全文获取类型
收费全文 | 2016篇 |
免费 | 119篇 |
国内免费 | 419篇 |
专业分类
化学 | 2060篇 |
晶体学 | 32篇 |
力学 | 32篇 |
综合类 | 39篇 |
数学 | 96篇 |
物理学 | 295篇 |
出版年
2024年 | 3篇 |
2023年 | 16篇 |
2022年 | 78篇 |
2021年 | 72篇 |
2020年 | 71篇 |
2019年 | 57篇 |
2018年 | 57篇 |
2017年 | 96篇 |
2016年 | 93篇 |
2015年 | 72篇 |
2014年 | 93篇 |
2013年 | 201篇 |
2012年 | 132篇 |
2011年 | 104篇 |
2010年 | 100篇 |
2009年 | 108篇 |
2008年 | 122篇 |
2007年 | 117篇 |
2006年 | 105篇 |
2005年 | 130篇 |
2004年 | 98篇 |
2003年 | 77篇 |
2002年 | 78篇 |
2001年 | 65篇 |
2000年 | 41篇 |
1999年 | 50篇 |
1998年 | 48篇 |
1997年 | 39篇 |
1996年 | 45篇 |
1995年 | 19篇 |
1994年 | 33篇 |
1993年 | 16篇 |
1992年 | 28篇 |
1991年 | 17篇 |
1990年 | 21篇 |
1989年 | 15篇 |
1988年 | 14篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1982年 | 6篇 |
1981年 | 4篇 |
1980年 | 1篇 |
排序方式: 共有2554条查询结果,搜索用时 15 毫秒
31.
选用CAPCELL PAK C18色谱柱为分离柱,柱温为30℃,进样体积为10.0μL,并用不同比例的(A)甲醇、(B)四氢呋喃和(C)0.008 2mol·L^-1高氯酸溶液的混合液作为流动相,按程序梯度洗脱模式对市售防晒产品中所用的15种防晒剂的标准品进行色谱分离,并在波长311nm处进行紫外检测。实样分析时,称取样品0.25g,用甲醇、四氢呋喃、水和高氯酸(体积比为250∶450∶300∶0.2)的混合液(以下简称混合溶剂)15 mL超声提取30 min,用混合溶剂定容至25.0mL,离心10min,分取上清液1.0mL,加入混合溶剂定容至10.0mL,经0.45μm滤膜过滤,取滤液按仪器工作条件进行高效液相色谱分析。结果表明:所测定的15种防晒剂在一定的质量浓度范围内与其对应的峰面积呈线性关系。选定其中的二苯酮-3为参照物,并根据其余14种化合物的质量浓度和峰面积计算了各化合物的相对校正因子和相对保留时间等参数,确定了用一测多评法(QAMS)测定防晒产品中15种防晒剂的条件。还对色谱柱的型号、色谱仪器的型号以及柱温、进样量等对相对校正因子和保留时间可能产生影响的因素进行了系统试验。证明了在选定的色谱柱型号的前提下,用QAMS方法可实现防晒产品中15种防晒剂含量的同时测定。应用QAMS方法测定了6个批次防晒产品中的防晒剂含量,所得结果与用标准曲线法计算的结果基本一致,表明QAMS方法在降低检测成本和节省检测时间方面效果显著。 相似文献
32.
Barium dichromate is used as a mild oxidizing agent for the selective conversion of primary and secondary alcohols to their corresponding aldehydes and ketones, respectively. Over-oxidation does not occur and primary alcohols undergo oxidation to the aldehyde. Primary and secondary benzylic alcohols are oxidized faster and more efficiently. 相似文献
33.
气相色谱-质谱法分析土壤中神经性毒剂及糜烂性毒剂 总被引:1,自引:1,他引:1
建立了土壤中神经性毒剂及糜烂性毒剂GC—MS-SIM分析法,对土壤中6种毒剂的样品制备和二步萃取方法进行了研究;该法的回收率在80.7%~89.5%,6种毒剂在0.5~10mg/L范围内毒剂质量浓度和峰面积有良好的线性相关,方法检出限为4~20ng/g,该法适用于痕量化学战剂分析。 相似文献
34.
J. M. Hernndez Ana M. Herrera J. García‐Serrano J. F. Rivas‐Silva 《International journal of quantum chemistry》2002,88(3):342-346
Conformations of p‐methacryloylaminophenylarsonic acid (p‐MAPHA) are determined through molecular mechanics and DFT/B3LYP calculations. Solvation effects are studied within the self‐consistent isodensity continuum model (SCI‐PCM). The stationary points were found to correspond to minima as verified by the analysis of vibrational frequencies in the molecule. The molecular optical absorption was obtained by using different solvent environments. The present results are in good agreement with the available experimental data. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献
35.
