全文获取类型
收费全文 | 1576篇 |
免费 | 330篇 |
国内免费 | 411篇 |
专业分类
化学 | 1476篇 |
晶体学 | 12篇 |
力学 | 51篇 |
综合类 | 18篇 |
数学 | 176篇 |
物理学 | 584篇 |
出版年
2023年 | 19篇 |
2022年 | 37篇 |
2021年 | 41篇 |
2020年 | 60篇 |
2019年 | 52篇 |
2018年 | 54篇 |
2017年 | 48篇 |
2016年 | 67篇 |
2015年 | 79篇 |
2014年 | 98篇 |
2013年 | 115篇 |
2012年 | 122篇 |
2011年 | 151篇 |
2010年 | 132篇 |
2009年 | 109篇 |
2008年 | 124篇 |
2007年 | 103篇 |
2006年 | 117篇 |
2005年 | 96篇 |
2004年 | 80篇 |
2003年 | 76篇 |
2002年 | 105篇 |
2001年 | 104篇 |
2000年 | 66篇 |
1999年 | 54篇 |
1998年 | 41篇 |
1997年 | 16篇 |
1996年 | 9篇 |
1995年 | 15篇 |
1994年 | 13篇 |
1993年 | 16篇 |
1992年 | 10篇 |
1991年 | 18篇 |
1990年 | 6篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1982年 | 2篇 |
1974年 | 2篇 |
1973年 | 4篇 |
1969年 | 4篇 |
1968年 | 7篇 |
1967年 | 3篇 |
1966年 | 5篇 |
1962年 | 2篇 |
1936年 | 1篇 |
1903年 | 2篇 |
排序方式: 共有2317条查询结果,搜索用时 31 毫秒
61.
Rui Yan Li Zhi Ru Li Di Wu Xi Yun Hao Ru Jiao Li Chia Chung Sun 《International journal of quantum chemistry》2005,103(2):157-166
Using four basis bets, (6‐311G(d,p), 6‐31+G(d,p), 6‐31++G(2d,2p), and 6‐311++G(3df,3pd), the optimized structures with all real frequencies were obtained at the MP2 level for the dimers CH2O? HF, CH2O? H2O, CH2O? NH3, and CH2O? CH4. The structures of CH2O? HF, CH2O? H2O, and CH2O? NH3 are cycle‐shaped, which result from the larger bend of σ‐type hydrogen bonds. The bend of σ‐type H‐bond O…H? Y (Y?F, O, N) is illustrated and interpreted by an attractive interaction of a chemically intuitive π‐type hydrogen bond. The π‐type hydrogen bond is the interaction between one of the H atoms of CH2O and lone pair(s) on the F atom in HF, the O atom in H2O, or the N atom in NH3. In contrast with the above three dimers, for CH2O? CH4, because there is not a π‐type hydrogen bond to bend its linear hydrogen bond, the structure of CH2O? CH4 is noncyclic shaped. The interaction energy of hydrogen bonds and the π‐type H‐bond are calculated and discussed at the CCSD (T)/6‐311++G(3df,3pd) level. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
62.
A pressurized gradient capillary electrochromatography (pCEC) instrument was developed to separate 18 amino acid derivatives. A reversed-phase C18 column (3 microm, 130 mm x 75 microm I.D.) and an acetate buffer (50 mmol/l NaAc, pH 6.4) with an ion-pair reagent (1% N,N-dimethylformamide) were used to separate derivatized amino acids from a standard solution (2 microg/ml), and the wavelength of the UV-Vis detector was 360 nm. The pressure on the capillary column was kept at approx. 70 Pa and 3 kV positive voltage was added on the outlet end of column. The effect of voltage on the eluting order of amino acids and the resolution of separation were studied, and it was found that when the voltage was higher than 3 kV, the adsorption of amino acids in the porous C18 column occurred. The effect of salt concentration, injection volume, and column length on the separation of amino acids was determined. The amino acid sample was separated by pCEC, and RSDs of the migration times of each amino acid were all less than 2.5%. 相似文献
63.
单取代二茂铁西佛碱型液晶化合物的合成及介晶性研究 总被引:5,自引:0,他引:5
报道了两个系列二茂铁衍生物,FcC_6H_4N=CHC_6H_4OC_nH_(2n+1)(系列I) 和FcC_6H_4N=CHC_6H_4O_2CC_6H_4OC_nH_(2n+1)(系列II)(Fc:ferrocenyl;n = 2,4,6,8,10,12,14,16),并通过DSC和热台偏光显微镜对其介晶性进行 了研究。系列I不具有介晶性,系列II呈较窄的液晶温度范围。其结果显示分子的 刚性部分长度对介晶性有重要影响。 相似文献
64.
