全文获取类型
收费全文 | 23058篇 |
免费 | 4149篇 |
国内免费 | 2968篇 |
专业分类
化学 | 16843篇 |
晶体学 | 320篇 |
力学 | 1389篇 |
综合类 | 182篇 |
数学 | 2716篇 |
物理学 | 8725篇 |
出版年
2024年 | 66篇 |
2023年 | 495篇 |
2022年 | 846篇 |
2021年 | 861篇 |
2020年 | 1011篇 |
2019年 | 1023篇 |
2018年 | 864篇 |
2017年 | 848篇 |
2016年 | 1212篇 |
2015年 | 1238篇 |
2014年 | 1469篇 |
2013年 | 1784篇 |
2012年 | 2206篇 |
2011年 | 2191篇 |
2010年 | 1459篇 |
2009年 | 1500篇 |
2008年 | 1612篇 |
2007年 | 1328篇 |
2006年 | 1268篇 |
2005年 | 1085篇 |
2004年 | 857篇 |
2003年 | 633篇 |
2002年 | 588篇 |
2001年 | 495篇 |
2000年 | 372篇 |
1999年 | 434篇 |
1998年 | 317篇 |
1997年 | 287篇 |
1996年 | 269篇 |
1995年 | 262篇 |
1994年 | 208篇 |
1993年 | 177篇 |
1992年 | 154篇 |
1991年 | 142篇 |
1990年 | 132篇 |
1989年 | 87篇 |
1988年 | 72篇 |
1987年 | 55篇 |
1986年 | 58篇 |
1985年 | 44篇 |
1984年 | 30篇 |
1983年 | 34篇 |
1982年 | 14篇 |
1981年 | 19篇 |
1980年 | 8篇 |
1979年 | 11篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1975年 | 7篇 |
1974年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 578 毫秒
991.
Dr. Bo Peng Dr. Nuno Maulide 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13274-13287
The direct functionalization of C? H bonds is an attractive strategy in organic synthesis. Although several advances have been made in this area, the selective activation of inert sp3 C? H bonds remains a daunting challenge. Recently, a new type of sp3 C? H activation mode through internal hydride transfer has demonstrated the potential to activate remote sp3 C? H linkages in an atom‐economic manner. This Minireview attempts to classify recent advances in this area including the transition to non‐activated sp3 C? H bonds and asymmetric hydride transfers. 相似文献
992.
993.
994.
Linlin Li Dr. Shengjie Peng Yanling Cheah Peifen Teh Jin Wang Grace Wee Yahwen Ko Dr. Chuiling Wong Prof. Madhavi Srinivasan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(19):5892-5898
Novel, porous NiCo2O4 nanotubes (NCO‐NTs) are prepared by a single‐spinneret electrospinning technique followed by calcination in air. The obtained NCO‐NTs display a one‐dimensional architecture with a porous structure and hollow interiors. The effect of precursor concentration on the morphologies of the products is investigated. Due to their unique structure, the prepared NCO‐NT electrode exhibits a high specific capacitance (1647 F g?1 at 1 A g?1), excellent rate capability (77.3 % capacity retention at 25 A g?1), and outstanding cycling stability (6.4 % loss after 3000 cycles), which indicates it has great potential for high‐performance electrochemical capacitors. The desirable enhanced capacitive performance of NCO‐NTs can be attributed to the relatively large specific surface area of these porous and hollow one‐dimensional nanostructures. 相似文献
995.
Dr. Peng Cui Dr. Thomas P. Spaniol Prof. Dr. Laurent Maron Prof. Dr. Jun Okuda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13437-13444
The rare‐earth‐metal? hydride complexes [{(1,7‐Me2TACD)LnH}4] (Ln=La 1 a , Y 1 b ; (1,7‐Me2TACD)H2=1,7‐dimethyl‐1,4,7,10‐tetraazacyclododecane, 1,7‐Me2[12]aneN4) were synthesized by hydrogenolysis of [{(1,7‐Me2TACD)Ln(η3‐C3H5)}2] with 1 bar H2. The tetrameric structures were confirmed by 1H NMR spectroscopy and single‐crystal X‐ray diffraction of compound 1 a . Both complexes catalyze the dehydrogenation of secondary amine? borane Me2NH ? BH3 to afford the cyclic dimer (Me2NBH2)2 and (Me2N)2BH under mild conditions. Whilst the complete conversion of Me2NH ? BH3 was observed within 2 h with lanthanum? hydride 1 a , the yttrium homologue 1 b required 48 h to reach 95 % conversion. Further reactions of compound 1 a with Me2NH ? BH3 in various stoichiometric ratios gave a series of intermediate products, [{(1,7‐Me2TACD)LaH}4](Me2NBH2)2 ( 2 a ), [(1,7‐Me2TACDH)La(Me2NBH3)2] ( 3 a ), [(1,7‐Me2TACD)(Me2NBH2)La(Me2NBH3)] ( 4 a ), and [(1,7‐Me2TACD)(Me2NBH2)2La(Me2NBH3)] ( 5 a ). Complexes 2 a , 3 a , and 5 a were isolated and characterized by multinuclear NMR spectroscopy and single‐crystal X‐ray diffraction studies. These intermediates revealed the activation and coordination modes of “Me2NH ? BH3” fragments that were trapped within the coordination sphere of a rare‐earth‐metal center. 相似文献
996.
