全文获取类型
收费全文 | 20990篇 |
免费 | 3642篇 |
国内免费 | 3465篇 |
专业分类
化学 | 16219篇 |
晶体学 | 320篇 |
力学 | 893篇 |
综合类 | 231篇 |
数学 | 2242篇 |
物理学 | 8192篇 |
出版年
2024年 | 25篇 |
2023年 | 416篇 |
2022年 | 563篇 |
2021年 | 761篇 |
2020年 | 873篇 |
2019年 | 860篇 |
2018年 | 748篇 |
2017年 | 809篇 |
2016年 | 1098篇 |
2015年 | 1119篇 |
2014年 | 1386篇 |
2013年 | 1714篇 |
2012年 | 2101篇 |
2011年 | 2227篇 |
2010年 | 1586篇 |
2009年 | 1467篇 |
2008年 | 1583篇 |
2007年 | 1428篇 |
2006年 | 1308篇 |
2005年 | 1002篇 |
2004年 | 723篇 |
2003年 | 582篇 |
2002年 | 650篇 |
2001年 | 564篇 |
2000年 | 408篇 |
1999年 | 427篇 |
1998年 | 287篇 |
1997年 | 244篇 |
1996年 | 199篇 |
1995年 | 166篇 |
1994年 | 122篇 |
1993年 | 129篇 |
1992年 | 98篇 |
1991年 | 95篇 |
1990年 | 56篇 |
1989年 | 64篇 |
1988年 | 40篇 |
1987年 | 39篇 |
1986年 | 43篇 |
1985年 | 30篇 |
1984年 | 9篇 |
1983年 | 9篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1976年 | 2篇 |
1959年 | 2篇 |
1957年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 263 毫秒
991.
Li Zhang Li Tong Zhang Jing He Zhi Jun Lin Yan Jiang Li Fu Chen 《Journal of Sol-Gel Science and Technology》2013,68(1):150-154
Aluminum nitride (AlN) fibers were prepared from alumina gel fibers and by heat-treatment in ammonia. The influence of silica on the formation of AlN was investigated. It was shown that phase transformation of alumina (γ-Al2O3 to α-Al2O3) and nitridation reaction took place above 1,100 °C for pure alumina fiber. The addition of a small amount of silica (3 wt%) suppressed the formation of α-Al2O3 and preserved the highly reactive metastable alumina, and nitridation rate was enhanced. Fine grain (~20 nm) AlN fibers were obtained for pyrolysis at 1,150–1,250 °C for 3 h in ammonia, and AlN was identified as the sole crystalline phase. 相似文献
992.
Li‐Wei Zhao Hui‐Min Shi Zhe An Jiu‐Zhao Wang Prof. Jing He 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(37):12350-12355
Effectively enhancing the enantioselectivity is a persistent challenge in heterogeneous asymmetric catalysis. Here, the validity of a layered double hydroxides (LDH) nanosheet as an efficient planar substituent to enhance the enantioselectivity has been investigated theoretically; first in vanadium‐catalyzed asymmetric epoxidation of allylic alcohols, and then in zinc‐catalyzed direct asymmetric aldol addition. The computational predication is further confirmed experimentally in zinc‐catalyzed direct asymmetric aldol addition by controlling the location of catalytic sites. 相似文献
993.
Yan Tang Hui‐Ran Yang Hui‐Bin Sun Prof. Shu‐Juan Liu Jing‐Xia Wang Prof. Qiang Zhao Dr. Xiang‐Mei Liu Dr. Wen‐Juan Xu Prof. Sheng‐Biao Li Prof. Wei Huang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1311-1319
Biothiols, such as cysteine (Cys) and homocysteine (Hcy), play very crucial roles in biological systems. Abnormal levels of these biothiols are often associated with many types of diseases. Therefore, the detection of Cys (or Hcy) is of great importance. In this work, we have synthesized an excellent “OFF‐ON” phosphorescent chemodosimeter 1 for sensing Cys and Hcy with high selectivity and naked‐eye detection based on an IrIII complex containing a 2,4‐dinitrobenzenesulfonyl (DNBS) group within its ligand. The “OFF‐ON” phosphorescent response can be assigned to the electron‐transfer process from IrIII center and C^N ligands to the DNBS group as the strong electron‐acceptor, which can quench the phosphorescence of probe 1 completely. The DNBS group can be cleaved by thiols of Cys or Hcy, and both the 3M LCT and 3LC states are responsible for the excited‐state properties of the reaction product of probe 1 and Cys (or Hcy). Thus, the phosphorescence is switched on. Based on these results, a general principle for designing “OFF‐ON” phosphorescent chemodosimeters based on heavy‐metal complexes has been provided. Importantly, utilizing the long emission‐lifetime of phosphorescence signal, the time‐resolved luminescent assay of 1 in sensing Cys was realized successfully, which can eliminate the interference from the short‐lived background fluorescence and improve the signal‐to‐noise ratio. As far as we know, this is the first report about the time‐resolved luminescent detection of biothiols. Finally, probe 1 has been used successfully for bioimaging the changes of Cys/Hcy concentration in living cells. 相似文献
994.
