全文获取类型
收费全文 | 1625篇 |
免费 | 287篇 |
国内免费 | 131篇 |
专业分类
化学 | 1251篇 |
晶体学 | 15篇 |
力学 | 111篇 |
综合类 | 10篇 |
数学 | 116篇 |
物理学 | 540篇 |
出版年
2024年 | 5篇 |
2023年 | 35篇 |
2022年 | 25篇 |
2021年 | 62篇 |
2020年 | 65篇 |
2019年 | 65篇 |
2018年 | 59篇 |
2017年 | 39篇 |
2016年 | 78篇 |
2015年 | 79篇 |
2014年 | 79篇 |
2013年 | 99篇 |
2012年 | 160篇 |
2011年 | 165篇 |
2010年 | 96篇 |
2009年 | 85篇 |
2008年 | 118篇 |
2007年 | 104篇 |
2006年 | 101篇 |
2005年 | 99篇 |
2004年 | 60篇 |
2003年 | 38篇 |
2002年 | 45篇 |
2001年 | 30篇 |
2000年 | 29篇 |
1999年 | 36篇 |
1998年 | 23篇 |
1997年 | 25篇 |
1996年 | 16篇 |
1995年 | 18篇 |
1994年 | 12篇 |
1993年 | 7篇 |
1992年 | 13篇 |
1991年 | 20篇 |
1990年 | 15篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1983年 | 5篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1947年 | 1篇 |
1946年 | 1篇 |
排序方式: 共有2043条查询结果,搜索用时 15 毫秒
91.
Screening and analysis of metabolites in rat urine after oral administration of Apocynum venetum L. extracts using HPLC–TOF‐MS 下载免费PDF全文
Liang Zhao Lei Lv Hai Zhang Guang guo‐Tan Yifeng Chai Guoqing Zhang 《Journal of separation science》2014,37(5):515-526
HPLC with diode array detection and ESI‐TOF‐MS was used for the study of the constituents in Apocynum venetum L. extracts and the metabolites in rat urine after oral administration of A. venetum L. extracts. A formula database of the known constituents in A. venetum L. was established, and 21 constituents were rapidly identified by accurately matching their molecular masses with the formulae of the compounds in the database. Furthermore, 34 metabolites were detected and elucidated in the rat urine. The scientific and plausible biotransformation pathways of the flavonoid components in A. venetum L. were also proposed together with the presentation of clues for potential mechanisms of bioactivity. This specific and sensitive HPLC–ESI‐TOF‐MS method can be used to identify the chemical components in the extracts of A. venetum L. and their metabolites in rat urine. This method can also be used to reveal the possible metabolic mechanisms of action of the extract components in vivo. 相似文献
92.
Bao-Shan Chai Chang-Ling Liu Hui-Chao Li Shao-Wu Liu Ying Xu Yu-Quan Song Jun-Biao Chang 《中国化学快报》2014,25(1):137-140
Pyriminostrobin, a new acaricide, was discovered in our previous studies. Because introducing fluorine into organic compounds can increase bioactivity, pyriminostrobin was modified as a series of strobilurin-pyrimidine derivatives for biological screening. The compounds were characterized by 1H NMR, MS and elemental analysis. Preliminary bioassays demonstrated that compounds 7e and 7i exhibited significant control against Tetranychus cinnabarinus (Boisd.) at 0.625 mg L^-1, and their acaricidal potencies were higher than pyriminostrobin in a greenhouse. The relationship between structure and acaricidal activity was also studied. 相似文献
93.
Dr. Jun-Dong Yi Dr. Ruikuan Xie Prof. Zai-Lai Xie Prof. Guo-Liang Chai Prof. Tian-Fu Liu Prof. Rui-Ping Chen Prof. Yuan-Biao Huang Prof. Rong Cao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(52):23849-23856
It is still a great challenge to achieve high selectivity of CH4 in CO2 electroreduction reactions (CO2RR) because of the similar reduction potentials of possible products and the sluggish kinetics for CO2 activation. Stabilizing key reaction intermediates by single type of active sites supported on porous conductive material is crucial to achieve high selectivity for single product such as CH4. Here, Cu2O(111) quantum dots with an average size of 3.5 nm are in situ synthesized on a porous conductive copper-based metal–organic framework (CuHHTP), exhibiting high selectivity of 73 % towards CH4 with partial current density of 10.8 mA cm−2 at −1.4 V vs. RHE (reversible hydrogen electrode) in CO2RR. Operando infrared spectroscopy and DFT calculations reveal that the key intermediates (such as *CH2O and *OCH3) involved in the pathway of CH4 formation are stabilized by the single active Cu2O(111) and hydrogen bonding, thus generating CH4 instead of CO. 相似文献
94.
采用化学气相沉积法在云母衬底上制备了二维InSe纳米片, 研究了生长温度对二维InSe纳米片晶相、 形貌、 尺寸及厚度的影响. 构筑了基于二维InSe纳米片的光探测器并研究了其光探测性能, 结果表明, 在808 nm的近红外光辐照下, 其光响应度为1.5 A/W, 外量子效率为230%, 可探测度为3.1×10 8 Jones(1 Jones=1 cm·Hz 1/2·W -1), 上升和衰减时间分别为0.5 和0.8 s. 相似文献
95.
