全文获取类型
收费全文 | 26765篇 |
免费 | 4421篇 |
国内免费 | 4029篇 |
专业分类
化学 | 20583篇 |
晶体学 | 425篇 |
力学 | 1315篇 |
综合类 | 299篇 |
数学 | 2951篇 |
物理学 | 9642篇 |
出版年
2024年 | 94篇 |
2023年 | 489篇 |
2022年 | 930篇 |
2021年 | 990篇 |
2020年 | 1063篇 |
2019年 | 1125篇 |
2018年 | 947篇 |
2017年 | 988篇 |
2016年 | 1289篇 |
2015年 | 1333篇 |
2014年 | 1669篇 |
2013年 | 2072篇 |
2012年 | 2483篇 |
2011年 | 2541篇 |
2010年 | 1947篇 |
2009年 | 1837篇 |
2008年 | 1949篇 |
2007年 | 1805篇 |
2006年 | 1684篇 |
2005年 | 1345篇 |
2004年 | 989篇 |
2003年 | 783篇 |
2002年 | 741篇 |
2001年 | 652篇 |
2000年 | 573篇 |
1999年 | 481篇 |
1998年 | 354篇 |
1997年 | 312篇 |
1996年 | 266篇 |
1995年 | 254篇 |
1994年 | 233篇 |
1993年 | 168篇 |
1992年 | 146篇 |
1991年 | 135篇 |
1990年 | 121篇 |
1989年 | 89篇 |
1988年 | 73篇 |
1987年 | 53篇 |
1986年 | 61篇 |
1985年 | 49篇 |
1984年 | 19篇 |
1983年 | 18篇 |
1982年 | 19篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1978年 | 3篇 |
1971年 | 4篇 |
1957年 | 4篇 |
1936年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
221.
Li Y Reeve J Wang Y Thomas RK Wang J Yan H 《The journal of physical chemistry. B》2005,109(33):16070-16074
The micellization of a novel family of nonionic surfactants poly(oxyethylene) glycol alkyl ethers has been studied by microcalorimetry. One of the surfactants has adamantane, and the other nonionic surfactants have a benzene ring in their hydrophobic chains, which moves from the terminal of the hydrophobic chain toward the headgroup. Moreover, the alkyl chain of the nonionic surfactants is straight or branched. Both the critical micelle concentration (cmc) and the thermodynamic parameters associated with the micelle formation have been obtained. The cmc decreases and the enthalpy of micelle formation (deltaH(mic)) becomes less positive gradually as the length of hydrophobic chain increases, whereas the values of cmc and deltaH(mic) tend to increase for the surfactants with a longer ethylene oxide chain. However, the deltaH(mic) value of the surfactant with seven carbon atoms in a hydrophobic chain is more positive than that of the surfactant with six carbon atoms in a hydrophobic chain. Comparing with the nonionic surfactant with a methylene hydrophobic chain, the surfactants with benzene rings and adamantane groups have larger cmc values and the cmc values increase with the size of the groups. Furthermore, moving the phenyl group from the terminal of the hydrophobic chain to the neighbor of the hydrophilic headgroup leads to the decreased cmc. Both the variation of hydrophobic interaction from the movement of phenyl group and pi-pi interaction among adjacent phenyl groups affect deltaH(mic) values. 相似文献
222.
Density functional theory (DFT) and Monte Carlo (MC) simulation with free energy perturbation (FEP) techniques have been used to study the tautomeric proton transfer reaction of 2-amino-2-oxazoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline in the gas phase and in water. Two reaction pathways were considered: the direct and water-assisted transfers. The optimized structures and thermodynamic properties of stationary points for the title reaction system in the gas phase were calculated at the B3LYP/6-311+G(d, p) level of theory. The potential energy profiles along the minimum energy path in the gas phase and in water were obtained. The study of the solvent effect of water on the proton transfer of 2-amino-2-oxozoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline indicates that water as a solvent is favorable for the water-assisted process and slows down the rate of the direct transfer pathway. 相似文献
223.
224.
225.
Balamurugan S Ista LK Yan J López GP Fick J Himmelhaus M Grunze M 《Journal of the American Chemical Society》2005,127(42):14548-14549
Surface-grafted, environmentally responsive polymers have shown great promise for controlling adsorption and desorption of macromolecules and cells on solid surfaces. In the paper, we demonstrate that certain mixed self-assembled monolayers (SAMs) of oligo(ethylene glycol) (OEG) and methyl-terminated alkanethiolates on gold form surfaces with switchable hydrophobicity and tendency for protein adsorption and cellular attachment. At temperatures above 32 degrees C, SAMs with a surface density of approximately 50% OEG adsorbed significant amounts of pyruvate kinase and lysozyme, whereas below this temperature, these same SAMs were resistant to the adsorption of these proteins. Furthermore, protein layers adsorbed to these SAMs above 32 degrees C were removed upon rinsing with water below this temperature. Similar results were seen for attachment and release of the marine bacterium, Cobetia marina. The change from nonresistance to adsorptive state of the SAMs was concomitant with a change in advancing water contact angle. Vibrational sum frequency generation spectroscopy suggests that the temperature-induced changes coincide with a disorder-to-partial order transition of the hydrated methylene chains of the OEG moieties within the SAMs. Mixed OEG-methyl SAMs represent both a convenient means of controlling macromolecular and cellular adsorption within the laboratory and a useful tool for relating adsorption properties to molecular structures within the SAMs. 相似文献
226.
