全文获取类型
收费全文 | 8616篇 |
免费 | 1633篇 |
国内免费 | 920篇 |
专业分类
化学 | 5787篇 |
晶体学 | 86篇 |
力学 | 718篇 |
综合类 | 65篇 |
数学 | 1127篇 |
物理学 | 3386篇 |
出版年
2024年 | 8篇 |
2023年 | 177篇 |
2022年 | 201篇 |
2021年 | 285篇 |
2020年 | 337篇 |
2019年 | 315篇 |
2018年 | 283篇 |
2017年 | 278篇 |
2016年 | 419篇 |
2015年 | 407篇 |
2014年 | 447篇 |
2013年 | 630篇 |
2012年 | 739篇 |
2011年 | 827篇 |
2010年 | 552篇 |
2009年 | 529篇 |
2008年 | 612篇 |
2007年 | 476篇 |
2006年 | 517篇 |
2005年 | 375篇 |
2004年 | 314篇 |
2003年 | 252篇 |
2002年 | 234篇 |
2001年 | 201篇 |
2000年 | 190篇 |
1999年 | 190篇 |
1998年 | 182篇 |
1997年 | 172篇 |
1996年 | 166篇 |
1995年 | 136篇 |
1994年 | 116篇 |
1993年 | 111篇 |
1992年 | 90篇 |
1991年 | 69篇 |
1990年 | 75篇 |
1989年 | 61篇 |
1988年 | 44篇 |
1987年 | 34篇 |
1986年 | 34篇 |
1985年 | 22篇 |
1984年 | 18篇 |
1983年 | 14篇 |
1982年 | 15篇 |
1981年 | 3篇 |
1980年 | 7篇 |
1979年 | 2篇 |
1975年 | 1篇 |
1957年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
121.
芥子气模拟剂2-氯乙基乙基硫醚的光催化降解 总被引:4,自引:0,他引:4
利用连续流动微反、原位红外和GC/MS等手段考察了芥子气模拟剂2-氯乙基乙基硫醚(2-CEES)在P25 TiO2上的光催化降解反应,证实CO2和H2O是这个反应的最终产物.详细的跟踪分析表明,除了CO2和H2O外,在反应的气相混合物中可检测到C2H4、CH3CHO、CH4、CO、HCl和H2S;少量小分子的羧酸、醚和砜;微量C2H5SC2H5、C2H5S2C2H5、C2H5SC2H4Cl和CH2ClCH2Cl等中间产物;在反应后的催化剂表面可检测到C2H5S2C2H5、C2H5SC2H4OH、C4H9S2C2H5和C2H5S2C2H4OH、等物.根据这些结果提出了2-CEES光催化降解的反应机理,推断2-CEES的光催化降解涉及脱氯、C-S键断裂、有机硫化物光聚合和裂解等复杂过程最终转化为CO2和H2O.认为各种硫物种在表面的积聚引起了催化剂的缓慢失活. 相似文献
122.
123.
用高效液相色谱手性固定相法拆分芳香仲醇及芳香乙二 醇类手性化合物 总被引:4,自引:0,他引:4
在ChiralcelOD和ChiralcelOJ两支多糖类手性固定相上,以各种不同配比的正己烷-异丙醇为洗脱剂对38种带有不同取代基的芳香仲醇及芳香乙二醇类手性化合物的对映体进行拆分,考察了这些外消旋体在这两支手性柱上的色谱行为。结果表明,扬长避短一柱对这些化合物的拆分能力与化合物取代基的性质和位置有关,这些化合物与手性固定相之间的氢键作用和π-π作用是影响手性拆分的重要原因。拆分方法已应用于潜手性酮不对称还原产物的光学纯度的鉴定,并取得了很好的效果。 相似文献
124.
纳米CoHCF修饰电极的制备及其对血红蛋白的电化学测定研究 总被引:1,自引:0,他引:1
A cobalt hexacyanoferrate (CoHCF) nanoparticle (size ca. 60 nm) chemically modified electrode (CME) was fabricated and the electrochemical behavior of hemoglobin (Hb) at this nanosized CoHCF CME was studied. In comparison with a bare glassy carbon electrode (GCE) and a general CoHCF CME electrodeposited in a traditional manner, the present nanosized CoHCF CME performed efficiently electrocatalytic reduction for Hb with relatively high sensitivity, stability, and longlife, Combined with liquid chromatography (LC), the nanosized CoHCF CME was used as the electrochemical detector of Hb in the established flow injection analysis-electrochemical determination (FIA-ECD) system. The peak current was a linear function of concentrations in the range from 2.5×10^-8 to 5.0×10^-6mol/L for Hb, with detection limit of 1.4×10^-8 mol/L. The FIA-ECD system has been successfully applied to assess the Hb content of clinic blood samples with advantages of sensitiveness, speediness, easy control and small sample-consumption. 相似文献
125.
