全文获取类型
收费全文 | 4392篇 |
免费 | 293篇 |
国内免费 | 842篇 |
专业分类
化学 | 4592篇 |
晶体学 | 81篇 |
力学 | 135篇 |
综合类 | 54篇 |
数学 | 315篇 |
物理学 | 350篇 |
出版年
2024年 | 4篇 |
2023年 | 62篇 |
2022年 | 92篇 |
2021年 | 77篇 |
2020年 | 161篇 |
2019年 | 176篇 |
2018年 | 186篇 |
2017年 | 176篇 |
2016年 | 191篇 |
2015年 | 146篇 |
2014年 | 190篇 |
2013年 | 438篇 |
2012年 | 506篇 |
2011年 | 240篇 |
2010年 | 196篇 |
2009年 | 239篇 |
2008年 | 289篇 |
2007年 | 293篇 |
2006年 | 253篇 |
2005年 | 227篇 |
2004年 | 211篇 |
2003年 | 176篇 |
2002年 | 144篇 |
2001年 | 98篇 |
2000年 | 124篇 |
1999年 | 105篇 |
1998年 | 92篇 |
1997年 | 72篇 |
1996年 | 66篇 |
1995年 | 47篇 |
1994年 | 42篇 |
1993年 | 23篇 |
1992年 | 50篇 |
1991年 | 25篇 |
1990年 | 28篇 |
1989年 | 19篇 |
1988年 | 15篇 |
1987年 | 6篇 |
1986年 | 6篇 |
1985年 | 5篇 |
1984年 | 7篇 |
1983年 | 5篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1973年 | 2篇 |
排序方式: 共有5527条查询结果,搜索用时 0 毫秒
51.
采用弱碱性阴离子交换树脂HJ-30对发酵液中1,6-二磷酸果糖的分离进行了研究。详细地研究了树脂的吸附和脱附性能。实验结果表明,HJ-30树脂对FDP的吸附量达0.28gFDP/g湿树脂,以0.05mol/LNaCl洗脱光机磷和1mol/LNaCl洗脱1,6-二磷酸果糖,产品的收率和纯度分别为92%和99.4%。 相似文献
52.
高稳定性CaO-ZrO2固体碱催化剂的表征和催化性能 总被引:3,自引:0,他引:3
用共沉淀法经高温焙烧制备了CaO摩尔分数从10%至50%的CaO-ZrO2系列催化剂, 将其应用于碳酸丙烯酯和甲醇酯交换合成碳酸二甲酯过程, 并通过XRD, FT-IR, BET, ICP, CO2-TPD, XPS等表征手段研究了催化剂的物性及其催化性能随组成变化的的规律. 结果表明, 当CaO摩尔分数高于30%时, 表面出现游离的CaO, 虽然具有强碱性和高活性, 但是稳定性差; 而当CaO摩尔分数低于30%时, Ca2+进入ZrO2晶格, CaO与ZrO2形成连续固溶体, 并且随着CaO含量的增加, 晶格氧的电荷密度增加, 催化剂的碱性增强, 使得CaO-ZrO2催化剂在碳酸丙烯酯和甲醇酯交换合成碳酸二甲酯过程中获得了高活性和高稳定性. 相似文献
53.
As an extension of previous reports, the barium carbonate procedure has been optimized in detail for the preparation of apolar columns. The aim was to produce optimum overall column characteristics, and to maintain them unchanged under the prolonged influence of the highest possible temperature. The main parameters under optimization were glass variety, leaching of glass surface with aqueous HCl, and amount of barium carbonate deposited, while deactivation and coating were kept constant. The basic column characteristics were adsorption properties and thermostability of deactivation, acid/base behaviour and separation efficiency. They were determined by a new, quantitative testing procedure. Intense leaching was able to eliminate almost totally the differences between glass varieties and to create a well-defined glass surface. While untreated glass, leached glass, and barium carbonate treated glass showed specific weak points in the respective column quality, the combination of leaching and barium carbonate treatment yielded the highest and most stable quality. Some technical modifications of the preparation procedure are described, including deactivation in the gas phase, and use of pentane as a solvent for static coating. 相似文献
54.
Tautomerism of Nunsubstituted benzohydroxamic acids and their anions in the gas phase was investigated by the semiempirical AM1 method. The possibility of estimating pK
a in aqueous solutions using calculated characteristics of molecules is demonstrated. 相似文献
55.
56.
