全文获取类型
收费全文 | 31707篇 |
免费 | 5748篇 |
国内免费 | 2806篇 |
专业分类
化学 | 11693篇 |
晶体学 | 124篇 |
力学 | 4811篇 |
综合类 | 628篇 |
数学 | 10434篇 |
物理学 | 12571篇 |
出版年
2024年 | 50篇 |
2023年 | 316篇 |
2022年 | 546篇 |
2021年 | 763篇 |
2020年 | 904篇 |
2019年 | 848篇 |
2018年 | 915篇 |
2017年 | 1124篇 |
2016年 | 1304篇 |
2015年 | 1199篇 |
2014年 | 1897篇 |
2013年 | 2473篇 |
2012年 | 1909篇 |
2011年 | 2114篇 |
2010年 | 1814篇 |
2009年 | 2062篇 |
2008年 | 2212篇 |
2007年 | 2237篇 |
2006年 | 1958篇 |
2005年 | 1763篇 |
2004年 | 1662篇 |
2003年 | 1449篇 |
2002年 | 1204篇 |
2001年 | 981篇 |
2000年 | 889篇 |
1999年 | 820篇 |
1998年 | 706篇 |
1997年 | 648篇 |
1996年 | 551篇 |
1995年 | 562篇 |
1994年 | 367篇 |
1993年 | 313篇 |
1992年 | 259篇 |
1991年 | 257篇 |
1990年 | 188篇 |
1989年 | 121篇 |
1988年 | 160篇 |
1987年 | 117篇 |
1986年 | 95篇 |
1985年 | 95篇 |
1984年 | 73篇 |
1983年 | 38篇 |
1982年 | 57篇 |
1981年 | 48篇 |
1980年 | 34篇 |
1979年 | 43篇 |
1978年 | 25篇 |
1977年 | 20篇 |
1976年 | 13篇 |
1957年 | 14篇 |
排序方式: 共有10000条查询结果,搜索用时 593 毫秒
991.
By means of the addition of Ba into the Bi-Ca-Sr-Cu-O 2122 system, a series of Bi2CaSr2-xBaxCu2O8+δ (0 ≤ × ≤ 2) quinary metal oxides were prepared by the citrate route and by the conventional powder reaction method. The samples prepared by the former method have better properties than the latter. It was found that 5 was not equal to zero for all of them and that it increased with decreasing Tc. Two phases were indentified in the oxides containing all five metal elements. One is the Bi-Ca-Sr-Cu-O 2122 phase, the other is a new insulating phase which probably contains Bi-Ca-Ba-Cu-O with undetermined stoichiometry. Superconductivity was found in those samples for which × ≤ 1.50 with their Tc onsets between 93–78 K by resistivity measurements. Superconductivity decreased monotonically with increasing x. However, residual resistance was found in those samples for which 1.00 ≤ × ≤ 1.50, The Meissner effect appears in the samples where × ≤ 1.00 with Tc onsets between 88–80 K. For x = 1.75 and 2.00, the samples were semiconductors with resistivities of 6.66 × 102 and 6.96 × 103 Ω cm at 290 K, and activation energies of 0.109, and 0.298 eV, respectively. 相似文献
992.
A new one-dimensional copper coordination polymer chain has been prepared and fully characterized by single-crystal X-ray diffraction,elemental analyses and IR spectroscopy. The compound {[Cu2(C2O4)2(inta)4](inta)}n1 crystallizes in the triclinic system,space group P1,with a=8.4722(5),b=10.9825(6),c=11.6128(6),α=104.8050(10),β=102.5740(10),γ= 109.6890(10)o,V=927.18(9)3,Mr=929.79,Z=1,Dc=1.665 g/cm3,F(000)=475,μ=1.231 mm-1,R=0.0453 and wR=0.1185 for 3290 observed reflections (I > 2σ(I)). Of the compound,the Cu center is octahedrally coordinated with oxalate acting as a tetra-dentate ligand coordinated to the copper atom and each inta serving as a terminal ligand by employing only one N-donor to coordinate with the Cu center. An infinite {Cu2(C2O4)2}∞ chain is formed along the c axis. Furthermore,the 1D chains are held together via extensive hydrogen-bonding interactions to generate a three-dimensional network with 1D channels (ca. 5.491×11.507) where inta molecules are filled. 相似文献
993.
Sapelnikova S Dock E Solná R Skládal P Ruzgas T Emnéus J 《Analytical and bioanalytical chemistry》2003,376(7):1098-1103
Screen-printing technology for electrode fabrication enables construction of amperometric devices suitable for combination of several enzyme electrodes. To develop a biosensor array for characterisation of wastewaters, tyrosinase and horseradish peroxidase (HRP) or cholinesterase-modified electrodes were combined on the same array. The behaviour of the tyrosinase-modified electrode in the presence of hydrogen peroxide (required co-substrate for the HRP-modified electrode) and acetylthiocholine chloride (required co-substrate for cholinesterase) was studied. Performance of bi-enzyme biosensor arrays in the batch mode and in the flow-injection system are discussed. 相似文献
994.
O. Yu. Slabko N. V. Ageenko G. A. Verbitski V. A. Kaminski 《Chemistry of Heterocyclic Compounds》2002,38(2):226-230
Oxidative coupling of 4,9-diaza-1,2,4,9-tetrahydro-9H-fluorenes with o-aminophenol and o-aminothiophenol in the presence of MnO2 gives o-hydroxyphenyl- and o-mercaptophenylquinonediimines, cyclization of which gives derivatives of phenoxazine and phenothiazine. 相似文献
995.
