全文获取类型
收费全文 | 2073篇 |
免费 | 367篇 |
国内免费 | 83篇 |
专业分类
化学 | 2257篇 |
晶体学 | 4篇 |
力学 | 2篇 |
综合类 | 8篇 |
数学 | 27篇 |
物理学 | 225篇 |
出版年
2024年 | 3篇 |
2023年 | 29篇 |
2022年 | 43篇 |
2021年 | 83篇 |
2020年 | 162篇 |
2019年 | 106篇 |
2018年 | 89篇 |
2017年 | 67篇 |
2016年 | 128篇 |
2015年 | 129篇 |
2014年 | 128篇 |
2013年 | 151篇 |
2012年 | 115篇 |
2011年 | 111篇 |
2010年 | 85篇 |
2009年 | 80篇 |
2008年 | 94篇 |
2007年 | 118篇 |
2006年 | 115篇 |
2005年 | 92篇 |
2004年 | 94篇 |
2003年 | 88篇 |
2002年 | 45篇 |
2001年 | 35篇 |
2000年 | 31篇 |
1999年 | 42篇 |
1998年 | 33篇 |
1997年 | 43篇 |
1996年 | 38篇 |
1995年 | 27篇 |
1994年 | 19篇 |
1993年 | 23篇 |
1992年 | 12篇 |
1991年 | 6篇 |
1990年 | 8篇 |
1989年 | 8篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1972年 | 2篇 |
1970年 | 3篇 |
1968年 | 2篇 |
排序方式: 共有2523条查询结果,搜索用时 15 毫秒
101.
The generation of free radicals is a key process in the formation and the collapse of the bubbles in water, however, the direct and dynamic observation of the radicals in this process at single bubbles has never been achieved. Here, the hydroxyl (OH.) and oxygen (O2.−) radicals at single oxygen bubbles are continuously traced using chemiluminescence (CL), in which these radicals at the bubble react with the surrounding luminol in the solution emitting the light. Varied increase trends of luminescence are observed in the generation of a bubble, floating, short parking at the water/air interface and the final explosion, revealing the complexity in the distribution of radicals at the bubble unprecedentedly. Despite more radicals are observed at the bubble generated at a deep position under the water for the stabilization, almost the same amount of radicals are included in the bubbles that is independent on the water pressure during the production of the bubble. This rich information collected from the dynamic study of bubbles illustrates the complicated generation and distribution process of radicals at the bubbles, and will facilitate the understanding of the function about the bubbles. 相似文献
102.
Dr. Christian M. Hoidn Dr. Daniel J. Scott Prof. Dr. Robert Wolf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(6):1886-1902
Recently there has been great interest in the reactivity of transition-metal (TM) centers towards white phosphorus (P4). This has ultimately been motivated by a desire to find TM-mediated alternatives to the current industrial routes used to transform P4 into myriad useful P-containing products, which are typically indirect, wasteful, and highly hazardous. Such a TM-mediated process can be divided into two steps: activation of P4 to generate a polyphosphorus complex TM-Pn, and subsequent functionalization of this complex to release the desired phosphorus-containing product. The former step has by now become well established, allowing the isolation of many different TM-Pn products. In contrast, productive functionalization of these complexes has proven extremely challenging and has been achieved only in a relative handful of cases. In this review we provide a comprehensive summary of successful TM-Pn functionalization reactions, where TM-Pn must be accessible by reaction of a TM precursor with P4. We hope that this will provide a useful resource for continuing efforts that are working towards this highly challenging goal of modern synthetic chemistry. 相似文献
103.
Xiao-Fan Jiang Dr. Song-De Han Dr. A-Ni Wang Dr. Jie Pan Prof. Dr. Guo-Ming Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(4):1410-1415
The intermarriage of neutral and tripodal imidazole ligand, tris(4-(1H-imidazol-1-yl)phenyl)amine (TIPA), with zinc phosphite yields two hybrid phosphites, [Zn2(HPO3)2(TIPA)]⋅2 H2O ( 1 ) and [Zn3(HPO3)3(TIPA)]⋅6 H2O ( 2 ). Compound 1 has a hybrid sheet with neutral zinc-phosphite chains as supramolecular building blocks (SBBs), whereas 2 exhibits a 3D hybrid architecture with other neutral zincophosphite chains as supramolecular building blocks. The structural discrepancy between 1 and 2 is mainly due to the distinct linkage modes between organic TIPA ligands and inorganic zincophosphite chains. Interestingly, compounds 1 and 2 feature fast photochromism in response to UV light irradiation under ambient conditions. The discrepancy of photochromic performance between 1 and 2 is mainly due to the different geometrical configuration of the TIPA ligand. Different to majority of reported hybrid photochromic compounds driven by photochromic active units, the photochromism in 1 and 2 is derived from the electron transfer (ET) between phosphite and non-photochromic triimidazole-derivative ligand TIPA. Compared with the widely explored nonphotochromic polypyridine-derivative as electron acceptors (EAs), our work provides a new EA model for the design of hybrid photochromic materials based on the ligand-to-ligand ET mechanism. A multiple anti-counterfeiting application based on 1 and 2 was investigated. 相似文献
104.
The products of base-catalyzed oxidation of secondary aromatic amines were identified by the GC-MS and EPR techniques as nitroxyls, quinone nitrones, quinone imines, and for diarylamines also as the products of C-N bond cleavage-substituted nitrobenzenes, anilines and phenols. It was shown that nitroxyl radicals are the primary paramagnetic products of the reaction and do not form by the interaction of aminyl radicals with dioxygen. A mechanism of the amide ion oxidation through the nonradical addition of dioxygen to the amide ion at the rate-limiting stage is suggested and discussed.The previous report see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1746–1751, October, 1994. 相似文献
105.
