全文获取类型
收费全文 | 13552篇 |
免费 | 2245篇 |
国内免费 | 1501篇 |
专业分类
化学 | 9373篇 |
晶体学 | 126篇 |
力学 | 910篇 |
综合类 | 91篇 |
数学 | 1676篇 |
物理学 | 5122篇 |
出版年
2024年 | 46篇 |
2023年 | 290篇 |
2022年 | 494篇 |
2021年 | 533篇 |
2020年 | 546篇 |
2019年 | 487篇 |
2018年 | 470篇 |
2017年 | 413篇 |
2016年 | 584篇 |
2015年 | 654篇 |
2014年 | 751篇 |
2013年 | 1002篇 |
2012年 | 1143篇 |
2011年 | 1163篇 |
2010年 | 810篇 |
2009年 | 758篇 |
2008年 | 838篇 |
2007年 | 775篇 |
2006年 | 698篇 |
2005年 | 580篇 |
2004年 | 426篇 |
2003年 | 356篇 |
2002年 | 342篇 |
2001年 | 297篇 |
2000年 | 245篇 |
1999年 | 293篇 |
1998年 | 271篇 |
1997年 | 201篇 |
1996年 | 223篇 |
1995年 | 221篇 |
1994年 | 191篇 |
1993年 | 166篇 |
1992年 | 135篇 |
1991年 | 152篇 |
1990年 | 151篇 |
1989年 | 110篇 |
1988年 | 92篇 |
1987年 | 79篇 |
1986年 | 59篇 |
1985年 | 64篇 |
1984年 | 28篇 |
1983年 | 33篇 |
1982年 | 26篇 |
1981年 | 20篇 |
1980年 | 13篇 |
1979年 | 10篇 |
1978年 | 8篇 |
1977年 | 10篇 |
1974年 | 6篇 |
1973年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
951.
Dr. Shi Tang Dr. Zhi Wang Yanzi Xu Huili Ma Dr. Jia Wang Dr. Christian Larsen Prof. Dongfeng Dang Prof. Ergang Wang Prof. Ludvig Edman 《Angewandte Chemie (International ed. in English)》2023,62(23):e202302874
The emission efficiency of organic semiconductors (OSCs) often suffers from aggregation caused quenching (ACQ). An elegant solution is aggregation-induced emission (AIE), which constitutes the design of the OSC so that its morphology inhibits quenching π–π interactions and non-radiative motional deactivation. The light-emitting electrochemical cell (LEC) can be sustainably fabricated, but its function depends on motion of bulky ions in proximity of the OSC. It is therefore questionable whether the AIE morphology can be retained during LEC operation. Here, we synthesize two structurally similar OSCs, which are distinguished by that 1 features ACQ while 2 delivers AIE. Interestingly, we find that the AIE-LEC significantly outperforms the ACQ-LEC. We rationalize our finding by showing that the AIE morphology remains intact during LEC operation, and that it can feature appropriately sized free-volume voids for facile ion transport and suppressed non-radiative excitonic deactivation. 相似文献
952.
Xiangyu Li Ailing Tang Helin Wang Zongtao Wang Mengzhen Du Qiang Guo Qing Guo Erjun Zhou 《Angewandte Chemie (International ed. in English)》2023,62(39):e202306847
A third component featuring a planar backbone structure similar to the binary host molecule has been the preferred ingredient for improving the photovoltaic performance of ternary organic solar cells (OSCs). In this work, we explored a new avenue that introduces 3D-structured molecules as guest acceptors. Spirobifluorene (SF) is chosen as the core to combine with three different terminal-modified (rhodanine, thiazolidinedione, and dicyano-substituted rhodanine) benzotriazole (BTA) units, affording three four-arm molecules, SF-BTA1, SF-BTA2, and SF-BTA3, respectively. After adding these three materials to the classical system PM6 : Y6, the resulting ternary devices obtained ultra-high power-conversion efficiencies (PCEs) of 19.1 %, 18.7 %, and 18.8 %, respectively, compared with the binary OSCs (PCE=17.4 %). SF-BTA1-3 can work as energy donors to increase charge generation via energy transfer. In addition, the charge transfer between PM6 and SF-BTA1-3 also acts to enhance charge generation. Introducing SF-BTA1-3 could form acceptor alloys to modify the molecular energy level and inhibit the self-aggregation of Y6, thereby reducing energy loss and balancing charge transport. Our success in 3D multi-arm materials as the third component shows good universality and brings a new perspective. The further functional development of multi-arm materials could make OSCs more stable and efficient. 相似文献
953.
