全文获取类型
收费全文 | 8761篇 |
免费 | 1470篇 |
国内免费 | 782篇 |
专业分类
化学 | 6139篇 |
晶体学 | 79篇 |
力学 | 490篇 |
综合类 | 51篇 |
数学 | 1045篇 |
物理学 | 3209篇 |
出版年
2024年 | 9篇 |
2023年 | 152篇 |
2022年 | 183篇 |
2021年 | 239篇 |
2020年 | 350篇 |
2019年 | 359篇 |
2018年 | 279篇 |
2017年 | 261篇 |
2016年 | 358篇 |
2015年 | 395篇 |
2014年 | 483篇 |
2013年 | 669篇 |
2012年 | 777篇 |
2011年 | 779篇 |
2010年 | 570篇 |
2009年 | 537篇 |
2008年 | 608篇 |
2007年 | 501篇 |
2006年 | 499篇 |
2005年 | 402篇 |
2004年 | 365篇 |
2003年 | 266篇 |
2002年 | 259篇 |
2001年 | 190篇 |
2000年 | 133篇 |
1999年 | 141篇 |
1998年 | 136篇 |
1997年 | 152篇 |
1996年 | 143篇 |
1995年 | 105篇 |
1994年 | 114篇 |
1993年 | 85篇 |
1992年 | 56篇 |
1991年 | 49篇 |
1990年 | 57篇 |
1989年 | 39篇 |
1988年 | 27篇 |
1987年 | 17篇 |
1986年 | 28篇 |
1985年 | 25篇 |
1984年 | 20篇 |
1983年 | 16篇 |
1982年 | 11篇 |
1981年 | 13篇 |
1980年 | 15篇 |
1979年 | 10篇 |
1978年 | 22篇 |
1977年 | 10篇 |
1976年 | 13篇 |
1974年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
1.
A numerical model was developed and validated to investigate the fluid–structure interactions between fully developed pipe flow and core–shell-structured microcapsule in a microchannel. Different flow rates and microcapsule shell thicknesses were considered. A sixth-order rotational symmetric distribution of von Mises stress over the microcapsule shell can be observed on the microcapsule with a thinner shell configuration, especially at higher flow rate conditions. It is also observed that when being carried along in a fully developed pipe flow, the microcapsule with a thinner shell tends to accumulate stress at a higher rate compared to that with a thicker shell. In general, for the same microcapsule configuration, higher flow velocity would induce a higher stress level over the microcapsule shell. The deformation gradient was used to capture the microcapsule's deformation in the present study. The effect of Young's modulus on the microcapsule shell on the microcapsule deformation was investigated as well. Our findings will shed light on the understanding of the stability of core–shell-structured microcapsule when subjected to flow-induced shear stress in a microfluidic system, enabling a more exquisite control over the breakup dynamics of drug-loaded microcapsule for biomedical applications. 相似文献
2.
Fu Xibiao Liu Jun Ren Zheng Zhang Siqin Xiao Fangzhu Peng Guowen 《Journal of Radioanalytical and Nuclear Chemistry》2022,331(2):889-902
Journal of Radioanalytical and Nuclear Chemistry - Metal-organic frameworks (MOFs) MIL-101(Cr)-PMIDA with phosphate groups were prepared for the adsorption of U(VI). The morphology and structure of... 相似文献
3.
