全文获取类型
收费全文 | 4823篇 |
免费 | 1094篇 |
国内免费 | 1936篇 |
专业分类
化学 | 3505篇 |
晶体学 | 225篇 |
力学 | 440篇 |
综合类 | 171篇 |
数学 | 880篇 |
物理学 | 2632篇 |
出版年
2024年 | 11篇 |
2023年 | 53篇 |
2022年 | 180篇 |
2021年 | 173篇 |
2020年 | 183篇 |
2019年 | 182篇 |
2018年 | 159篇 |
2017年 | 240篇 |
2016年 | 162篇 |
2015年 | 233篇 |
2014年 | 267篇 |
2013年 | 368篇 |
2012年 | 343篇 |
2011年 | 398篇 |
2010年 | 391篇 |
2009年 | 456篇 |
2008年 | 512篇 |
2007年 | 483篇 |
2006年 | 477篇 |
2005年 | 400篇 |
2004年 | 321篇 |
2003年 | 255篇 |
2002年 | 222篇 |
2001年 | 260篇 |
2000年 | 273篇 |
1999年 | 139篇 |
1998年 | 77篇 |
1997年 | 59篇 |
1996年 | 55篇 |
1995年 | 57篇 |
1994年 | 41篇 |
1993年 | 50篇 |
1992年 | 41篇 |
1991年 | 33篇 |
1990年 | 23篇 |
1989年 | 42篇 |
1988年 | 36篇 |
1987年 | 25篇 |
1986年 | 23篇 |
1985年 | 14篇 |
1984年 | 14篇 |
1983年 | 15篇 |
1982年 | 15篇 |
1981年 | 10篇 |
1980年 | 11篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1977年 | 7篇 |
1965年 | 19篇 |
1958年 | 5篇 |
排序方式: 共有7853条查询结果,搜索用时 10 毫秒
101.
102.
Synthesis of the third-order nonlinear materials:bis (1,4-dihydroxynaphthalene) tetrathiafulvalene and bis (1,4-dialkoxylnaphthalene) tetrathiafulvalene has been achieved in four steps, starting from 2,3-dichloro-1,4-naphthaquinone. The materials exhibit larger third-order nonlinear optical susceptibilities χ. 相似文献
103.
SincethediscoveryofphosphoniumylidebyWittig',carbanionsstabilizedbyadjacentfifthorsixthgrouponiumionshavebeendevelopedasavaluablereactiveintermediate.However,despitethegreateffortsinylidechemistryinthepastfewdecades',relativelylittleisknownaboutthethermodynamicstabilitiesofylidecarbanions.Itiswellknowthatthequantitativemeasuresofthecarbanionstabilityhavecontributedagreatdealtothedevelopmentoforganicchemistry,thereforeitshouldbeexpectedthattheknowledgeaboutylidestabilitywillalsoprovidavaluableg… 相似文献
104.
贝壳杉烯化合物。在以甜叶菊甙(stevioside,2)为原料在进行对映贝壳杉烯二萜的合成研究中,我们试图合成1及其衍生物3和4以进行抗旱孕活性试验及构效关系的研究。 合成的关键是引进C_(9.11)双键,此可通过C_(17)—OH先引入C_(11)—OH,然后脱羟而成。文献曾报道几乎定量地将17羟基对映贝壳杉—19—酸甲酯(5)转化成C_(11,17)环醚化合物 6(Scheme1)。氧化环 相似文献
105.
The ENDOR spectrum of ~(14)N-~(63)Cu-HAP complex in DMSO/EtOH (5:1) freezing solution at 20 K has been studied using orientational selective method in this paper. The anisotropic superhyperfine coupling tensor and qusdrupole coupling tensor of ligand ~(14)N nucleus, and the superhyperfine coupling tensor of various ~1H nuclei have been measured precisely. Comparing the superhyperfine coupling tensor of ~(14)N-nucleus with previous work shows that the analytical method of spectrum is reasonable and the data are reliable in our previous work. 相似文献
106.