Zhaoyu Zhang Dr. Yufei Zhang Dr. Minghui Ye Dr. Zhipeng Wen Dr. Yongchao Tang Prof. Xiaoqing Liu Prof. Cheng Chao Li 《Angewandte Chemie (International ed. in English)》2023,62(44):e202311032
The artificial solid electrolyte interphase (SEI) plays a pivotal role in Zn anode stabilization but its long-term effectiveness at high rates is still challenged. Herein, to achieve superior long-life and high-rate Zn anode, an exquisite electrolyte additive, lithium bis(oxalate)borate (LiBOB), is proposed to in situ derive a highly Zn2+-conductive SEI and to dynamically patrol its cycling-initiated defects. Profiting from the as-constructed real-time, automatic SEI repairing mechanism, the Zn anode can be cycled with distinct reversibility over 1800 h at an ultrahigh current density of 50 mA cm−2, presenting a record-high cumulative capacity up to 45 Ah cm−2. The superiority of the formulated electrolyte is further demonstrated in the Zn||MnO2 and Zn||NaV3O8 full batteries, even when tested under harsh conditions (limited Zn supply (N/P≈3), 2500 cycles). This work brings inspiration for developing fast-charging Zn batteries toward grid-scale storage of renewable energy sources. 相似文献
954.
Dr. Ying-Jie Sun Wen-Da Chen Dr. Ji Liu Jun-Jin Li Yu Zhang Wei-Qi Cai Prof. Li Liu Xin-Jing Tang Jian Hou Prof. Ming Wang Prof. Liang Cheng 《Angewandte Chemie (International ed. in English)》2023,62(5):e202212413
The CRISPR/Cas system is one of the most powerful tools for gene editing. However, approaches for precise control of genome editing and regulatory events are still desirable. Here, we report the spatiotemporal and efficient control of CRISPR/Cas9- and Cas12a-mediated editing with conformationally restricted guide RNAs (gRNAs). This approach relied on only two or three pre-installed photo-labile substituents followed by an intramolecular cyclization, representing a robust synthetic method in comparison to the heavily modified linear gRNAs that often require extensive screening and time-consuming optimization. This tactic could direct the precise cleavage of the genes encoding green fluorescent protein (GFP) and the vascular endothelial growth factor A (VEGFA) protein within a predefined cutting region without notable editing leakage in live cells. We also achieved light-mediated myostatin (MSTN) gene editing in embryos, wherein a new bow-knot-type gRNA was constructed with excellent OFF/ON switch efficiency. Overall, our work provides a significant new strategy in CRISPR/Cas editing with modified circular gRNAs to precisely manipulate where and when genes are edited. 相似文献
955.
Feifan Li Xinyang Mu Xueqing Tang Ge Song Hongzhao Sun Xiuling Zha Peiyan Sun Jianhui Fang Dongmei Hu Shan Cong Zhigang Zhao 《Angewandte Chemie (International ed. in English)》2023,62(12):e202218055
Non-metallic materials have emerged as a new family of active substrates for surface-enhanced Raman scattering (SERS), with unique advantages over their metal counterparts. However, owing to their inefficient interaction with the incident wavelength, the Raman enhancement achieved with non-metallic materials is considerably lower with respect to the metallic ones. Herein, we propose colourful semiconductor-based SERS substrates for the first time by utilizing a Fabry-Pérot cavity, which realize a large freedom in manipulating light. Owing to the delicate adjustment of the absorption in terms of both frequency and intensity, resonant absorption can be achieved with a variety of non-metal SERS substrates, with the sensitivity further enhanced by ≈100 times. As a typical example, by introducing a Fabry-Pérot-type substrate fabricated with SiO2/Si, a rather low detection limit of 10−16 M for the SARS-CoV-2S protein is achieved on SnS2. This study provides a realistic strategy for increasing SERS sensitivity when semiconductors are employed as SERS substrates. 相似文献
956.
Bingyu Huang Xiannong Tang Yaoshuai Hong Longbin Li Prof. Ting Hu Prof. Kai Yuan Prof. Yiwang Chen 《Angewandte Chemie (International ed. in English)》2023,62(33):e202306667
Catalysts with metal-Nx sites have long been considered as effective electrocatalysts for oxygen reduction reaction (ORR), yet the accurate structure-property correlations of these active sites remain debatable. Report here is a proof-of-concept method to construct 1,4,8,11-tetraaza[14]annulene (TAA)-based polymer nanocomposites with well-managed electronic microenvironment via electron-donors/acceptors interaction of altering electron-withdrawing β-site substituents. DFT calculation proves the optimal −Cl substituted catalyst (CoTAA−Cl@GR) tailored the key OH* intermediate interaction with Co−N4 sites under the d-orbital regulation, hence reaching the top of ORR performance with excellent turnover frequency (0.49 e s−1 site−1). The combination of in situ scanning electrochemical microscopy and variable-frequency square wave voltammetry techniques contribute the great ORR kinetics of CoTAA−Cl@GR to the relatively high accessible site density (7.71×1019 site g−1) and fast electron outbound propagation mechanism. This work provides theoretical guidance for rational design of high-performance catalysts for ORR and beyond. 相似文献
957.