Sanders L Halder M Xiao TL Ding J Armstrong DW Petrich JW 《Photochemistry and photobiology》2005,81(1):183-186
We report the first separation of the enantiomers of hypericin. Their steady-state optical spectra and ultrafast primary photoprocesses are investigated in chiral environments. Within experimental error, there is no difference between the two enantiomers in any of the systems considered. This is consistent with the emerging picture that the rich and extended absorption spectrum of hypericin is not a result of ground-state heterogeneity. It is also consistent with the observation that the spectra and photophysics of hypericin are generally insensitive to environments in which it does not aggregate. 相似文献
126.
Zhichao Tao Yong fang Chenghua Zhang Tingzhen Li Mingyue Ding Hongwei Xiang Yongwang Li 《天然气化学杂志》2007,16(3):278-285
The effects of Manganese(Mn)incorporation on a precipitated iron-based Fischer-Tropsch synthesis(FTS)catalyst were investigated using N_2 physical adsorption,air differential thermal analysis (DTA),H_2 temperature-programmed reduction(TPR),and M(?)ssbauer spectroscopy.The FTS perfor- mances of the catalysts were tested in a slurry phase reactor.The characterization results indicated that Mn increased the surface area of the catalyst,and improved the dispersion ofα-Fe_2O_3 and reduced its crystallite size as a result of the high dispersion effect of Mn and the Fe-Mn interaction.The Fe-Mn inter- action also suppressed the reduction ofα-Fe_2O_3 to Fe_3O_4,stabilized the FeO phase,and(or)decreased the carburization degree of the catalysts in the H_2 and syngas reduction processes.In addition,incorporated Mn decreased the initial catalyst activity,but improved the catalyst stability because Mn restrained the reoxidation of iron carbides to Fe_3O_4,and improved further carburization of the catalysts.Manganese suppressed the formation of CH_4 and increased the selectivity to light olefins(C_(2-4)~=),but it had little effect on the selectivities to heavy(C_(5 )) hydrocarbons.All these results indicated that the strong Fe-Mn interaction suppressed the chemisorptive effect of the Mn as an electronic promoter,to some extent,in the precipitated iron-manganese catalyst system. 相似文献
127.
C. T. Peng S.-F. Ding R.-L. Hua 《Journal of Radioanalytical and Nuclear Chemistry》1988,123(2):411-420
Retention indexes (RI's) on SE-30 and Carbowax 20M columns are characteristic and can be used for identification purposes. A method for predicting RI on the basis of the number of atoms and contributions from substituents and functional groups is discussed. This method establishes a structure retention index relationship (SRIR), capable of relating structure to RI and is useful for suggesting structure to match with radioactive peaks. Examples of labeled side products tentatively identified in this manner are given. 相似文献
128.
Tanaka K Ding MY Helaleh MI Taoda H Takahashi H Hu W Hasebe K Haddad PR Fritz JS Sarzanini C 《Journal of chromatography. A》2002,956(1-2):209-214
In this preliminary study, a new approach to ion-exclusion chromatography is proposed to overcome the relatively poor conductivity detection response which occurs in ion-exclusion chromatography when acids are added to the eluent in order to improve peak shape. This approach, termed vacancy ion-exclusion chromatography, requires the sample to be used as eluent and a sample of water to be injected onto a weakly acidic cation-exchange column (TSKgel OApak-A). Vacancy peaks for each of the analytes appear at the retention times of these analytes. Highly sensitive conductivity detection is possible and sharp, well-shaped peaks are produced, leading to efficient separations. Retention times were found to be affected by the concentration of the analytes in the eluent, and also by the presence of an organic modifier such as methanol in the eluent. Detection limits for oxalic, formic, acetic, propionic, butyric and valeric acids were 0.1, 0.2, 0.3, 0.3, 0.4 and 0.5 microM, respectively, and linear ranges for some acids extended over two orders of magnitude. Precision values for retention times were 0.21% and for peak areas were <1.90%. The vacancy ion-exclusion chromatography method was found to give detection responses four to 10 times higher than conventional ion-exclusion chromatography using sulfuric acid eluent and two to five times higher than conventional ion-exclusion chromatography using benzoic acid eluent. 相似文献
129.
稀土掺杂的(K, Sr)Cl·SiO2复合凝胶的荧光性能 总被引:1,自引:0,他引:1
采用sol gel法制备了单掺铕及共掺铕、铈的(K,Sr)Cl·SiO2复合凝胶,研究了复合凝胶的荧光性能。根据荧光测试结果,复合凝胶中,Eu3+在没有还原剂的作用下,可以与基质作用形成还原态的Eu2+,复合凝胶表现出相应的Eu2+荧光性能;研究认为,Ce3+,Eu3+共掺杂时,复合凝胶激发光谱与发射光谱峰位基本不变,但强度有所不同。330nm处的激发光谱明显增强,且发射光谱随Ce3+的掺杂量增加而增强。当Ce3+掺杂浓度为3.0%(原子分数)时,复合凝胶具有最大的荧光发射强度,表明Ce3+具有很好的敏化作用。在Ce3+,Eu3+共掺杂复合凝胶体系中,复合凝胶荧光强度增大的原因既可能是电子转移过程,也可能是Ce3+→Eu2+的能量传递过程所致。 相似文献
130.