全文获取类型
收费全文 | 23177篇 |
免费 | 2185篇 |
国内免费 | 6371篇 |
专业分类
化学 | 29062篇 |
晶体学 | 380篇 |
力学 | 132篇 |
综合类 | 187篇 |
数学 | 101篇 |
物理学 | 1871篇 |
出版年
2024年 | 37篇 |
2023年 | 219篇 |
2022年 | 547篇 |
2021年 | 634篇 |
2020年 | 828篇 |
2019年 | 693篇 |
2018年 | 706篇 |
2017年 | 782篇 |
2016年 | 1100篇 |
2015年 | 1079篇 |
2014年 | 1359篇 |
2013年 | 2300篇 |
2012年 | 1599篇 |
2011年 | 1655篇 |
2010年 | 1391篇 |
2009年 | 1599篇 |
2008年 | 1645篇 |
2007年 | 1727篇 |
2006年 | 1746篇 |
2005年 | 1650篇 |
2004年 | 1590篇 |
2003年 | 1353篇 |
2002年 | 879篇 |
2001年 | 601篇 |
2000年 | 511篇 |
1999年 | 527篇 |
1998年 | 476篇 |
1997年 | 431篇 |
1996年 | 334篇 |
1995年 | 331篇 |
1994年 | 288篇 |
1993年 | 275篇 |
1992年 | 262篇 |
1991年 | 138篇 |
1990年 | 93篇 |
1989年 | 88篇 |
1988年 | 73篇 |
1987年 | 41篇 |
1986年 | 28篇 |
1985年 | 36篇 |
1984年 | 28篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 9篇 |
1980年 | 7篇 |
1978年 | 2篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Yuanbo Gao Tingting Yang Xueli Wang Jizong Chen Yong He 《Journal of polymer science. Part A, Polymer chemistry》2022,60(10):1610-1623
Two series of novel alternating copolyoxamides (PAnT-alt-n2 and PAn2-alt-62) are synthesized via solution/solid-state polycondensation (SSP). The alternating structures are analyzed carefully with 1H NMR and 13C NMR spectra. The melting behaviors, thermal stabilities, crystal structures and crystallinities are systematically evaluated by DSC, TGA and WAXD. The results reveal that these alternating copolyoxamides possess almost perfect alternating chain structures and have high melting temperature (Tm > 270 °C), high crystallinity (Xc > 32%) and high decomposition temperature (T5 > 405 °C) as well as low saturated water absorption (<3.5 wt%), which suggests that they have high potential as engineering plastic of high heat resistant. 相似文献
2.
Qianqian Fan Zirui Liu Feng Qiu Prof. Yong Mao Prof. Qingju Liu Prof. Longzhou Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(63):e202202700
The artificially accurate design of nonmetal electrocatalysts’ active site has been a huge challenge because no pure active species with the specific structure could be strictly controlled by traditional synthetic methods. Species with a multiconfiguration in the catalyst hinder identification of the active site and the subsequent comprehension of the reaction mechanism. We have developed a novel electro-assisted molecular assembly strategy to obtain a pure pentagon ring on perfect graphene avoiding other reconstructed structures. More importantly, the active atom was confirmed by the subtle passivation process as the topmost carbon atom. Recognition of the carbon-defect electrocatalysis reaction mechanism was first downsized to the single-atom scale from the experimental perspective. It is expected that this innovative electro-assisted molecular assembly strategy could be extensively applied in the active structure-controlled synthesis of nonmetal electrocatalysts and verification of the exact active atom. 相似文献
3.
Kento Nishikibe Keisuke Nishikawa Momochika Kumagai Matsumi Doe Yoshiki Morimoto 《化学:亚洲杂志》2022,17(1):e202101137
There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis. 相似文献
4.
《Mendeleev Communications》2022,32(1):105-108
A mixed-metal 1D coordination polymer [CaCu(HBTC)2(H2O)8]n (where H3BTC – benzene-1,3,5-tric arboxylic acid) was obtained in a solvothermal synthesis of a well-known copper-containing metal–organic framework [Cu3(BTC)2(H2O)3]n (HKUST-1) in autoclaves 3D-printed from commercial polypropylene. This material was a source of calcium ions, apparently, leaking from a colorant (calcium carbonate) promoted by glacial acetic acid as a modulator used to produce large single crystals of HKUST-1. This finding was confirmed by elemental analysis and a model experiment that resulted in a new calcium-based 1D coordination polymer [Ca(H2BTC)2(H2O)5]n under the same solvothermal conditions with no copper or calcium salts put into a 3D-printed autoclave. 相似文献
5.
Reza Kordnezhadian Bing-Yu Li Armir Zogu Dr. Joachim Demaerel Prof. Dr. Wim M. De Borggraeve Dr. Ermal Ismalaj 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201491
Pentafluorosulfanyl (SF5)-containing compounds and corresponding analogs are a highly valuable class of fluorine-containing building blocks owing to their unique properties. The reason for that is the set of peculiar and tremendously beneficial characteristics they can impart on molecules once introduced onto them. Despite this, their application in distinct scientific fields remains modest, given the extremely harsh reaction conditions needed to access such compounds. The recent synthetic approaches via S−F, and C−SF5 bond formation as well as the use of SF5-containing building blocks embody a “stairway-to-heaven” loophole in the synthesis of otherwise-inaccessible chemical scaffolds only a few years ago. Herein, we report and evaluate the properties of the SF5 group and analogs, by summarizing synthetic methodologies available to access them as well as following applications in material science and medicinal chemistry since 2015. 相似文献
6.