Dr. Qiu‐Feng Lü Jia‐Yin Zhang Jun Yang Zhi‐Wei He Prof. Dr. Chang‐Qing Fang Qilang Lin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(33):10935-10944
Self‐assembled poly(N‐methylaniline)–lignosulfonate (PNMA–LS) composite spheres with reactive silver‐ion adsorbability were prepared from N‐methylaniline by using lignosulfonate (LS) as a dispersant. The results show that the PNMA–LS composite consisted of spheres with good size distribution and an average diameter of 1.03–1.27 μm, and the spheres were assembled by their final nanofibers with an average diameter of 19–34 nm. The PNMA–LS composite spheres exhibit excellent silver‐ion adsorption; the maximum adsorption capacity of silver ions is up to 2.16 g g?1 at an adsorption temperature of 308 K. TEM and wide‐angle X‐ray results of the PNMA–LS composite spheres after absorption of silver ions show that silver ions are reduced to silver nanoparticles with a mean diameter of about 11.2 nm through a redox reaction between the PNMA–LS composite and the silver ions. The main adsorption mechanism between the PNMA–LS composite and the silver ions is chelation and redox adsorption. In particular, a ternary PNMA–LS–Ag composite achieved by using the reducing reaction between PNMA–LS composite spheres and silver ions can be used as an antibacterial material with high bactericidal rate of 99.95 and 99.99 % for Escherichia coli and Staphylococcus aureus cells, respectively. 相似文献
997.
Dr. Peng Wu Ting Zhao Yunfei Tian Dr. Lan Wu Prof. Dr. Xiandeng Hou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(23):7473-7479
Proteins typically have nanoscale dimensions and multiple binding sites with inorganic ions, which facilitates the templated synthesis of nanoparticles to yield nanoparticle–protein hybrids with tailored functionality, water solubility, and tunable frameworks with well‐defined structure. In this work, we report a protein‐templated synthesis of Mn‐doped ZnS quantum dots (QDs) by exploring bovine serum albumin (BSA) as the template. The obtained Mn‐doped ZnS QDs give phosphorescence emission centered at 590 nm, with a decay time of about 1.9 ms. A dual‐channel sensing system for two different proteins was developed through integration of the optical responses (phosphorescence emission and resonant light scattering (RLS)) of Mn‐doped ZnS QDs and recognition of them by surface BSA phosphorescent sensing of trypsin and RLS sensing of lysozyme. Trypsin can digest BSA and remove BSA from the surface of Mn‐doped ZnS QDs, thus quenching the phosphorescence of QDs, whereas lysozyme can assemble with BSA to lead to aggregation of QDs and enhanced RLS intensity. The detection limits for trypsin and lysozyme were 40 and 3 nM , respectively. The selectivity of the respective channel for trypsin and lysozyme was evaluated with a series of other proteins. Unlike other protein sensors based on nanobioconjugates, the proposed dual‐channel sensor employs only one type of QDs but can detect two different proteins. Further, we found the RLS of QDs can also be useful for studying the BSA–lysozyme binding stoichiometry, which has not been reported in the literature. These successful biosensor applications clearly demonstrate that BSA not only serves as a template for growth of Mn‐doped ZnS QDs, but also impacts the QDs for selective recognition of analyte proteins. 相似文献
998.
