全文获取类型
收费全文 | 20832篇 |
免费 | 3501篇 |
国内免费 | 2392篇 |
专业分类
化学 | 14478篇 |
晶体学 | 208篇 |
力学 | 1526篇 |
综合类 | 196篇 |
数学 | 2320篇 |
物理学 | 7997篇 |
出版年
2024年 | 69篇 |
2023年 | 401篇 |
2022年 | 708篇 |
2021年 | 770篇 |
2020年 | 830篇 |
2019年 | 797篇 |
2018年 | 680篇 |
2017年 | 587篇 |
2016年 | 969篇 |
2015年 | 1016篇 |
2014年 | 1159篇 |
2013年 | 1527篇 |
2012年 | 1789篇 |
2011年 | 1962篇 |
2010年 | 1247篇 |
2009年 | 1190篇 |
2008年 | 1219篇 |
2007年 | 1127篇 |
2006年 | 1117篇 |
2005年 | 933篇 |
2004年 | 832篇 |
2003年 | 613篇 |
2002年 | 573篇 |
2001年 | 506篇 |
2000年 | 455篇 |
1999年 | 431篇 |
1998年 | 380篇 |
1997年 | 323篇 |
1996年 | 335篇 |
1995年 | 320篇 |
1994年 | 299篇 |
1993年 | 232篇 |
1992年 | 247篇 |
1991年 | 205篇 |
1990年 | 180篇 |
1989年 | 152篇 |
1988年 | 91篇 |
1987年 | 89篇 |
1986年 | 75篇 |
1985年 | 75篇 |
1984年 | 42篇 |
1983年 | 44篇 |
1982年 | 37篇 |
1981年 | 22篇 |
1980年 | 15篇 |
1979年 | 8篇 |
1977年 | 5篇 |
1975年 | 6篇 |
1969年 | 4篇 |
1957年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
951.
Yongfeng Li Chaoji Chen Jianwei Song Chunpeng Yang Yudi Kuang Azhar Vellore Emily Hitz Mingwei Zhu Feng Jiang Yonggang Yao Amy Gong Ashlie Martini Liangbing Hu 《中国化学》2020,38(8):823-829
Lightweight structural materials are important for the energy efficiency of applications, particularly those in the building sector. Here, inspired by nature, we developed a strong, superhydrophobic, yet lightweight material by simple in situ growth of nano‐SiO2 and subsequent densification of the wood substrate. In situ generation of SiO2 nanoparticles both inside the wood channels and on the wood surfaces gives the material superhydrophobicity, with static and dynamic contact angles of 159.4o and 3o, respectively. Densification of the wood to remove most of the spaces among the lumen and cell walls results in a laminated, dense structure, with aligned cellulose nanofibers, which in turn contributes to a high mechanical strength up to 384.2 MPa (7‐times higher than natural wood). Such treatment enables the strong and superhydrophobic wood (SH‐Wood) to be stable and have excellent water, acid, and alkaline resistance. The high mechanical strength of SH‐Wood combined with its excellent structural stability in harsh environments, as well its low density, positions the strong and superhydrophobic wood as a promising candidate for strong, lightweight, and durable structural materials that could potentially replace steel. 相似文献
952.
Yunong Li Lei Wang Jingxiang Low Di Wu Canyu Hu Wenbin Jiang Jun Ma Chengming Wang Ran Long Li Song Hangxun Xu Yujie Xiong 《中国化学快报》2020,31(1):231-234
Efficient catalytic system with low energy consumption exhibits increasing importance due to the upcoming energy crisis.Given this situation,it should be an admirable strategy for reducing energy input by effectively utilizing incident solar energy as a heat source during catalytic reactions.Herein,aza-fused7 r-conjugated microporous polymer(aza-CMP)with broad light absorption and high photothermal conversion efficiency was synthesized and utilized as a support for bimetallic AuPd nanocatalysts in light-driven benzyl alcohol oxidation.The AuPd nanoparticles anchored on aza-CMP(aza-CM P/Au_xPdy)exhibited excellent catalytic performance for benzyl alcohol oxidation under 50 mW/cm^2 light irradiation.The improved catalytic performance by the aza-CMP/Au_xPdy is attributed to the unique photothermal effect induced by aza-CMP,which can promote the catalytic benzyl alcohol oxidation occurring at Au Pd.This work presents a novel approach to effectively utilize solar energy for conventional catalytic reactions through photothermal effect. 相似文献
953.
