全文获取类型
收费全文 | 25786篇 |
免费 | 4343篇 |
国内免费 | 3994篇 |
专业分类
化学 | 19999篇 |
晶体学 | 423篇 |
力学 | 1273篇 |
综合类 | 299篇 |
数学 | 2940篇 |
物理学 | 9189篇 |
出版年
2024年 | 24篇 |
2023年 | 464篇 |
2022年 | 612篇 |
2021年 | 839篇 |
2020年 | 1042篇 |
2019年 | 1105篇 |
2018年 | 915篇 |
2017年 | 965篇 |
2016年 | 1251篇 |
2015年 | 1268篇 |
2014年 | 1614篇 |
2013年 | 2024篇 |
2012年 | 2427篇 |
2011年 | 2540篇 |
2010年 | 1947篇 |
2009年 | 1836篇 |
2008年 | 1947篇 |
2007年 | 1804篇 |
2006年 | 1685篇 |
2005年 | 1347篇 |
2004年 | 988篇 |
2003年 | 776篇 |
2002年 | 714篇 |
2001年 | 624篇 |
2000年 | 545篇 |
1999年 | 470篇 |
1998年 | 345篇 |
1997年 | 295篇 |
1996年 | 249篇 |
1995年 | 249篇 |
1994年 | 231篇 |
1993年 | 165篇 |
1992年 | 140篇 |
1991年 | 135篇 |
1990年 | 121篇 |
1989年 | 89篇 |
1988年 | 71篇 |
1987年 | 52篇 |
1986年 | 61篇 |
1985年 | 49篇 |
1984年 | 18篇 |
1983年 | 18篇 |
1982年 | 18篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1979年 | 8篇 |
1973年 | 2篇 |
1971年 | 4篇 |
1957年 | 4篇 |
1936年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
41.
Dr. Si-Yong Qin Yan Jiang Dr. Han Sun Han Liu Prof. Ai-Qing Zhang Prof. Xinxiang Lei 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17245-17251
Residual dipolar coupling (RDC), a robust anisotropic NMR parameter for structural elucidation of organic molecules, is only accessible in an anisotropic environment. Herein, we introduce a novel alignment medium based on the molecular self-assembly of oligopeptide amphiphile (OPA). This medium is compatible with different intermediate and polar solvent systems, such as CD3OD, [D6]DMSO, and D2O. The preparation of the OPA-based medium is simple and rapid, while only very weak background signals were observed from OPAs. Furthermore, we show that the purity of OPA has only a minor influence on the quality of the RDC data. These advantages allow RDC measurements of organic molecules with different polarities and solubilities with high efficiency and accuracy. 相似文献
42.
Shuzhen Li Bo Lu Xiaoyu Fang Prof. Dongpeng Yan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(50):22812-22819
Smart molecular crystals with light-driven mechanical responses have received interest owing to their potential uses in molecular machines, artificial muscles, and biomimetics. However, challenges remain in control over both the dynamic photo-mechanical behaviors and static photonic properties of molecular crystals based on the same molecule. Herein, we show the construction of isostructural co-crystals allows their light-induced cracking and jumping behaviors (photosalient effect) to be controlled. Hydrogen-bonded co-crystals from 4-(1-naphthylvinyl)pyridine ( NVP ) with co-formers (tetrafluoro-4-hydroxybenzoic acid ( THA ) and tetrafluorobenzoic acid ( TA )) crystallize as isostructural crystals, but have different static and dynamic photo-mechanical behaviors. These differences are due to alternations in the orientation of NVP and hydrogen-bonding modes of the co-formers. After light activation, the 1D NVP-TA crystal splits and shears off within 1 s. For NVP-THA , its photostability and high quantum yield give novel photonic properties, including low optical waveguide loss, highly polarized anisotropy, and efficient up-conversion fluorescence. 相似文献
43.
