全文获取类型
收费全文 | 3528篇 |
免费 | 78篇 |
国内免费 | 585篇 |
专业分类
化学 | 2973篇 |
晶体学 | 59篇 |
力学 | 64篇 |
综合类 | 1篇 |
数学 | 182篇 |
物理学 | 912篇 |
出版年
2024年 | 4篇 |
2023年 | 136篇 |
2022年 | 51篇 |
2021年 | 41篇 |
2020年 | 99篇 |
2019年 | 61篇 |
2018年 | 65篇 |
2017年 | 70篇 |
2016年 | 69篇 |
2015年 | 52篇 |
2014年 | 81篇 |
2013年 | 239篇 |
2012年 | 263篇 |
2011年 | 187篇 |
2010年 | 142篇 |
2009年 | 183篇 |
2008年 | 217篇 |
2007年 | 351篇 |
2006年 | 188篇 |
2005年 | 153篇 |
2004年 | 153篇 |
2003年 | 116篇 |
2002年 | 102篇 |
2001年 | 99篇 |
2000年 | 92篇 |
1999年 | 146篇 |
1998年 | 177篇 |
1997年 | 91篇 |
1996年 | 97篇 |
1995年 | 70篇 |
1994年 | 94篇 |
1993年 | 77篇 |
1992年 | 51篇 |
1991年 | 51篇 |
1990年 | 23篇 |
1989年 | 20篇 |
1988年 | 20篇 |
1987年 | 18篇 |
1986年 | 5篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 11篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1978年 | 1篇 |
1969年 | 2篇 |
排序方式: 共有4191条查询结果,搜索用时 31 毫秒
51.
SAPO-5,-11和-34分子筛模板剂的脱除及其结构的热致变化 总被引:2,自引:0,他引:2
用水热法合成了SAPO-5,-11和-34硅磷酸铝类分子筛。并对经不同温度焙烧处理的样品进行表征,结果表明:分子筛中模块剂的热分解过程与其结构和孔大小有较大的关系。在SAPO-5和SAPO-34分子筛中,外部联接的T-O-T键的反对称伸缩振动峰(1240cm~(-1)-1038cm~(-1))和其对称伸缩振动(734cm~(-1)-600cm~(-1))及双环的变形振动(600-500cm~(-1))的吸收峰对样品的结晶度比较敏感。但在SAPO-11中,分子筛骨架中T-O-T反对称伸缩振动(1225cm~(-1)和1038cm~(-1))随结晶度的下降而基本保持不变,但内四面体(TO_4)的对称伸缩振动,反对称伸缩振动峰及T-O弯曲振动峰随样品焙烧温度的升高而减弱并分裂。红外吸收带向低频方向移动。SEM-EDAX结果表明:随样品焙烧温度的升高,结晶度下降,分子筛晶形变得不规则,晶面越来越粗糙,但结晶度的下降并非由于其中PO_4四面体的热分解所引起,而是由外部联结的T-O-T键的断裂,双环被破坏及骨架元素间的重排所引起。 相似文献
52.
One novel complex [Co(p-MBA)2(2,2'-bipy)(H2O)]·(H2O) has been synthesized by the reaction of p-methylbenzoic acid with 2,2'-bipyridine in the solvent mixture of water and methanol. It crystallizes in triclinic, space group P-1 with a=0.70479(14), b=1.1211(2), c=1.6718(3) nm, α=103.806(3), β=90.795(3), γ=104.207(3)°, V=1.2399(4) nm3, Mr=512.41, Dc=1.373 g/cm3, Z=2, F(000)=532, μ=0.733 mm-1, R=0.0432 and wR=0.0957. The crystal structural analysis shows that the cobalt atom is coordinated with three oxygen atoms from two p-methylbenzoic acids and one water molecule and two nitrogen atoms from one 2,2'-bipyridine,forming a distorted square-pyramidal coordination geometry. The cyclic voltammetry behavior of the complex is also reported. 相似文献
53.
TONG Yi-Ping 《结构化学》2007,26(1)
The zinc(Ⅱ) complex with Hpbx (Hpbx = 2-(benzoxazol-2-yl)phenol) and Hpbm (Hpbm=2-(benzimidazol-2-yl)phenol),namely[Zn(pbm)2]1.633[Zn(bpx)2]2.367·DMF·2H2O1,has been synthesized and characterized by X-ray crystallography,FTIR and elemental analysis.The coordination structures are statistically disordered and can be regarded as a co-crystal of [Zn(pbm)2]and [Zn(pbx)2] with the ratio of ca.0.408/0.592.Solvate water and DMF molecules are also present in the lattice.Crystal data for 1:monoclinic,space group P21/c,Mr= 2049.02,Z = 2,α = 9,7571(6),b = 25.6415(16),c = 19.8675(10)(A),β = 111.342(2)°,V = 4629.7(5) (A)3,Dc = 1.470 g/cm3,μ =1.100 mm-1,F(000) = 2104,R = 0.0575 and wR = 0.1282 for 5528 observed reflections (I> 2σ(I)).The photoluminescent spectra for this compound have also been studied. 相似文献
54.
