全文获取类型
收费全文 | 102314篇 |
免费 | 18959篇 |
国内免费 | 10956篇 |
专业分类
化学 | 70037篇 |
晶体学 | 1007篇 |
力学 | 6899篇 |
综合类 | 684篇 |
数学 | 12169篇 |
物理学 | 41433篇 |
出版年
2024年 | 119篇 |
2023年 | 2231篇 |
2022年 | 2313篇 |
2021年 | 3251篇 |
2020年 | 4401篇 |
2019年 | 3997篇 |
2018年 | 3589篇 |
2017年 | 3183篇 |
2016年 | 5130篇 |
2015年 | 4861篇 |
2014年 | 5923篇 |
2013年 | 7672篇 |
2012年 | 9381篇 |
2011年 | 9903篇 |
2010年 | 6525篇 |
2009年 | 6352篇 |
2008年 | 6765篇 |
2007年 | 5998篇 |
2006年 | 5698篇 |
2005年 | 4590篇 |
2004年 | 3624篇 |
2003年 | 2766篇 |
2002年 | 2423篇 |
2001年 | 2160篇 |
2000年 | 1907篇 |
1999年 | 2136篇 |
1998年 | 1846篇 |
1997年 | 1800篇 |
1996年 | 1805篇 |
1995年 | 1581篇 |
1994年 | 1410篇 |
1993年 | 1195篇 |
1992年 | 1063篇 |
1991年 | 959篇 |
1990年 | 790篇 |
1989年 | 637篇 |
1988年 | 450篇 |
1987年 | 389篇 |
1986年 | 380篇 |
1985年 | 324篇 |
1984年 | 181篇 |
1983年 | 154篇 |
1982年 | 135篇 |
1981年 | 77篇 |
1980年 | 56篇 |
1979年 | 18篇 |
1977年 | 5篇 |
1975年 | 6篇 |
1969年 | 4篇 |
1957年 | 38篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Core–Shell Carbon‐Coated CuO Nanocomposites: A Highly Stable Electrode Material for Supercapacitors and Lithium‐Ion Batteries 下载免费PDF全文
Dr. Tao Wen Dr. Xi‐Lin Wu Dr. Shouwei Zhang Prof. Xiangke Wang Prof. An‐Wu Xu 《化学:亚洲杂志》2015,10(3):595-601
Herein we present a simple method for fabricating core–shell mesostructured CuO@C nanocomposites by utilizing humic acid (HA) as a biomass carbon source. The electrochemical performances of CuO@C nanocomposites were evaluated as an electrode material for supercapacitors and lithium‐ion batteries. CuO@C exhibits an excellent capacitance of 207.2 F g?1 at a current density of 1 A g?1 within a potential window of 0–0.46 V in 6 M KOH solution. Significantly, CuO electrode materials achieve remarkable capacitance retentions of approximately 205.8 F g?1 after 1000 cycles of charge/discharge testing. The CuO@C was further applied as an anode material for lithium‐ion batteries, and a high initial capacity of 1143.7 mA h g?1 was achieved at a current density of 0.1 C. This work provides a facile and general approach to synthesize carbon‐based materials for application in large‐scale energy‐storage systems. 相似文献
992.
Synthesis of Nanoporous Ni‐Co Mixed Oxides by Thermal Decomposition of Metal‐Cyanide Coordination Polymers 下载免费PDF全文
Mohamed B. Zakaria Dr. Ming Hu Dr. Malay Pramanik Dr. Cuiling Li Dr. Jing Tang Prof. Ali Aldalbahi Prof. Saad M. Alshehri Dr. Victor Malgras Prof. Yusuke Yamauchi 《化学:亚洲杂志》2015,10(7):1541-1545
A straightforward strategy to prepare nanoporous metal oxides with well‐defined shapes is highly desirable. Through thermal treatment and a proper selection of metal‐cyanide coordination polymers, nanoporous nickel‐cobalt mixed oxides with different shapes (i.e., flakes and cubes) can be easily prepared. Our nanoporous materials demonstrate high electrocatalytic activity for oxygen evolution reaction. 相似文献
993.
