全文获取类型
收费全文 | 10577篇 |
免费 | 1908篇 |
国内免费 | 2096篇 |
专业分类
化学 | 7852篇 |
晶体学 | 235篇 |
力学 | 688篇 |
综合类 | 166篇 |
数学 | 1372篇 |
物理学 | 4268篇 |
出版年
2024年 | 21篇 |
2023年 | 247篇 |
2022年 | 345篇 |
2021年 | 468篇 |
2020年 | 551篇 |
2019年 | 524篇 |
2018年 | 409篇 |
2017年 | 513篇 |
2016年 | 522篇 |
2015年 | 589篇 |
2014年 | 738篇 |
2013年 | 881篇 |
2012年 | 991篇 |
2011年 | 1022篇 |
2010年 | 822篇 |
2009年 | 773篇 |
2008年 | 834篇 |
2007年 | 689篇 |
2006年 | 667篇 |
2005年 | 524篇 |
2004年 | 440篇 |
2003年 | 278篇 |
2002年 | 340篇 |
2001年 | 284篇 |
2000年 | 260篇 |
1999年 | 166篇 |
1998年 | 111篇 |
1997年 | 73篇 |
1996年 | 62篇 |
1995年 | 55篇 |
1994年 | 62篇 |
1993年 | 35篇 |
1992年 | 43篇 |
1991年 | 38篇 |
1990年 | 28篇 |
1989年 | 23篇 |
1988年 | 17篇 |
1987年 | 23篇 |
1986年 | 13篇 |
1985年 | 18篇 |
1984年 | 11篇 |
1983年 | 9篇 |
1982年 | 7篇 |
1981年 | 11篇 |
1980年 | 8篇 |
1977年 | 5篇 |
1976年 | 3篇 |
1974年 | 4篇 |
1971年 | 3篇 |
1959年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 203 毫秒
81.
Ying Huang Rui Sun Qiaojie Luo Ying Wang Kai Zhang Xuliang Deng Weipu Zhu Xiaodong Li Zhiquan Shen 《Journal of polymer science. Part A, Polymer chemistry》2016,54(1):99-107
In this study, a facile method to fabricate reduction‐responsive core‐crosslinked micelles via in situ thiol‐ene “click” reaction was reported. A series of biodegradable poly(ether‐ester)s with multiple pendent mercapto groups were first synthesized by melt polycondensation of diol poly(ethylene glycol), 1,4‐butanediol, and mercaptosuccinic acid using scandium trifluoromethanesulfonate [Sc(OTf)3] as the catalyst. Then paclitaxel (PTX)‐loaded core‐crosslinked (CCL) micelles were successfully prepared by in situ crosslinking hydrophobic polyester blocks in aqueous media via thiol‐ene “click” chemistry using 2,2′‐dithiodiethanol diacrylate as the crosslinker. These PTX‐loaded CCL micelles with disulfide bonds exhibited reduction‐responsive behaviors in the presence of dithiothreitol (DTT). The drug release profile of the PTX‐loaded CCL micelles revealed that only a small amount of loaded PTX was released slowly in phosphate buffer solution (PBS) without DTT, while quick release was observed in the presence of 10.0 mM DTT. Cell count kit (CCK‐8) assays revealed that the reduction‐sensitive PTX‐loaded CCL micelles showed high antitumor activity toward HeLa cells, which was significantly higher than that of reduction‐insensitive counterparts and free PTX. This kind of biodegradable and biocompatible CCL micelles could serve as a bioreducible nanocarrier for the controlled antitumor drug release. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 99–107 相似文献
82.
Research on Chemical Intermediates - The structure and racemization mechanism of l-aspartic acid (l-ASP) and l-ASP-intercalated layered double hydroxide (l-ASP-LDH, with intercalated... 相似文献
83.
Mono‐ and Dinuclear Phosphorescent Rhenium(I) Complexes: Impact of Subcellular Localization on Anticancer Mechanisms 下载免费PDF全文
Rui‐Rong Ye Dr. Cai‐Ping Tan Mu‐He Chen Liang Hao Prof. Liang‐Nian Ji Prof. Zong‐Wan Mao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(23):7800-7809
Elucidation of relationship among chemical structure, cellular uptake, localization, and biological activity of anticancer metal complexes is important for the understanding of their mechanisms of action. Organometallic rhenium(I) tricarbonyl compounds have emerged as potential multifunctional anticancer drug candidates that can integrate therapeutic and imaging capabilities in a single molecule. Herein, two mononuclear phosphorescent rhenium(I) complexes ( Re1 and Re2 ), along with their corresponding dinuclear complexes ( Re3 and Re4 ), were designed and synthesized as potent anticancer agents. The subcellular accumulation of Re1–Re4 was conveniently analyzed by confocal microscopy in situ in live cells by utilizing their intrinsic phosphorescence. We found that increased lipophilicity of the bidentate ligands could enhance their cellular uptake, leading to improved anticancer efficacy. The dinuclear complexes were more potent than the mononuclear counterparts. The molecular anticancer mechanisms of action evoked by Re3 and Re4 were explored in detail. Re3 with a lower lipophilicity localizes to lysosomes and induces caspase‐independent apoptosis, whereas Re4 with higher lipophilicity specially accumulates in mitochondria and induces caspase‐independent paraptosis in cancer cells. Our study demonstrates that subcellular localization is crucial for the anticancer mechanisms of these phosphorescent rhenium(I) complexes. 相似文献
84.