995.
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
996.
Wen‐Jing Shi Dr. Mohamed E. El‐Khouly Dr. Kei Ohkubo Prof. Shunichi Fukuzumi Prof. Dennis K. P. Ng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(34):11332-11341
An efficient functional mimic of the photosynthetic antenna‐reaction center has been designed and synthesized. The model contains a near‐infrared‐absorbing aza‐boron‐dipyrromethene (ADP) that is connected to a monostyryl boron‐dipyrromethene (BDP) by a click reaction and to a fullerene (C60) using the Prato reaction. The intramolecular photoinduced energy and electron‐transfer processes of this triad as well as the corresponding dyads BDP‐ADP and ADP‐C60 have been studied with steady‐state and time‐resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge‐separated states. Such calculations show that electron transfer from the singlet excited ADP (1ADP*) to C60 yielding ADP.+‐C60.? is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from 1BDP* to ADP in the dyad BDP‐ADP and electron transfer from 1ADP* to C60 in the dyad ADP‐C60. Sequential energy and electron transfer have also been clearly observed in the triad BDP‐ADP‐C60. By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈1011 s?1). The dynamics of electron transfer through 1ADP* has also been studied by monitoring the formation of C60 radical anion at 1000 nm. A fast charge‐separation process from 1ADP* to C60 has been detected, which gives the relatively long‐lived BDP‐ADP.+C60.? with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge‐separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP‐ADP and ADP‐C60, and the triad BDP‐ADP‐C60 are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems. 相似文献
997.
Tao Zheng Prof. Dr. Juan M. Clemente‐Juan Prof. Dr. Jing Ma Prof. Dr. Lin Dong Dr. Song‐Song Bao Dr. Jian Huang Prof. Dr. Eugenio Coronado Prof. Dr. Li‐Min Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(48):16394-16402
Two cobalt phosphonates, [Co2(2,2′‐bpy)2(H2O)(pbtcH)] ( 1 ) and [Co2(H2O)(pbtcH)(phen)2] ( 2 ; pbtcH5=5‐phosphonatophenyl‐1,2,4‐tricarboxylic acid, 2,2′‐bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline), with layer structures are reported. Compound 1 contains O‐C‐O and O‐P‐O bridged tetramers of Co4, which are further connected by pbtcH4? units to form a layer. In compound 2 , the cobalt tetramers made up of water‐bridged Co2 dimers and O‐P‐O linkages are connected into a layer by pbtcH4? units. Upon dehydration, compounds 1 and 2 experience single‐crystal‐to‐single‐crystal (SC–SC) structural transformations to form [Co2(2,2′‐bpy)2(pbtcH)] ( 1 a ) and [Co2(pbtcH)(phen)2] ( 2 a ), respectively. The process is reversible in each case. Notably, a breathing effect is observed for 1 , accompanied by pore opening and closing due to the reorientation of the coordinated 2,2′‐bpy molecules. The transformation was also monitored by in situ IR measurements. Magnetic studies reveal that antiferromagnetic interactions are mediated between the magnetic centers in compounds 1 and 1 a , whereas ferromagnetic interactions are dominant in compound 2 . 相似文献
998.