设计合成了3种基于香豆素骨架的紫外-可见发光二极管(UV/Vis-LED)可激发的新型吡啶鎓盐光引发剂, 并研究了这3种香豆素吡啶鎓盐的构效关系及其作为单组分自由基光引发剂在丙烯酸酯体系中的光引发活性. 紫外-可见吸收光谱分析表明, 这3种香豆素吡啶鎓盐在300~400 nm区域有较强吸收. 在LED@365 nm和LED@405 nm光源辐照下, 研究了3种光引发剂的稳态光解和光聚合动力学. 研究表明, 这3种香豆素吡啶鎓盐光引发剂在相应光辐照下都具有较好的光解速率. 此外, 3种光引发剂对丙烯酸酯都具有较好的引发活性. 构效关系研究表明, 吡啶环4号位引入推电子的甲氧基会使其引发丙烯酸酯单体聚合的活性降低; 而引入吸电子的乙酰基会使其引发丙烯酸酯单体聚合的活性增加. 差示扫描量热(DSC)实验表明, 此类吡啶鎓盐光引发剂具有较好的热稳定性. 当3种光引发剂与丙烯酸单体混合时可提升体系的热稳定性; 通过电子自旋共振(ESR)证明了活性物种的产生, 并对该类引发剂的引发机理进行了探讨. 相似文献
4.
Yingying Bi Lijun Han Fayi Qin Shuangyu Song Xinru Lv Qin Dong Chengkui Qiao Bo Ren 《Biomedical chromatography : BMC》2022,36(5):e5342
Trifloxystrobin (TFS) is a widely used strobilurin fungicide and its residues accumulating in animal-derived food could result in potential harm to consumers. By optimization of extraction solvents and cleanup sorbents, a residue analysis method for TFS and its metabolite trifloxystrobin acid (TFSA) was established in milk, eggs and pork based on QuEChERS sample preparation and LC–MS/MS. The calibration curves exhibited good linearity with determination coefficients (R2) >0.9930 over the range of 0.5–250 ng/ml for both TFS and TFSA. The recoveries of the two analytes were 81–100% with RSD 3–10% and 76–96% with RSD 2–13%, respectively. The limit of quantification (LOQ) was 1 ng/g for both analytes. The milk, egg and pork samples, 30 each, were collected from the 30 main producing regions in China, and residues of TFS and TFSA were analyzed. The concentrations of both analytes were lower than the corresponding LOQs and maximum residue limits. Long-term dietary risk assessment showed that the hazard quotients were 0.001–0.003%, indicating an absence of unacceptable risks in milk, eggs and pork to the health of common consumers in China. 相似文献
5.
ZIF-8是一种Zn基金属有机骨架材料, 可以吸附丙酮气体从而作为电容式丙酮传感器的气敏材料, 然而ZIF-8的传统使用形式为粉末态, 这导致其不能成为具备柔性的整体, 从而限制了传感器的柔性. 结合包埋种子和二次生长法将ZIF-8与纳米纤维结合成纤维型柔性材料, 并将其作为气敏层制备了柔性电容式丙酮气体传感器. 该传感器在9种常见挥发性有机化合物中表现出良好的选择性, 对250~2000 cm3/m3的丙酮气体具有灵敏的响应、良好的循环响应及长期稳定性. 值得注意的是该柔性传感器不仅在室温下进行传感, 而且在弯折180°的状态下对丙酮气体的响应值与不弯折(0°)状态下几乎一致, 在200次以内的180°弯折-恢复后同样表现出了传感性能的稳定, 表明了其在柔性传感器方面的潜力. 相似文献
6.
Yao Wen Chen Yangfan Li Jiangling Yang Jian Ren Shan Liu Weizao Liu Qingcai 《Research on Chemical Intermediates》2022,48(5):1813-1829
Research on Chemical Intermediates - Industrial wastewater is becoming a universal environmental problem, wherein toxic organic compounds are important sources of pollution. For the degradation... 相似文献
7.
