全文获取类型
收费全文 | 1118篇 |
免费 | 186篇 |
国内免费 | 289篇 |
专业分类
化学 | 980篇 |
晶体学 | 12篇 |
力学 | 47篇 |
综合类 | 11篇 |
数学 | 146篇 |
物理学 | 397篇 |
出版年
2024年 | 5篇 |
2023年 | 18篇 |
2022年 | 48篇 |
2021年 | 33篇 |
2020年 | 45篇 |
2019年 | 53篇 |
2018年 | 35篇 |
2017年 | 39篇 |
2016年 | 63篇 |
2015年 | 40篇 |
2014年 | 48篇 |
2013年 | 89篇 |
2012年 | 91篇 |
2011年 | 115篇 |
2010年 | 67篇 |
2009年 | 56篇 |
2008年 | 85篇 |
2007年 | 72篇 |
2006年 | 66篇 |
2005年 | 73篇 |
2004年 | 52篇 |
2003年 | 58篇 |
2002年 | 73篇 |
2001年 | 74篇 |
2000年 | 37篇 |
1999年 | 34篇 |
1998年 | 26篇 |
1997年 | 24篇 |
1996年 | 15篇 |
1995年 | 16篇 |
1994年 | 10篇 |
1993年 | 4篇 |
1991年 | 3篇 |
1990年 | 9篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有1593条查询结果,搜索用时 15 毫秒
51.
En‐Qing Gao Dai‐Zheng Liao Zong‐Hui Jiang Shi‐Ping Yan 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(7):807-809
A hydrogen‐bonded coordination supramolecule, (meso‐5,7,7,12,14,14‐hexamethyl‐1,4,8,11‐tetraazacyclotetradecane‐κ4N)nickel(II) [N,N‐o‐phenylenebis(oxamato)‐κ4O,N,N′,O′]nickelate(II) dihydrate, [Ni(C16H36N4)][Ni(C10H4N2O6)]·2H2O or [Ni(meso‐cth)][Ni(opba)]·2H2O, has been prepared and characterized by X‐ray crystallographic analysis. The two complex ions, i.e. [Ni(meso‐cth)]2+ and [Ni(opba)]2?, are hydrogen bonded to each other, resulting in two‐dimensional neutral supramolecular sheets. The sheets stack along the a direction to produce a three‐dimensional architecture with one‐dimensional channels in which hydrogen‐bonded chains of water molecules are included. 相似文献
52.
A new method for the simultaneous determination of fluorine and iodine in urine by ion chromatography(IC) with electrochemical pretreatment has been developed.The pretreatment was performed in a novel electrochemical oxidation-neutralization device(EOND),in which iodide of the sample was oxidized to iodate and the alkaline digestion sample solution was neutralized.Under the optimized conditions,the limits of detection(LOD,S/N = 3) were 2.5μg/L for fluoride and 20μg/L for iodate,respectively.The recoverie... 相似文献
53.
Wei Zong Haiqi Gao Yue Ouyang Kaibin Chu Hele Guo Leiqian Zhang Wei Zhang Ruwei Chen Yuhang Dai Fei Guo Jiexin Zhu Zhenfang Zhang Chumei Ye Dr. Yue-E. Miao Prof. Johan Hofkens Dr. Feili Lai Prof. Tianxi Liu 《Angewandte Chemie (International ed. in English)》2023,62(27):e202218122
Competition from hydrogen/oxygen evolution reactions and low solubility of N2 in aqueous systems limited the selectivity and activity on nitrogen fixation reaction. Herein, we design an aerobic-hydrophobic Janus structure by introducing fluorinated modification on porous carbon nanofibers embedded with partially carbonized iron heterojunctions (Fe3C/Fe@PCNF-F). The simulations prove that the Janus structure can keep the internal Fe3C/Fe@PCNF-F away from water infiltration and endow a N2 molecular-concentrating effect, suppressing the competing reactions and overcoming the mass-transfer limitations to build a robust “quasi-solid–gas” state micro-domain around the catalyst surface. In this proof-of-concept system, the Fe3C/Fe@PCNF-F exhibits excellent electrocatalytic performance for nitrogen fixation (NH3 yield rate up to 29.2 μg h−1 mg−1cat. and Faraday efficiency (FE) up to 27.8 % in nitrogen reduction reaction; NO3− yield rate up to 15.7 μg h−1 mg−1cat. and FE up to 3.4 % in nitrogen oxidation reaction). 相似文献
54.