Luminescent Nanofibers Fabricated from Phenanthroimidazole Derivatives by Organogelation: Fluorescence Response towards Acid with High Performance 下载免费PDF全文
Jiang Peng Dr. Jingbo Sun Peng Gong Dr. Pengchong Xue Zhenqi Zhang Gonghe Zhang Prof. Ran Lu 《化学:亚洲杂志》2015,10(8):1717-1724
Nanofibers based on phenanthroimidazole derivatives PCC , PDC , and PSC were fabricated by organogelation processes, and their fluorescence sensory properties towards acid were investigated. It was found that the emission of PCC in the nanofiber‐based film could be quenched significantly upon exposure to gaseous TFA due to the formation of protonated PCC , in which ICT (intramolecular charge transfer) would occur. On the other hand, TFA vapor led to the emitting colors of PDC and PSC in the nanofiber‐based films to turn to yellow and green from sky blue and blue, respectively. Additionally, we found that the decay times of PCC were 0.1 s and 1.9 s in probing the saturated vapor of TFA in nanofiber‐based film and in spin‐coated film, respectively. The results suggested that the high surface‐to‐volume ratio and large interspace in the nanofiber‐based networks favored the enhanced adsorption, accumulation, and diffusion of gaseous molecules, resulting in such a high performance. 相似文献
994.
995.
Preparation and Electrochemical Properties of Tin–Iron–Carbon Nanocomposite as the Anode of Lithium‐Ion Batteries 下载免费PDF全文
Dr. Xu Yang Dr. Rongyu Zhang Dr. Xiaofei Bie Prof. Chunzhong Wang Malin Li Dr. Nan Chen Prof. Yingjin Wei Prof. Gang Chen Dr. Fei Du 《化学:亚洲杂志》2015,10(11):2460-2466
Tin–iron–carbon nanocomposite is successfully prepared by a sol–gel method followed by a chemical vapor deposition (CVD) process with acetylene gas as the carbon source. The structural properties, morphology, and electrochemical performances of the nanocomposite are comprehensively studied in comparison with those properties of tin–carbon and iron–carbon nanocomposites. Sheet‐like carbon architecture and different carbon contents are induced thanks to the catalytic effect of iron during CVD. Among three nanocomposites, tin–iron–carbon demonstrates the highest reversible capacity of 800 mA h g?1 with 96.9 % capacity retention after 50 cycles. It also exhibits the best rate capability with a discharge capacity of 420 mA h g?1 at a current density of 1000 mA g?1. This enhanced performance is strongly related to the carbon morphology and content, which can not only accommodate the large volume change, but also improve the electronic conductivity of the nanocomposite. Hence, the tin–iron–carbon nanocomposite is expected to be a promising anode for lithium‐ion batteries. 相似文献
996.
The evolution of the intracellular caspase family is crucial in cell apoptosis. To evaluate this process, a universal platform of in situ activation and monitoring of the evolution of intracellular caspase is designed. Using well-known gold nanostructure as a model of both nanocarrier and matter inducing the cell apoptosis for photothermal therapy, a nanoprobe is prepared by assembly of two kinds of dye-labelled peptides specific to upstream caspase-9 and downstream caspase-3 as the signal switch, and folic acid as a targeting moiety. The energy transfer from dyes to the gold nanocarrier at two surface plasmon resonance absorption wavelengths leads to their fluorescence quenching. Upon endocytosis of the nanoprobe to perform the therapy against cancer cells, the peptides are successively cleaved by intracellular caspase activation with the evolution from upstream to downstream, which lights up the fluorescence of the dyes sequentially, and can be used to quantify both caspase-9 and caspase-3 activities in cancer cells and to monitor their evolution in living mice. The recovered fluorescence could also be used to assess therapeutic efficiency. This work provides a novel powerful tool for studying the evolution of the intracellular caspase family and elucidating the biological roles of caspases in cancer cell apoptosis. 相似文献
997.
