全文获取类型
收费全文 | 22738篇 |
免费 | 3626篇 |
国内免费 | 3057篇 |
专业分类
化学 | 16190篇 |
晶体学 | 304篇 |
力学 | 1358篇 |
综合类 | 271篇 |
数学 | 2968篇 |
物理学 | 8330篇 |
出版年
2024年 | 29篇 |
2023年 | 319篇 |
2022年 | 506篇 |
2021年 | 637篇 |
2020年 | 782篇 |
2019年 | 806篇 |
2018年 | 712篇 |
2017年 | 703篇 |
2016年 | 1059篇 |
2015年 | 1092篇 |
2014年 | 1345篇 |
2013年 | 1673篇 |
2012年 | 1932篇 |
2011年 | 2080篇 |
2010年 | 1582篇 |
2009年 | 1590篇 |
2008年 | 1742篇 |
2007年 | 1489篇 |
2006年 | 1487篇 |
2005年 | 1235篇 |
2004年 | 988篇 |
2003年 | 809篇 |
2002年 | 894篇 |
2001年 | 648篇 |
2000年 | 575篇 |
1999年 | 466篇 |
1998年 | 349篇 |
1997年 | 268篇 |
1996年 | 258篇 |
1995年 | 198篇 |
1994年 | 173篇 |
1993年 | 140篇 |
1992年 | 134篇 |
1991年 | 124篇 |
1990年 | 82篇 |
1989年 | 78篇 |
1988年 | 75篇 |
1987年 | 55篇 |
1986年 | 43篇 |
1985年 | 39篇 |
1984年 | 27篇 |
1983年 | 27篇 |
1982年 | 13篇 |
1981年 | 16篇 |
1980年 | 17篇 |
1978年 | 18篇 |
1977年 | 9篇 |
1976年 | 14篇 |
1975年 | 10篇 |
1973年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 265 毫秒
991.
FT‐IR spectroscopic and thermodynamic measurements were designed to explore the effect of a macromolecular crowder, dextran, on the temperature and pressure‐dependent phase diagram of the protein Ribonuclease A (RNase A), and we compare the experimental data with approximate theoretical predictions based on configuration entropy. Exploring the crowding effect on the pressure‐induced unfolding of proteins provides insight in protein stability and folding under cell‐like dense conditions, since pressure is a fundamental thermodynamic variable linked to molecular volume. Moreover, these studies are of relevance for understanding protein stability in deep‐sea organisms, which have to cope with pressures in the kbar range. We found that not only temperature‐induced equilibrium unfolding of RNase A, but also unfolding induced by pressure is markedly prohibited in the crowded dextran solutions, suggesting that crowded environments such as those found intracellularly, will also oppress high‐pressure protein unfolding. The FT‐IR spectroscopic measurements revealed a marked increase in unfolding pressure of 2 kbar in the presence of 30 wt % dextran. Whereas the structural changes upon thermal unfolding of the protein are not significantly influenced in the presence of the crowding agent, through stabilization by dextran the pressure‐unfolded state of the protein retains more ordered secondary structure elements, which seems to be a manifestation of the entropic destabilization of the unfolded state by crowding. 相似文献
992.
993.
以HF、HCl、H2O和NaAc溶液为调节剂合成了4种MOF-Fe样品,用X射线衍射(XRD)、透射电镜(TEM)、N2等温吸附-脱附、综合热分析(TG/DTG和DTA)和质子电位滴定研究了4种样品的结构与表面性质,以及对亚硒酸根(Se(Ⅳ))等温吸附特性。MOF-Fe(HF)、MOF-Fe(HCl)、MOF-Fe(H2O)和MOF-Fe(NaAc)四种样品均具有八面体MIL-100(Fe)的晶体结构,但它们的结晶度和晶面取向略有差异。4种样品的比表面积分别为1 683、1 517、1 641和1 734 m2·g-1,其总孔体积依次降低,微孔孔径分别为1.27、1.22、1.22和1.17 nm。MOF-Fe(HF)样品的脱羧基失重峰温度最高(415℃),苯环碳化失重峰温度最低(462℃);MOF-Fe(HCl)、MOF-Fe(H2O)和MOF-Fe(NaAc)样品出现了因氧化铁被碳还原所致的失重平台(566~716℃)。样品悬浮液从pH=6.0降到3.0时,消耗H+的量表现为MOF-Fe(H2O) > MOF-Fe(HCl) > MOF-Fe(HF)=MOF-Fe(NaAc),它们的电荷零点(pHZPC)依次为3.1、3.5、3.6和3.5。MOF-Fe(NaAc)、MOF-Fe(HCl)、MOF-Fe(H2O)和MOF-Fe(HF)对Se(Ⅳ)的吸附亲和力依次减小,它们对Se(Ⅳ)的吸附容量(Qm)分别为77.69、107.07、117.40和87.15 mg·g-1。显著性分析显示,MOF-Fe的羟基密度与样品吸附Se(Ⅳ)的Qm显著正相关。研究结果表明,MOF-Fe样品的结构热稳定性和羟基/配位水分子等活性位点密度受合成样品时加入的调节剂影响,用HF作为调节剂合成MOF-Fe样品有利于提高样品中羧基与苯环之间的C-C键合强度和热分解产物的稳定性,降低苯环碳化温度;HCl和H2O作为调节剂有利于提高样品的活性位点密度,可提高MOF-Fe样品对Se(Ⅳ)吸附容量。 相似文献
994.
