全文获取类型
收费全文 | 26785篇 |
免费 | 5129篇 |
国内免费 | 9138篇 |
专业分类
化学 | 20328篇 |
晶体学 | 1077篇 |
力学 | 1809篇 |
综合类 | 886篇 |
数学 | 4105篇 |
物理学 | 12847篇 |
出版年
2024年 | 61篇 |
2023年 | 311篇 |
2022年 | 971篇 |
2021年 | 988篇 |
2020年 | 1006篇 |
2019年 | 945篇 |
2018年 | 933篇 |
2017年 | 1266篇 |
2016年 | 1037篇 |
2015年 | 1444篇 |
2014年 | 1615篇 |
2013年 | 2203篇 |
2012年 | 2211篇 |
2011年 | 2430篇 |
2010年 | 2303篇 |
2009年 | 2364篇 |
2008年 | 2499篇 |
2007年 | 2377篇 |
2006年 | 2277篇 |
2005年 | 2013篇 |
2004年 | 1547篇 |
2003年 | 1073篇 |
2002年 | 1135篇 |
2001年 | 1122篇 |
2000年 | 1160篇 |
1999年 | 675篇 |
1998年 | 350篇 |
1997年 | 313篇 |
1996年 | 298篇 |
1995年 | 263篇 |
1994年 | 270篇 |
1993年 | 246篇 |
1992年 | 219篇 |
1991年 | 129篇 |
1990年 | 122篇 |
1989年 | 142篇 |
1988年 | 99篇 |
1987年 | 83篇 |
1986年 | 80篇 |
1985年 | 60篇 |
1984年 | 67篇 |
1983年 | 42篇 |
1982年 | 50篇 |
1981年 | 43篇 |
1980年 | 25篇 |
1979年 | 41篇 |
1978年 | 22篇 |
1976年 | 13篇 |
1974年 | 15篇 |
1965年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 62 毫秒
991.
The attempt to prepare structurally well-defined polymer/inorganic composite particles, i.e., poly(methyl methacrylate) (PMMA)/CaCO3/SiO2 three-component composite particles, via reverse atom transfer radical polymerization (ATRP), using 2-2′-azo-bis-isobutyronitrile as initiator and Cu(II) bromide as catalyst was reported. CaCO3/SiO2 two-component composite particles were first obtained through sol–gel method, and their morphology and surface element information were determined by transmission electron microscopy and X-ray photoelectron spectroscopy, respectively. The results indicate that the CaCO3 was encapsulated by the obtained SiO2. After being modified by silane coupling agent, the CaCO3/SiO2 composite particles copolymerized with methyl methacrylate (MMA) under standard reverse ATRP conditions to produce PMMA/CaCO3/SiO2 three-component composite particles. In the case concerned, first-order kinetic plots and linear increase of molecular weight (Mn) vs conversion and narrow molecular weight distribution for the graft polymer samples were observed. Furthermore, the gel permeation chromatography results illustrated that both the free PMMA chains from the solvent and the graft PMMA chains from the surface of CaCO3/SiO2 two-component composite particles were growing at the same rate. Characterizations of the PMMA-grafted CaCO3/SiO2 composite particles were done by Fourier transform infrared and thermogravimetric analysis. The results showed that the surface of the modified inorganic particles was grafted by the MMA and that the grafting percentage was about 8.7%. 相似文献
992.
LI Shu-Lan LIU De-Xin YANG Zhao-HeDepartment of Chemistry Shandong University Jinan Shandong China National Laboratory of Crystal Materials Shandong University Jinan Shandong China 《中国化学》1997,15(1):54-59
Monoaqua salicylaldehyde-o-aminobenzoic acid Ni(Ⅱ) monohydrate (cp1) and monoaqua o-vanillin-o-aminobenzoic acid Ni(Ⅱ) monohydrate (cp2) were synthesized. The composition and structures of these two compounds were analyzed. Their thermal stability and non-isothermal kinetics were also investigated by use of TG and DTG curves. The possible reaction mechanisms in their first steps of thermal decomposition reactions were deduced by means of integral and differential methods. Thermodecomposition kinetic equations of the compounds are as follows:Cp1: da/At = A . exp(-E/RT) . 3/2(1 - a)4/3 . [1/(1 - a)1/3 -1]-1 Cp2 : da/At = A . exp(-E/RT) . (1 - a) 相似文献
993.
Ordered ZnS semiconductor nanoparticles were in situ synthesized in metal halide perovskite organic/inorganic layered hybrids (CnH2n 1NH3)2ZnCl4 (n=10 and 12) by reaction of their spin-casting films with H2S gas. Transmission electron microscopy, UV-vis spectroscopy and small-angle X-ray diffraction were used to characterize the morphology and the structure of formed nanoparticles. Obtained results indicate an effective way to incorporate functional inorganic nanoparticles into structured organic matrices. 相似文献
994.
