全文获取类型
收费全文 | 7580篇 |
免费 | 1583篇 |
国内免费 | 956篇 |
专业分类
化学 | 5429篇 |
晶体学 | 136篇 |
力学 | 446篇 |
综合类 | 96篇 |
数学 | 905篇 |
物理学 | 3107篇 |
出版年
2024年 | 20篇 |
2023年 | 227篇 |
2022年 | 307篇 |
2021年 | 333篇 |
2020年 | 447篇 |
2019年 | 415篇 |
2018年 | 339篇 |
2017年 | 328篇 |
2016年 | 428篇 |
2015年 | 438篇 |
2014年 | 474篇 |
2013年 | 625篇 |
2012年 | 716篇 |
2011年 | 710篇 |
2010年 | 524篇 |
2009年 | 474篇 |
2008年 | 451篇 |
2007年 | 419篇 |
2006年 | 339篇 |
2005年 | 320篇 |
2004年 | 262篇 |
2003年 | 210篇 |
2002年 | 183篇 |
2001年 | 156篇 |
2000年 | 117篇 |
1999年 | 141篇 |
1998年 | 106篇 |
1997年 | 89篇 |
1996年 | 91篇 |
1995年 | 75篇 |
1994年 | 64篇 |
1993年 | 44篇 |
1992年 | 35篇 |
1991年 | 46篇 |
1990年 | 41篇 |
1989年 | 26篇 |
1988年 | 21篇 |
1987年 | 18篇 |
1986年 | 13篇 |
1985年 | 13篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1978年 | 2篇 |
1964年 | 1篇 |
1959年 | 1篇 |
1957年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
931.
Multifunctional Nano‐Bioprobes Based on Rattle‐Structured Upconverting Luminescent Nanoparticles
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Shan Lu Dr. Datao Tu Ping Hu Jin Xu Renfu Li Dr. Meng Wang Dr. Zhuo Chen Prof. Mingdong Huang Prof. Dr. Xueyuan Chen 《Angewandte Chemie (International ed. in English)》2015,54(27):7915-7919
Lanthanide‐doped upconversion nanoparticles (UCNPs) have shown great promise in versatile bioapplications. For the first time, organosilica‐shelled β‐NaLuF4:Gd/Yb/Er nanoprobes with a rattle structure have been designed for dual‐modal imaging and photodynamic therapy (PDT). Benefiting from the unique rattle structure and aromatic framework, these nanoprobes are endowed with a high loading capacity and the disaggregation effect of photosensitizers. After loading of β‐carboxyphthalocyanine zinc or rose Bengal into the nanoprobes, we achieved higher energy transfer efficiency from UCNPs to photosensitizers as compared to those with conventional core–shell structure or with pure‐silica shell, which facilitates a large production of singlet oxygen and thus an enhanced PDT efficacy. We demonstrated the use of these nanoprobes in proof‐of‐concept X‐ray computed tomography (CT) and UC imaging, thus revealing the great potential of this multifunctional material as an excellent nanoplatform for cancer theranostics. 相似文献
932.
Computational Insights into the Charge Relaying Properties of β‐Turn Peptides in Protein Charge Transfers
下载免费PDF全文
![点击此处可从《Chemphyschem》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Ru Zhang Dr. Jinxiang Liu Dr. Hongfang Yang Shoushan Wang Meng Zhang Prof. Dr. Yuxiang Bu 《Chemphyschem》2015,16(2):436-446
Density functional theory calculations suggest that β‐turn peptide segments can act as a novel dual‐relay elements to facilitate long‐range charge hopping transport in proteins, with the N terminus relaying electron hopping transfer and the C terminus relaying hole hopping migration. The electron‐ or hole‐binding ability of such a β‐turn is subject to the conformations of oligopeptides and lengths of its linking strands. On the one hand, strand extension at the C‐terminal end of a β‐turn considerably enhances the electron‐binding of the β‐turn N terminus, due to its unique electropositivity in the macro‐dipole, but does not enhance hole‐forming of the β‐turn C terminus because of competition from other sites within the β‐strand. On the other hand, strand extension at the N terminal end of the β‐turn greatly enhances hole‐binding of the β‐turn C terminus, due to its distinct electronegativity in the macro‐dipole, but does not considerably enhance electron‐binding ability of the N terminus because of the shared responsibility of other sites in the β‐strand. Thus, in the β‐hairpin structures, electron‐ or hole‐binding abilities of both termini of the β‐turn motif degenerate compared with those of the two hook structures, due to the decreased macro‐dipole polarity caused by the extending the two terminal strands. In general, the high polarity of a macro‐dipole always plays a principal role in determining charge‐relay properties through modifying the components and energies of the highest occupied and lowest unoccupied molecular orbitals of the β‐turn motif, whereas local dipoles with low polarity only play a cooperative assisting role. Further exploration is needed to identify other factors that influence relay properties in these protein motifs. 相似文献
933.
