbonding pi molecular orbitals that are populated by electron pairs; and van der Waals repulsion between the two terminal oxygen atoms forcing these atoms apart to yield the bond angle of 117° as a compromise. Both the assumptions and the resulting bonding picture are in accord with the photoelectron spectroscopic data, the results from sophisticated molecular orbital calculations, and the common physical properties of ozone. 相似文献