You-An Xiao Zhi-Qiang Wang Xue-Min Wang Yi Hui Yong Ling Xin-Yang Wang Li-Qin He 《中国化学快报》2013,24(8):727-730
Novel 2-aminoimidazolone derivatives were synthesized.Most compounds displayed strong anticancer activities against human carcinoma cells in vitro.Compounds 8a,8b and 8j exhibited optimal activity superior to 5-FU in most cancer cells tested.Especially,the lC50s of 8b(12.6-21.5μmol/L) against five tumor cells were 1 -4 fold less than those of 5-FU(18.4-56.1μmol/L) in vitro.Furthermore,comp以ound 8b could induce SMMC-7721 cell apoptosis in a dose-dependent manner.Therefore,our novel findings may provide a new framework for the design of new 2-aminoimidazolone derivatives for the treatment of cancer. 相似文献
995.
An approximate method has been established to calculate the depth of the potential acting on an electron in a molecule at the saddle point along a chemical bond, denoted by Dpb. It is a new indicator which can be used for predicting the strength of a chemical bond. In this work, as a practical application for demonstrating thismethod, we calculated the Dpb of deoxyribonucleosides and ribonucleosides along all C-H and N-H chemical bonds using the method. The results are in fair agreement with those results of previously reported experimental and theoretical observations. 相似文献
996.
Yang Sun Zhipeng Ran Hongyan Tang Yong Li Wenshuang Song Qingguang Ren Wuli Yang Jilie Kong 《中国化学》2013,31(6):787-793
Mesoporous silica nanoparticles (MSN) were coated by pH‐responsive polymer chitosan‐poly (methacrylic acid) (CS‐PMAA). This nano drug delivery system showed good application prospects and the polymer‐coated microspheres were promising site‐specific anticancer drug delivery carriers in biomedical field. A continuous detection of pH‐responsive drug delivery system in cells in situ, utilizing MSN/CS‐PMAA composite microspheres, was proposed. Two kinds of different cell lines, tumor cell line (Hela) and normal somatic cells (293T), were used to investigate the behaviours of the drug loaded system in the cells. Conclusions could be drawn from the fluorescent images obtained by confocal laser scanning microscopy (CLSM), modified drug‐loaded microspheres (MSN/CS‐PMAA) were ingested into cells more easily, the uptake of DOX@FITC‐MSN/CS‐PMAA by HeLa/293T cells were performed at pH 7.4/pH 6.8, DOX was released during the ingestion process, fluorescence intensity decreased with time because of efflux transport and photo‐bleaching. Fluoresence detection by flow cytometry was performed as comparison. The continuous fluorescent observation in situ could be widely used in the pH‐responsive releasing process of drug delivery system in the cells. 相似文献
997.
以2,2'-二硫代二苯甲酸、2,2'-联吡啶、咪唑、硝酸锌和硝酸锰为原料,使用水热方法合成了配合物[Zn(EBLA)(2,2'-bipy)(H2O)](EBLA=2,2'-二苯甲酸硫醚)(2,2'-bipy=2,2'-联吡啶)(1),自然挥发法制备了配合物[Mn(EBSA)(im)2(H2O)]n(EBSA=2,2'-二硫代二苯甲酸)(im=咪唑)(2).利用元素分析、红外和热重分析对其进行了表征.利用X-射线单晶衍射对结构进行了测定,并研究了配合物1的荧光性质.配合物1中,2,2'-二苯甲酸硫醚是通过水热方法由2,2'-二硫代二苯甲酸发生原位反应制备,Zn2+离子是五配位的四角锥双核结构;配合物2中,Mn2+离子是六配位的变形八面体一维链状结构.配合物中存在氢键和π-π堆积等弱的分子间作用力. 相似文献
998.
采用溶胶-浸渍法,以CuSO4为烧结助剂在碳纤维表面制得TiO2涂层。利用XRD、SEM和TEM分析了涂层相组成及形貌,通过静态等温氧化实验考察了涂层碳纤维抗氧化性能。结果表明:掺杂CuSO4制备TiO2涂层均匀完整致密,涂层相组成均为锐钛矿型TiO2,且涂层厚度从45 nm提高至185 nm;与普通TiO2涂层碳纤维相比,完全氧化温度从667 ℃上升到800 ℃,氧化活化能从118.390 kJ·mol-1提高到152.562 kJ·mol-1,CuSO4的掺杂大大提高了TiO2涂层碳纤维的抗氧化性能。 相似文献
999.
合成和表征了一种锌(Ⅱ)配合物[Zn2(L)Cl3]2[ZnCl4]·CH3CN·CH3OH·3H2O(L=1,1,4,7,7-五(2-吡啶甲基)-二乙基三胺),并用对硝基苯磷酸酯(PNPP)作为反应底物测试了它的催化活性。研究结果表明配合物中的1个Zn(Ⅱ)形成变形的八面体构型,另1个Zn(Ⅱ)形成变形的三角双锥构型。它催化PNPP的水解符合米氏方程模型。在不同的条件下测试了几种反应动力学参数Vmax、Km和Kcat,发现锌(Ⅱ)配合物在30 ℃和pH=8.0时有最大的催化活性。 相似文献
1000.