Interplay between Cation–π and Coinage‐Metal–Oxygen Interactions: An Ab Initio Study and Cambridge Structural Database Survey
下载免费PDF全文
![点击此处可从《Chemphyschem》网站下载免费的PDF全文](/ch/ext_images/free.gif)
The interplay between cation–π and coinage‐metal–oxygen interactions are investigated in the ternary systems N???PhCCM???O (N=Li+, Na+, Mg2+; M=Ag, Au; O=water, methanol, ethanol). A synergetic effect is observed when cation–π and coinage‐metal–oxygen interactions coexist in the same complex. The cation–π interaction in most triads has a greater enhancing effect on the coinage‐metal–oxygen interaction. This effect is analyzed in terms of the binding distance, interaction energy, and electrostatic potential in the complexes. Furthermore, the formation, strength, and nature of both the cation–π and coinage‐metal–oxygen interactions can be understood in terms of electrostatic potential and energy decomposition. In addition, experimental evidence for the coexistence of both interactions is obtained from the Cambridge Structural Database (CSD). 相似文献
934.
935.
936.
Yang Zhao Yue‐Jiao Zhang Jin‐Hui Meng Shu Chen Rajapandiyan Panneerselvam Chao‐Yu Li Sain Bux Jamali Xia Li Zhi‐Lin Yang Jian‐Feng Li Zhong‐Qun Tian 《Journal of Raman spectroscopy : JRS》2016,47(6):662-667
Silver nanoparticles (Ag NPs) enjoy a reputation as an ultrasensitive substrate for surface‐enhanced Raman spectroscopy (SERS). However, large‐scale synthesis of Ag NPs in a controlled manner is a challenging task for a long period of time. Here, we reported a simple seed‐mediated method to synthesize Ag NPs with controllable sizes from 50 to 300 nm, which were characterized by scanning electron microscopy (SEM) and UV–Vis spectroscopy. SERS spectra of Rhodamine 6G (R6G) from the as‐prepared Ag NPs substrates indicate that the enhancement capability of Ag NPs varies with different excitation wavelengths. The Ag NPs with average sizes of ~150, ~175, and ~225 nm show the highest SERS activities for 532, 633, and 785‐nm excitation, respectively. Significantly, 150‐nm Ag NPs exhibit an enhancement factor exceeding 108 for pyridine (Py) molecules in electrochemical SERS (EC‐SERS) measurements. Furthermore, finite‐difference time‐domain (FDTD) calculation is employed to explain the size‐dependent SERS activity. Finally, the potential of the as‐prepared SERS substrates is demonstrated with the detection of malachite green. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
937.
The DNA structure is an ideal building block for the construction of functional nano-objects. In this direction, metal coordinating base pairs (ligandosides) are an appealing tool for the future specific functionalization of such nano-objects. We present here a study, in which we combine the metal ion coordinating pyrazole ligandoside with the interstrand crosslinking salen ligandoside system. We show that both ligandosides, when combined, are able to create stable multi-copper ion complexing DNA double helix structures in a cooperative fashion. 相似文献
938.