Effects of coupling agents on mechanical and morphological behavior of the PP/HDPE blend with two different CaCO3 总被引:1,自引:0,他引:1
《European Polymer Journal》2002,38(12):2465-2475
The main purpose of incorporating fillers, such as calcium carbonate, into blends of polyolefins is to decrease costs and change tensile and impact properties. Structural differences between both components give rise to the formation of large filler agglomerates in the polymer matrix, which influence the mechanical response of the material. Therefore, the coupling agents of the Lica 12 type at various concentrations was used to facilitate the link between filler and matrix (the latter consisting of PP/HDPE 80/20 wt). Filler was added to the PP/HDPE blend at a 30 wt.% concentration. Two types of calcium carbonate (CaCO3) were used. These have different average sizes (3.0 and 1.8 μm) which were determined by means of laser diffraction techniques. In addition other coupling agents of the titanate type, such as Lica 09, Lica 01, zirconates ZN 12, and a 1:1 mixture of Lica 12 and Lica 01, were used. This study clearly demonstrated that the addition of the coupling agent to CaCO3 modifies the mechanical properties of the PP/HDPE/CaCO3 composites. Values of the mechanical properties indicate that due to its characteristics, each coupling agent gives rise to increases in a particular mechanical property. In the case of Lica 01 an increase was verified in Young’s modulus at 0.7 wt.% and in elongation at break at both concentrations (0.3 and 0.7 wt.%), whereas ZN 12 brought about an increase in elongation at break. The 1:1 mixture of Lica 12 and Lica 01 caused impact resistance of the blend of PP/HDPE with CaCO3 to increase considerably. 相似文献
36.
Hiratake J 《Chemical record (New York, N.Y.)》2005,5(4):209-228
Carefully designed molecules that are intimately related to the reaction mechanism of enzymes are often highly selective and potent inhibitors that serve as extremely useful chemical probes for understanding the reaction mechanism and structure of enzymes. This article describes the design, synthesis, and applications of specific inhibitors of two mechanistically distinct groups of enzymes, ATP-dependent amide ligases and Ser- and Thr-hydrolases. Our strategy is based on the premise that stable analogues of the transition state (transition-state analogues) are highly potent inhibitors that serve as good mechanistic probes, and that a key structure of a good inhibitor of one enzyme is also utilized for the inhibitors of other enzymes that share the same chemistry in their catalyzed reactions, irrespective of the degree of structural similarity and evolutionary link between the enzymes. According to these principles, we designed and synthesized a series of phosphinate- and sulfoximine-based transition-state analogue inhibitors of glutathione synthetase, gamma-glutamylcysteine synthetase and asparagine synthetase. For the second group of enzymes, we synthesized a gamma-monofluorophosphono glutamate analogue for mechanism-based affinity labeling of gamma-glutamyltranspeptidase and fluorescent phosphonic acid esters for the active-site titration of lipase. These inhibitors were used successfully as ligands for detailed kinetic analyses, X-ray crystallography, and mass analysis of the enzymes to identify the key amino acid residues responsible for catalysis and substrate recognition in the transition state. 相似文献
37.
本文研究了标题试剂(简称H_2A)与Th(Ⅳ)的络合作用及萃取行为,考查了H_2A对Fe(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Pb(Ⅱ)、Cu(Ⅱ)、La(Ⅲ)、Yb(Ⅲ)和U(Ⅵ)的萃取作用,试验了它对Th(Ⅳ)与上述元素及Ca(Ⅱ)、Mg(Ⅱ)、Cr(Ⅲ)、In(Ⅲ)、V(Ⅴ)、Zr(Ⅵ)的分离效果。 相似文献
38.
若干3d过渡金属的硫代脯氨酸配合物 总被引:4,自引:0,他引:4
合成了七个新的过渡金属的硫代脯氨酸(tcH)配合物,它们分别是:[M(tc)_2](M=Mn(Ⅱ),Co((Ⅱ))和Ni(Ⅱ)),[Ni(tc)(Ac)(H_2O)],[Ni(tc)(tcH)(H_2O)]NO_3·H_2O,[Ni(tc)(Py)_2(H_2O)NO_3和[Fe(tc)_2(Cl)(H_2O)]。上述配合物的磁化率,摩尔电导,热量分析,红外及电子光谱数据表明,它们都具有八面体构型,tcH主要通过亚氨氮和羧基氧原子与金属键合。文章对这些配合物的可能结构作了初步的讨论。 相似文献
39.
Xiangfu Zhang Fei XieZhonglin Pen Yong ZhangYinxi Zhang Wen Zhou 《European Polymer Journal》2002,38(1):1-6
The effect of the sorbital nucleating agent on properties of the ethylene-octene copolymer (POE) toughened polypropylene (PP) was studied. The results show that the addition of POE increases notched Izod and Charpy impact strength significantly but impair the tensile strength and flexural modulus. As a nucleating agent (1,3,2,4-di(p-methylbenzylidene) sorbitol, DM) was added, the toughness and stiffness of toughed PP increased simultaneously at the same content of POE. This result shows that the toughness and stiffness of toughed PP are in balance. Polarized light microscopy analysis shows that with the addition of POE and nucleating agent, only a low level of PP spherulites were observed. 相似文献
40.
原油乳状液破乳的动态法研究 总被引:5,自引:0,他引:5
The stability of different crude oil emulsions from ASP flooding production well is studied by the method of a stirred tank. The demulsifying of crude-oil emulsion by different demulsifying agents is discussed. The breakage of the crude oil emulsions from the well PO11 by the different types and concentrations of the emulsifying agents is also discussed. The breaking mechanism of the demulsifying agent is described microscopically. 相似文献