Chang Liu Yunci Zhang Shanshan Tang Yi Wang Jing Tian Dongyu Gu Yi Yang 《Journal of separation science》2023,46(10):2200958
Robinia pseudoacacia flowers have attracted much attention because of numerous bioactivities. In this study, its extract showed the potential scavenging ability for 2,2′-azinobis-(3-ethylbenzthiazoline-6-sulphonate) and 1,1-diphenyl-2-picrylhydrazyl free radicals. Under the guidance of antioxidant activity, the antioxidant extract was enriched by liquid-liquid extraction. The partition coefficients of the two main components in antioxidant extracts differed greatly, so in this study, elution-extrusion counter-current chromatography with the solvent system of n-hexane-ethyl acetate-methanol-water (2.5:5:2.5:5, v/v) was used to enhance the separation efficiency, and the two main components were successfully obtained. Among them, kaempferol showed strong antioxidant activity, which can be responsible for the activity of the extract. In order to deeply understand the antioxidant mechanism of kaempferol, the thermodynamics, frontier molecular orbital, and kinetics of scavenging free radicals were investigated by density functional theory. The results showed that 4′-OH in kaempferol was the most active group, which can scavenge free radicals by hydrogen atom transfer in non-polar solvents and activate 3-OH to generate double hydrogen atom transfer in the gas phase. But in polar solvents, it was more inclined to clear radicals through single electron transfer and proton transfer. The kinetic result showed that kaempferol needed 9.17 kcal/mol of activation energy to scavenge free radicals. 相似文献
958.
本文设计开发了一种以2,6-二甲酰基对甲苯酚为母体的新型荧光探针HMI,可用于高效识别EtOH-H2O (8/2, v/v, HEPES 10 mM, pH =7.4)体系中的CO32-。HMI在660 nm处显示发射带,加入CO32-后,在600 nm的等吸收点激发时,原来在660 nm处的荧光淬灭,而以540 nm为中心的新发射带荧光显着增加,为比率型荧光探针。HMI对CO32-表现出高选择性且具有较强的抗干扰能力。此外,荧光探针HMI对CO32-荧光响应的检测限较低,可达到3.938×10-6 M。更具有意义的是,HMI探针对CO32-的检测能够在实际水样中起到很好的应用,而且细胞成像研究表明,HMI可用于活体MCF-7细胞中CO32-的成像。 相似文献
959.
Tao Wang Juan Du Yong Sun Xing Tang Zuo-Jun Wei Xianhai Zeng Shi-Jie Liu Lu Lin 《中国化学快报》2021,32(3):1186-1190
Catalytic transfer hydroge nation(CTH) of furfural(FF) to furfu ryl alcohol(FFA) has received great intere st in recent years.He rein,Cu-Cs bimetallic supported catalyst,CuCs(2)-MCM,was developed for the CTH of FF to FFA using formic as hydrogen donor.CuCs(2)-MCM achieved a 99.6% FFA yield at an optimized reaction conditions of 170℃,1 h.Cu species in CuCs(2)-MCM had dual functions in catalytically decomposing formic acid to generate hydrogen and hydrogenating FF to FFA.The doping of Cs made the size of Cu particles smaller and improved the dispersion of the Cu active sites.Impo rtantly,the Cs species played a favorable role in enhancing the hydrogenation activity as a promoter by adjusting the surface acidity of Cu species to an appropriate level.Correlation analysis showed that surface acidity is the primary factor to affect the catalytic activity of CuCs(2)-MCM. 相似文献
960.
Lu Luo Shuai Tang Jiangyue Wu Shiwei Jin Hua Zhang 《Chemical record (New York, N.Y.)》2023,23(4):e202300023
Aromatic organoboron compounds are highly valuable building blocks in organic chemistry. They were mainly synthesized through aromatic C−H and C−Het borylation, in which transition metal-catalysis dominate. In the past decade, with increasing attention to sustainable chemistry, numerous transition metal-free C−H and C−Het borylation transformations have been developed and emerged as efficient methods towards the synthesis of aromatic organoboron compounds. This account mainly focuses on recent advances in transition metal-free aromatic C−H, C−N, C−S, and C−O borylation transformations and provides insights to where further developments are required. 相似文献