全文获取类型
收费全文 | 6677篇 |
免费 | 1042篇 |
国内免费 | 667篇 |
专业分类
化学 | 4903篇 |
晶体学 | 56篇 |
力学 | 320篇 |
综合类 | 15篇 |
数学 | 737篇 |
物理学 | 2355篇 |
出版年
2024年 | 23篇 |
2023年 | 179篇 |
2022年 | 286篇 |
2021年 | 288篇 |
2020年 | 312篇 |
2019年 | 295篇 |
2018年 | 243篇 |
2017年 | 235篇 |
2016年 | 365篇 |
2015年 | 344篇 |
2014年 | 393篇 |
2013年 | 473篇 |
2012年 | 607篇 |
2011年 | 640篇 |
2010年 | 409篇 |
2009年 | 411篇 |
2008年 | 400篇 |
2007年 | 380篇 |
2006年 | 313篇 |
2005年 | 282篇 |
2004年 | 192篇 |
2003年 | 179篇 |
2002年 | 154篇 |
2001年 | 111篇 |
2000年 | 96篇 |
1999年 | 114篇 |
1998年 | 95篇 |
1997年 | 89篇 |
1996年 | 83篇 |
1995年 | 70篇 |
1994年 | 60篇 |
1993年 | 47篇 |
1992年 | 58篇 |
1991年 | 38篇 |
1990年 | 27篇 |
1989年 | 28篇 |
1988年 | 18篇 |
1987年 | 12篇 |
1986年 | 8篇 |
1985年 | 11篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有8386条查询结果,搜索用时 0 毫秒
991.
New Cu(I) Coordination Complexes Based on Tetrathiafulvalene Substituted Triazol‐pyridine Ligand: Synthesis,Properties and Theoretical Studies 下载免费PDF全文
Two Cu(I) complexes based on the thioethyl‐bridged triazol‐pyridine ligand with tetrathiafulvalene unit (TTF‐TzPy, L ), [Cu(I)(Binap)(L)]BF4 ( 5 , Binap=2,2’‐bis(diphenylphosphino)‐1,1’‐binaphthyl) and [Cu(I)(Xantphos)(L)]BF4 ( 6 , Xantphos=9,9‐dimethyl‐4,5‐bis(diphenylphosphino)‐xanthene), have been synthesized. All new compounds are characterized by elemental analyses, 1H NMR and mass spectroscopies. The complex 5 has been determined by X‐ray structure analyses which shows that the central copper (I) ion assumes distorted tetrahedral geometry. The photophysical, computational and electrochemical properties of L and 5 ‐ 6 have been investigated. The most representative molecular orbital energy‐level diagrams and the spin‐allowed singlet? singlet electronic transitions of the three compounds have been calculated with density functional theory (DFT) and time‐dependent DFT (TD‐DFT). The luminescence bands of Cu(I) complexes 5 ‐ 6 have been assigned as mixed intraligand and metal‐to‐ligand charge transfer 3(MLCT+π→π*) transitions through analysis of the photophysical properties and DFT calculations. The electrochemical studies reveal that 5 ‐ 6 undergo reversible TTF/TTF+?/TTF2+ redox processes and one irreversible Cu+→Cu2+ oxidation process. 相似文献
992.
SDS‐PAGE represents a quick and simple method for qualitative and quantitative analysis of protein and protein‐containing conjugates, mostly pegylated proteins. PEG‐maleimide (MAL) is frequently used to site‐specifically pegylate therapeutic proteins via free cysteine residue by forming a thiosuccinimide structure for pursuing homogeneous products. The C–S linkage between protein and PEG‐MAL is generally thought to be relatively stable. However, loss of intact PEG chain in routine SDS‐PAGE analysis of PEG‐maleimide modified protein was observed. It is a thiol‐independent thioether cleavage and the shedding of PEG chain exclusively happens to PEG‐MAL modified conjugates although PEG‐vinylsulfone conjugates to thiol‐containing proteins also through a C–S linkage. Cleavage kinetics of PEG40k‐MAL modified ciliary neurotrophic factor showed this kind of degradation could immediately happen even in 1 min incubation at high temperature and could be detected at physiological temperature and pH, although the rate was relatively slow. This may provide another degradation route for maleimide‐thiol conjugate irrespective of reactive thiol, although the specific mechanism is still not very clear for us. It would also offer a basis for accurate characterization of PEG‐MAL modified protein/peptide by SDS‐PAGE analysis. 相似文献
993.