A sol-gel chemistry-based polymer coating approach was developed for the preparation of a novel polysiloxane-coated silica stationary phase for capillary liquid chromatography. SE-30, a commercial polysiloxane stationary phase used in gas chromatography, was incorporated into the properly designed sol solution. Then the sol-gel mixture was introduced into a silica gel-packed capillary column by pressure. A thin film of sol-gel SE-30-coating is chemically bonded to the surface of silica gel particles by hydrolytic polycondensation under mild conditions without any free radical cross-linking procedures, therefore the sol-gel approach offers a simple and effective pathway to create a hybrid polymer-coated silica stationary phase. Various factors affecting column making were optimized and discussed in this report. The resulting stationary phase showed good permeability, mechanical robustness, high durability to alkaline mobile phase and satisfactory chromatographic performance in separations of polar and non-polar aromatic compounds. Linear solvation energy relationships (LSERs) studies indicate that the stationary phase has a reversed-phased character with SE-30 providing chromatographic functionality. The solute size and the solute hydrogen bond ability are major factors that principally govern the retention of test solutes. 相似文献
227.
Li Yan Liang Shao Ping Ren Yi Quan Zheng Man Geng Lu Guangzhou Institute of Chemistry Chinese Academy of Sciences Guangzhou China Key Laboratory of Polymer Materials for Electronics Guangdong China Graduate School of the Chinese Academy of Sciences Beijing China 《中国化学快报》2007,18(2):225-228
A series of novel liquid crystalline epoxides with lateral substituents were cured with anhydrides and the cure kinetics was investigated by non-isothermal DSC technique. The results showed that the lengths of lateral substituents have great effect on the value of Ea. The curing reaction became less active, when the liquid crystalline epoxides have long lateral substituents and were controlled by diffusion at the late stage of cure. A nematic structure was observed by POM and XRD. 相似文献
228.
Guangyin Zhou Wen Jiang Yan Zhao Guang-En Ma Shengguang Li Wenjuan Xin Baolu Zhao 《Research on Chemical Intermediates》2002,28(4):277-289
Adriamycin (ADR) is a powerful and widely used antitumor drug, but its dose dependent cardiotoxicity limits its application. This side effect is believed to be caused by the adriamycin semiquinone free radical (ASFR). The primary focus of this work is to test effects of sodium tanshinone IIA sulfonate (STS) on ASFR and adriamycin–induced lipid peroxidation. It was found that ADR, whether in the system of heart homogenate, heart mitochondria or heart submitochondria, with NADH as the substrate or in xanthine/xanthine oxidase under anaerobic conditions, all produced ASFR rapidly. STS was shown to effectively scavenge ASFR in all these systems and postpone the appearance of ASFR. The delayed time was proportional to the amount of STS. Under aerobic conditions, ASFR could be oxidized to generate oxygen free radicals. STS could not scavenge these oxygen free radicals, but it could effectively scavenge lipid free radicals generated from membrane lipid peroxidation of heart mitochondria. STS could significantly reduce mitochondrial swelling and lipid peroxidation induced by ADR. Animal experiments show that treatment of STS could inhibit endogenous lipid peroxidation caused by ADR. Here, a protective mechanism of STS is suggested that STS can rapidly and univalently oxidize ASFR, causing the cycle of adriamycin between its quinone form and semiquinone form and inhibiting the accumulation of ASFR. Under aerobic condition, STS can protect heart mitochondria by scavenging lipid free radicals generated from adriamycin-induced mitochondrial lipid peroxidation. This investigation shows that STS may be a physiological drug to antagonize the cardiotoxicity of ADR. 相似文献
229.
以正庚烷的转化为探针反应 ,研究了添加元素锆对铂重整催化剂性能的影响规律。结果表明 ,在 4 50℃和连续流动条件下 ,Pt/γ -Al2 O3催化剂中引入锆不仅能够提高铂催化剂的稳定性和芳构化产率、抑制氢解和异构化 ,而且能使铂催化剂保持初活性。锆含量在 0 .56%左右 ,其调变作用最为显著。 相似文献
230.
Yingxin Liu Zuojun Wei Jiyan Zhang Wei Yan 《Reaction Kinetics and Catalysis Letters》2007,92(1):121-127
Ni-La2O3-SiO2 catalysts were prepared by wetness impregnation and sol-gel method followed by conventional drying and supercritical drying,
respectively. Their physico-chemical properties and activity for the hydrogenation of m-dinitrobenzene to m-phenylenediamine were investigated by BET, XRD, TPR, H2-TPD and activity tests. The results showed that the structural and catalytic properties of the Ni-La2O3-SiO2 catalysts obviously depended on the preparation method and the drying mode. The catalyst prepared by the sol-gel method in
combination with conventional drying exhibited the highest catalytic activity among the catalysts tested, attributable to
its well-dispersed nickel particles and larger active nickel surface area. 相似文献