Three unsymmetrical tetradentate Schiff base ligands, H2salipn, H2salipn-Br4 and H2salipn-Cl2, have been synthesized from the typical condensation reactions of treating 1,2-diaminopropane with salicylaldehyde, 3,5-dibromosalicylaldehyde and 5-chlorosalicylaldehyde, respectively. Treatment of [RuCl2(PPh3)3] with one equivalent of H2salipn or H2salipn-Br4 in the presence of triethylamine in tetrahydrofuran (THF) afforded the corresponding ruthenium(III) complexes [RuIIICl(PPh3)(salipn)] (1) and [RuIIICl(PPh3)(salipn-Br4)] (2). Interaction of [RuHCl(CO)(PPh3)3] with one equivalent of H2salipn-Cl2 or H2salipn-Br4 under the same conditions led to isolation of ruthenium(II) complexes [RuII(CO)(PPh3)(salalipn-Cl2)] (3) and [RuII(CO)(PPh3)(salalipn-Br4)] (4), respectively, in which one of the imine bonds was nucleophilically attacked by hydride to result in the formation of a mixed imine-amine ligand. The molecular structures of 1?1.5CH2Cl2, 2, 3?0.5CH2Cl2 and 4 have been determined by single-crystal X-ray crystallography. The electrochemical properties of 1–4 were also investigated. Their cyclic voltammograms displayed quasi-reversible Ru(IV)/Ru(III) and Ru(III)/Ru(II) couples with Eo ranging from 0.67 to 1.05 V and 0.74 to 0.80 V vs. Ag/AgCl (0.1 M), respectively. 相似文献
57.
Three new cobalt complexes were synthesized by solid-state reaction at room temperature. It was found that one mole of complex reacted with two moles of oxygen at room temperature. And the oxygenated complexes [Co·(L1)2·2O2](NO3)2·2H2O (L1=N,N′-bis(4-hydroxyl-3-methoxy-benzyl)-triethylenetetramine), [Co·(L2)2·2O2](NO3)2 ·2H2O (L2=N,N′-bis(4-hydroxyl-benzyl)-triethylenetetramine) and [Co·L3·2O2](NO3)2·2H2O (L3=N,N′-bis(2-hydroxyl-benzyl)-triethylenetetramine) were obtained and characterized by elemental analysis, IR spectra, 1H NMR, TG/DTA, UV-Vis and molar conductance. The coordinated oxygen contents in the oxygenated complex were also determined by weight method. It was found that one O2 molecule coordinated to the Co ion and formed superoxo type oxygenated complex. 相似文献
58.
The EPR spectra of three new gadolinium complexes with noncyclic polyether Schiff bases in powder and those of these complexes in organic solvents were investigated at different temperatures. It was observed that EPR spectra of nine and four peaks of Gd(Ⅲ) complexes in polycrystalline powder and freezing samples appeared at low temperature respectively for the first time. The interpretations of these results obtained on the basis of spin Hamiltonian of s = 7/2 system are satisfactory. The correlations of EPR feature between crystal-field strength in complexes and local symmetry around Gd3+ ions were revealed. The crystal-field parameters b20 and the asymmetry parameters λ' of complexes were estimated. A series of interesting regularity and new results were obtained. 相似文献
59.
研究了新型Schiff碱双锰配合物在模拟酶催化亚碘酰苯单加氧化环已烷反应及 被亚碘酰苯氧化破坏反应中的温度效应。结果表明,在模拟酶催化反应体系中同时 存在催化环已烷单加氧反应及催化剂的氧化破坏反应;催化反应速率及氧化破坏反 应速率均随反应温度升高有规律地增大,但氧化破坏反应比催化反应对反应温度更 敏感;催化反应总产率一般随反应温度升高而降低;最适宜的反应温度为25 ℃。 相似文献
60.
Green Bis-(2-iminoisopropyl-thiophenolato)nickel(II) and other Similar NiII Complexes The compounds [NiII(iitp)2] 1 (iitp = 2-iminoisopropyl-thiophenolate), [Ni(imptp)2] · 2 CH3OH 2 , a dinuclear compound with an Ni? Ni distance of 276 pm, and [PPh4] · [NiII(imptp)(SCN)] 3 (imptp = 2-(2-iminopentane-4-on)-thiophenolate) have been prepared by the reaction of nickel(II)-acetate-tetrahydrate with 2-iminoisopropyl-thiophenole and 2-(2-iminopentane-4-on)-thiophenole in methanol, respectively. They have been characterized by single-crystal X-ray structure analysis and other physical methods. The redox behaviour of 1–3 has been studied in detail (chemically as well as by cyclovoltammetry and ESR spectroscopy). Particularly interesting are the electronic properties of 1 and its reduction with NaBH4 and the following reaction of the product with O2. The complexes are model compounds for some Ni-containing enzymes. For details of the crystal structure determination see “Inhaltsübersicht”. 相似文献