全文获取类型
收费全文 | 40678篇 |
免费 | 1394篇 |
国内免费 | 31篇 |
专业分类
化学 | 23381篇 |
晶体学 | 189篇 |
力学 | 846篇 |
综合类 | 1篇 |
数学 | 6699篇 |
物理学 | 10987篇 |
出版年
2022年 | 229篇 |
2021年 | 369篇 |
2020年 | 551篇 |
2019年 | 394篇 |
2018年 | 490篇 |
2017年 | 480篇 |
2016年 | 1082篇 |
2015年 | 917篇 |
2014年 | 1033篇 |
2013年 | 2187篇 |
2012年 | 1783篇 |
2011年 | 2142篇 |
2010年 | 1109篇 |
2009年 | 942篇 |
2008年 | 2013篇 |
2007年 | 1954篇 |
2006年 | 1747篇 |
2005年 | 1568篇 |
2004年 | 1251篇 |
2003年 | 1074篇 |
2002年 | 983篇 |
2001年 | 788篇 |
2000年 | 695篇 |
1999年 | 484篇 |
1998年 | 437篇 |
1997年 | 425篇 |
1996年 | 549篇 |
1995年 | 490篇 |
1994年 | 499篇 |
1993年 | 572篇 |
1992年 | 481篇 |
1991年 | 369篇 |
1990年 | 402篇 |
1989年 | 331篇 |
1988年 | 349篇 |
1987年 | 336篇 |
1986年 | 314篇 |
1985年 | 498篇 |
1984年 | 478篇 |
1983年 | 447篇 |
1982年 | 447篇 |
1981年 | 450篇 |
1980年 | 435篇 |
1979年 | 384篇 |
1978年 | 421篇 |
1977年 | 399篇 |
1976年 | 348篇 |
1975年 | 332篇 |
1974年 | 318篇 |
1973年 | 321篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
Stress fields between interacting small particles ( approximately 100 nm) have been investigated by transmission electron microscopy. The background for these TEM observations is discussed in terms of adhesion stress fields (due to surface forces), the action of an applied point force, possibly magnetic, and dislocations or misfit strains due to an unfavorable matching of crystal lattices at the grain boundary. A further explanation might be sought along the line "squeezed-in oxide" which can be visualized as a coherent particle or a dislocation loop. Accompanying theoretical calculations have been performed and compared with the experimental results. 相似文献
942.
Zhang G Wang D Gu ZZ Möhwald H 《Langmuir : the ACS journal of surfaces and colloids》2005,21(20):9143-9148
In this work, superhydrophobic surfaces were derived from binary colloidal assemblies. CaCO(3)-loaded hydrogel spheres and silica or polystyrene ones were consecutively dip-coated on silicon wafers. The former assemblies were recruited as templates for the latter self-assembly. Due to the hydrophilicity difference between silicon wafers and CaCO(3)-loaded hydrogel spheres, the region selective localization of silica or polystyrene spheres leads to irregular binary structures with a hierarchical roughness. The subsequent modification with low surface energy molecules yields a superhydrophobic surface. The heating treatment may largely enhance the mechanical stability of the resulting binary structures, which allows regeneration of the surface superhydrophobicity, providing a good durability in practice. 相似文献
943.
Weber JM Ioffe IN Berndt KM Löffler D Friedrich J Ehrler OT Danell AS Parks JH Kappes MM 《Journal of the American Chemical Society》2004,126(27):8585-8589
Ultraviolet photoelectron spectroscopy in an ion beam was used to investigate the electronic properties of isolated DNA oligonucleotides [dA(5)-4H](4-) and [dT(5)-4H](4-), carrying four excess negative charges. We find the fourth adiabatic electron affinity to be slightly negative for [dA(5)-4H](4-), while it is positive for [dT(5)-4H](4-). This implies a significant influence of the base composition on energetics, which is in turn relevant for analytic applications and also for charge transport properties. 相似文献
944.
