全文获取类型
收费全文 | 2288篇 |
免费 | 91篇 |
国内免费 | 320篇 |
专业分类
化学 | 2146篇 |
晶体学 | 17篇 |
力学 | 5篇 |
综合类 | 16篇 |
数学 | 242篇 |
物理学 | 273篇 |
出版年
2024年 | 9篇 |
2023年 | 68篇 |
2022年 | 50篇 |
2021年 | 75篇 |
2020年 | 151篇 |
2019年 | 105篇 |
2018年 | 95篇 |
2017年 | 115篇 |
2016年 | 106篇 |
2015年 | 67篇 |
2014年 | 131篇 |
2013年 | 508篇 |
2012年 | 167篇 |
2011年 | 137篇 |
2010年 | 99篇 |
2009年 | 114篇 |
2008年 | 111篇 |
2007年 | 121篇 |
2006年 | 116篇 |
2005年 | 86篇 |
2004年 | 88篇 |
2003年 | 56篇 |
2002年 | 11篇 |
2001年 | 12篇 |
2000年 | 12篇 |
1999年 | 8篇 |
1998年 | 10篇 |
1997年 | 12篇 |
1996年 | 7篇 |
1995年 | 9篇 |
1994年 | 5篇 |
1993年 | 9篇 |
1992年 | 3篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有2699条查询结果,搜索用时 15 毫秒
71.
1999年,Chilcott研究了α-甘氨酸单晶电阻抗随温度的变化,发现晶体在304 K开始导电。为了了解其导电机理,本文研究90 K到340 K的拉曼光谱,发现在α-甘氨酸单晶中NH3+扭曲振动模式分裂,表现为N-H(6)…O(1)(491 cm-1)和N-H(7)…O(2)(483 cm-1)模式,以及CO2-摇摆模式(503cm-1),在304 K均有不连续性变化,并与变温中子衍射晶体结构层内的氢键N-H(6)…O(1)键角和N-H(7)…O(2)长度出现转折点一致。由于α-甘氨酸晶胞中NH3+和CO2-基团构成的电偶极子在变温下重新定向,出现两性离子电荷重心变化致使晶体极化,引起晶体在304 K左右发生了铁电相变。 相似文献
72.
S. Munavalli D. K. Rohrbaugh H. D. Durst 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1657-1671
Trifluoromethylthiocopper has been found to catalyze the opening of the epoxide ring and to furnish not-so-easily accessible novel trifluoromethylthiolated α-hydroxy compounds. This communication presents the mechanism of the formation of the various compounds and their mass spectral data. 相似文献
73.
V. Padmavathi T. V. Ramana Reddy A. Balaiah K. Audisesha Reddy D. Bhaskar Reddy 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5):1223-1235
Some new heterocyclic compounds containing selenadiazole, thiadiazole and diazaphosphole fused to cyclohexanones have been prepared and characterized by spectral data. 相似文献
74.
《合成通讯》2013,43(20):3575-3581
Abstract The nucleophilic substitution of the benzotriazolyl group in the N-(α-benzotriazol-1-ylalkyl)amides and N-(α-benzotriazol-1-ylalkyl) sulfonamides with allylsamarium bromide was investigated, and the corresponding homoallylamides or homoallylsulfonamides were obtained in good to excellent yields. 相似文献
75.
The synthesis of the first series of 5-alkoxy-1,3-thiazole-based liquid crystals is reported. The aforementioned liquid crystals were synthesised through a Lawesson's reagent-mediated cyclisation of appropriate α-benzamido esters. This methodology was found to be highly efficient, even on a large scale, and the resulting 5-alkoxy-1,3-thiazoles could be purified without the use of column chromatography. The synthesis and mesomorphic properties of a family of 5-alkoxy-2-(4-cyanophenyl)-1,3-thiazole liquid crystals prepared via this approach are discussed and compared with their thiophene and phenyl analogues. 相似文献
76.
Use of the calcium-ethylenediamine and sodium-liquid ammonia reduction systems for the ring opening of dihydropyran derivatives was studied. (Z)-Alkenyl alcohols and (E)-alkenyl alcohols were stereoselectively synthesized respectively. 相似文献
77.
78.
《Journal of Coordination Chemistry》2012,65(16):2912-2922
Two d10 metal coordination polymers, [Zn(µ-Me2biim)Cl2] n (1) and [Cd3(MeHbiim)2(1,4-BDC)3] n (2) (Me2biim?=?N,N′-dimethyl-2,2′-biimidazole, MeHbiim?=?N-methyl-2,2′-biimidazole, 1,4-BDC?=?1,4-benzenedicarboxylate), were synthesized under hydrothermal conditions and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single-crystal X-ray crystallography. Complex 1 features an infinite neutral zigzag 1-D chain. Interchain hydrogen-bonding interactions further extend the 1-D arrangement to generate a 2-D supramolecular architecture. Complex 2 features a 3-D coordination polymer with α-Po net topology, based on linear trinuclear {Cd3O14N4} clusters. Both complexes have high thermal stability and exhibit strong luminescence at room temperature. 相似文献
79.
Exhaled breath condensate is a promising, non-invasive, diagnostic sample obtained by condensation of exhaled breath. Starting from a historical perspective of early attempts of breath testing towards the contemporary state-of-the-art breath analysis, this review article focuses mainly on the progress in determination of non-volatile compounds in exhaled breath condensate. The mechanisms by which the aerosols/droplets of non-volatile compounds are formed in the airways are discussed with methodological consequences for sampling. Dilution of respiratory droplets is a major problem for correct clinical interpretation of the measured data and there is an urgent need for standardization of EBC. This applies also for collection instrumentation and therefore various commercial and in-house built devices are described and compared with regard to their design, function and collection parameters. The analytical techniques and methods for determination of non-volatile compounds as potential markers of oxidative stress and lung inflammation are scrutinized with an emphasis on method suitability, sensitivity and appropriateness. The relevance of clinical findings for each group of possible non-volatile markers of selected pulmonary diseases and methodological recommendations with emphasis on interdisciplinary collaboration that is essential for future development into a fully validated clinical diagnostic tool are given. 相似文献
80.
《Journal of Coordination Chemistry》2012,65(22):4102-4116
The tetra α- or β-thiophene substituted metal and metal-free phthalocyanines (Pcs) M[Pc(α-OCH2Thiopen)4] and M[Pc(β-OCH2Thiopen)4] {(α-ThMet-MPc), (β-ThMet-MPc) [ThMet: Thiophene methoxy], M = Zn(II), Co(II) and, 2H} were synthesized from the corresponding 3’-(thiophen-3-ylmethoxy)phthalonitrile or 4’-(thiophen-3-ylmethoxy)phthalonitrile (ThMePN). The structural characterization, spectral, and antioxidant properties of a series of new Pcs were also presented. Both α- and β-substituted Pc complexes increased solubility in polar solvents, such as THF, DMF, and DMSO. FT-IR, 1H-NMR, 13C-NMR, UV–vis, MALDI-TOF/MS spectral, and elemental analysis data were used to characterize the compounds. The aggregation behaviors of 3–8 were also investigated at different concentrations in THF. Antioxidant test methods, α,α-diphenyl-β-picrylhydrazyl radical scavenging activity, metal chelating activity, and reducing power, were used to determine the antioxidant activities. 6 showed very good ferrous ion chelating activity of 81 ± 1%. 6, 5, 4, and 3 showed better reducing power than trolox, ascorbic, acid and butylated hydroxytoluene, commercially used antioxidants. 相似文献