Multicomponent Self‐Assembly with a Shape‐Persistent N‐Heterotriangulene Macrocycle on Au(111) 下载免费PDF全文
Kang Cui Dr. Florian Schlütter Dr. Oleksandr Ivasenko Dr. Milan Kivala Dr. Matthias G. Schwab Dr. Shern‐Long Lee Dr. Stijn F. L. Mertens Dr. Kazukuni Tahara Prof. Yoshito Tobe Prof. Klaus Müllen Dr. Kunal S. Mali Prof. Steven De Feyter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1652-1659
Multicomponent network formation by using a shape‐persistent macrocycle ( MC6 ) at the interface between an organic liquid and Au(111) surface is demonstrated. MC6 serves as a versatile building block that can be coadsorbed with a variety of organic molecules based on different types of noncovalent interactions at the liquid–solid interface. Scanning tunneling microscopy (STM) reveals the formation of crystalline bicomponent networks upon codeposition of MC6 with aromatic molecules, such as fullerene (C60) and coronene. Tetracyanoquinodimethane, on the other hand, was found to induce disorder into the MC6 networks by adsorbing on the rim of the macrocycle. Immobilization of MC6 itself was studied in two different noncovalently assembled host networks. MC6 assumed a rather passive role as a guest and simply occupied the host cavities in one network, whereas it induced a structural transition in the other. Finally, the central cavity of MC6 was used to capture C60 in a complex three‐component system. Precise immobilization of organic molecules at discrete locations within multicomponent networks, as demonstrated here, constitutes an important step towards bottom‐up fabrication of functional surface‐based nanostructures. 相似文献
994.
Tuning the Basicity of Cyano‐Containing Ionic Liquids to Improve SO2 Capture through Cyano–Sulfur Interactions 下载免费PDF全文
Dr. Guokai Cui Fengtao Zhang Xiuyuan Zhou Prof. Haoran Li Prof. Jianji Wang Prof. Congmin Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5632-5639
A new approach has been developed to improve SO2 sorption by cyano‐containing ionic liquids (ILs) through tuning the basicity of ILs and cyano–sulfur interaction. Several kinds of cyano‐containing ILs with different basicity were designed, prepared, and used for SO2 capture. The interaction between these cyano‐containing ILs and SO2 was investigated by FTIR and NMR methods. Spectroscopic investigations and quantum chemical calculations showed that dramatic effects on SO2 capacity originate from the basicity of the ILs and enhanced cyano–sulfur interaction. Furthermore, the captured SO2 was easy to release by heating or bubbling N2 through the ILs. This efficient and reversible process, achieved by tuning the basicity of ILs, is an excellent alternative to current technologies for SO2 capture. 相似文献
995.
Fluorescent In Situ Targeting Probes for Rapid Imaging of Ovarian‐Cancer‐Specific γ‐Glutamyltranspeptidase 下载免费PDF全文
Feiyi Wang Prof. Ying Zhu Li Zhou Liang Pan Zhifen Cui Qiang Fei Sihang Luo Dr. Dun Pan Prof. Rui Wang Prof. Chunchang Zhao Prof. He Tian Prof. Chunhai Fan 《Angewandte Chemie (International ed. in English)》2015,54(25):7349-7353
γ‐Glutamyltranspeptidase (GGT) is a tumor biomarker that selectively catalyzes the cleavage of glutamate overexpressed on the plasma membrane of tumor cells. Here, we developed two novel fluorescent in situ targeting (FIST) probes that specifically target GGT in tumor cells, which comprise 1) a GGT‐specific substrate unit (GSH), and 2) a boron–dipyrromethene (BODIPY) moiety for fluorescent signalling. In the presence of GGT, sulfur‐substituted BODIPY was converted to amino‐substituted BODIPY, resulting in dramatic fluorescence variations. By exploiting this enzyme‐triggered photophysical property, we employed these FIST probes to monitor the GGT activity in living cells, which showed remarkable differentiation between ovarian cancer cells and normal cells. These probes represent two first‐generation chemodosimeters featuring enzyme‐mediated rapid, irreversible aromatic hydrocarbon transfer between the sulfur and nitrogen atoms accompanied by switching of photophysical properties. 相似文献
996.
Wrinkled Graphene Monoliths as Superabsorbing Building Blocks for Superhydrophobic and Superhydrophilic Surfaces 下载免费PDF全文
Li‐Bing Lv Tian‐Lu Cui Bing Zhang Hong‐Hui Wang Prof. Xin‐Hao Li Prof. Jie‐Sheng Chen 《Angewandte Chemie (International ed. in English)》2015,54(50):15165-15169
Superhydrophobic and superhydrophilic surfaces are of great interest because of a large range of applications, for example, as antifogging and self‐cleaning coatings, as antibiofouling paints for boats, in metal refining, and for water–oil separation. An aqueous ink based on three‐dimensional graphene monoliths (Gr) can be used for constructing both superhydrophobic and superhydrophilic surfaces on arbitrary substrates with different surficial structures from the meso‐ to the macroscale. The surface wettability of a Gr‐coated surface mainly depends on which additional layers (air for a superhydrophobic surface and water for a superhydrophilic surface) are adsorbed on the surface of the graphene sheets. Switching a Gr‐coated surface between being superhydrophobic and superhydrophilic can thus be easily achieved by drying and prewetting with ethanol. The Gr‐based superhydrophobic membranes or films should have great potential as efficient separators for fast and gravity‐driven oil–water separation. 相似文献
997.