The reaction of Pt2Ru4(CO)18, 1 with 1,8-bis(phenylethynyl)naphthalene, 2 has yielded two metal carbonyl cluster complexes: Ru2(CO)6[-
2-C10H6C4Ph2], 3 (60% yield) and Ru2Pt(CO)6[-
2-C10H6C4Ph2]2, 4 (8% yield). Both compounds were characterized by a single crystal X-ray diffraction analysis. Both products were formed as a result of fragmentation of the Pt2Ru4 cluster of 1. Compound 3 contains two ruthenium atoms. They are bridged by a tricyclic C10H6C4Ph2 ligand formed by the coupling of the two -carbon atoms of the alkyne groups. The -carbon atoms of the alkynes are -bonded to one of the ruthenium atoms to form a metallacycle and this entire group is -bonded to the second ruthenium atom. Compound 4 contains two ruthenium atoms with a platinum atom between them. This molecule contains two tricyclic C10H6C4Ph2 ligands similar to that in 3, and two metallacycles formed by coordination of the -carbon atoms of both ligands to the platinum atom. One ligand is -bonded to each of the ruthenium atoms. 相似文献
996.
Matthias Schüler Thomas Kovar Hans Lischka Ron Shepard Robert J. Harrison 《Theoretical chemistry accounts》1993,84(6):489-509
Summary In this work a parallel implementation of the COLUMBUS MRSDCI program system is presented. A coarse grain parallelization approach using message passing via the portable toolkit TCGMSG is used. The program is very well portable and runs on shared memory machines like the Cray Y-MP, Alliant FX/2800 or Convex C2 and on distributed memory machines like the iPSC/860. Further implementations on a network of workstations and on the Intel Touchstone Delta are in progress. Overall, results are quite satisfactory considering the complexity and the prodigious requirements, especially the I/O bandwidth, of MRCI programs in general. For our largest test case we obtain a speedup of a factor of 7.2 on an eight processor Cray Y-MP for that section of the program (hamiltonian matrix times trial vector product) which has been parallelized. The speedup for one complete diagonalization iteration amounts to 5.9. An absolute speed close to 1 GFLOPS is found. Results for the iPSC/860 show that ordinary disk I/O is certainly not sufficient in order to guarantee a satisfactory performance. As a solution for that problem, the implementation of a fully asynchronous distributed-memory model for certain data files is in preparation.
On leave from: Bereich Informatik, Universität Leipzig, Augustusplatz 10/11, O-7010 Leipzig, Germany 相似文献
997.
The polymerization of acrylonitrile (AN) in aqueous nitric acid initiated by metavanadate-containing anion exchange resin (PV)-thiourea (TU) redox system at 20—40℃. has been investigated. The overall rate of polymerization (R_p) is given byR_p=1.92×10~4e~(-6.860/RT) [AN]~(1.2) [PV]~(0.44) [TU]~(1.0)[HNO_3]~(1.0)The kinetic parameters differed from those of V~(5+)-TU system indicated that the generation of the primary radicals is mainly a difffusion-controlled reaction. The effect of macromolecular field arisen from the polymer matrix exerts a great influence on the polymerization process. 相似文献
998.
Patrick Gredin Ariel De Kozak Michel Quarton Jean Renaudin Grard Ferey 《无机化学与普通化学杂志》1993,619(6):1088-1094
The liquid-solid phase diagram of the binary system BaF2? ScF3 is established by D.T.A. and radiocrystallography. Three fluorides are disclosed: Ba3Sc2F12, Ba5Sc3F19 and a cubic high temperature phase Ba1?xScxF2+x (x = 0.17), the structure of which derives from that of BaF2. A solid solution between BaF2 and ScF3 is also evidenced at high temperature. The ternary system BaF2? CuF2? ScF3 is investigated by radiocrystallography and an isothermal section at 670°C is given. It shows the existence of four phases: a complex quaternary fluoride Ba10Cu12ScF47, two “polytypic” phases the structure of which derives from that of BaCuF4 and a tetragonal solid solution Ba5Sc3?xCuxF19?x with 0 ≤ x ≤ 1. 相似文献
999.
Two analogues of diphenylethene carrying phenanthrene (1-(9-phenanthryl)-1-phenylethene (PPE)) and anthracene (1-(2-anthryl)-1-phenylethene (APE)) units were used in radical polymerization of styrene (St) and methyl methacrylate (MMA) at 80 °C using AIBN as initiator. Because of the nature of the polymerization, the resulting polymers possess the corresponding chromophoric groups. Using the methodology of a DPE system, these labelled polymers were further used for the synthesis of block copolymers. In this way poly(methyl methacrylate)-b-poly(styrene) and poly(methyl methacrylate)-b-poly(acrylonitrile) with molar masses of 60,000-90,000 g/mol were synthesized. Incorporation of the chromophoric groups into both homo- and block copolymers was confirmed by spectral measurements. 相似文献
1000.
Sandra S. Pröckl 《Tetrahedron》2005,61(41):9855-9859
In situ generation of highly active palladium species by intermediate dissolution of Pd from solid supported catalysts has been demonstrated to be a very successful approach for the activation of aryl chlorides in Heck reactions. The new ‘heterogeneous’ Pd catalysts act as reservoir for molecular Pd species with unsaturated coordination sphere in solution. Crucial Pd leaching and re-deposition onto the support can be controlled by optimization of reaction conditions and by the properties of the catalysts. Pd is re-deposited onto the support at the end of the reaction. The catalysts, palladium supported on activated carbon, on various metal oxides or fluorides and Pd complexes in zeolites, are easy to prepare, though the preparation conditions are crucial. The catalysts convert all aryl bromides completely within minutes (TON 100,000). Aryl chlorides (even deactivated ones) are converted with high yields, within 2-6 h. The catalysts belong to the most active ones in Heck reactions at all (including best homogeneous systems) and fulfill all relevant requirements for practical applications in laboratory and industry. 相似文献