全文获取类型
收费全文 | 13509篇 |
免费 | 1243篇 |
国内免费 | 4344篇 |
专业分类
化学 | 14113篇 |
晶体学 | 412篇 |
力学 | 493篇 |
综合类 | 142篇 |
数学 | 1673篇 |
物理学 | 2263篇 |
出版年
2024年 | 22篇 |
2023年 | 123篇 |
2022年 | 307篇 |
2021年 | 333篇 |
2020年 | 374篇 |
2019年 | 310篇 |
2018年 | 331篇 |
2017年 | 405篇 |
2016年 | 471篇 |
2015年 | 392篇 |
2014年 | 626篇 |
2013年 | 1058篇 |
2012年 | 1399篇 |
2011年 | 752篇 |
2010年 | 628篇 |
2009年 | 844篇 |
2008年 | 972篇 |
2007年 | 1046篇 |
2006年 | 968篇 |
2005年 | 952篇 |
2004年 | 865篇 |
2003年 | 719篇 |
2002年 | 626篇 |
2001年 | 497篇 |
2000年 | 500篇 |
1999年 | 470篇 |
1998年 | 406篇 |
1997年 | 360篇 |
1996年 | 350篇 |
1995年 | 340篇 |
1994年 | 302篇 |
1993年 | 217篇 |
1992年 | 272篇 |
1991年 | 201篇 |
1990年 | 159篇 |
1989年 | 117篇 |
1988年 | 88篇 |
1987年 | 64篇 |
1986年 | 67篇 |
1985年 | 48篇 |
1984年 | 34篇 |
1983年 | 18篇 |
1982年 | 23篇 |
1981年 | 10篇 |
1980年 | 7篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1972年 | 2篇 |
1936年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 17 毫秒
991.
Bosco Christin Maria Arputham Ashwin Chokalingam Saravanan Marimuthu Senthilkumaran Ragupathi Sumathi Palanisamy Suresh 《Supramolecular chemistry》2018,30(1):32-41
The host–guest interaction of α-tocopherol (vitamin E) with p-sulfonatocalix[4]arene (p-SC4) in solution state is studied using emission and cyclic voltammetric techniques. The lipid soluble α-tocopherol (α-T) forms a solid complex with p-SC4. FTIR and NMR spectral analysis of the solid complex reveals the tight packing of α-T inside the cavity of p-SC4. The structural deformation is confirmed by XRD analysis. SEM images differentiate the highly porous gel like structure of vitamin E aggregate and the solid structure of the host–guest complex prepared. NOESY spectra confirm the tight penetration of α-T within the hydrophobic cavity of p-SC4. 相似文献
992.
In this study, bis(diphenylphosphinemethyl)dimethyl silane ( L1 ) and its palladium(II) halide complex, L1 /PdCl2 ( C1 ), were synthesized and characterized. Single‐crystal X‐ray analysis of the complex revealed bidentate coordination at the Pd center. In combination with methylaluminoxane (MAO) as co‐catalyst, C1 exhibited excellent catalytic activity and selectivity for ethylene dimerization toward butene. The maximum catalytic activity obtained from the C1 /MAO system for ethylene dimerization to yield butenes was 7.33 × 105 g/(molPd · h). The selectivity toward butene remained stable and high (> 96%) over the various conditions. 相似文献
993.
Dinuclear Cu(II) complexes based on p‐xylylene‐bridged bis(1,4,7‐triazacyclononane) ligands: Synthesis,characterization, DNA cleavage abilities and evaluation of superoxide dismutase‐ and catalase‐like activities
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Three new dinuclear Cu(II) complexes with the formulas [Cu2(pxdmbtacn)Cl4] ( 1 ), [Cu2(pxdmbtacn)Cl0.7(NO3)1.3(OH)2(H2O)1.3]?6H2O ( 2 ) and [Cu2(pxdiprbtacn)Cl4] ( 3 ) together with one previously reported complex, [Cu2(pxbtacn)Cl4] ( 4 ), were obtained from Cu(II) salts with three p‐xylylene‐bridged bis‐tacn ligands bearing pendant alkyl substituents or without pendant group. Complex 2 was structurally characterized as a centrosymmetric dinuclear molecule with each metal center being coordinated to some labile ligands in addition to one tacn ring. Based on the results of mass spectrometry and UV–visible spectroscopy, complexes 1 and 3 are capable of existing in aqueous solution as dinuclear species but 4 can partially form a dimer of the original dinuclear motif. Complexes 1 , 3 and 4 can all effectively cleave supercoiled DNA oxidatively in the presence of hydrogen peroxide. The superoxide dismutase (SOD) activities of 1 and 3 measured under physiological conditions are comparable to that of the native CuZnSOD enzyme but the enzymatic activity of 4 is about three‐ to fourfold lower. Furthermore, complexes 1 , 3 and 4 demonstrate moderate scavenging effect on hydrogen peroxide and their catalase activities are in the decreasing order of 3 > 1 > 4 . 相似文献
994.