Colibactin represents a structurally undefined class of bacterial genotoxin inducing DNA damage and genomic instability in mammalian cells, thus promoting tumour development and exacerbating lymphopenia in animal models. The colibactin biosynthetic gene cluster (clb) has been known for ten years and it encodes a hybrid nonribosomal peptide synthetase (NRPS)/polyketide synthase (PKS) assembly line. Nevertheless, the final chemical product(s) remain unknown. Previously, we and others reported several colibactin pathway-related metabolites including N-myristoyl-d-asparagine (1) as part of a prodrug precursor that is cleaved from the putative precolibactin to form active colibactin by the peptidase ClbP. Herein, we report two new colibactin pathway-related metabolites (2 and 3) isolated from a clbP mutant of the probiotic E. coli Nissle 1917 strain. Their structures were established by HRMS and NMR. Compound 2 shows an additional 4-aminopenatanoic acid moiety with respect to 1, while 3 is characterized by the presence of an unusual 7-methyl-4-azaspiro[2.4]hept-6-en-5-one residue. Moreover, we propose the biosynthetic pathway towards both intermediates on the basis of extensive gene inactivation and feeding experiments. The identification of 2 and 3 provides further insight into colibactin biosynthesis including the involvement and formation of a rare 1-aminocyclopropanecarboxylic acid unit. Thus, our work establishes additional steps of the pathway forming the bacterial genotoxin colibactin. 相似文献
998.
Dali Wang Chunlai Tu Yue Su Chuan Zhang Udo Greiser Xinyuan Zhu Deyue Yan Wenxin Wang 《Chemical science》2015,6(7):3775-3787
Despite of great advances of phospholipids and liposomes in clinical therapy, very limited success has been achieved in the preparation of smart phospholipids and controlled-release liposomes for in vivo drug delivery and clinical trials. Here we report a supramolecular approach to synthesize novel supramolecularly engineered phospholipids based on complementary hydrogen bonding of nucleosides, which greatly reduces the need of tedious chemical synthesis, including reducing the strict requirements for multistep chemical reactions, and the purification of the intermediates and the amount of waste generated relative more traditional approaches. These upgraded phospholipids self-assemble into liposome-like bilayer structures in aqueous solution, exhibiting fast stimuli-responsive ability due to the hydrogen bonding connection. In vitro and in vivo evaluations show the resulted supramolecular liposomes from nucleoside phospholipids could effectively transport drug into tumor tissue, rapidly enter tumor cells, and controllably release their payload in response to an intracellular acidic environment, thus resulting in a much higher antitumor activity than conventional liposomes. The present supramolecularly engineered phospholipids represent an important evolution in comparison to conventional covalent-bonded phospholipid systems. 相似文献
999.
Xu Zhang Lei Zhang Meng‐Jie Wang Kou‐Lin Zhang 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(9):776-782
Two new coordination polymers (CPs) formed from 5‐iodobenzene‐1,3‐dicarboxylic acid (H2iip) in the presence of the flexible 1,4‐bis(1H‐imidazol‐1‐yl)butane (bimb) auxiliary ligand, namely poly[[μ2‐1,4‐bis(1H‐imidazol‐1‐yl)butane‐κ2N3:N3′](μ3‐5‐iodobenzene‐1,3‐dicarboxylato‐κ4O1,O1′:O3:O3′)cobalt(II)], [Co(C8H3IO4)(C10H14N4)]n or [Co(iip)(bimb)]n, (1), and poly[[[μ2‐1,4‐bis(1H‐imidazol‐1‐yl)butane‐κ2N3:N3′](μ2‐5‐iodobenzene‐1,3‐dicarboxylato‐κ2O1:O3)zinc(II)] trihydrate], {[Zn(C8H3IO4)(C10H14N4)]·3H2O}n or {[Zn(iip)(bimb)]·3H2O}n, (2), were synthesized and characterized by FT–IR spectroscopy, thermogravimetric analysis (TGA), solid‐state UV–Vis spectroscopy, single‐crystal X‐ray diffraction analysis and powder X‐ray diffraction analysis (PXRD). The iip2− ligand in (1) adopts the (κ1,κ1‐μ2)(κ1, κ1‐μ1)‐μ3 coordination mode, linking adjacent secondary building units into a ladder‐like chain. These chains are further connected by the flexible bimb ligand in a trans–trans–trans conformation. As a result, a twofold three‐dimensional interpenetrating α‐Po network is formed. Complex (2) exhibits a two‐dimensional (4,4) topological network architecture in which the iip2− ligand shows the (κ1)(κ1)‐μ2 coordination mode. The solid‐state UV–Vis spectra of (1) and (2) were investigated, together with the fluorescence properties of (2) in the solid state. 相似文献
1000.
Qingquan Lu Jian Zhang Pan Peng Guanghui Zhang Zhiliang Huang Hong Yi Jeffrey T. Miller Aiwen Lei 《Chemical science》2015,6(8):4851-4854
An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(ii) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(i) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(ii) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfones are synthesized with good to excellent yields under mild conditions. 相似文献