Hazardous 4-nitrophenol (4-NP) has created serious threats to humans and the environment; therefore, it is highly desirable to develop a facile and practical method for the monitoring of 4-NP in environment and food. Here, a fluorescence method based on modified polyethyleneimine-capped carbon dots (mPEI-CDs) was developed for sensitive and selective determination of 4-NP in water, fruit, and vegetable samples. First, highly fluorescent mPEI-CDs (quantum yield about 40.3%) were easily synthesized via a one-step hydrothermal method by using novel acetic anhydride modified polyethyleneimine (mPEI) and citric acid as precursors. Compared to the unmodified PEI-CDs, the acetic anhydride mPEI-CDs exhibited excellent fluorescent stability in a wider pH range of 4.0–9.0. Under pH 8.0, a selective determination of 4-NP was achieved based on the inner filter effect (IFE) mechanism. After optimization, good linear relationships between fluorescence intensity function (F0-F)/F0 and the concentration of 4-NP were obtained in ranges of 0.5–10 and 10–100 μM, respectively, while efficiently avoiding the interferences from two other nitrophenol isomers, possible coexisting metal cations and anions in samples. Finally, the proposed approach was successfully applied for the determination of 4-NP in water, honey, strawberry, and tomato samples. 相似文献
44.
PENG Xiaoyu ZHAO Anran HUANG Kelin HU Tingju LIU Buming HUANG Yan CHEN Hailan CHAI Ling LIN Cuiwu 《高等学校化学研究》2020,36(5):795-803
Structural modification of native compounds is an effective way to develop new drugs with increased pharmacological activities and improved material characteristics. In this study, caffeic acid sulphonamide derivatives(CSs) were synthesised by conjugating sulphonamides to the backbone of caffeic acid. The structures of these derivatives were elucidated by means of Fourier transform infrared spectroscopy(FTIR), 1H NMR, 13C NMR, and electrospray ionization mass spectroscopy(ESI-MS). A content determination method was established by ultraviolet detection. The lipophilicity, 2,2-diphenyl-1-picrylhydrazy free radical(DPPH) scavenging capacity, anti-coagulant effects, anti-bacterial activity, cytotoxicity, in vitro anti-proliferative activity against tumour cells, and the ability of the compounds to promote the proliferation of chondrocytes were evaluated. The results indicate that CSs exhibit strong DPPH scavenging activity, high lipophilicity, good anti-coagulant activities, wide anti-bacterial activity range, low cytotoxicity, and an excellent ability to promote chondrocyte proliferation. 相似文献
45.
Yong-Jin Zhao Jian-Ping Ma Jianzhong Fan Yan Geng Yu-Bin Dong 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(6):605-615
The tridentate organic ligand 4,4′,4′′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6,10‐triyl)tribenzoic acid ( H3L ) has been synthesized (as the methanol 1.25‐solvate, C48H39NO6·1.25CH3OH). As a donor–acceptor motif molecule, H3L possess strong intramolecular charge transfer (ICT) fluorescence. Through hydrogen bonds, H3L molecules construct a two‐dimensional (2D) network, which pack together into three‐dimensional (3D) networks with an ABC stacking pattern in the crystalline state. Based on H3L and M(NO3)2 salts (M = Cd and Zn) under solvothermal conditions, two metal–organic frameworks (MOFs), namely, catena‐poly[[triaquacadmium(II)]‐μ‐10‐(4‐carboxyphenyl)‐4,4′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6‐diyl)dibenzoato], [Cd(C48H37NO6)(H2O)3]n, I , and poly[[μ3‐4,4′,4′′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6,10‐triyl)tribenzoato](μ3‐hydroxido)zinc(II)], [Zn2(C48H36NO6)(OH)]n, II , were synthesized. Single‐crystal analysis revealed that both MOFs adopt a 3D structure. In I , partly deprotonated HL 2? behaves as a bidentate ligand to link a CdII ion to form a one‐dimensional chain. In the solid state of I , the existence of weak interactions, such as O—H…O hydrogen bonds and π–π interactions, plays an essential role in aligning 2D nets and 3D networks with AB packing patterns for I . The deprotonated ligand L 3? in II is utilized as a tridentate building block to bind ZnII ions to construct 3D networks, where unusual Zn4O14 clusters act as connection nodes. As a donor–acceptor molecule, H3L exhibits fluorescence with a photoluminescence quantum yield (PLQY) of 70% in the solid state. In comparison, the PL of both MOFs is red‐shifted with even higher PLQYs of 79 and 85% for I and II , respectively. 相似文献
46.