One Step Preparation of Reduced Graphene Oxide/Pd–Fe3O4@Polypyrrole Composites and Their Application in Catalysis 下载免费PDF全文
Dr. Tongjie Yao Hao Wang Quan Zuo Dr. Jie Wu Dr. Xiao Zhang Dr. Fang Cui Dr. Tieyu Cui 《化学:亚洲杂志》2015,10(9):1940-1947
The simple preparation of catalysts with superior catalytic activity and good reusability is highly desirable. Herein, we report a novel strategy to construct reduced graphene oxide (rGO)/Pd–Fe3O4@polypyrrole (PPy) catalysts with Pd and Fe3O4 nanoparticles anchored on a rGO nanosheet surface and wrapped in a PPy shell. The synthesis and assembly of both the Pd and Fe3O4 nanoparticles, the preparation of the PPy layer, and the reduction of graphene oxide nanosheets were finished in one step. In the system, the PPy layer not only prevented aggregation of Pd and Fe3O4 nanoparticles, but also generated a synergistic effect with precursor Pd2+ ions, which led to a high dispersity of as‐prepared Pd nanoparticles. Although the procedure was simplified to one step, the catalytic activity and reusability were not sacrificed. In the reduction of 4‐nitrophenol, their catalytic performance was better than that in recent reports. Moreover, the catalysts showed good reusability owing to their magnetic properties. 相似文献
998.
纳米TiO2修饰的La0.6Sr0.4Co0.2Fe0.8O3-δ(LSCF)阴极被直接应用于YSZ电解质电池上. TiO2可阻止LSCF和YSZ间的化学反应,抑制SrZrO3的形成. LSCF-0.25 wt% TiO2阴极电池在0.7 V和600°C下的电流密度是LSCF阴极电池的1.6倍.电化学阻抗谱结果表明, TiO2修饰显著加快了氧离子注入电解质的过程,这可能与TiO2抑制了阴极/电解质界面处高电阻SrZrO3层的形成有关.本文为在ZrO2基电解质上使用高性能的(La,Sr)(Co,Fe)O3阴极材料提供了一种简单有效的方法. 相似文献
999.
利用半导体光催化技术将太阳能转化为化学能或直接降解和矿化有机污染物,是解决能源短缺和环境污染等问题的有效途径。聚合物类石墨相氮化碳(g-C3N4)具有类似石墨烯的结构,由于其优异的化学稳定性和独特的电子能带结构,可作为太阳能转化、环境污染物降解的催化剂而得到了广泛关注。g-C3N4制备原料便宜易得、制备方法简单,可作为廉价、稳定、不含金属的可见光光催化剂应用于光催化降解污染物、水分解制氢制氧及有机合成领域。然而光生电荷易复合,使得g-C3N4的催化活性还不能满足大规模应用的需求。本文针对g-C3N4光催化活性的提高,综述了国内外在g-C3N4复合改性方面的重要研究进展,如金属/非金属掺杂、半导体复合、表面金属沉积等,并讨论了复合物的催化机理。 相似文献
1000.
A facile, efficient and environment friendly method is established to prepare poly(vinyl alcohol)(PVA) based graphene oxide-montmorillonite(GO-MMT) nanocomposites in aqueous media. GO-MMT nanohybrid is obtained by the combination of GO and MMT in water without any reducing or stabilizing agents. The formation of GO-MMT nanohybrid is due to the hydrogen bonding and crosslinking effects. The sodium ions within MMT sheets act as crosslinkers between GO sheets and MMT platelets. The resultant nanocomposites are characterized by means of X-ray diffraction(XRD), scanning electron microscopy(SEM), differential scanning calorimetry(DSC), thermogravimetric analysis(TGA) and mechanical testing. Compared to that of pure PVA, PVA nanocomposites show enhanced thermal stabilities and mechanical properties, which results from strong interfacial adhesion of the nanoadditives in PVA matrix. The further increase in the tensile strength and modulus results from strong interaction between PVA chains and layered GO-MMT as well as good mechanical properties of GO-MMT hybrid, compared to PVA/GO and PVA/MMT nanocompsoites. 相似文献