大气颗粒物中棕色碳(BrC)在近紫外波段具有强吸光性,并因其显著的气候效应被广泛关注。BrC组成、来源、演变和光学性质的不确定性是造成气候模型估算气溶胶辐射强迫不确定性的重要因素。本文综述了大气颗粒物中BrC的化学组成、来源和生成机制,聚焦分子水平上BrC组成、二次生成机制和吸光间的关联。大气颗粒物中BrC的主要类别包括有机溶剂(甲醇)提取的碳质组分、水溶性有机碳及类腐殖质; 分子水平上,硝基芳香烃和含氮杂环有机物是BrC的主要发色团。BrC的来源包括生物质等不完全燃烧一次排放和挥发性有机物氧化二次生成; 二次生成途径主要包括人为源芳香烃氧化生成硝基芳香烃等含氮组分、羰基化合物与铵/胺反应生成含氮杂环组分或低聚物。前体物和反应条件影响二次生成BrC的组成和吸光性质; BrC在大气传输过程中还会发生“光漂白”现象。在分子水平上识别和阐明BrC的发色团、二次生成机制及其演变过程是未来该领域的重点研究方向。 相似文献
954.
由活性层和支撑层组成的薄层复合(TFC)聚酰胺(PA)膜,是目前广泛应用于纳滤、反渗透、正渗透和压力延迟渗透过程中的高性能脱盐膜,具有水通量大和截盐率高等优异性能。然而,由于TFC-PA膜存在活性层疏水性强、支撑层孔径大等特点,致使TFC-PA膜在实际使用过程中极易受到膜污染,制约了TFC-PA膜的进一步推广和使用。本文讨论分析了TFC-PA膜的结构特点和表面性质,总结归纳了在不同膜过程中TFC-PA膜污染形成的原因及特点,详细论述了国内外抗污染TFC-PA膜的研究进展。本文重点介绍了活性层抗污染改性和支撑层抗污染改性方法,并对其抗污染机理以及存在的问题进行了阐述与分析,最后对抗污染TFC-PA膜的结构设计与表面改性策略进行了总结及展望。 相似文献
955.
The ATP-binding cassette (ABC) transporter P-glycoprotein (P-gp) is a physiologically essential membrane protein that protects many tissues against xenobiotic molecules, but limits the access of chemotherapeutics into tumor cells, thus contributing to multidrug resistance. The atomic-level mechanism of how substrates and inhibitors differentially affect the ATP hydrolysis by P-gp remains to be elucidated. In this work, atomistic molecular dynamics simulations in an explicit membrane/water environment were performed to explore the effects of substrate and inhibitor binding on the conformational dynamics of P-gp. Distinct differences in conformational changes that mainly occurred in the nucleotide-binding domains (NBDs) were observed from the substrate- and inhibitor-bound simulations. The binding of rhodamine-123 can increase the probability of the formation of an intermediate conformation, in which the NBDs were closer and better aligned, suggesting that substrate binding may prime the transporter for ATP hydrolysis. By contrast, the inhibitor QZ-Leu stabilized NBDs in a much more separated and misaligned conformation, which may result in the deficiency of ATP hydrolysis. The significant differences in conformational modulation of P-gp by substrate and inhibitor binding provided a molecular explanation of how these small molecules exert opposite effects on the ATPase activity. A further structural analysis suggested that the allosteric communication between transmembrane domains (TMDs) and NBDs was primarily mediated by two intracellular coupling helices. Our computational simulations provide not only valuable insights into the transport mechanism of P-gp substrates, but also for the molecular design of P-gp inhibitors. 相似文献
956.
