全文获取类型
收费全文 | 11021篇 |
免费 | 969篇 |
国内免费 | 219篇 |
专业分类
化学 | 8865篇 |
晶体学 | 23篇 |
力学 | 35篇 |
综合类 | 5篇 |
数学 | 85篇 |
物理学 | 3196篇 |
出版年
2023年 | 86篇 |
2022年 | 150篇 |
2021年 | 210篇 |
2020年 | 349篇 |
2019年 | 268篇 |
2018年 | 250篇 |
2017年 | 184篇 |
2016年 | 374篇 |
2015年 | 348篇 |
2014年 | 457篇 |
2013年 | 698篇 |
2012年 | 416篇 |
2011年 | 498篇 |
2010年 | 405篇 |
2009年 | 486篇 |
2008年 | 498篇 |
2007年 | 553篇 |
2006年 | 478篇 |
2005年 | 387篇 |
2004年 | 334篇 |
2003年 | 363篇 |
2002年 | 1238篇 |
2001年 | 233篇 |
2000年 | 173篇 |
1999年 | 198篇 |
1998年 | 183篇 |
1997年 | 106篇 |
1996年 | 108篇 |
1995年 | 132篇 |
1994年 | 67篇 |
1993年 | 59篇 |
1992年 | 50篇 |
1991年 | 42篇 |
1990年 | 31篇 |
1988年 | 24篇 |
1987年 | 25篇 |
1985年 | 92篇 |
1984年 | 118篇 |
1983年 | 106篇 |
1982年 | 150篇 |
1981年 | 113篇 |
1980年 | 97篇 |
1979年 | 100篇 |
1978年 | 106篇 |
1977年 | 144篇 |
1976年 | 118篇 |
1975年 | 129篇 |
1974年 | 165篇 |
1973年 | 133篇 |
1972年 | 82篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
Benjamin Prek Jure Bezenšek Marta Kasunič Uroš Grošelj Jurij Svete Branko Stanovnik 《Tetrahedron》2014
Herein a simple one-pot metal-free synthesis of alkyl-, aryl-, heteroaryl- and alkoxycarbonyl substituted 1,3-bis(dimethylamino)benzene derivatives is described. The products were prepared from the corresponding methyl ketones or compounds with an α-methylene group in regard to the carbonyl group, using N,N-dimethylacetamide dimethyl acetal (DMADMA) as the reagent. 相似文献
72.
Functionalized 6-substituted-thiosalicylates are key intermediates for the synthesis of pyrimidinyl(thio)salicylic acids, a group of important herbicides targeting plant acetohydroxyacid synthase. Therefore, it is of great interest to develop an efficient method for the syntheses of 6-substituted-thiosalicylates. Herein, we have developed a direct and efficient method for the synthesis of functionalized 6-substituted-thiosalicylates (4) from aryl iodide (1) by using an improved microwave-assisted Suzuki cross-coupling reaction. Almost all the reactions proceeded smoothly and afforded moderate to excellent yields of products. Moreover, this protocol is obviously superior to the traditional available methods and could be utilized to synthesize pyrimidinyl(thio)salicylic acid and its derivatives. 相似文献
73.
A facile efficient synthesis of novel 3-aryl-5,6-dihydro-1,4,2-oxathiazin-6-ols from the reaction of (E)-N-hydroxyarylimidoyl chlorides and 1,4-dithiane-2,5-diol in the presence of triethylamine is described. This transformation presumably proceeds via in situ generation of 2-mercaptoacetaldehyde and nitrile oxide and their concomitant [3+3] annulation. 相似文献
74.
《Arabian Journal of Chemistry》2014,7(5):623-629
The multi-component reaction of 1-benzothiopyran-4-ones with heterocyclic amines and dimethylformamide-dimethylacetal (DMFDMA) in DMF at 150 °C under controlled microwave heating afforded novel poly-heterocyclic ring systems. Also, reaction of 3-dimethylaminomethylene-1-benzothiopyran-4-one with activemethylene derivatives was investigated. The structure of all products was established on the bases of spectral data and elemental analyses and alternative synthesis if possible. The prepared compounds were screened for their antitumor activity against HCT-116 “colon” cancer cell line and some derivatives showed promising activity. 相似文献
75.
Katharina Röser Bettina Berger Prof. Michael Widhalm Prof. Mario Waser 《ChemistryOpen》2021,10(8):756-759
We herein report an asymmetric protocol to access a series of orthogonally functionalized acyclic chiral target molecules containing a quaternary stereogenic center by carrying out the enantioselective α-alkylation of novel orthogonally functionalized dioxolane-containing cyanoacetates under chiral ammonium salt catalysis. By using just 1 mol % of Maruoka's spirocyclic ammonium salt catalysts enantioselectivities up to e.r.=97.5 : 2.5 could be achieved and further functional group manipulations of the products were carried out as well. 相似文献
76.