连续变化法测定络合物组成和稳定常数是大学化学中的经典学生实验。但针对1:2和1:3的络合反应,实验教科书的设计中可能出现数据点过少也就是溶液配制过少的问题。如果按照要求配制溶液,由于没有完全反应的混合溶液,而其他混合溶液给出的数据又都呈良好的线性,就缺少了用来估算曲线的数据点,结果是,将没有足够的数据对稳定常数进行估算。对这种可能出现的数据点过少的实验设计的原因、结果和解决方法进行了探讨。 相似文献
995.
《中国化学会会志》2018,65(2):217-224
A new and simple potentiometric method is developed to determine the stability constants of cysteine complexes with Mn(II), Cu(II), Zn(II), Cd(II), and Ce(III) metal ions using a modified Bjerrum method. Potentiometric titrations were performed in water and water/dioxane mixtures at five different temperatures. The least and highest stable complexes were those of Cu(II) and Zn(II), respectively. Furthermore, by conducting the experiments at temperatures of 15, 20, 25, 35, and 45 °C, the thermodynamic parameters ΔH°, ΔS°, and ΔG° for the pertinent complexes were calculated. The results show that the ΔH° values of the complexes are positive except for Zn(II). Negative values of ΔG° are evidence for the spontaneity of the reactions. 相似文献
996.
《Journal of Coordination Chemistry》2012,65(13):2215-2222
A new Fe(II) complex, [Fe(HIM2Py)2(N(CN)2)2]?·?2H2O (HIM2py?=?1-hydroxyl-2(2′-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1?H-imidazole), has been synthesized and characterized. The X-ray analysis reveals that HIM2py ligands are coordinated to iron as an unusual six-membered bidentate chelate with κ2N(py), O(HIM) mode. The variable-temperature magnetic susceptibility suggests that weak antiferromagnetic interactions exist in the complex. 相似文献
997.
The identification of protein complexes in protein–protein interaction (PPI) networks has greatly advanced our understanding of biological organisms. Existing computational methods to detect protein complexes are usually based on specific network topological properties of PPI networks. However, due to the inherent complexity of the network structures, the identification of protein complexes may not be fully addressed by using single network topological property. In this study, we propose a novel MultiObjective Evolutionary Programming Genetic Algorithm (MOEPGA) which integrates multiple network topological features to detect biologically meaningful protein complexes. Our approach first systematically analyzes the multiobjective problem in terms of identifying protein complexes from PPI networks, and then constructs the objective function of the iterative algorithm based on three common topological properties of protein complexes from the benchmark dataset, finally we describe our algorithm, which mainly consists of three steps, population initialization, subgraph mutation and subgraph selection operation. To show the utility of our method, we compared MOEPGA with several state-of-the-art algorithms on two yeast PPI datasets. The experiment results demonstrate that the proposed method can not only find more protein complexes but also achieve higher accuracy in terms of fscore. Moreover, our approach can cover a certain number of proteins in the input PPI network in terms of the normalized clustering score. Taken together, our method can serve as a powerful framework to detect protein complexes in yeast PPI networks, thereby facilitating the identification of the underlying biological functions. 相似文献
998.
This paper presents an efficient procedure for overcoming the deficiency of weighted essentially non‐oscillatory schemes near discontinuities. Through a thorough incorporation of smoothness indicators into the weights definition, up to ninth‐order accurate multistep methods are devised, providing weighted essentially non‐oscillatory schemes with enhanced order of convergence at transition points from smooth regions to a discontinuity, while maintaining stability and the essentially non‐oscillatory behavior. We also provide a detailed analysis of the resolution power and show that the solution enhancements of the new method at smooth regions come from their ability to render smoothness indicators closer to uniformity. The new scheme exhibits similar fidelity as other multistep schemes; however, with superior characteristics in terms of robustness and efficiency, as no logical statements or mapping function is needed. Extensions to higher orders of accuracy present no extra complexity. Numerical solutions of linear advection problems and nonlinear hyperbolic conservation laws are used to demonstrate the scheme's improved behavior for shock‐capturing problems. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
999.
《Analytical letters》2012,45(3):179-184
Abstract Inhibition of instantaneous current due to the reduction at the mercury electrode of Co(NH3)6 3+ ions by the addition of acridine hydrochloride are presented in terms of orientations of the adsorbed organic additive. Unusual catalytic effects at high cathodic potentials were observed and are discussed. 相似文献
1000.
在溶剂热条件下,5-羧酸-1-萘膦酸(5-pncH3)和稀土硝酸盐反应合成得到3例萘羧酸膦酸镧系配合物:[Pr (5-pnc)(H2O)]·2H2O (1)、[Sm (5-pnc)(H2O)]·H2O (2)和[Eu (5-pnc)(H2O)]·H2O (3)。采用单晶X射线衍射、粉末X射线衍射、元素分析、红外光谱、热重分析和荧光光谱对配合物进行了表征。晶体结构表明,每个七配位的镧系离子由来自5个膦酸盐配体的6个O原子和来自1个配位水分子的一个O原子配位。[LnO7]通过O—C—O、O—P—O或—O—单元连接成一维双金属链结构,一维双金属链再进一步由萘羧酸膦酸配体(5-pnc3-)连接成三维开放骨架结构。荧光性质研究表明,配合物3在330 nm的激发光下,发射Eu的红色特征荧光,而配合物1和2在蓝光区显示出非常宽的配体中心发射带。 相似文献