Highly fluorescent CdTe quantum dots (QDs) stabilized by 3-mercaptopropionic acid were prepared by an aqueous solution approach and used as a fluorescent label to link substance P (SP) in studying the interaction of SP with NK-1 receptor, which was expressed on the AR4-2J cell line. Nonspecific adsorptions of CdTe QDs on the AR4-2J cell membrane were observed, whereas the QD-SP conjugates successfully crossed the cell membrane and entered the cytosol. SP is a neurotransmitter, and neurotransmitter-induced calcium concentration oscillation is a common phenomenon in diverse cells especially of secretory type. Cytosolic calcium concentration responses were studied in the AR4-2J cell line during stimulation with SP and QD-SP conjugates. The oscillations triggered by SP and QD-SP conjugates were dose-dependent and very similar. Such QD-SP conjugates readily internalized into the cytosol as would be expected of an active NK-1 ligand. Therefore QD-SP conjugates could be used successfully to study ligand and NK-1 receptor interactions in live cells. Our research may provide a meaningful reference for congener research. 相似文献
55.
56.
The first total synthesis of penicimutanin A (1) was achieved within 10 steps (LLS). Key innovations in this synthesis consist of (1) a highly efficient electro-oxidative dearomatization; (2) an unprecedented bisoxirane-directed intermolecular aldol reaction from the sterically hindered face of the ketone and (3) the diastereoselective one-step Meerwein–Eschenmoser–Claisen rearrangement enabling the construction of vicinal quaternary stereocenters. Related family members e.g. penicimutanolone (3) and penicimutatin (5) have also been synthesized alongside, elucidating their absolute configurations, hence the absolute configuration of 1.The first total synthesis of penicimutanin A (1) was achieved within 10 steps (LLS). 相似文献
57.
A series of novel rare earth complexes with 11-tungstoferrate as ligand, K15Ln(FeW11 O39)2 .xH2O(Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er or Yb) were prepared and characterized by elemental analyses, IR, UV-vis, polarograms, magnetic susceptibility and thermal measurement.Keywords Heteropoly complex, Rare earth complex, Synthesis, Bis(undecatungstoferrate) lanthanates of potassium 相似文献
58.
TianboZhao HuiyingZhang FengyanLi ChaoYang BaoningZong 《天然气化学杂志》2005,14(2):95-100
ZSM-5/β co-crystalline zeolites with different content of ZSM-5 have been synthesized by adding different amount of ZSM-5 to the synthetic system of β zeolite with NaAlO2, silica sol as the source of aluminum and silica, respectively, and TEA as the template under controlled condition of the synthesis. The ZSM-5/β co-crystalline zeolite was studied by XRD, SEM, BET and NH3-TPD. The reaction activity of toluene alkylation was investigated with a mixture of toluene-methanol as the feedstock in a pulse micro-reactor over the ZSM-5/β co-crystalline zeolite. It is found that ZSM-5/β co-crystalline zeolite has two kinds of zeolite structure including ZSM-5 and β zeolite, not in the form of a physical mixture. The pore structure of ZSM-5/β co-crystalline zeolites is different from that for β zeolite, ZSM-5 and their physical mixture. In addition, the peaks of both high and low temperature desorption of ammonia over the ZSM-5/β co-crystalline zeolite shift 23 ℃ to lower temperatures and the acid amount of its strong acid is 3% more than the physical mixture. So the ZSM-5/β co-crystalline zeolite produces the highest content of xylene, which is 10.4% higher than the physical mixture. And the ZSM-5/β co-crystalline zeolite has better selectivity for toluene alkylation and weaker de-methylation than β zeolite, ZSM-5 and their physical mixture. 相似文献
59.
Direct asymmetric aldol addition of methyl ketones to 2,2,2-trifluoro-1-phenylethanone and its ring-substituted derivatives was achieved using L-proline as a chiral promoter. Various optically active β-trifluoromethyl-β-hydroxy ketones were obtained in almost quantitative yields with moderate enantioselectivities up to 64 % ee. 相似文献
60.
IntroductionElectrontransferreactionsarethekeystepsinphoto synthesis ,respirationandmanyotherbiochemicalprocess es.1Cytochromeb5isaredoxproteinexistingwidelyinnature ,whichactsasanelectron carrierduringvariouselectrontransferprocessesinthebiologicalsystem .2Cytochromeb5isamembraneproteinwithmolecularweightofapproximately 16kDa ,ofwhichthehydrophobicC terminaldomainanchorscytochromeb5tothemem brane ,andthehydrophilicN terminaldomaincontainshemeprostheticgroupandexhibitsthebiologicalfunctionsof… 相似文献