Tapasi Chand Laxmikanta Khamari Deepak Chopra Saptarshi Mukherjee Manmohan Kapur 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(43):e202200723
A one-step Rh-catalyzed site-selective ortho-C−H alkynylation of perylene as well as naphthalene mono- and diimides is reported. A single step regioselective access to ortho-C−H alkynylated derivatives of these ryleneimides not only increases the step economy of the ortho-functionalization on these dyes but also provides a quick access route towards highly functionalized dyes that have potential optoelectronic applications. Increased solubility of tetra(triisopropylsilyl)acetylenyl PDIs in organic solvents greatly enhances their utility for further derivatization. 相似文献
7.
Dr. Antonio M. Rodríguez Dr. Pilar Prieto Prof. Antonio de la Hoz Prof. Ángel Díaz-Ortiz D. Raúl Martín Prof. José I. García 《ChemistryOpen》2015,4(3):308-317
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation. 相似文献
8.
Functional zinc(II) phthalocyanines bearing Schiff base complexes as oxidation catalysts for bleaching systems 下载免费PDF全文
Oxidation catalysis is used to increase the performance of hydrogen peroxide in laundry bleach applications. Bleach catalysts provide cost‐effective, energy‐saving and environmentally friendly bleach systems yielding perfect stain removal at lower temperatures. This comparative study is based on the synthesis of bis[bis(salicylhydrazonephenoxy)manganese(III)] phthalocyaninatozinc(II) ( 2 ), bis[bis(salicylhydrazonephenoxy)cobalt(III)] phthalocyaninatozinc(II) ( 3 ) and bis[bis(salicylhydrazonephenoxy)iron(III)] phthalocyaninatozinc(II) ( 4 ) as tri‐nuclear complexes consisting of two Schiff base complexes substituting a zinc phthalocyanine. Complexion on the periphery to obtain complexes 2 , 3 , 4 was performed through the reaction of a Schiff base‐substituted phthalocyanine using MnCl2?4H2O, CoCl2?6H2O or FeCl3?6H2O salts in basic condition in dimethylformamide. Fourier transform infrared, 1H NMR, 13C NMR, UV–visible, inductively coupled plasma optical emission and mass spectra were applied to characterize the prepared compounds. The bleach performances of the three phthalocyanine compounds 2 , 3 , 4 were examined by the degradation of morin as hydrophilic dye. The degradation progress in the presence of catalysts 2 , 3 , 4 /H2O2 combination in aqueous solution was investigated using an online spectrophotometric method. It was found that the catalysts 2 , 3 , 4 exhibited better bleaching performance at 25 °C than tetraactylethylethylenediamine as bleach activator used in powder detergent formulations for stain removal. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
9.
以4-羟基吲哚为原料,经吲哚环4位乙酰基化、3位亲电取代、酰胺化和还原加氢等反应合成目标化合物7.通过核磁共振氢谱及碳谱对化合物进行结构表征,并对目标化合物进行体外抗氧化生物活性测试.初步生物活性测试结果表明,化合物7a,7b,7c和7d对DPPH·均有很强的清除作用(清除率为85.25%~90.73%),7e,7f,7g,7h作用较差;目标化合物与Vc相比,对·OH的清除作用稍差,最高清除率25.66%(Vc的最高清除率为34.67),但各化合物整体水平相当;在清除O-2·能力上化合物7a,7d,7g,7h最大清除率(分别为19.34,35.35,27.93和31.74)均强于同等浓度的Vc(17.58). 相似文献
10.
The paper presents the synthesis and catalytic activity of CuFe2O4 nanoparticles. The CuFe2O4 nanoparticles have been prepared by sonochemical route under low power ultrasonic irradiation (UI) and using silent stirring at room temperature only (ST) along with co-precipitation method, without using any additive/capping agent. The synthesized magnetic nanoparticles were successfully used and compared for the synthesis of 4H-chromene-3-carbonitrile derivatives. The CuFe2O4 nanoparticles obtained by sonochemical route exhibit higher catalytic activity because of small size (0.5–5 nm), high surface area (214.55 m2/g), high thermal stability up to 700 °C, recyclability and reusability due to its magnetic characteristics than CuFe2O4 nanoparticles obtained by room temperature silent stirring. The synthesized CuFe2O4 nanoparticles were characterized by FT-IR, SEM–EDX, HR-TEM, XRD, TGA/DTA/DTG, BET, VSM techniques. The present method is of great interest due to its salient features such as environmentally compatible, efficient, short reaction time, chemoselectivity, high yield, cheap, moisture insensitive, green and recyclable catalyst which make it sustainable protocol. 相似文献