Brønsted acid-catalyzed inverse-electron demand (IED) aza-Diels-Alder reactions between 2-aza-dienes and ethylene were studied using quantum chemical calculations. The computed activation energy systematically decreases as the basic sites of the diene progressively become protonated. Our activation strain and Kohn-Sham molecular orbital analyses traced the origin of this enhanced reactivity to i) “Pauli-lowering catalysis” for mono-protonated 2-aza-dienes due to the induction of an asynchronous, but still concerted, reaction pathway that reduces the Pauli repulsion between the reactants; and ii) “LUMO-lowering catalysis” for multi-protonated 2-aza-dienes due to their highly stabilized LUMO(s) and more concerted synchronous reaction path that facilitates more efficient orbital overlaps in IED interactions. In all, we illustrate how the novel concept of “Pauli-lowering catalysis” can be overruled by the traditional concept of “LUMO-lowering catalysis” when the degree of LUMO stabilization is extreme as in the case of multi-protonated 2-aza-dienes. 相似文献
77.
In situ and operando techniques providing information regarding adsorbate bonding and atomic arrangements on the electrode surface along with pure electrochemical measurements are needed to more fully understand the detailed mechanism of electrocatalytic reactions on high surface areas/nanoparticle electrocatalysts. X-ray adsorption spectroscopy (XAS) is a powerful tool to interrogate the electronic structure and local coordination environment of such electrocatalysts under working conditions, but it should be acknowledged that standard XAS methods are not intrinsically surface sensitive. This review will present recent in situ XAS studies on single-atom, metal, and metal oxide electrocatalysts, highlighting the approaches taken to achieve surface sensitivity by careful designing of the sample under investigation. 相似文献
78.
The volatile compounds from insects (Tenebrio molitor and Zophobas morio larvae) roasted at 160, 180, or 200 °C and fed with potato starch or blue corn flour were isolated by solid-phase microextraction (SPME), and identified by gas chromatography–mass spectrometry (GC-MS). In the tested material, 48 volatile compounds were determined. Among them, eight are pyrazines, aroma compounds that are formed in food products during thermal processing due to the Maillard reaction. Eleven of the identified compounds influenced the roast, bread, fat, and burnt aromas that are characteristic for traditional baked dishes (meat, potatoes, bread). Most of them are carbonyl compounds and pyrazines. To confirm the contribution of the most important odorants identified, their odor potential activity values (OAVs) and %OAV were calculated. The highest value was noted for isobuthylpyrazine, responsible for roast aroma (%OAV > 90% for samples roasted at lower temperatures), and 2,5-dimethylpyrazine, responsible for burnt aroma (%OAV > 20% for samples roasted at the highest temperature). According to the study, the type of feed did not significantly affect the results of the sensory analysis of roasted insects. The decisive influence was the roasting temperature. The highest scores were achieved for Tenebrio molitor larvae heat-treated at 160 °C. 相似文献
79.
Fabricio R. Bisogno Rosario Fernndez Jose María Lassaletta Gonzalo de Gonzalo 《Molecules (Basel, Switzerland)》2021,26(2)
Room temperature ionic liquids (RTILs) have been widely used as (co)solvents in several catalytic processes modifying, in most of the cases, the catalyst activity and/or the selectivity for the studied reactions. However, there are just a few examples of their use in hydrogen bonding organocatalysis. In this paper, we show the positive effect of a set of imidazole-based ionic liquids ([bmim]BF4 and [hmim]PF6) in the enantioselective addition of formaldehyde tert-butylhydrazone to prochiral α-keto esters catalyzed by a sugar-based chiral thiourea. Reactions performed in the presence of low percentages of RTILs led to an increase of the catalyst activity, thereby making possible to work at lower temperatures. Thus, the chiral tert-butyl azomethyl tertiary alcohols could be obtained with moderate to good conversions and higher enantioselectivities for most of the studied substrates when using up to 30 vol% of [hmim]PF6 as a cosolvent in processes performed in toluene. 相似文献
80.
The structure of uleine type alkaloids is characterized by the presence of a bridged tetracyclic hexahydro-1H-1,5-methanoazocino[4,3-b]indole ring system 1 . Various strategies have been developed to access this polycyclic structural motif. We report herein a one-step conversion of appropriately functionalized 1,3,4-trisubstituted cyclopent-1-ene to 1 by way of an integrated oxidation/reduction/cyclization (iORC) process. This domino sequence, initiated by oxidative cleavage of cyclopentene ring, generated subsequently a cyclohexenone, an indole and a 1,3-bridged piperidine ring through formation of one C−C and two C−N bonds. Compound 1 is subsequently converted to nordasycarpidone, dasycarpidone and uleine. The chirality of the molecule was introduced by enzymatic desymmetrization of commercially available meso cis-3,5-diacetoxy-1-cyclopentene. 相似文献