Electrochemical Hydroxylation of Arenes Catalyzed by a Keggin Polyoxometalate with a Cobalt(IV) Heteroatom 下载免费PDF全文
Dr. Alexander M. Khenkin Miriam Somekh Dr. Raanan Carmieli Prof. Dr. Ronny Neumann 《Angewandte Chemie (International ed. in English)》2018,57(19):5403-5407
The sustainable, selective direct hydroxylation of arenes, such as benzene to phenol, is an important research challenge. An electrocatalytic transformation using formic acid to oxidize benzene and its halogenated derivatives to selectively yield aryl formates, which are easily hydrolyzed by water to yield the corresponding phenols, is presented. The formylation reaction occurs on a Pt anode in the presence of [CoIIIW12O40]5? as a catalyst and lithium formate as an electrolyte via formation of a formyloxyl radical as the reactive species, which was trapped by a BMPO spin trap and identified by EPR. Hydrogen was formed at the Pt cathode. The sum transformation is ArH+H2O→ArOH+H2. Non‐optimized reaction conditions showed a Faradaic efficiency of 75 % and selective formation of the mono‐oxidized product in a 35 % yield. Decomposition of formic acid into CO2 and H2 is a side‐reaction. 相似文献
106.
L. N. Novikova N. A. Ustynyuk B. L. Tumanskii P. V. Petrovskii A. A. Borisenko S. V. Kukharenko V. V. Strelets 《Russian Chemical Bulletin》1995,44(7):1306-1310
The oxidation of the carbon-centered [(6-C13H9)Cr(CO)3]– anion (1
–) results in formation of (-6:6-9,9-bifluorenyl)bis-chromiumtricarbonyl (3) due to coupling of the intermediate carbon-centered radical (1.). The oxidation of the metal-centered anion [(5-C13H9)Cr(CO)3]– (2
–), which is isomeric to the 1– anion, gives an equilibrium mixture of the chromium-centered radical {(5-C13H9)Cr(CO)3}. (2
.) and its dimer [(5-C13H9)Cr(CO)3]2 (6). Radical2
. readily reacts with MeI and the solvent (THF); the resulting derivatives, (5-C13H9)Cr(CO)3R (R=Me (10); R=H (7)), undergo fast ricochet inter-ring 56 rearrangements into (6-9R-C13H9)Cr(CO)3 (R=CH3 (9); R=H (4)).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1354–1358, July, 1995.The authors are grateful to D. V. Zagorevskii who recorded the mass spectra. This study was financially supported by the Russian Foundation for Basic Research (Grant No. 94-03-05209) and the International Science Foundation (Grant Nos. MQ 4000 and REV 000). 相似文献
107.
A. M. Churakov A. Yu. Tyurin E. L. Goncharova S. L. Ioffe Yu. A. Strelenko V. A. Tartakovsky 《Russian Chemical Bulletin》1995,44(5):890-896
The addition of 1-aryl-2-bromodiazene 1-oxides to olefins yields 1-aryl-2-(2-bromoalkyl)diazene 1-oxides (4). A radical mechanism of the reaction has been suggested. Compounds4 decompose to give bromohydrazones of formaldehyde and aldehydes. The structural factors that affect the rate of this process are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 917–923, May, 1995.The work was carried out in the Scientific Educational Center of the Institute of Organic Chemistry of the RAS with financial support of the Russian Foundation for Basic Research (Project No. 93-03-18461). 相似文献
108.
Mixed-ligand NiIII complexes with -nitroso--naphthol, -nitroso--naphthol,o-ethylxanthate, andN,N-diethyldithiocarbamate as ligands have been studied by ESR in liquid and frozen solutions. The degrees of symmetry distortion for the first coordination sphere of these complexes have been determined. It is shown that the transition from planar square NiIIL2 complexes to more stable octahedral NiIIIL2L and NiIIILL2 complexes occursvia the radical addition mechanism. A method for trapping short-lived radicals is suggested on the basis of the complex formation scheme.Translted fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1513–1515, August, 1995.The work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5050) 相似文献
109.
Tullio Caronna Bruno M. Vittimberga Matthew E. Kornn W. Grant McGimpsey 《Journal of photochemistry and photobiology. A, Chemistry》1995,90(2-3):137-140
The photochemistry of a variety of dicyanopyridines (2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dicyanopyridine) in solution at room temperature was investigated. Pulsed UV (308 nm) laser irradiation in deoxygenated acetonitrile yields the triplet state with lifetimes between 4 and 10 μs and absorption bands in the 400 and 320 nm regions. In the presence of added HCl an air-insensitive transient (τ ≈ 10–12 μs, λmax ≈ 360–380 nm) was observed, suggesting the formation of a protonated excited state.
Irradiation in the presence of amines resulted in the production of the pyridyl radical anion (τ ≈ 40–80 μs, air sensitive, λmax ≈ 360–380 nm) formed by electron transfer from the amine to the pyridine triplet excited state. Stern-Volmer analysis gave electron transfer rate constants in the range (1–8) × 10−8 M−1 s−1.
In methanol solvent, irradiation yielded an air-insensitive transient assigned as the neutral pyridyl radical (τ ≈ 30–200 μs, λmax ≈ 370–385 nm). The formation of these transients is discussed in the context of previous photochemical electron spin resonance and product studies. 相似文献
110.