Dr. Xiaolong Liang Xiaoda Li Lijia Jing Peng Xue Lingdong Jiang Prof. Qiushi Ren Prof. Dr. Zhifei Dai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(47):16113-16121
This paper reports the facile design and synthesis of a series of lipidic organoalkoxysilanes with different numbers of triethoxysilane headgroups and hydrophobic alkyl chains linked by glycerol and pentaerythritol for the construction of cerasomes with regulated surface siloxane density and controlled release behavior. It was found that the number of triethoxysilane headgroups affected the properties of the cerasomes for encapsulation efficiency, drug loading capacity, and release behavior. For both water‐soluble doxorubicin (DOX) and water‐insoluble paclitaxel (PTX), the release rate from the cerasomes decreased as the number of triethoxysilane headgroups increased. The slower release rate from the cerasomes was attributed to the higher density of the siloxane network on the surface of the cerasomes, which blocks the drug release channels. In contrast to the release results with DOX, the introduction of one more hydrophobic alkyl chain into the cerasome‐forming lipid resulted in a slower release rate of PTX from the cerasomes due to the formation of a more compact cerasome bilayer. An MTT viability assay showed that all of these drug‐loaded cerasomes inhibited proliferation of the HepG2 cancer cell line. The fine tuning of the chemical structure of the cerasome‐forming lipids would foster a new strategy to precisely regulate the release rate of drugs from cerasomes. 相似文献
999.
Wenwen Zhu Yinyin Yu Prof. Dr. Hanmin Yang Li Hua Yunxiang Qiao Xiuge Zhao Prof. Dr. Zhenshan Hou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(6):2059-2066
The use of transition‐metal nanoparticles/ionic liquid (IL) as a thermoregulated and recyclable catalytic system for hydrogenation has been investigated under mild conditions. The functionalized ionic liquid was composed of poly(ethylene glycol)‐functionalized alkylimidazolium as the cation and tris(meta‐sulfonatophenyl)phosphine ([P(C6H4‐m‐SO3)3]3?) as the anion. Ethyl acetate was chosen as the thermomorphic solvent to avoid the use of toxic organic solvents. Due to a cooperative effect regulated by both the cation and anion of the ionic liquid, the nanocatalysts displayed distinguished temperature‐dependent phase behavior and excellent catalytic activity and selectivity, coupled with high stability. In the hydrogenation of α,β‐unsaturated aldehydes, the ionic‐liquid‐stabilized palladium and rhodium nanoparticles exhibited higher selectivity for the hydrogenation of the C?C bonds than commercially available catalysts (Pd/C and Rh/C). We believe that the anion of the ionic liquid, [P(C6H4‐m‐SO3)3]3?, plays a role in changing the surrounding electronic characteristics of the nanoparticles through its coordination capacity, whereas the poly(ethylene glycol)‐functionalized alkylimidazolium cation is responsible for the thermomorphic properties of the nanocatalyst in ethyl acetate. The present catalytic systems can be employed for the hydrogenation of a wide range of substrates bearing different functional groups. The catalysts could be easily separated from the products by thermoregulated phase separation and efficiently recycled ten times without significant changes in their catalytic activity. 相似文献
1000.
Fangyuan Zheng Prof. Fang Zeng Changmin Yu Xianfeng Hou Prof. Shuizhu Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):936-942
Owing to the considerable significance of fluoride anions for health and environmental issues, it is of great importance to develop methods that can rapidly, sensitively and selectively detect the fluoride anion in aqueous media and biological samples. Herein, we demonstrate a robust fluorescent turn‐on sensor for detecting the fluoride ion in a totally aqueous solution. In this study, a biocompatible hydrophilic polymer poly(ethylene glycol) (PEG) is incorporated into the sensing system to ensure water solubility and to enhance biocompatibility. tert‐Butyldiphenylsilyl (TBDPS) groups were then covalently introduced onto the fluorescein moiety, which effectively quenched the fluorescence of the sensor. Upon addition of fluoride ion, the selective fluoride‐mediated cleavage of the Si? O bond leads to the recovery of the fluorescein moiety, resulting in a dramatic increase in fluorescence intensity under visible light excitation. The sensor is responsive and highly selective for the fluoride anion over other common anions; it also exhibits a very low detection limit of 19 ppb. In addition, this sensor is operative in some real samples such as running water, urine, and serum and can accurately detect fluoride ions in these samples. The cytotoxicity of the sensor was determined to be Grade I toxicity according to United States Pharmacopoeia and ISO 10993‐5, suggesting the very low cytotoxicity of the sensor. Moreover, it was found that the senor could be readily internalized by both HeLa and L929 cells and the sensor could be utilized to track fluoride level changes inside the cells. 相似文献