Kumar K Michalik D Garcia Castro I Tillack A Zapf A Arlt M Heinrich T Böttcher H Beller M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):746-757
A practical route for the synthesis of new biologically active 5-HT(2 A) receptor antagonists has been developed. In only three catalytic steps, this class of central nervous system (CNS) active compounds can be synthesized efficiently with high diversity. As the initial step, an anti-Markovnikov addition of amines to styrenes provides an easy route to N-(arylalkyl)piperazines, which constitute the core structure of the active molecules. Here, base-catalyzed hydroamination reactions of styrenes with benzylated piperazine proceeded in high yield even at room temperature. After catalytic debenzylation, the free amines were successfully carbonylated with different aromatic and heteroaromatic halides and carbon monoxide to yield the desired compounds in good to excellent yields. The two key reactions, base-catalyzed hydroamination of styrenes and palladium-catalyzed aminocarbonylation of haloarenes/heterocycles, showed tolerance towards various functional groups, thereby demonstrating the potential to synthesize a wide variety of new derivatives of this promising class of pharmaceuticals. 相似文献
945.
An enantioselective gas chromatography (GC) method has been developed and validated for determination of the enantiomers of citronellol in kinetic resolution experiments. S-(-)-beta-Citronellol is a precursor of rose oxide. After solid-phase extraction (SPE) with ethyl acetate, the enantiomers of R-(+)-beta-citronellol and S-(-)-beta-citronellol and their corresponding acetate- and butyrate esters were separated through enantioselective GC respectively. The method was validated and found to be reproducible, specific, accurate, and precise. Analyte recoveries and detection limits were also determined. The applicability of this method was shown in a kinetic resolution experiment using lipase A of Bacillus subtilis. 相似文献
946.
Wolfgang A. Herrmann Martina Flöel Cornelia Weber John L. Hubbard Adolf Schäfer 《Journal of organometallic chemistry》1985,286(3):369-397
The eighteen new μ-alkylidene ruthenium complexes 5a–r and 5t are very easily and cleanly obtained along the diazoalkane or the hydrazone routes that involve treatment of the dinuclear, metal-metal doubly bonded precursor compound [(η5-C5H5)Ru(μ-NO)]2 (3) either with the diazoalkanes oxidizing agent (e.g., MnO2), with the respective hydrazones. Similarly, sulfur dioxide adds cleanly to the RuRu double bond of 3, thus giving the complex (μ-SO2)[(η5-C5H5)Ru(NO)]2 (5s). Regardless of the nature of the carbene bridge ligands, the dimetallacyclopropanes exhibit, in contrast to their iron analogues, exclusively terminal nitrosyl ligands. cis/trans-Isomerism with predominating amounts of the trans-isomers is observed for the derivatives that display unsymmetrically substituted carbene bridges.Treatment of the μ-methylene- and μ-ethylidene complexes (μ-CH2)[(η5-C5H5)Ru(NO)]2 (5a) and (μ-CHCH3)[(η5-C tetrafluoroboric acid or trifluoromethanesulfonic acid in diethyl ether yields, at ambient temperature, quantitatively the ionic complexes 6a,b and 7a,b, respectively, which were shown by 1H NMR spectroscopy to contain metal-metal bridging hydrogen functionalities. The reaction of hydrogen bromide with 5a under the same conditions gives the neutral bromo(methyl) complex 6d. This latter compound results from the isolable ionic intermediate of composition [(μ-CH2)(μ-H){(η5C5H5)Ru(NO)}2]+Br? (6c), which reaction stems from the nucleophilicity of the halide ion present in 6c. 相似文献
947.