Four chiral polymers P-1, P-2, P-3 and P-4 were synthesized by the polymerization of (S)-2,2'-dioctoxy-1,1'- binaphthyl-6,6'-boronic acid (S-M-3) with (S)-6,6'-dibromo-1,1'-binaphthol (S-M-1), (R)-6,6'-dibromo-1,1'- binaphthol (R-M-1), (S)-3,3'-diiodo-1,1'-binaphthol (S-M-2) and (R)-3,3'-diiodo-1,1'-binaphthol (R-M-2) under Pd-catalyzed Suzuki reaction, respectively. All four polymers can show good solubility in some common solvents due to the nonplanarity of the polymers in the main chain backbone and flexible alkyl groups in the side chain. The analysis results indicate that specific rotation and circular dichroism (CD) spectral signals of the alternative S-S chiral polymers P-1 and P-3 are larger than those of S-R chiral polymers P-2 and P-4, but their UV-Vis and fluorescence spectra are almost similar. The results of asymmetric enantioselectivity of four polymers for diethylzinc addition to benzaldehyde indicate that catalytically active center is (R) or (S)-1, 1'-binaphthol moieties. 相似文献
107.
The synthesis and crystal structure of Li3AlB2O6 with different cell parameters are reported and these cells are transformed each other from the confirmation of crystallographic structural analyses. The absorption spectrum, luminescence and lifetimes of the Li3AlB2O6 and LiSrBO3 solid compounds are measured and the comparisons are made between them. It is shown that the absorption edges are at about 400 nm (or band gap 3.1 eV) and there is one of absorption peaks at about 350 nm for the Li3AlB2O6 and LiSrBO3. The emission band (530 nm) makes a red shift and fluorescence decay time (24.39 ns) of the Li3AlB2O6 becomes smaller compared with the emission band (480 nm) and lifetime (93.16 ns) of the LiSrBO3 at the visible region. The transition energies and oscillator strengths of the clusters (Li3AlB2O6)2 and (LiSrBO3)2 lying at low excited states are calculated by the time-dependent Hartree-Fock method. The obtained results are used to model the photophysical properties and discuss the origin of spectral bands of the Li3AlB2O6 and LiSrBO3. 相似文献
108.
利用水和乙醇混合溶剂合成了稀土三氯醋酸盐与2份1,10-邻菲绕啉(phen)配合物RE(CCl_3COO)_3(phen)_2·nH_2O(RE=Nd,Sm,n=0;RE=Eu,n=2)的单晶.结构测定表明,Nd(CCl_3COO)_3(phen)_2为三斜晶系,每个三氯醋酸盐均以双齿配位,2个phen亦为双齿配位,故配位单元中钕为10配位;Eu(CCl_3COO)_3(phen)_2·2H_2O为单斜晶系,1个三氯醋酸根在外界,2个三氯醋酸根为单齿配位,2个phen为双齿配位,另有2分配位水,故配位单元中Eu为8配位. 相似文献
109.
Four dithiooxalato (Dto) bridged one-dimensional Ni(ll) and Ni(ll)Cu(ll) complexes (Me6[14]dieneN4)Ni2(Dto)2) (1), (Me6[14]dieneN4)CuNi(Dto)2 (2), (Me6[14]aneN4)Ni2(Dto)2 (3), and (Me6[14]aneN4)CuNi(Dto)2(4), were synthesized. These complexes have been characterized by elemental analysis, IR, UV and ESR spectra. The crystal structure of complex 3 was determined. It crystallizes in the monoclinic system, space group C2/c with a = 2.2425(4) nm, b = 1.0088(2) nm, c=1.4665(3) nm, β= 125.32(3)° ;Z=4; R = 0.076, Rw = 0.079. In the complex, Ni(1) coordinates four sulphur atoms of two Dto ligands in plane square environment. Ni(2) lies in the center of mac-rocyclic ligand. For Dto ligand, two sulphur atoms coordinate Ni(1), and O(1) coordinates Ni(2) and forms weak coordination bond. O(2) is linked to N(2) of macrocyclic ligand through hydrogen bond. 相似文献
110.
Precursor molecule (R)-6,6′-bis(triethoxysilylethen-2-yl)-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (R-2) was synthesized by Pd-catalyzed Heck reaction of (R)-6,6′-dibromo-2,2′-di(methoxyethoxymethyloxy)-1,1′-binaphthyl (R-1) intermediate with vinyltriethoxysilane. The hydrolysis and polycondensation of the precursor R-2 produced the corresponding xerogel. Both precursor and xerogel were analysed by NMR, FTIR, UV, CD spectra, fluorescent spectroscopy, polarimetry and elemental analysis. The precursor and xerogel can emit strong blue fluorescence and are expected to have a potential application in the separation of chiral molecules as fluorescent sensor. The precursor exhibits strong Cotton effect in its circular dichroism (CD) spectrum indicating a highly rigid structure. 相似文献