全文获取类型
收费全文 | 3913篇 |
免费 | 99篇 |
国内免费 | 12篇 |
专业分类
化学 | 2939篇 |
晶体学 | 12篇 |
力学 | 66篇 |
数学 | 536篇 |
物理学 | 471篇 |
出版年
2023年 | 24篇 |
2022年 | 27篇 |
2021年 | 28篇 |
2020年 | 47篇 |
2019年 | 43篇 |
2018年 | 24篇 |
2017年 | 22篇 |
2016年 | 105篇 |
2015年 | 78篇 |
2014年 | 74篇 |
2013年 | 153篇 |
2012年 | 170篇 |
2011年 | 258篇 |
2010年 | 129篇 |
2009年 | 130篇 |
2008年 | 248篇 |
2007年 | 199篇 |
2006年 | 203篇 |
2005年 | 180篇 |
2004年 | 180篇 |
2003年 | 127篇 |
2002年 | 118篇 |
2001年 | 71篇 |
2000年 | 77篇 |
1999年 | 48篇 |
1998年 | 47篇 |
1997年 | 67篇 |
1996年 | 56篇 |
1995年 | 60篇 |
1994年 | 72篇 |
1993年 | 67篇 |
1992年 | 37篇 |
1991年 | 53篇 |
1990年 | 43篇 |
1989年 | 46篇 |
1988年 | 57篇 |
1987年 | 41篇 |
1986年 | 40篇 |
1985年 | 54篇 |
1984年 | 40篇 |
1983年 | 40篇 |
1982年 | 43篇 |
1981年 | 49篇 |
1980年 | 31篇 |
1979年 | 30篇 |
1978年 | 21篇 |
1977年 | 24篇 |
1976年 | 32篇 |
1975年 | 28篇 |
1973年 | 22篇 |
排序方式: 共有4024条查询结果,搜索用时 15 毫秒
151.
152.
Letf(n) be the smallest integer such that every tournament of orderf(n) contains every oriented tree of ordern. Sumner has just conjectures thatf(n)=2n–2, and F. K. Chung has shown thatf(n)(1+o(1))nlog2
n. Here we show thatf(n)12n andf(n)(4+o(1))n. 相似文献
153.
154.
Jürgen Stockburger Ulrich Weiss Roland Görlich 《Zeitschrift für Physik B Condensed Matter》1991,84(3):457-465
A variety of amorphous metals exhibit a characteristic behavior in their acoustic properties at low frequencies which differs from the predictions of the standard tunneling model. We point out that a lower cut-off min for the tunnel matrix element, which is needed for consistency of the tunneling model, leads to an upper bound on relaxation times induced by the conduction electrons. We derive explicit expressions for the velocity shift and internal friction for the normalconducting and superconducting case. It is shown that a maximum relaxation time plays an essential role at audio frequencies. The corresponding change of the acoustic properties is in qualitative agreement with vibrating reed experiments. 相似文献
155.
Roland Duduchava 《Integral Equations and Operator Theory》1992,15(3):412-426
Conditions on the kernel of the classical Wiener-Hopf equation are obtained which provide the same smoothness of any solution in terms of its inclusion in different spaces of smooth functions such as
as the function in the right side of the equation. 相似文献
156.
Tamm M Bannenberg T Fröhlich R Grimme S Gerenkamp M 《Dalton transactions (Cambridge, England : 2003)》2004,(3):482-491
Sterically demanding cycloheptatrienylium (tropylium) salts of the type (1,3,5-C7H4R3)BF4 [R = t-Bu, (3a)BF4; R = SiMe3, (3b)BF4] have been prepared from the corresponding 1,3,5-trisubstituted benzene derivatives 1 by ring expansion with diazomethane followed by hydride abstraction with triphenylcarbenium tetrafluoroborate, (Ph3C)BF4. Complexation can be achieved by arene exchange and Mo(CO)3 group transfer employing [(eta6-p-xylene)Mo(CO)3] (4) to yield the cationic complexes (5)BF4. In refluxing mesitylene, [(eta7-C7H4t-Bu3)Mo(CO)3]BF4, (5a)BF4, undergoes CO substitution to furnish the mesitylene sandwich complex (6a)BF4. A cyclic voltammetric study reveals that this complex exhibits a reversible one-electron oxidation to the dicationic 17e complex 6a2+, which can also be accessed by chemical oxidation with AgBF4. On the contrary, the reduction of 6a+ is irreversible and does not yield a stable 19e complex 6a. To study the fate of the reduced 19e form, (5a)BF4 was treated with Na2Hg to diastereoselectively afford the C-C coupled bicycloheptatriene complex 7a. Paramagnetic, dinuclear complexes of the type [(eta7-C7H4R3)Mo(mu-Cl)3Mo(eta7-C7H4R3)] (8) have been obtained from the reaction of (5)BF4 with Me3SiCl. These can be regarded as mixed-valence Mo(0)/Mo(+I) compounds with a metal-metal bond order of 0.5. Cyclic voltammetric studies reveal that both complexes 8a and 8b undergo reversible one-electron oxidation as well as reduction. Treatment with one equivalent of ferrocenium hexafluorophosphate leads to removal of the unpaired electron and formation of the diamagnetic complexes (8)PF6. Theoretical DFT calculations have been carried out to further elucidate the bonding in these systems. In addition, the X-ray crystal structures of (5b)BF4, (6a)BF4 x CH2Cl2, (6a)(BF4)2 x (acetone)2, 7a x CH2Cl2, 8a x 0.5C6H14, and (8a)PF6 x Et2O are reported. 相似文献
157.