A pair of novel heptentriol stereoisomers, hept‐6‐ene‐2,4,5‐triols 2 and 3 , were isolated from the culture broth of the ascomycete Daldinia concentrica (Bolton : Fries ) Cesati & De Notaris , besides three known compounds, i.e., 2,3‐dihydro‐5‐hydroxy‐2‐methyl‐4H‐1‐benzopyran‐4‐one ( 1 ), 3,5‐dihydroxy‐2‐(1‐oxobutyl)‐cyclohex‐2‐en‐1‐one ( 4 ), and pyroglutamic acid (=5‐oxo‐L ‐proline; 5 ). Their structures were determined by spectroscopic means, including 2D‐NMR (HMQC, HMBC, 1H,1H‐COSY). 相似文献
995.
高效液相色谱-串联质谱法结合多糖衍生物手性固定相拆分氰戊菊酯 总被引:1,自引:0,他引:1
建立了以多糖衍生物为手性固定相的高效液相色谱-串联质谱(HPLC-MS/MS)直接拆分氰戊菊酯对映体的方法。在反相液相色谱条件下,考察了手性固定相的种类、流动相组成、柱温、流速对氰戊菊酯4个立体异构体分离的影响。同时,利用热力学方法对氰戊菊酯的立体异构体与固定相之间的色谱保留和分离的热力学机理进行了探讨。结果表明:采用Lux Cellulose-3(纤维素-三(4-甲基苯甲酸酯))手性色谱柱,在以流动相为乙腈-水(5 mmol/L甲酸铵)=(55:45,V:V)流速0.4 mL/min,柱温30℃的条件下,可在14 mins内实现氰戊菊酯4个立体异构体的基线分离。拓展了HPLC-MS/MS在菊酯类手性农药对映体分离及检测上的应用。 相似文献
996.
通过酸浸和模板合成处理,海泡石直接合成有序介孔二氧化硅和含铝的介孔二氧化硅. 海泡石用盐酸处理后120 ℃下在NaOH溶液中处理72 h, 得到具有HMS结构特征的介孔分子筛;在含铝的碱性溶液中处理后得到具有AlSBA结构的介孔分子筛. 并用SAXRD、BET、TPD表征了介孔分子筛的物相结构、比表面积、孔径分布和表面酸性. 两种介孔分子筛的比表面积分别为508 m2•g-1和946 m2•g-1,孔径分别为3.4 nm和3.9 nm,且孔径分布窄. NH3-TPD结果表明分子筛表面都有两个酸中心,随着Al原子的引入,表面酸性增强. 相似文献
997.
Non-negative matrix factorization (NMF), with the constraints of non-negativity, has been recently proposed for multi-variate data analysis. Because it allows only additive, not subtractive, combinations of the original data, NMF is capable of producing region or parts-based representation of objects. It has been used for image analysis and text processing. Unlike PCA, the resolutions of NMF are non-negative and can be easily interpreted and understood directly. Due to multiple solutions, the original algorithm of NMF [D.D. Lee, H.S. Seung, Nature 401 (1999) 788] is not suitable for resolving chemical mixed signals. In reality, NMF has never been applied to resolving chemical mixed signals. It must be modified according to the characteristics of the chemical signals, such as smoothness of spectra, unimodality of chromatograms, sparseness of mass spectra, etc. We have used the modified NMF algorithm to narrow the feasible solution region for resolving chemical signals, and found that it could produce reasonable and acceptable results for certain experimental errors, especially for overlapping chromatograms and sparse mass spectra. Simulated two-dimensional (2-D) data and real GUJINGGONG alcohol liquor GC-MS data have been resolved soundly by NMF technique. Butyl caproate and its isomeric compound (butyric acid, hexyl ester) have been identified from the overlapping spectra. The result of NMF is preferable to that of Heuristic evolving latent projections (HELP). It shows that NMF is a promising chemometric resolution method for complex samples. 相似文献
998.
999.
应用高能球磨法制备Mg-x%Mg1.8La0.2Ni(x=10、20和30)纳米复合储氢材料.X射线衍射(XRD)、透射电镜(TEM)和选区电子衍射(SAED)测试表明,该复合材料具有纳米晶和非晶态混合结构的性质,吸氢温度降低,较好的吸放氢动力学性能,在423K,2.5MPa氢压的条件下,50s内即可达到最大吸氢量. 相似文献
1000.
采用浸渍法制备了一系列Ag/ZrO2催化剂, 考察了Ag/ZrO2催化剂对1,2-丙二醇选择性氧化合成丙酮醛反应的催化性能. 实验结果表明: 在原料气配比为V(N2)∶V(O2)=300∶19, n(O2)/n(alcohol)=1.2, 反应物液时空速为3.2 g/(g•h), 反应温度为673 K时, 1,2-丙二醇选择性氧化合成丙酮醛反应的转化率为95.7%, 选择性为55.3%, 高于传统电解银催化剂. UV-Vis DRS和XPS的研究结果表明: 在Ag/ZrO2催化剂上存在大量的Ag+和Agnδ+有利于促进催化活性的提高. 相似文献