Sicheng Yang Dr. Jiaoyu Ren Prof. Hong Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(7):e202103867
The drug delivery system based on nano/micromotors has become a research hot spot in recent years. However, naked micromotors may be ruptured or passivated under the complex biological environment, which will result in the leakage of drugs in advance or limited self-propulsion performance. Herein, an injectable micromotor@hydrogel drug delivery system to protect micromotors from the external environment is proposed. The micromotors were prepared through layer-by-layer assembly technology. The asymmetric decomposition of hydrogen peroxide catalyzed by the locally distributed platinum nanoparticles enabled efficient propulsion of the micromotors in low concentration of hydrogen peroxide. In order to protect micromotors, they were loaded into the Schiff base hydrogel. The micromotor@hydrogel system can be injected directly into the lesion to release micromotors in response to the environment, reducing external influence on micromotors and improving the sustained-release effect. Erythromycin (Ery) loaded into the micromotors and the micromotor@hydrogel system demonstrated excellent antibacterial effect. Micromotors released from the hydrogel underwent enhanced diffusion in the surroundings of bacteria without addition of exogenous hydrogen peroxide, which was manifested by their appearance in edge of the inhibition zone. The proposed micromotor@hydrogel drug delivery system offers a new strategy for the treatment of bacterial infections. 相似文献
8.
Dr. Qiuhua Liu Wanjie Ren Siwei Zhang Dr. Yang Huang Dilong Chen Dr. Wennan Zeng Prof. Dr. Zaichun Zhou Prof. Dr. Lin He Prof. Dr. Wenping Guo Prof. Dr. Jianfeng Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202103892
Both geometric architecture and electronic configurations of heme proteins contribute to its activity. In this work we designed and synthesized a series of four copper(II) porphyrin complexes ( 4 -, 3 -, 2 - and 1 -Cu) where the molecular conformations are modulated by a pair of stepwise shortened straps on the same porphyrin side (cis-ortho) to give double bow-shaped skeletons. Single crystal structures demonstrate that the straps gradually increase the saddle deformation and the deviation of the metal centers, which is in accordance with two, unusual d-orbital reconstructions of two different ground states, as revealed by 4 K EPR and DFT calculations. In the study of the electrocatalytic hydrogen evolution reaction (HER), 1 -Cu, with the shortest straps, showed the most apparent improvement of activity. Second coordination sphere (SCS) effects created by the double bow-shaped architecture and the strong saddle porphyrin core in 1 -Cu are found to play key roles in proton trapping during the catalytic process. The work contributes a novel strategy to improve the catalytic performance of heme analogs through ligand geometric modulation. 相似文献
9.
Zeynep Güven Lars Denker Hadi Dolati Daniela Wullschläger Dr. Bartosz Trzaskowski Dr. René Frank 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(32):e202200673
Donor-acceptor cyclopropanes or cyclobutanes are dipolar reagents, which are widely used in the synthesis of complex organic (hetero)cycles in ring expansion reactions. Applying this concept to boron containing heterocycles, the four-membered borete cyclo-iPr2N-BC10H6 reacted with the carbon donor ligands 2,6-xylylisonitrile and the carbene IMes :C(NMesCH)2 with ring expansion and ring fusion, respectively. In particular, the tetracyclic structure formed with IMes displays zwitterionic character and absorption in the visible region. In contrast to the carbene IMes, the heavier carbenoids :Si(NDippCH)2 and :Ga(AmIm) with a two-coordinate donor atom afford spiro-type bicyclic compounds, which display four-coordinate geometry at silicon or gallium. (TD-)DFT calculations provide deeper insight into the mechanism of formation and the absorption properties of these new compounds. 相似文献
10.
Cheng Ren Guanghao Ji Xiankai Li Prof. Jing Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(53):e202201442
The direct hydrodimerization of acrylates and acrylonitrile offers a general streamlined access to industrially important intermediates to nylon 6,6. However, a practical catalytic method for this process has thus far underdeveloped owing to the challenges in regioselectivity and environmental compatibility of applied reagents. Here, we report a cobalt-catalyzed tail-to-tail hydrodimerization of activated alkenes driven by a visible-light photoredox catalysis at ambient temperature, which is applicable to both adipates and adiponitrile synthesis from potentially renewable feedstocks. This protocol utilizes half equivalent of hantzsch ester as a recyclable two-electron and two-proton donor with the assistance of catalytic amount of base as a proton shuttle, and has been shown to be highly regioselective and efficient for hydrodimerizing various activated alkenes to 1,4-difunctionalized butane derivatives. 相似文献