全文获取类型
收费全文 | 35071篇 |
免费 | 5445篇 |
国内免费 | 3273篇 |
专业分类
化学 | 24036篇 |
晶体学 | 237篇 |
力学 | 2178篇 |
综合类 | 211篇 |
数学 | 4226篇 |
物理学 | 12901篇 |
出版年
2023年 | 738篇 |
2022年 | 676篇 |
2021年 | 1038篇 |
2020年 | 1498篇 |
2019年 | 1413篇 |
2018年 | 1106篇 |
2017年 | 1012篇 |
2016年 | 1480篇 |
2015年 | 1474篇 |
2014年 | 1878篇 |
2013年 | 2451篇 |
2012年 | 3130篇 |
2011年 | 3186篇 |
2010年 | 2141篇 |
2009年 | 2011篇 |
2008年 | 2161篇 |
2007年 | 1931篇 |
2006年 | 1818篇 |
2005年 | 1509篇 |
2004年 | 1281篇 |
2003年 | 964篇 |
2002年 | 829篇 |
2001年 | 670篇 |
2000年 | 641篇 |
1999年 | 749篇 |
1998年 | 630篇 |
1997年 | 599篇 |
1996年 | 666篇 |
1995年 | 576篇 |
1994年 | 529篇 |
1993年 | 452篇 |
1992年 | 439篇 |
1991年 | 347篇 |
1990年 | 309篇 |
1989年 | 224篇 |
1988年 | 191篇 |
1987年 | 153篇 |
1986年 | 112篇 |
1985年 | 126篇 |
1984年 | 119篇 |
1983年 | 95篇 |
1982年 | 75篇 |
1981年 | 50篇 |
1980年 | 39篇 |
1979年 | 30篇 |
1978年 | 24篇 |
1977年 | 20篇 |
1976年 | 27篇 |
1975年 | 31篇 |
1974年 | 23篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Er-Xia Chen Mei Qiu Yong-Fan Zhang Liang He Ya-Yong Sun Hui-Li Zheng Xin Wu Jian Zhang Qipu Lin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2022,134(1):e202111622
Two new chemically stable metalloporphyrin-bridged metal-catechol frameworks, InTCP-Co and FeTCP-Co, were constructed to achieve artificial photosynthesis without additional sacrificial agents and photosensitizers. The CO2 photoreduction rate over FeTCP-Co considerably exceeds that obtained over InTCP-Co, and the incorporation of uncoordinated hydroxyl groups, associated with catechol, into the network further promotes the photocatalytic activity. The iron-oxo coordination chain assists energy band alignment and provides a redox-active site, and the uncoordinated hydroxyl group contributes to the visible-light absorptance, charge-carrier transfer, and CO2-scaffold affinity. With a formic acid selectivity of 97.8 %, FeTCP-OH-Co affords CO2 photoconversion with a reaction rate 4.3 and 15.7 times higher than those of FeTCP- Co and InTCP-Co, respectively. These findings are also consistent with the spectroscopic study and DFT calculation. 相似文献
2.
Wu Jinxiu Qi Yuanhao Liu Zhaogang Jia Huiling Hu Yanhong Feng Fushan 《Journal of solution chemistry》2022,51(1):14-30
Journal of Solution Chemistry - The interaction between Dy(Ш)/Rutin complexes and bovine serum albumin (BSA) was studied by fluorescence, ultraviolet (UV) absorption, three-dimensional... 相似文献
3.
Leia Fan Elaine Jian Wen-Chun Chang Yvonne Wu Jason Lin Andy Tseng Jessica Tseng Renee Wan Annie Yu Eric Lee 《Electrophoresis》2022,43(21-22):2227-2233
Diffusiophoresis phenomenon of aoft particles suspended in binary electrolyte solutions is explored theoretically in this study based on the spherical cell model, focusing on the chemiphoresis component in absence of diffusion potential. Both the electrostatic and hydrodynamic aspects of the boundary confinement, or steric effect, due to the presence of neighboring particles are examined extensively under various electrokinetic conditions. Significant local extrema are found in mobility profiles expressed as functions of the Debye length in general, synchronized with the strength of the motion-inducing double layer polarization. Moreover, a seemingly peculiar phenomenon is observed that the soft particles may move faster in more concentrated suspensions. The competition between the simultaneous enhancement of the motion-inducing electric driving force and the motion-retarding hydrodynamic drag force from the boundary confinement effect of the neighboring particles is found to be responsible for it. The above findings are also demonstrated experimentally in a very recent study on the diffusiophoretic motion of soft particles through porous collagen hydrogels. The results presented here are useful in various practical applications of soft particles like drug delivery. 相似文献
4.
5.
Zhang Yingying Bi Haijie Wu Bingwei Yuan Da Shi Yan Feng Xiandong 《Journal of Radioanalytical and Nuclear Chemistry》2022,331(9):3723-3733
The NaI(Tl) detector has been an important research topic and application in the field of in situ marine radioactive automatic monitoring because of its advantages of low power consumption, low cost, and good efficiency. However, its energy resolution is not high enough. This paper investigated an analytical method: spectrum de-noising, background correction based on the SNIP operator, peak search based on the top-hat transform and peak fitting using Gaussian distribution. Simulation and gamma spectra measured from seawater showed that the established energy spectrum analysis method presents satisfactory automatic analytical ability for identification and quantitatively analysis.
相似文献6.