Peng Wang Dr. Lijiang Yang Dr. Pengcheng Liu Prof. Dr. Yi Qin Gao Prof. Dr. Xin Sheng Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(19):5909-5916
An increasing number of proteins are found to contain a knot in their polypeptide chain. Although some studies have looked into the folding mechanism of knotted proteins, why and how these complex topologies form are still far from being fully answered. Moreover, no experimental information about how the knot moves during the protein‐folding process is available. Herein, by combining single‐molecule fluorescence resonance energy transfer (smFRET) experiments with molecular dynamics (MD) simulations, we performed a detailed study to characterize the knot in the denatured state of TrmD, a knotted tRNA (guanosine‐1) methyltransferase from Escherichia coli, as a model system. We found that the knot still existed in the unfolded state of TrmD, consistent with the results for two other knotted proteins, YibK and YbeA. More interestingly, both smFRET experiments and MD simulations revealed that the knot slid towards the C‐terminal during the unfolding process, which could be explained by the relatively strong interactions between the β‐sheet core at the N terminal of the native knot region. The size of the knot in the unfolded state is not larger than that in the native state. In addition, the knot slid in a “downhill” mode with simultaneous chain collapse in the denatured state. 相似文献
999.
A Rapid and Efficient Way to Dynamic Creation of Cross‐Reactive Sensor Arrays Based on Ionic Liquids
Wei Zhu Weina Li Haowei Yang Yin Jiang Chen Wang Prof. Dr. Yu Chen Prof. Dr. Guangtao Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(35):11603-11612
Based on the simple counterion exchange of ionic liquids, a rapid, facile, and efficient strategy to create a cross‐reactive sensor array with a dynamic tunable feature was developed, and exemplified by the construction of a sensor array for the identification and classification of nitroaromatics and explosives mimics. To achieve a good sensing system with fast response, good sensitivity, and low detection limit, the synthesized ionic liquid receptors were tethered onto a silica matrix with a macro‐mesoporous hierarchical structure. Through the facile anion exchange approach, abundant ionic‐liquid‐based individual receptors with diversiform properties, such as different micro‐environments, diverse molecular interactions, and distinctive physico‐chemical properties, were easily and quickly synthesized to generate a distinct fingerprint of explosives for pattern recognition. The reversible anion exchange ability further endowed the sensor array with a dynamic tunable feature as well as good controllability and practicality for real‐world application. With the assistance of statistical analysis, such as principal component analysis (PCA) and linear discrimination analysis (LDA), an optimized‐size array with a good resolution was rationally established from a large number of IL‐based receptors. The performed experiments suggested that the ionic‐liquid‐based sensing protocol is a general and powerful strategy for creating a cross‐reactive sensor array that could find a wide range of applications for sensing various analytes or complex mixtures. 相似文献
1000.
Feng Huang Ying‐Ying Pei Hui‐Hui Zuo Jia‐Liang Chen Yin Yang Prof. Xun‐Cheng Su 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(50):17141-17149
Site‐specific labeling of proteins with lanthanide ions offers great opportunities for investigating the structure, function, and dynamics of proteins by virtue of the unique properties of lanthanides. Lanthanide‐tagged proteins can be studied by NMR, X‐ray, fluorescence, and EPR spectroscopy. However, the rigidity of a lanthanide tag in labeling of proteins plays a key role in the determination of protein structures and interactions. Pseudocontact shift (PCS) and paramagnetic relaxation enhancement (PRE) are valuable long‐range structure restraints in structural‐biology NMR spectroscopy. Generation of these paramagnetic restraints generally relies on site‐specific tagging of the target proteins with paramagnetic species. To avoid nonspecific interaction between the target protein and paramagnetic tag and achieve reliable paramagnetic effects, the rigidity, stability, and size of lanthanide tag is highly important in paramagnetic labeling of proteins. Here 4′‐mercapto‐2,2′: 6′,2′′‐terpyridine‐6,6′′‐dicarboxylic acid (4MTDA) is introduced as a a rigid paramagnetic and fluorescent tag which can be site‐specifically attached to a protein by formation of a disulfide bond. 4MTDA can be readily immobilized by coordination of the protein side chain to the lanthanide ion. Large PCSs and RDCs were observed for 4MTDA‐tagged proteins in complexes with paramagnetic lanthanide ions. At an excitation wavelength of 340 nm, the complex formed by protein–4MTDA and Tb3+ produces high fluorescence with the main emission at 545 nm. These interesting features of 4MTDA make it a very promising tag that can be exploited in NMR, fluorescence, and EPR spectroscopic studies on protein structure, interaction, and dynamics. 相似文献