Fang Hu Guobin Qi Kenry Duo Mao Shiwei Zhou Min Wu Wenbo Wu Bin Liu 《Angewandte Chemie (International ed. in English)》2020,59(24):9288-9292
Protected by the host cells, the hidden intracellular bacteria are typically difficult to kill by common antibiotics and cannot be visualized without complex cellular pretreatments. Herein, we successfully developed a bacteria‐metabolizable dual‐functional probe TPEPy‐d ‐Ala, which is based on d ‐alanine and a photosensitizer with aggregation‐induced emission for fluorescence turn‐on imaging of intracellular bacteria in living host cells and photodynamic ablation in situ. Once metabolically incorporated into bacterial peptidoglycan, the intramolecular motions of TPEPy‐d ‐Ala are inhibited, leading to an enhanced fluorescent signal, which allows the clear visualization of the intracellular bacteria. Moreover, TPEPy‐d ‐Ala can effectively ablate the labeled intracellular bacteria in situ owing to covalent ligation to peptidoglycan, yielding a low intracellular minimum inhibitory concentration (MIC) of 20±0.5 μg mL?1, much more efficient than that of a commonly used antibiotic, vancomycin. 相似文献
957.
Wenjun Yang Bo Ling Bowen Hu Haolin Yin Jianyou Mao Patrick J. Walsh 《Angewandte Chemie (International ed. in English)》2020,59(1):161-166
An umpolung 1,4‐addition of aryl iodides to enals promoted by cooperative (terpy)Pd/NHC catalysis was developed that generates various bioactive β,β‐diaryl propanoate derivatives. This system is not only the first reported palladium‐catalyzed arylation of NHC‐bound homoenolates but also expands the scope of NHC‐induced umpolung transformations. A diverse array of functional groups such as esters, nitriles, alcohols, and heterocycles are tolerated under the mild conditions. This method also circumvents the use of moisture‐sensitive organometallic reagents. 相似文献
958.
Chao Wang Min Hu Yueying Chu Xue Zhou Qiang Wang Guodong Qi Shenhui Li Jun Xu Feng Deng 《Angewandte Chemie (International ed. in English)》2020,59(18):7198-7202
The understanding of catalyst deactivation represents one of the major challenges for the methanol‐to‐hydrocarbon (MTH) reaction over acidic zeolites. Here we report the critical role of intermolecular π‐interactions in catalyst deactivation in the MTH reaction on zeolites H‐SSZ‐13 and H‐ZSM‐5. π‐interaction‐induced spatial proximities between cyclopentenyl cations and aromatics in the confined channels and/or cages of zeolites are revealed by two‐dimensional solid‐state NMR spectroscopy. The formation of naphtalene as a precursor to coke species is favored due to the reaction of aromatics with the nearby cyclopentenyl cations and correlates with both acid density and zeolite topology. 相似文献
959.
Shijia Feng Tuo Wang Bin Liu Congling Hu Lulu Li Zhi‐Jian Zhao Jinlong Gong 《Angewandte Chemie (International ed. in English)》2020,59(5):2044-2048
A facile photoetching approach is described that alleviates the negative effects from bulk defects by confining the oxygen vacancy (Ovac) at the surface of BiVO4 photoanode, by 10‐minute photoetching. This strategy could induce enriched Ovac at the surface of BiVO4, which avoids the formation of excessive bulk defects. A mechanism is proposed to explain the enhanced charge separation at the BiVO4 /electrolyte interface, which is supported by density functional theory (DFT) calculations. The optimized BiVO4 with enriched surface Ovac presents the highest photocurrent among undoped BiVO4 photoanodes. Upon loading FeOOH/NiOOH cocatalysts, photoetched BiVO4 photoanode reaches a considerable water oxidation photocurrent of 3.0 mA cm?2 at 0.6 V vs. reversible hydrogen electrode. An unbiased solar‐to‐hydrogen conversion efficiency of 3.5 % is realized by this BiVO4 photoanode and a Si photocathode under 1 sun illumination. 相似文献
960.
Peng‐Ju Xia Dan Song Zhi‐Peng Ye Yuan‐Zhuo Hu Jun‐An Xiao Hao‐Yue Xiang Xiao‐Qing Chen Hua Yang 《Angewandte Chemie (International ed. in English)》2020,59(17):6706-6710
A photoinduced SET process enables the direct B?H bond activation of NHC–boranes. In contrast to common hydrogen atom transfer (HAT) strategies, this photoinduced reaction simply takes advantage of the beneficial redox potentials of NHC–boranes, thus obviating the need for extra radical initiators. The resulting NHC–boryl radical was used for the borylation of a wide range of α‐trifluoromethylalkenes and alkenes with diverse electronic and structural features, providing facile access to highly functionalized borylated molecules. Labeling and photoquenching experiments provide insight into the mechanism of this photoinduced SET pathway. 相似文献