A novel complex [Pb(qina)2(DMSO)]·H2O was synthesized, of which qina- is the quinaldic acid radical and DMSO the dimethyl sulfoxide. Elemental analysis, IR spectra, and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. This complex belongs to monoclinic system, space group P121/n1, with a = 7.1553(17), b = 17.543(2), c = 17.306(2)(A),β = 91.671(4)°, C22H20N2O6PbS, Mr = 647.65, Z = 4, V= 2171.5(6)(A)3, Dc= 1.981g/cm3,μ = 7.908 mm-1, F(000) = 1248, -9≤h≤6, -23≤k≤ 19, -22≤l≤22, R= 0.0221 and wR =0.0488. Weak coordinate bond is formed between oxygen atom in DMSO and Pb(Ⅱ ). There are also weak interactions, such as π-π interaction, hydrogen bonds and so on, among the complex molecules. 相似文献
55.
A novel coordination polymer [{Cd(hmbdc)(H2O)3}·2H2O]n (hmbdc=5-hydroxy- isophthalic acid) has been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with a=9.599(3), b=18.699(5), c=7.557(2) (A), β= 108.198(4)°, V=1288.6(6) (A)3, Z=4, Mr=382.60, Dc=1.972 g/cm3, F(000)=760, μ=1.740, the final R=0.0555 and wR=0.0995 for 1732 observed reflections with Ⅰ > 2σ(Ⅰ). The structural analysis shows that the intermolecular hydrogen bonds and π-π interactions result in a three-dimensional supramolecular framework. 相似文献
56.
Ludwik Adamowicz Rodney J. Bartlett Józef S. Kwiatkowski Willis B. Person 《Theoretical chemistry accounts》1988,73(2-3):135-145
The diatomic systems, PO and PO– are studied, using numerical Hartree-Fock (NHF) and coupled-cluster calculations. The latter employs a hybrid NHF and Slater orbital basis set. Highly accurate CCSD methods predict bond lengths accurate to <0.004 Å and frequencies to 60 cm–1. In addition the electron affinity of PO is computed to be 0.89 eV compared to an experimental value of 1.09±0.01. Comparisons are made with SCF and MBPT(2) results for PO+ using conventional basis sets.Dedicated to Professor J. Koutecký on the occasion of his 65th birthdayGuggenheim Fellow 相似文献
57.
综述了三配位五价磷化合物的结构犊 征及其所具有的加成反应,络合反应,磷中心的亲电反应等化学性质。参考文献22篇。 相似文献
58.
含氰基侧基聚芳醚砜的合成与表征 总被引:1,自引:0,他引:1
汉2,6-二卤苯甲腈、4,4′-二氯二苯砜、4,4′-二羟基二苯砜、间苯二酚、对苯二酚、酚酞及双酚A为主要原料,合成了含不同结构单元和不同氰基含量的含氰基侧基的聚芳醚砜,并采用IR、^13CNMR等分析手段对其结构进行了表征,同时研究了结构单元和氰基含量对聚芳醚砜性能的影响。 相似文献
59.
Kiyotake Suenaga Tsuyoshi Mutou Takashi Itoh Noboru Takada Masaki Takagi Hideo Kigoshi Kiyoyuki Yamada 《Tetrahedron》2004,60(38):8509-8527
The bioassay-guided fractionation of the cytotoxic constituents of the Japanese sea hare Dollabella auricularia led to the isolation of aurilide (1), a 26-membered cyclodepsipeptide. The gross structure of 1 was established by spectroscopic analysis including 2D NMR techniques. The absolute stereostructure was determined by chiral HPLC analysis of acid hydrolysates of 1 and by the enantioselective synthesis of a degradation product arising from a dihydroxylated fatty acid portion. The enantioselective synthesis of 1 was achieved in 12% overall yield (16 steps) and confirmed the absolute stereostructure of 1. The cytotoxicity of 1 was evaluated using a synthetic sample, which was found to exhibit potent cytotoxicity against HeLa S3 cells with an IC50 of 0.011 μg/mL. Further biological and pharmacological studies of 1 have been carried out by using synthetic 1. 相似文献
60.
The Mg3−xZnxSb2 phases with x=0-1.34 were prepared by direct reactions of the elements in tantalum tubes. According to the X-ray single crystal and powder diffraction, the Mg3−xZnxSb2 phases crystallize in the same P3¯m1 space group as the parent Mg3Sb2 phase. The Mg3−xZnxSb2 structure is different from the other substituted structures of Mg3Sb2, such as (Ca, Sr, Ba) Mg2Sb2 or Mg5.23Sm0.77Sb4, in a way that in Mg3−xZnxSb2 the Mg atoms on the tetrahedral sites are replaced, while in the other structures Mg on the octahedral sites is replaced. Thermoelectric performance for the two members of the series, Mg3Sb2 and Mg2.36Zn0.64Sb2, was evaluated from low to room temperatures through resistivity, Seebeck coefficient and thermal conductivity measurements. In contrast to Mg3Sb2 which is a semiconductor, Mg2.36Zn0.64Sb2 is metallic and exhibits an 18-times larger dimensionless figure-of-merit, ZT, at room temperature. However, thermoelectric performance of Mg2.36Zn0.64Sb2 is still poor and it is mostly due to its large electrical resistivity. 相似文献