Nabih S. Girgis Roland K. Robins Howard B. Cottam 《Journal of heterocyclic chemistry》1990,27(7):1989-1991
Nucleosides of pyrrolo[2,3-d]pyridazin-4(5H)-ones were prepared by the single-phase sodium salt glycosylation of appropriately functionalized pyrrole precursors. The glycosylation of the sodium salt of ethyl 4,5-dichloro-2-formyl-1H-pyrrole-3-carboxylate ( 4 ), or its azomethino derivative 7 , with 1-bromo-2,3,5-tri-O-benzoyl-D-ribofuranose in acetonitrile afforded the corresponding substituted pyrrole nucleosides ethyl 4,5-dichloro-2-formyl-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-1H-pyrrole-3-carboxylate ( 5 ) and ethyl 4,5-dichloro-2-phenylazomethino-1-(2,3,5-tri-O-benzoyl-β-D-ribofuranosyl)-1H-pyrrole-3-carboxylate ( 8 ), respectively. The latter, upon treatment with hydrazine, afforded the annulated product 2,3-dichloro-1-β-D-ribofuranosyl-1H-pyrrolo[2,3-d]pyridazin-4(5H)-one ( 6 ), in good yield. The unsubstituted analog 1-β-D-ribofuranosyl-1H-pyrrolo[2,3-d]pyridazin-4(5H)-one ( 9 ), was obtained upon catalytic dehalogenation of 6 . This report represents the first example of the synthesis of nucleosides of pyrrolopyridazines. 相似文献
158.
Jacob de Boer Quy T. Dao Peter G. Wester Sren Bwadt Udo A. Th. Brinkman 《Analytica chimica acta》1995,300(1-3):155-165
The mono-ortho chlorobiphenyls (CBs) 60, 74, 114, 123, 157, 167 and 189 were determined in Aroclor mixtures and aquatic organisms by multidimensional gas chromatography with electron capture detection (MDGC/ECD), using a combination of an Ultra 2 and an FFAP column. MDGC/ECD is recommended as the most suitable technique for direct determination of these CBs, without a liquid chromatographic (LC) pre-separation of mono-ortho CBs from the other CBs. Dependent, to some extent, on the stationary phase used, single-column determinations of these CBs easily yield too high results due to the presence of interferences. The contribution of the mono-ortho CBs studied to the total 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TEQs) from CBs in fish is highly dependent on the toxic equivalency factors (TEFs) used and varies between 0.02 and 22%. This contribution is mainly due to CBs 74, 114, 157 and 167 which may easily be determined by taking three heart-cuts and combining them into one MDGC/ECD run. The analytical error is negligible compared with the huge uncertainty of the TEFs. A need for more precise TEFs is emphasized. 相似文献
159.
Cano Sierra J Hüerländer D Hill M Kehr G Erker G Fröhlich R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3618-3622
The titanium complex [(C(5)H(4)bond;allyl)TiCl(3)] (2) undergoes olefin metathesis coupling when treated with 3 mol % of [Cl(2)(L(1))(L(2))Ru=CHPh] (L(1)=L(2)=PCy(3), 4 a; L(1)=PCy(3), L(2)=(H(2)IMes), 4 b) to yield the dimetallic complex [Cl(3)Ti(C(5)H(4))-CH(2)CH=CHCH(2)-(C(5)H(4))TiCl(3)] (5). The allyl-substituted titanocene complex [Cp(C(5)H(4)bond;allyl)TiCl(2)] (3) analogously yields the dimetallic system 6 when treated with 4. The ansa-zirconocene complex [Me(2)Si(C(5)H(4))(C(5)H(3)bond;allyl)ZrCl(2)] (7) cleanly yields the analogous dimetallic coupling product 8 (>95 % isomerically pure), when treated with catalytic amounts of 4 b in toluene. Complex 8 gives an active homogeneous ethene or propene polymerization catalyst, especially at elevated temperatures, when treated with excess methylalumoxane. 相似文献
160.
Leitner Christian Hess Johann Galhaup Christiane Ludwig Roland Nidetzky Bernd Kulbe Klaus D. Haltrich Dietmar 《Applied biochemistry and biotechnology》2002,98(1-9):497-507
The wood-degrading fungus Trametes multicolor secretes several laccase isoforms when grown on a simple medium containing copper in the millimolar range for stimulating
laccase synthesis. The main isoenzyme laccase II was purified to apparent homogeneity from the culture supernatant by using
anion-exchange chromatography and gel filtration. Laccase II is a monomeric glycoprotein with a molecular mass of 63 kDa as
determined by sodium dodecylsulfate polyacrylamide gel electrophoresis, contains 18% glycosylation, and has a pI of 3.0. It oxidizes a variety of phenolic substrates as well as ferrocyanide and iodide. The pH optimum depends on the substrate
employed and shows a bell-shaped pH activity profile with an optimum of 4.0 to 5.0 for the phenolic substrates, while the
nonphenolic substrates ferrocyanide and 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonate) show a monotonic pH profile with
a rate decreasing with increasing pH. 相似文献