47.
Xiaoke Song Dr. Jun-Peng Wang Dr. Yan Song Prof. Tao Qi Prof. Guo Liang Li 《ChemistryOpen》2020,9(3):272-276
Camouflage and wound healing are two vital functions for cephalopods to survive from dangerous ocean risks. Inspired by these dual functions, herein, we report a new type of healable mechanochromic (HMC) material. The bifunctional HMC material consists of two tightly bonded layers. One layer is composed of polyvinyl alcohol (PVA) and titanium dioxide (TiO2) for shielding. Another layer contains supramolecular hydrogen bonding polymers and fluorochromes for healing. The as-synthesized HMC material exhibits a tunable and reversible mechanochromic function due to the strain-induced surface structure of composite film. The mechanochromic function can be further restored after damage because of the incorporated healable polyurethane. The healing efficiency of the damaged HMC materials can even reach 98 % at 60 °C for 6 h. The bioinspired HMC material is expected to have potential applications in the information encryption and flexible displays. 相似文献
48.
49.
Jihua Liu Huizhu Gan Ting Li Jia Wang Guangguang Du Yang An Xiaojing Yan Cong Geng 《Biomedical chromatography : BMC》2020,34(8):e4856
Ocotillol, pseudo-ginsenoside RT5 (RT5), and pseudo-ginsenoside F11 (PF11) are ocotillol-type saponins that have the same aglycone structure but with different numbers of glucose at the C-6 position. In this study, the metabolites of ocotillol, RT5, and PF11 in rat plasma, stomach, intestine, urine, and feces after oral administration were investigated by ultra-performance liquid chromatography coupled with time-of-flight mass spectrometry. The results showed that RT5 was easily biotransformed into metabolites in vivo, whereas PF11 and RT5 were difficult to be biotransformed. Hydrogenation, dehydrogenation, dehydration, deglycosylation, deoxygenation, hydration, phosphorylation, deoxidation, glucuronidation, and reactions combining amino acid were speculated to be involved in the biotransformation of ocotillol, RT5, and PF11. Based on the structural analysis of metabolites, it was deduced that hydrogenation, dehydration, deoxidation, and reactions combining amino acid occurred on the aglycone structure, whereas deglycosylation, hydration, and phosphorylation occurred on the glycosyl chain. Further, metabolites in plasma, urine, feces, and tissues were different: First, glucuronidation products were found in urine, stomach, intestine, and feces, but not in plasma. Second, the ocotillol prototype was not identified in urine samples. Third, the RT5 prototype was found in stomach, intestine, feces, and urine, but not in plasma. 相似文献
50.
Yangang Cheng Yan Liu Jinyan Tan Yanping Sun Wei Guan Yuan Liu Bingyou Yang Haixue Kuang 《Biomedical chromatography : BMC》2020,34(9):e4881
Our previous work demonstrated that total withanolides of Datura metel L. leaves (TWD) exhibited excellent therapeutic effects on psoriasis. However, current knowledge of its mechanisms is incomplete. In this study, integrated spleen and thymus untargeted metabolomics were used to analyze the changes in endogenous metabolites underlying the immunosuppressive activity of TWD on psoriasis animal models induced by imiquimod. The results suggested that TWD treatment markedly attenuated imiquimod-induced psoriasis and showed significant immunosuppressive activity as evidenced by decreased elevation index of spleen and thymus. Meanwhile, TWD significantly reversed the elevation of immunoregulatory factors, including IL-10, IL-17, IL-22 and IL-23. Multivariate trajectory analysis revealed that TWD treatment could restore the psoriasis-disturbed spleen and thymus metabolite profiles towards the normal metabolic status. A total of 25 and 27 metabolites associated with the immunomodulatory effects for which levels changed markedly upon treatment have been identified in spleen and thymus, respectively. These differential metabolites were mainly involved in amino acid metabolism, nucleotide metabolism, fatty acid metabolism and lipid metabolism. Our investigation provided a holistic view of TWD for intervention in psoriasis through immunoregulation and provided further scientific information in vivo about a clinical value of TWD for psoriasis. 相似文献