全文获取类型
收费全文 | 42609篇 |
免费 | 6303篇 |
国内免费 | 5697篇 |
专业分类
化学 | 31221篇 |
晶体学 | 779篇 |
力学 | 2193篇 |
综合类 | 523篇 |
数学 | 4915篇 |
物理学 | 14978篇 |
出版年
2024年 | 53篇 |
2023年 | 496篇 |
2022年 | 748篇 |
2021年 | 1154篇 |
2020年 | 1282篇 |
2019年 | 1466篇 |
2018年 | 1220篇 |
2017年 | 1252篇 |
2016年 | 1783篇 |
2015年 | 1900篇 |
2014年 | 2302篇 |
2013年 | 3114篇 |
2012年 | 3736篇 |
2011年 | 3934篇 |
2010年 | 2977篇 |
2009年 | 2911篇 |
2008年 | 3405篇 |
2007年 | 2992篇 |
2006年 | 2897篇 |
2005年 | 2596篇 |
2004年 | 2109篇 |
2003年 | 1663篇 |
2002年 | 1828篇 |
2001年 | 1360篇 |
2000年 | 1107篇 |
1999年 | 820篇 |
1998年 | 515篇 |
1997年 | 412篇 |
1996年 | 398篇 |
1995年 | 323篇 |
1994年 | 317篇 |
1993年 | 243篇 |
1992年 | 188篇 |
1991年 | 190篇 |
1990年 | 147篇 |
1989年 | 118篇 |
1988年 | 102篇 |
1987年 | 50篇 |
1986年 | 53篇 |
1985年 | 75篇 |
1984年 | 42篇 |
1983年 | 38篇 |
1982年 | 31篇 |
1981年 | 34篇 |
1980年 | 27篇 |
1979年 | 29篇 |
1978年 | 36篇 |
1977年 | 20篇 |
1976年 | 19篇 |
1975年 | 14篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Hu J Chekmenev EY Gan Z Gor'kov PL Saha S Brey WW Cross TA 《Journal of the American Chemical Society》2005,127(34):11922-11923
Recently available ultrahigh magnetic fields offer new opportunities for studies of quadrupole nuclei in biological solids because of the dramatic enhancement in sensitivity and resolution associated with the reduction of second-order quadrupole interactions. Here, we present a new approach for understanding the function and energetics of ion solvation in channels using solid-state 17O NMR spectroscopy of single-site 17O-labeled gramicidin A. The chemical shift and quadrupole coupling parameters obtained in powder samples of lyophilized material are similar to those shown in the literature for carbonyl oxygens. In lipid bilayers, it is found that the carbonyl 17O anisotropic chemical shift of Leu10, one of the three carbonyl oxygens contributing to the ion binding site in gramicidin A, is altered by 40 ppm when K+ ion binds to the channel, demonstrating a high sensitivity to such interactions. Moreover, considering the large breadth of the carbonyl 17O chemical shift (>500 ppm), the recording of anisotropic 17O chemical shifts in bilayers aligned with respect to magnetic field B0 offers high-quality structural restraints similar to 15N and 13C anisotropic chemical shifts. 相似文献
992.
原位氧化还原沉淀水热合成法制备LixMn2O4尖晶石 总被引:3,自引:0,他引:3
Li xMn2O4尖晶石是新一代的锂离子二次电池正极材料 [1], 其合成方法对材料的电化学性质影响很大[2].常规合成大多采用高温固相反应法, 此法具有反应温度高, 反应时间长, 容易产生缺陷和产物不纯净等缺点, 导致所合成的锂离子二次电池正极材料的性能较差. 目前用水热合成法制备电池正极材料Li xMn2O4尖晶石尚未见文献报道. 本文在常规水热合成法的基础上采用原位氧化还原沉淀水热合成法 [3]制备前驱物, 该法合成条件更温和, 而且使材料的综合性能得到了改善和提高. 相似文献
993.
Haengsoon Park 《Tetrahedron》2005,61(26):6352-6367
Only a limited number of ligands have been successfully employed for the Ni-catalyzed asymmetric hydrovinylation reaction. Diarylphosphinites, carrying β-acylamino groups prepared from readily available carbohydrates, in conjunction with highly dissociated counteranions {[(3,5-(CF3)2C6H3]4B− or SbF6−}, effect the hydrovinylation of vinylarenes under ambient pressure of ethylene with high enantioselectivity. Nitrogen substituents such as -COCF3 and COPh groups lead to isomerization of the primary products (3-arylbutenes) to Z- and E-2-aryl-2-butenes. In a prototypical synthesis of a 2-arylproionic acid, (S)-3-(4-bromophenyl)-1-butene (89% ee) has be transformed into (R)-ibuprofen by Ni-catalyzed cross-coupling with i-BuMgBr, followed by oxidation of the double bond with NaIO4 and KMnO4. Asymmetric codimerization of norbonene and ethylene using binaphthol-derived phosphoramidites as ligands gives 1:1, 2:1 or polymeric adducts depending on the relative configurations and nature of the BINAP and amine moieties. With one of the phosphoramidite-Ni complexes, counteranions BAr4− [Ar=3,5-(CF3)2C6H3] and SbF6−, which had been used interchangeably in other reactions, give either a 1:1 adduct or a 2:1 adduct, respectively. 相似文献
994.