Li Yang Fu Xuan Li Xu-Xin Zhang Fang Wu Qiang Wang Yun Yan Ze-Yi 《Journal of Radioanalytical and Nuclear Chemistry》2022,331(2):877-888
Journal of Radioanalytical and Nuclear Chemistry - In this study, the imidazole-based poly(ionic liquid)s (PILs) synthesized by one step method has been applied for the enrichment and recovery of... 相似文献
7.
Zheng Xinyan Hu Po Yao Ruxian cheng Jinhe Chang Yiheng Wu Haitao Mei Hongying Sun Shuxiang Chen Qingtai liu Fang Chen Shujing Wen Hua 《Journal of Radioanalytical and Nuclear Chemistry》2022,331(5):2217-2226
Journal of Radioanalytical and Nuclear Chemistry - Enhancement of U(VI) biomineralization by Saccharomyces cerevisiae through addition of inorganic phosphorus was studied in this work. The addition... 相似文献
8.
Wu Yitian Zhang Xiaojun Zhou Haoxi Zhang Jinming 《Journal of Radioanalytical and Nuclear Chemistry》2022,331(6):2705-2717
Journal of Radioanalytical and Nuclear Chemistry - Prostate-specific membrane antigen (PSMA)-targeted radiolabeled agents have been developed to diagnose and treat prostate cancer. In this study,... 相似文献
9.
Chen Kuang Zhang Xiaojun Wang Fei Wu Yitian Zhou Haoxi Zhang Ying Zou Wenbo Zhang Jinming Liu Rong 《Journal of Radioanalytical and Nuclear Chemistry》2022,331(7):2859-2868
Journal of Radioanalytical and Nuclear Chemistry - This study evaluated the potential of Al18F-labelled restrained complexing agent (RESCA)-ICG to assess hepatic function reserve on PET/CT imaging.... 相似文献
10.
CO2的有效利用有助于解决环境和生态问题.碳酸酐酶(CA)等酶分子可精准活化CO2分子以降低反应能垒,为CO2的高效和高选择性转化提供了一种有前景的途径.然而,酶离开生物体后易失活,且难以重复利用.目前,包埋型固定化酶是常用且有效的提高酶稳定性与回用率的方法之一,但载体的存在会造成反应物CO2内扩散阻力增加,降低反应活性.此外,CO2酶促转化是一个气-液-固三相反应过程,反应体系中CO2的外扩散性能也需要加强.金属有机骨架(MOFs),特别是咪唑酯骨架(ZIFs),常被用作酶固定化的载体.ZIFs的拓扑结构可被设计成不同形貌,进而通过ZIFs的结构工程来加强分子向其中的内扩散.Pickering乳液是指以固体颗粒代替常规表面活性剂而稳定的乳液.当固体颗粒具有催化活性时,催化剂颗粒会扩大液-液-固或气-液-固三相接触面积,从而有效协调反应物在不同相中的扩散时间.如果酶被用作这些颗粒的活性中心,所制备的Pickering乳液也可能具备类似的特性,可加强底物分子向酶的外扩散.本文选择两种具有不同结构的ZIFs(ZIF-L和ZIF-8),原位包埋CA后形成CA@ZIFs颗粒以稳定Pickeirng乳液.ZIF-L和CA@ZIF-L颗粒显示出独特的二维层状堆叠结构.ZIF-8和CA@ZIF-8颗粒呈棱角清晰的十二面体结构.与CA@ZIF-8颗粒相比,CA@ZIF-L颗粒显示出更大的孔径和更宽的孔径分布,这有助于CO2从CA@ZIF-L颗粒表面扩散至酶活性中心.利用酶活测试来研究内扩散是否通过结构工程得到了加强,发现CA@ZIF-L颗粒的活性比CA@ZIF-8颗粒高22.3%,推测这是由于CA@ZIF-L颗粒特殊的十字花状结构会缩短CO2从颗粒表面扩散至酶活性中心的距离.同时,十字花状结构可暴露更多的酶活性位点(CA@ZIF-L颗粒的暴露面积是CA@ZIF-8颗粒的~8倍),从而提升了反应物浓度并显示出更高的催化活性.本文还设计了吸附实验来进一步验证上述假设,发现BSA@ZIF-L颗粒对香豆素的吸附率远高于BSA@ZIF-8颗粒,说明与ZIF-8相比,酶包埋于ZIF-L具有更强的捕获小分子的能力,表明CO2分子向CA@ZIF-L的扩散速度更快,即CA@ZIF-L的十字花状结构可强化系统的内扩散过程.进一步比较了PIBS和游离多酶体系的催化活性,将CO2通入每个系统,在反应前20 min,PIBS的pH值下降速度比游离体系快得多,说明PIBS通过在气相和液相间构建更大的界面,缩短了CO2向CA的扩散距离,从而提高了催化效率,促进了CO2转化.上述假设也通过扩散动力学的计算得到了验证.为进一步研究PIBS的CO2矿化能力,本文开展了CaCO3矿化反应,发现PIBS的CaCO3产量远高于游离多酶体系,表明构建的PIBS在强化内外扩散方面具有显著优势.最后,评估了PIBS在工业应用中的性能,由CA@ZIF-L和CA@ZIF-8颗粒构建的PIBS显示出较好的可回收性,在第8个循环后,PIBS仍可保持8.9 mg/5 min的CaCO3产量.综上,PIBS可为CO2的酶促转化和框架提供一个新方法和新平台. 相似文献