Zhijun Zhang Yijia Guan Meng Li Andong Zhao Jinsong Ren Xiaogang Qu 《Chemical science》2015,6(5):2822-2826
Sandwich ELISA methods have been widely used for biomarker and pathogen detection because of their high specificity and sensitivity. However, the main drawbacks of this assay are the cost, the time-consuming procedure for the isolation of antibodies and their poor stability. To overcome these restrictions, we herein fabricated artificial antibodies based on imprinting technology and developed a sandwich ELISA for pathogen detection. Both the capture and detection antibodies were obtained via an in situ method, with simplicity, rapidity and low cost. The peroxidase mimics, the CeO2 nanoparticles, as signal generators were integrated with the detection antibody. The fabricated artificial antibodies exhibited not only natural antibody-like binding affinities and selectivities, but also superior stability and reusability. The detection limit was about 500 CFU mL–1, which is much lower than that of traditional ELISA methods (104 to 105 CFU mL–1). Furthermore, the capture antibody can disinfect pathogens in situ. 相似文献
939.
Wei Hong Shaoyun Chen Bin Sun Mark A. Arnould Yuezhong Meng Yuning Li 《Chemical science》2015,6(5):3225-3235
This study utilized high temperature NMR and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry to reveal that appreciable amounts of structural defects are present in the diketopyrrolopyrrole (DPP)–quaterthiophene copolymers (PDQT) synthesized by the Stille coupling polymerization with Pd(PPh3)2Cl2, Pd2(dba)3/P(o-tol)3, and Pd(PPh3)4 catalyst systems. It was proposed that these structural defects were produced via homocoupling side reactions of the C–Br bonds and the organostannane species. Model Stille coupling reactions further substantiated that the amount of structural defects are catalyst-dependent following the order of Pd(PPh3)2Cl2 > Pd2(dba)3/P(o-tol)3 > Pd(PPh3)4. To verify the structural assignments, “perfect” structurally regular PDQT polymers were prepared using Yamamoto coupling polymerization. When compared to the structurally regular polymers, the polymers containing defects exhibited notable redshifts in their absorption spectra. Surprisingly, the “perfect” structurally regular polymers showed poor molecular ordering in thin films and very low charge transport performance as channel semiconductors in organic thin film transistors (OTFTs). On the contrary, all the “defected” polymers exhibited much improved molecular ordering and significantly higher charge carrier mobility. 相似文献
940.
Meng Wen Zu‐Ping Xiao Chun‐Ya Wang Xi‐He Huang 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(2):136-139
The title compound, {[Zn4(C8H4O4)3(OH)2(C12H6N2O2)2]·2H2O}n, has been prepared hydrothermally by the reaction of Zn(NO3)2·6H2O with benzene‐1,4‐dicarboxylic acid (H2bdc) and 1,10‐phenanthroline‐5,6‐dione (pdon) in H2O. In the crystal structure, a tetranuclear Zn4(OH)2 fragment is located on a crystallographic inversion centre which relates two subunits, each containing a [ZnN2O4] octahedron and a [ZnO4] tetrahedron bridged by a μ3‐OH group. The pdon ligand chelates to zinc through its two N atoms to form part of the [ZnN2O4] octahedron. The two crystallographically independent bdc2− ligands are fully deprotonated and adopt μ3‐κO:κO′:κO′′ and μ4‐κO:κO′:κO′′:κO′′′ coordination modes, bridging three or four ZnII cations, respectively, from two Zn4(OH)2 units. The Zn4(OH)2 fragment connects six neighbouring tetranuclear units through four μ3‐bdc2− and two μ4‐bdc2− ligands, forming a three‐dimensional framework with uninodal 6‐connected α‐Po topology, in which the tetranuclear Zn4(OH)2 units are considered as 6‐connected nodes and the bdc2− ligands act as linkers. The uncoordinated water molecules are located on opposite sides of the Zn4(OH)2 unit and are connected to it through hydrogen‐bonding interactions involving hydroxide and carboxylate groups. The structure is further stabilized by extensive π–π interactions between the pdon and μ4‐bdc2− ligands. 相似文献