锐钛相虫蛀状介孔二氧化钛的表征 总被引:3,自引:0,他引:3
0IntroductionMesostructuredtitania(TiO2)hasattractedagreatdealofattention,inviewofcontrolleddelivery,catalytic,photocatlytic,orenergyconversionapplica-tions犤1犦.Theuseoftitaniumisopropoxidebis-acetylace-tonateprecursors,combinedwithalkylphosphatean-ionicsurfactantsastemplate,ledtothefirstdocu-mentedpuremesoporousTiO2犤2犦.Insubsequentyears,moresyntheticstrategieshavebeendevelopedusingavarietyofstructure-directingagents,forexample,car-boxylicacids犤3犦,alkylamine犤4犦,aminium犤5犦,blockcop-o… 相似文献
65.
N,N''''-硝基苯酰基取代苯酰氨基硫脲的合成与生物活性 总被引:6,自引:0,他引:6
酰氨基硫脲类化合物不仅具有广谱抗菌性能 ,还具有极好的杀虫和植物生长调节活性 [1~ 3] ,因而引起许多国内外学者对硫脲类化合物的合成及其化学结构与生物活性关系方面的研究 [4~ 8] .为了进一步研究不同的取代基团对此类化合物生物活性的影响 ,作者用硝基苯酰基异硫氰酸酯与芳基酰肼加成制得相应的 N ,N -硝基苯酰基取代苯酰氨基硫脲 ( ) ,并初步测定了它们抑制大肠杆菌和枯草杆菌生长的生物活性 .这些化合物尚未见文献报道 .Ar— COCl KSCN Ar—CONCS a~ cAr CONHNH2 ( 1 ~ 7) Ar—CONHC( S) NHNHCOAr Ar:a.o-N… 相似文献
66.
Yi‐Zhen Tang Hao Sun Ya‐Ru Pan Xiu‐Mei Pan Rong‐Shun Wang 《International journal of quantum chemistry》2007,107(6):1495-1501
The mechanisms for the reaction of CH3S with NO2 are investigated at the QCISD(T)/6‐311++G(d,p)//B3LYP/6‐311++G(d,p) on both single and triple potential energy surfaces (PESs). The geometries, vibrational frequencies, and zero‐point energy (ZPE) correction of all stationary points involved in the title reaction are calculated at the B3LYP/6‐311++G(d,p) level. More accurate energies are obtained at the QCISD(T)/6‐311++G(d,p). The results show that 5 intermediates and 14 transition states are found. The reaction is more predominant on the single PES, while it is negligible on the triple PES. Without any barrier height for the whole process, the main channel of the reaction is to form CH3SONO and then dissociate to CH3SO+NO. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
67.
68.
苯乙烯-丁二烯-苯乙烯/聚乙烯基甲基醚共混体系相容性的FT-IR及DSC研究 总被引:2,自引:0,他引:2
嵌段高聚物、均聚物共混体系相容性是近年来研究的热点。本工作以光学显微镜、DSC、FT-IR为手段,研究了三嵌段高聚物苯乙烯-丁二烯-苯乙烯(SBS);SBS-48、SBS-30,SBS-28与聚乙烯基甲基醚共混体系的相容性。DSC结果表明,随SBS中PS含量的升高,体系相容性变好,PS段分子量增大,也有助于体系相容。FT-IR结果表明PVME中COCH_3在1100cm~(-1)附近呈现的双峰的相对强度对体系的相容性十分敏感,而由于苯环C—H振动产生的698cm~(-1)峰位却不象PS/PVME体系那样随相容性的改变而有显著的改变。总而言之,嵌段高聚物SBS/均聚物PVME共混体系中,体系的相容性依赖于嵌段高聚物在体系中的组份含量及嵌段高聚物中PS的重量百分含量,PS段分子量的大小对体系相容性也有影响。 相似文献
69.
70.
The complex Eu(btfa)3 (phen) (btfa=4,4,4‐trifluoro‐1‐phenyl‐1, 3‐butanedione, phen = 1,10‐phenanthroline) has been prepared and characterized by elemental analysis, IR and UV spectroscopies. The crystal and molecular structures of the complex have been determined by X‐ray diffraction analysis. It belongs to the monoclinic crystal system, space group P21/c with a = 0.9700(2) nm, b = 3.7450(5) nm, c = 1.0917(3) nm, β = 92.51(2)°, V = 3.962(1) nm5, Z = 4, Dc = 1.639 g/cm3, μ = 1.676 mm?1, F(000) = 1936, R1, = 0.0388, wR2 = 0.0775. Structure analysis shows that the europium(III) ion is coordinated to six oxygen atoms of β‐diketonate anions and two nitrogen atoms of phenanthroline molecule. The coordination polyhedron is an approximate square antiprism. 相似文献