The crystal structure of the title compound has been determined from single crystal X-ray diffraction data and refined toR=0.125. The unit cell is triclinic, space group P,
(No. 2),a=5.688(1),b=5.701(1),c=8.583(1) Å, =81.32(1), =71.50(1), =67.95(1)° andZ=2. The structure consists of isolated [GeO4] tetrahedra linked together by four- and five-coordinate sodium atoms. Na4GeO4 is isostructural with Na4CoO4 (which has been described to be non-centrosymmetric and for which a centrosymmetric model is presented), K4GeO4, K4SnO4 and K4PbO4. 相似文献
948.
M. Leiterer J. W. Einax C. Löser A. Vetter 《Analytical and bioanalytical chemistry》1997,359(4-5):423-426
An analytical method for the quantitative determination of Al, Ti, V, Cr, Co, Ni, Cu, Zn, Mo, Cd, Ti and Pb in plant samples
by ICP-MS has been developed. Spectral interferences, plant matrix effects, precision and accuracy are discussed. Results
are demonstrated for selected samples concerned with the mass balance of heavy metals after utilization of non-food vegetable
materials in a power plant.
Received: 7 January 1997 / Revised: 2 June 1997 / Accepted: 18 June 1997 相似文献
949.
Goldfuss B Löschmann T Rominger F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(9):2028-2033
Not the expected phosphinofenchol 1 but phosphorane 2 is obtained after reaction of 2-lithio(diphenylphosphino)benzene with (-)-fenchone. Surprisingly, ONIOM(B3LYP/6-31G*:UFF) computations of 1 and 2 as well as B3LYP analyses of smaller model systems point to a lower thermodynamic stability of phosphoranes relative to their isomeric alkoxyphosphines. An analogue inherent instability is computed for the methylphosphorane 10, which is also synthesized and characterized by X-ray analysis. Decreasing ring size in cyclic phosphoranes, that is, from five- to four-membered ring systems, destabilizes cyclic phosphoranes even more. This computational prediction is verified experimentally by reaction of lithiomethyl(diphenylphosphine) with (-)-fenchone and subsequent isolation of the corresponding phosphinofenchol. Protonation or alkylation of phosphoranide intermediates can account for the formation of metastable phosphoranes. 相似文献
950.
Kozikowski AP Tückmantel W Böttcher G Romanczyk LJ 《The Journal of organic chemistry》2003,68(5):1641-1658
We report an improved synthesis of bis(5,7,3',4'-tetra-O-benzyl)epicatechin 4beta,8-dimer (3) from 5,7,3',4'-tetra-O-benzylepicatechin (1) and 5,7,3',4'-tetra-O-benzyl-4-(2-hydroxyethoxy)epicatechin (2) by replacing the previously employed Lewis acid, titanium tetrachloride, with the clay mineral Bentonite K-10. Under the same conditions, the benzyl-protected all-4beta,8-trimer, -tetramer, and -pentamer were obtained regioselectively from their lower homologues, albeit in rapidly decreasing yields. Reaction of 2 with an organoaluminum thiolate generated from 2-mercaptobenzothiazole and trimethylaluminum followed by acetylation produced 3-O-acetyl-4-[(2-benzothiazolyl)thio]-5,7,3',4'-tetra-O-benzylepicatechin (12). Medium-sized protected oligomers with 4beta,8-interflavan linkages are obtained in improved yields by using this compound as the electrophile and silver tetrafluoroborate as activator and are isolated by reversed-phase HPLC. Their deprotection by ester saponification followed by hydrogenolysis yielded the free procyanidins, which were characterized as their peracetates. The synthetic procyanidins are identical by normal-phase HPLC with fractions isolated from cocoa. The principle of chain extension by two members was demonstrated using a dimeric electrophile obtained by self-condensation of compound 12. Both the synthetic and natural pentamer 32 inhibit the growth of several breast cancer cell lines. Using the MDA MB 231 line, it was established that this outcome is based on the induction of cell cycle arrest in the G0/G1 phase. Subsequent cell death is more likely necrotic rather than apoptotic. Control experiments demonstrate that the polyphenol itself, rather than hydrogen peroxide potentially formed by its autoxidation, is the causative agent. 相似文献