Da Yeon Park 《Tetrahedron letters》2006,47(37):6641-6645
Polysubstituted benzene derivatives were synthesized starting from the Baylis-Hillman adducts via the sequential introduction of primary nitroalkane at the primary position, Michael addition to β-branched Michael acceptor, aldol condensation, elimination of nitrous acid, and the final aromatization process. 相似文献
995.
Yi Bo ZHOU Jun An MA Li Xin WANG Qi Lin ZHOU* State Key Laboratoratory Institute of Elemento-Organic Chemistry Nankai University Tianjin 《中国化学快报》2002,13(10)
During the last decade, 1-aminocyclopropanecarboxylic acid and its derivatives (ACCS) have attracted increasing attention of organic and bioorganic chemists due to their outstanding biological properties, ranging from antimicrobial, insecticidal, plant growth and fruit ripening controls, etc.1. Moreover, the three-membered carbocycle provides building blocks of unprecedented synthetic potential because it undergoes selective ring opening, ring enlargement or cycloaddition reactions2. The mo… 相似文献
996.
Yong‐Min Lee Yoon‐Bo Shim Seung Jae Lee Sung Kwon Kang Sung‐Nak Choi 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(12):o733-o734
The structure of the title compound, C15H27N2+·ClO4?, consists of a monoprotonated sparteinium cation and a perchlorate anion. The two tertiary N atoms of the cation, one perchlorate O atom and a H atom form a bifurcated hydrogen bond, the four hydrogen‐bonding atoms being nearly in the same plane. 相似文献
997.
Summary The essential oils have been isolated from tobacco leaves using a simple gas co-distillation apparatus. The method involves co-distillation with water under the continuous stream of an inert gas with subsequent single solvent extraction of the distillate. The extract is analysed on GC and GC/MS in splitless injection mode without further concentration. The method was evaluated for reproducibility using n-octadecane as an internal standard. The distillation-extraction procedure was reporducible with an average deviation of ±3% for the major constituents. The present method was applied to the analyses of the essential oils of other agricultural products.Dedicated to Dr. L. S. Ettre on the occasion of his 60th birthday. 相似文献
998.
Reductive coupling of 1-chloro-2-iodoperfluorocyclobutene (I), cyclopentene (III) and cyclohexene (VI) has been carried out with copper powder and a trace amount of dimethylformamide to give the corresponding 2,2′-dichloroperfluoro-(bi-1-cycloalken-1-yl) derivatives in 69%, 36% and 73% yield, respectively. A reduced by-product, 2H,2′H-dodecafluoro-(bi-1-cyclopenten-1-yl) was also obtained in the copper coupling of (III). Coupling of 1,2-di-iodoperfluorocyclobutene (IX) and cyclopentene (XII) under similar conditions gave good yields of cyclic trimers and tetramers. Mass spectra, infrared and 19F NMR data are discussed. 相似文献
999.
Adsorption of hydrogen chloride (HCl) on water ice films is studied in the temperature range of 100-140 K by using Cs+ reactive ion scattering (Cs+ RIS), low energy sputtering (LES), and temperature-programmed-desorption mass spectrometry (TPDMS). At 100 K, HCl on ice partially dissociates to hydronium and chloride ions and the undissociated HCl exists in two distinct molecular states (alpha- and beta-states). Upon heating of the ice films, HCl molecules in the alpha-state desorb at 135-150 K, whereas those in the beta-state first become ionized and then desorb via recombinative reaction of ions at 170 K. An adsorption kinetics study reveals that HCl adsorption into the ionized state is slightly favored over adsorption into the molecular states at 100 K, leading to earlier saturation of the ionized state. Between the two molecular states, the beta-state is formed first, and the alpha-state appears only at high HCl coverage. At 140 K, ionic dissociation of HCl is completed. The resulting hydronium ion can migrate into the underlying sublayer to a depth <4 bilayers, suggesting that the migration is assisted by self-diffusion of water molecules near the surface. When HCl is covered by a water overlayer at 100 K, its ionization efficiency is enhanced, but a substantial portion of HCl remains undissociated as molecules or contact ion pairs. The observation suggests that three-dimensional surrounding by water molecules does not guarantee ionic dissociation of HCl. Complete ionization of HCl requires additional thermal energy to separate the hydronium and chloride ions. 相似文献
1000.
Hang GONG Nian Fa YANG? Wei Jun TANG Qing Hua FAN Li Wen YANG The College of Chemistry Xiangtan University Xiangtan Laboratory of Chemical Biology Center for Molecular Science Institute of Chemistry Chinese Academy of Sciences Beijing 《中国化学快报》2005,16(8)
Among the reactions in which C-C bonds are formed, the Baylis-Hillman coupling of aldehydes with α, β-unsaturated carbonylic compounds is currently attracting much interest due to the atom economy, the mild conditions and the generation of functional groups1,2. Furthermore, compared to the Heck, Suzuki and other palladium catalyzed C-C bond forming reaction3, the Baylis-Hillman reaction can be promoted by using organic bases in the complete absence of any metal4. However, almost all the … 相似文献