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Shahan Zeb Khan Muhammad Kashif Amir Imdad Ullah Asma Aamir John M. Pezzuto Tamara Kondratyuk Francine Bélanger‐Gariepy Akbar Ali Sajid Khan Zia‐ur‐Rehman 《应用有机金属化学》2016,30(6):392-398
Two new heteroleptic palladium(II) complexes have been synthesized by reacting equimolar quantities of palladium(II) chloride, sodium 4‐(2‐methoxyphenyl)piperazine‐1‐carbodithioate and diphenyl‐p‐tolylphosphine ( 1 ) or tri‐p‐tolylphosphine ( 2 ). Complexes 1 and 2 have been characterized using elemental analysis, Fourier transform infrared spectroscopy, multinuclear NMR (1H, 13C and 31P) spectroscopy and single‐crystal X‐ray analysis. The latter technique confirms a pseudo square‐planar geometry in which two adjacent positions are occupied by bidentate dithiocarbamate while chloro and substituted triphenylphosphine are present at the remaining two positions. The anticancer activity of both complexes against five different cancer cell lines (LU – human lung carcinoma, established at UIC, Department of Surgical Oncology; MCF7 – human breast adenocarcinoma, ATCC number HTB‐22?; MDA‐MB‐231 – human breast adenocarcinoma, ATCC number HTB‐26?; Hepa‐1c1c7 – mouse liver hepatoma, ATCC number CRL‐2026?; PC‐3 – human prostate adenocarcinoma, ATCC number CRL‐1435?) was determined by MTT assay, revealing 2 has higher activity than 1 . A drug–calf thymus DNA binding study with UV–visible spectroscopy reveals a higher DNA binding affinity of 2 (3.511 × 104 M?1) than 1 (4.213 × 103 M?1). Density functional theory studies confirm the relatively more stable nature of 2 than 1 . Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
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Hydroaminomethylation of various olefins with primary and secondary amines was carried out using a simple and efficient rhodium–phosphinite complex catalyst. The influence of various reaction parameters including the effects of temperature, pressure, catalyst loading, time and solvents has been investigated. The present protocol is general with wider substrate applicability for the synthesis of an important class of aliphatic amines and arylethylamines. High activity and selectivity for amines was achieved with a very good substrate/catalyst molar ratio (turnover number 2500) under mild reaction conditions. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
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Synthesis of 1‐silacyclopent‐2‐ene derivatives using 1,2‐hydroboration, 1,1‐organoboration and protodeborylation 下载免费PDF全文
The reaction of di(alkyn‐1‐yl)vinylsilanes R1(H2C═CH)Si(C≡C―R)2 (R1 = Me ( 1 ), Ph ( 2 ); R = Bu (a), Ph (b), Me2HSi (c)) at 25°C with 1 equiv. of 9‐borabicyclo[3.3.1]nonane (9‐BBN) affords 1‐silacyclopent‐2‐ene derivatives ( 3a , 3b , 3c , 4a , 4b ), bearing one Si―C≡C―R function readily available for further transformations. These compounds are formed by consecutive 1,2‐hydroboration followed by intramolecular 1,1‐carboboration. Treated with a further equivalent of 9‐BBN in benzene they are converted at relatively high temperature (80–100°C) into 1‐alkenyl‐1‐silacyclopent‐2‐ene derivatives ( 5a , 5b 6a , 6b ) as a result of 1,2‐hydroboration of the Si―C≡C―R function. Protodeborylation of the 9‐BBN‐substituted 1‐silacyclopent‐2‐ene derivatives 3 , 4 , 5 , 6 , using acetic acid in excess, proceeds smoothly to give the novel 1‐silacyclopent‐2‐ene ( 7 , 8 , 9 , 10 ). The solution‐state structural assignment of all new compounds, i.e. di(alkyn‐1‐yl)vinylsilanes and 1‐silacyclopent‐2‐ene derivatives, was carried out using multinuclear magnetic resonance techniques (1H, 13C, 11B, 29Si NMR). The gas phase structures of some examples were calculated and optimized by density functional theory methods (B3LYP/6‐311+G/(d,p) level of theory), and 29Si NMR parameters were calculated (chemical shifts δ29Si and coupling constants nJ(29Si,13C)). Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
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We develop a fully calibrated positive mathematical programming model for Hawaii's local food systems—which captures the production and the consumer sides of the market. Then we use the model to assess two proposed policies—a general excise tax (GET) exemption on locally produced foods, and an investment in agricultural infrastructure. For the GET exemption case, our results indicate an economic gain of $118 per $100 cost. On the other hand, an investment in 1,200 acres of land injected to support local production may generate an economic gain of up to $357 per $100 annual cost of the investment. However, these estimates should be considered preliminary, and thus viewed with caution. Although the model is used to capture Hawaii's local food systems, we believe that our model is generalizable and can be adopted by other economies to assess their respective food localization policies. Recommendations for Resource Managers
- Local food policies need to be based on quantitative terms instead of mere armchair speculation because often their potential outcomes may vary significantly.
- The current modeling framework demonstrates the potential of using positive mathematical programming (PMP) in capturing the intricacies of local food systems. However, this exploratory exercise should be viewed as preliminary in nature and the ensuing results were taken with caution because many important factors such as labor availability may have been left out.
- Thus, further model refinements are necessary to better capture the complexities of local food systems such as farm heterogeneity, availability of farm labor, water availability, and interisland transportation of farm products in the case of Hawaii.
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Chemical fingerprint analysis and quantitative determination of steroidal compounds from Dioscorea villosa,Dioscorea species and dietary supplements using UHPLC‐ELSD 下载免费PDF全文
Bharathi Avula Yan‐Hong Wang Zulfiqar Ali Troy J. Smillie Ikhlas A. Khan 《Biomedical chromatography : BMC》2014,28(2):281-294
Ultra high‐performance liquid chromatography (UHPLC) with evaporative light scattering detection was used for the quantification of steroidal saponins and diosgenin from the rhizomes or tubers of various Dioscorea species and dietary supplements that were purported to contain Dioscorea. The analysis was performed on an Acquity UPLC? system with an UPLC? BEH Shield RP18 column using a gradient elution with water and acetonitrile. Owing to their low UV absorption, the steroidal saponins were observed by evaporative light scattering detection. The 12 compounds could be separated within 15 min using the developed UHPLC method with detection limits of 5–12 µg/mL with 2 μL injection volume. The analytical method was validated for linearity, repeatability, accuracy, limits of detection and limits of quantification. The relative standard deviations for intra‐ and inter‐day experiments were <3.1%, and the recovery efficiency was 97–101%. The total content of standard compounds was found to be in the ranges 0.01–14.5% and 0.9–28.6 mg daily intake for dry plant materials and solid commercial preparations, respectively. UHPLC–mass spectrometry with a quadrupole mass analyzer and ESI source was used only for confirmation of the identity of the various saponins. The developed method is simple, rapid and especially suitable for quality control analysis of commercial products. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献