Hong-Jun Yang Chen-Qiong Chai Yong-Kang Zuo Jin-Feng Huang Yi-Ye Song Li Jiang Wen-Yan Huang Qi-Min Jiang Xiao-Qiang Xue Bi-Biao Jiang 《高分子科学》2020,(3):231-239,I0005
Phosphazene base,t-BuP2,was employed to catalyze the proton transfer polymerization(PTP)of 2-hydroxyethyl acrylate(HEA),and PTP was further combined with ring-opening polymerization(ROP)to exploit a new type of hybrid copolymerization.The studies on homopolymerization showed that t-BuP2 was a particularly efficient catalyst for the polymerization of HEA at room temperature,giving an excellent monomer conversion.Throughout the polymerization,transesterification reactions were unavoidable,which increased the randomness in the structures of the resulting polymers.The studies on copolymerization showed that t-BuP2 could simultaneously catalyze the hybrid copolymerization via the combination of PTP and ROP at 25°C.During copolymerization,HEA not only provided hydroxyl groups to initiate the ROP ofε-caprolactone(CL)but also participated in the polymerization as a monomer for PTP.The copolymer composition was approximately equal to the feed ratio,demonstrating the possibility to adjust the polymeric structure by simply changing the monomer feed ratio.This copolymerization reaction provides a simple method for synthesizing degradable functional copolymers from commercially available materials.Hence,it is important not only in polymer chemistry but also in environmental and biomedical engineering. 相似文献
96.
Liejin Zhou Xingxing Wu Xing Yang Chengli Mou Runjiang Song Shuyan Yu Huifang Chai Lutai Pan Zhichao Jin Yonggui Robin Chi 《Angewandte Chemie (International ed. in English)》2020,59(4):1557-1561
The combined use of gold as transition metal catalyst and N‐heterocyclic carbene (NHC) as organic catalyst in the same solution for relay catalytic reactions was disclosed. The ynamide substrate was activated by gold catalyst to form unsaturated ketimine intermediate that subsequently reacted with the enals (via azolium enolate intermediate generated with NHC) effectively to form bicyclic lactam products with excellent diastereo‐ and enantio‐selectivities. The gold and NHC coordination and dissociation can be dynamic and tunable events, and thus allow the co‐existence of both active metal and carbene organic catalysts in appreciable concentrations, for the dual catalytic reaction to proceed. 相似文献
97.
Zhennan Wu Qiaofeng Yao Osburg Jin Huang Chai Nan Ding Wen Xu Shuangquan Zang Jianping Xie 《Angewandte Chemie (International ed. in English)》2020,59(25):9934-9939
Aggregation‐induced emission (AIE) provides an efficient strategy to synthesize highly luminescent metal nanoclusters (NCs), however, rational control of emission energy and intensity of metal NCs is still challenging. This communication reveals the impact of surface AuI‐thiolate motifs on the AIE properties of Au NCs, by employing a series of water‐soluble glutathione (GSH)‐coordinated Au complexes and NCs as a model ([Au10SR10], [Au15SR13], [Au18SR14], and [Au25SR18]?, SR=thiolate ligand). Spectroscopic investigations show that the emission wavelength of Au NCs is adjustable from visible to the near‐infrared II (NIR‐II) region by controlling the length of the AuI‐SR motifs on the NC surface. Decreasing the length of AuI‐SR motifs also changes the origin of cluster luminescence from AIE‐type phosphorescence to Au0‐core‐dictated fluorescence. This effect becomes more prominent when the degree of aggregation of Au NCs increases in solution. 相似文献
98.
A combination of fluorobenziodoxole (FBX) and BF3 ? OEt2 in cyclopentyl methyl ether promotes regio‐ and stereoselective addition of benziodoxole and methoxy groups to alkynes. This difunctionalization reaction tolerates a variety of functionalized internal and terminal alkynes to afford trans‐β‐alkoxyvinylbenziodoxoles, which represent versatile precursors to stereochemically well‐defined multisubstituted vinyl ethers. The reaction is proposed to involve cleavage of the I?F bond of FBX by BF3, followed by electrophilic activation of the alkyne by the resulting cationic IIII species that triggers the nucleophilic addition of the ethereal oxygen. 相似文献
99.
风机大型化是我国海上风电技术发展的重要方向. 东南沿海是我国海上风电发展的重要基地, 这一区域频繁发生的台风对海上风机的影响不可忽略. 台风风场与常规大风风场有不同的湍流特性, 同时台风期间较高的风速会引起巨大的台风浪. 本文考虑台风经过期间独特的风场及波浪场, 开展风浪联合作用对大型单桩海上风机影响的研究. 基于DTU 10 MW大型单桩风机, 运用一体化分析软件SIMA建立风浪联合作用下大型单桩风机的耦合数值模型, 研究台风经过不同阶段大型风力机的动力响应特性. 计算结果显示, 叶片变桨能有效降低台风经过时风机叶片所受风载荷, 变桨状态下单桩风机所受风载荷主要来源于塔筒. 在台风经过的不同阶段, 大型单桩海上风机结构表现出不同的动力特性. 台风全过程塔筒运动均受波浪激发一阶频率控制, 塔基上方结构动力载荷以惯性载荷为主, FOVS至FEWS阶段及BOVS阶段至BEWS阶段塔筒运动一阶频率处响应能量增长较小, 响应能量向低频及波频转移. 塔基下方泥面线处剪力响应受波频控制, 弯矩响应受一阶频率控制. 相似文献
100.
Nonlinear Dynamics - During the process of spacecraft launch, the extreme vibration environment is the major influence factor that induces the failure of the mission. Inspired by the smooth motions... 相似文献