Using a molecular dynamics simulation technique,we compared several commonly used ion-water models to describe the microscopic structures and dynamics in KSCN aqueous solutions.Results are compared with observations of femtosecond infrared vibrational-energy transfer and anisotropy measurements.The Jorgensen/TIP4P model is found to provide the best reproduction of clustering properties such as percentage of clustered ions,cluster-size distribution,concentration dependence of the water,and ion-rotation time constants. 相似文献
85.
以1,10-邻菲罗啉(phen)为配体,采用溶剂蒸发法在水中分别合成了羟基桥连和氯离子桥连的两个新型的含氮配体多核铜离子配合物[Cu4(phen)4(H2O)2(OH)4·(NO3)4·2H2O(1)和Cu2(phen)2Cl4(2)],其结构经元素分析和X-射线单晶衍射表征。1属三斜晶系,空间群P-1,晶胞参数a=10.143 0(9),b=11.900 1(11),c=12.629 9(13),α=111.060(2)°,β=91.070 0(10)°,γ=110.920(2)°,Z=1,V=1 309.8(2)3,F(000)=692。2属单斜晶系,空间群Cc,晶胞参数a=9.860 9(8),b=17.852 9(13),c=13.412 3(15),β=106.583(11)°,Z=4,V=2 263.0(4)3,F(000)=1 256。用荧光光谱和热分析分别研究了1和2的荧光性质和热稳定性,结果表明:在310 nm激发波长激发下,与phen相比,1和2的荧光发射峰分别发生红移和蓝移,λem分别位于451 nm和374 nm。1和2的初始分解温度分别为298℃和300℃。 相似文献
86.
基于学习过程,本文侧重讨论了目前物理教学中常见的几种教学改革模式的目的和功效,对进一步改善教学效果提出了相应的建议. 相似文献
87.
88.
Theoretical and experimental research on the self‐assembled system of molecularly imprinted polymers formed by salbutamol and methacrylic acid 下载免费PDF全文
The quantum chemical method was applied for screening functional monomers in the rational design of salbutamol‐imprinted polymers. Salbutamol was the template molecule, and methacrylic acid was the single functional monomer. The LC‐WPBE/6–31G(d,p) method was used to investigate the geometry optimization, active sites, natural bond orbital charges, binding energies of the imprinted molecule, and solvation energy. The mechanism of action between salbutamol and methacrylic acid was also discussed. The theoretical results show that salbutamol interacts with functional monomers by hydrogen bonds, and the salbutamol‐imprinted polymers with a ratio of 1:4 (salbutamol/methacrylic acid) in acetonitrile had the highest stability. The salbutamol‐imprinted polymers were prepared by precipitation polymerization. The experimental results indicated that the maximum adsorption capacity for salbutamol toward molecularly imprinted polymers was 7.33 mg/g, and the molecularly imprinted polymers had a higher selectivity for salbutamol than for norepinephrine and terbutaline sulfate. Herein, the studies can provide theoretical and experimental references for the salbutamol molecular imprinted system. 相似文献
89.
Discrimination of crude and processed rhubarb products using a chemometric approach based on ultra fast liquid chromatography with ion trap/time‐of‐flight mass spectrometry 下载免费PDF全文
Min Wang Jinfeng Fu Huimin Guo Yuan Tian Fengguo Xu Rui Song Zunjian Zhang 《Journal of separation science》2015,38(3):395-401
Crude rhubarb subjected to different processing procedures will produce different therapeutic effects that are possibly due to processing‐induced variation in chemical composition. In this study, a chemometric approach based on ultra fast liquid chromatography with ion trap/time‐of‐flight mass spectrometry was established to systematically investigate the chemical variations of rhubarb induced by different processing methods. The approach was validated based on pooled quality‐control samples from two perspectives: the individual properties of variables and the bulk properties of samples. Orthogonal partial least squares discriminant analysis was introduced to compare the differences between crude and processed rhubarb products. A total of 20 significantly different markers were screened out and unambiguously/tentatively characterized. This research proved that a chemometric method based on ultra fast liquid chromatography with ion trap/time‐of‐flight mass spectrometry can comprehensively analyze the chemical variation of herbal medicine and provide evidence for a deeper understanding of the pharmacological activities of processed rhubarb products. 相似文献