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71.
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Terhi Oja Petri Tähtinen Nadine Dreiack Pekka Mäntsälä Jarmo Niemi Mikko Metsä-Ketelä Karel D. Klika 《Tetrahedron: Asymmetry》2012,23(9):670-682
Two new pairs of stereoisomeric alnumycin As, A2 {(2)-(1R,1′RS,4′SR,5′SR)} and A3 {(2)-(1R,1′RS,4′SR,5′RS)}, are described. Similar to alnumycin A1 {(2)-(1R,1′RS,4′RS,5′SR)}, each of these naturally occurring compounds is also a pair of C-1 inverse epimers. The relative configurations of the dioxane ring sidechains were assigned on the basis of 1H NMR NOE contacts and molecular modeling using density functional theory (DFT) at the M06-2X/6-31G(d) level of theory. The absolute configurations of C-1 and the determination of inverse epimeric relationships were achieved by experimental electronic circular dichroism (ECD) measurements, with both aspects confirmed by using the chiral derivatizing agent (CDA) Mosher′s acid chloride {α-methoxy-α-trifluorophenylacetyl chloride (MTPACl)} to effect enantiodifferentiation. The absolute configurations of the dioxane ring using the CDA could only be effected in the case of alnumycin A1, the results of which were in agreement with previous assignments. The dioxane ring conformational mobility and the likely interaction between the MTPA groups coupled with the structural novelty of the diols in the dioxane ring with respect to CDA analysis precluded an absolute configuration assignment for alnumycins A2 and A3 based on empirical comparisons or by computational analysis of through-space NMR shieldings (TSNMRS) emanating from the phenyl groups of the MTPA moieties. 相似文献
74.
Masoud Behzad Karel Samec Sang-In Bak Yacine Kadi Claudio Tenreiro Seung-Woo Hong Jong-Seo Chai 《Journal of Radioanalytical and Nuclear Chemistry》2014,299(2):1001-1006
A worldwide challenge in the near future will be to find a way of producing radioisotopes in sufficient quantity without relying on research reactors. The motivation for this innovative work on targets lies in the accelerator-based production of radioisotopes using a neutron converter target as in the transmutation by adiabatic resonance crossing concept. Thermal analysis of a multi-channel helium cooled device is performed with the computational fluid dynamics code CFX. Different boundary conditions are taken into account in the simulation process and many important parameters such as maximum allowable solid target temperature as well as uniform inlet velocity and outlet pressure changes in the channels are investigated. The results confirm that the cooling configuration works well; hence such a solid target could be operated safely and may be considered for a prototype target. 相似文献
75.
Willem Karel M. Brauers 《Annals of Operations Research》2013,206(1):39-58
An approach is needed to localize in an optimal way a seaport facing different indicators, criteria or objectives sometimes from different groups or individuals. The internal mechanical solution of a Ratio System, producing dimensionless numbers, is preferred to Cost-Benefit or to Weights which most of the time are used to equalize the different units. The ratio system creates the opportunity to use a second approach: a non-subjective Reference Point Theory based on the found ratios. The two approaches form a control on each other. This theory is called MOORA (Multi-Objective Optimization by Ratio Analysis). As an application a ranking is made for the best location of a new seaport or for the expansion of an existing one given a set of objectives to be fulfilled. 相似文献
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Nina Gusarova Lambert Brandsma Svetlana Malysheva Svetlana Arbuzova Boris Trofimov 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Nucleophilic addition of phosphide anions generated from phosphorus red or phosphine to ethenes and ethynes in the presence of super bases to afford organylphosphines and -oxides has been performed. 相似文献
78.
The 2,5-diketopiperazine (DKP) moiety is a core feature of many natural products and medicinally relevant scaffolds. As part of our efforts directed towards a total synthesis of penicisulfuranol B, we have developed and report herein: (1) the preparation of an N-hydroxy diketopiperazine intermediate accessible via a molybdenum-mediated oxidation of a parent diketopiperazine, and (2) further synthetic studies leading to a novel spirocyclic dihydrobenzofuran-containing diketopiperazine. 相似文献
79.
David ilha Karolína varcov Tom Bajer Karel Krlovec Elika Tesaov Kristýna Mou
kov Marcela Pejchalov Petra Bajerov 《Molecules (Basel, Switzerland)》2020,25(23)
Hydrolates obtained via the hydrodistillation and steam distillation of Lavandula angustifolia Mill., Syzygium aromaticum L., Foeniculum vulgare Mill., and Laurus nobilis L. were analyzed by gas chromatography with flame ionization detector (GC-FID) and gas chromatography coupled to mass spectrometry (GC-MS). Additionally, the hydrolates were evaluated for antimicrobial activity (disk-diffusion and microdilution method), influence on biofilm formation (Christensen method) and cytotoxicity of concentrated hydrolates against human cell lines (A549) by xCELLigence system. Using chemical analysis, 48, 9, 13 and 33 different components were detected in lavender, clove, fennel and laurel hydrolates, respectively. Lavender hydrolate contained the largest proportion of 1,8-cineol, linalool furanoxide, and linalool. The main components of laurel hydrolate were 1,8-cineol, 4-terpineol and α-terpineol. Fenchone and estragole were the most abundant in fennel hydrolate, and eugenol and eugenyl acetate in clove hydrolate. Concentrated hydrolates showed significant antimicrobial activity. Clove hydrolate was among the most antimicrobially active agents, most preferably against C. albicans, with an inhibition zone up to 23.5 mm. Moreover, concentrated hydrolates did not show any cytotoxic effect again8 st human A549 cells. In the presence of the non-concentrated hydrolates, significantly reduced biofilm formation was observed; however, with concentrated clove hydrolate, there was an increase in biofilm formation, e.g., of A. thereius, A. lanthieri, and A. butzleri. Research shows new findings about hydrolates that may be important in natural medicine or for preservation purposes. 相似文献
80.
The Hydrazine–O2 Redox Couple as a Platform for Organocatalytic Oxidation: Benzo[c]cinnoline‐Catalyzed Oxidation of Alkyl Halides to Aldehydes
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Ilana B. Stone Dr. Janis Jermaks Dr. Samantha N. MacMillan Prof. Tristan H. Lambert 《Angewandte Chemie (International ed. in English)》2018,57(38):12494-12498
An organocatalytic oxidation platform that capitalizes on the capacity of hydrazines to undergo rapid autoxidation to diazenes is described. Commercially available benzo[c]cinnoline is shown to catalyze the oxidation of alkyl halides to aldehydes in a novel mechanistic paradigm involving nucleophilic attack, prototropic shift, and hydrolysis. The hydrolysis and reoxidation events occur readily with only adventitious oxygen and water. A survey of the scope of viable substrates is shown along with mechanistic and computational studies that give insight into this mode of catalysis. 相似文献