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91.
N-Lithioketimines, generated in situ from 2-substituted benzonitriles and t-BuLi, reacted with carbon monoxide to afford five-, six- or seven-membered cyclic products, involving participation by the ortho substituents. The reactions represent new selective transformations of carbonyllithium intermediate which previously were observed to lead to complicated reactions. 相似文献
92.
The ZnCl2 catalyzed reaction of p-methoxybenzyl chloride with alkenes yields the 1:1 addition products 3, which are converted into the γ-lactones 4 via Ru(VIII) catalyzed oxidative degradation of the aromatic ring. 相似文献
93.
Reaction of α-nitro olefins with secondary amines in the presence of palladium(O) catalyst affords allylic amines. 相似文献
94.
Xing Hai Li Xin Ling Yang Xiao Mei Liang Zhen Peng Kai Yun Ling Fu Heng Chen Dao Quan Wang 《中国化学快报》2007,18(12):1476-1478
α-Chlorocycloalkanones(Ⅳ) were synthesized from cycloalkanones via potassiumα-oxocycloalkylsulfonates(Ⅱ).A two-step mechanism was proposed to explain the formation ofⅣfromⅡ. 相似文献
95.
Kai Li Harald D. H. Stver 《Journal of polymer science. Part A, Polymer chemistry》1993,31(10):2473-2479
Narrow disperse microparticles are formed by dispersion polymerization of commercial divinylbenzene in acetonitrile or ethanol solution in the presence of 2,2′-azobis(2-methylpropionitrile) initiator and polyvinylpyrrolidone stabilizer. The particles have average diameters between 1 and 9 μm depending on monomer concentration, solvent, and temperature. While the smaller particles are relatively smooth, surface texture increases with diameter to give popcorn shapes at 9 μm diameter. High crosslinker concentration is shown to be essential for particle formation. © 1993 John Wiley & Sons, Inc. 相似文献
96.
Kai WuQing-Yun Chen 《Journal of fluorine chemistry》2002,113(1):79-83
Treatment of 2,2,2-trifluoroethyl chloride (HCFC-133a) with alcohols (phenols) and aqueous KOH in autoclave at 240-280 °C gives the corresponding 2,2,2-trifluoroethyl (2-chloro-1,1-difluoroethyl) ethers in good yields. 相似文献
97.
Li Z Chen Z Cui H Hales K Qi K Wooley KL Pochan DJ 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7533-7539
Disk and cylindrical micellar assemblies were formed through self-organization of poly(acrylic acid)-b-poly(methyl acrylate)-b-polystyrene (PAA-b-PMA-b-PS) amphiphilic triblock copolymers with organic diamines as counterions in water/ tetrahydrofuran (THF) solvent mixtures. The system was investigated by means of transmission electron microscopy and cryogenic transmission electron microscopy. It was found that the assembled-state morphologies could be modified by alteration of the type and concentration of cationic diamine counterion undergoing interaction with the negatively charged, polyelectrolyte PAA corona block, the relative amount of water in the water/THF mixture, and the hydrophobic block chain length. Multivalency of the organic amine counterion was critical for disk formation. It was further demonstrated that a single block copolymer underwent disc-to-cylindrical micellar transitions reversibly with variation in the relative water/THF ratio. The ability to form disks beginning from either THF-rich or water-rich solutions indicated that the disk morphology was thermodynamically stable and that THF was important in keeping the micellar structure from becoming kinetically frozen. The nanoassemblies were produced having low size dispersities and were stable for at least one month. Intermediate structures between disks and cylinders were also observed, indicating two distinct kinetic pathways between the two micelle structures. 相似文献
98.
Controlled kinetics of non-enzymatic chemiluminescence reactions for simple imaging of DNA and protein 总被引:1,自引:0,他引:1
A robust and sensitive non-enzymatic chemiluminescence (CL) imaging method is presented. In the method a fast-emitting CL reaction is tuned to furnish a slower-emitting reaction suitable for simple CL imaging. Typically, non-enzymatic CL reactions between luminol or fluorescein and oxygen species generated by KCN as catalyst, were rather fast and unsuitable for CL imaging; the speed of the reactions could, however, be reduced substantially by changing KCN for CH(3)CN or benzonitrile. Light emission from the tuned CL reaction was intense and long-lived, and even with a simple arrangement high sensitivity could be achieved. The maximum CL peak was reached after approximately 1.5 min in the presence of 25% acetonitrile, and as little as 16 fmol commercial isoluminol-labeled streptavidin was detected and visualized on either microplate or membrane. The approach was further illustrated by imaging of DNA on a membrane and of antibody on a microplate by use of biotin-streptavidin chemistry. Overall, this simple, economical, and sensitive CL imaging system is expected to be very useful in biochemical analysis, and greatly complements currently used enzyme-based CL imaging methods, especially in routine applications. 相似文献
99.
100.
Methyl radical complexes H3C…HCN and H3C…HNC have been investigated at the UMP2(full)/aug‐cc‐pVTZ level to elucidate the nature of hydrogen bonds. To better understand the intermolecular H‐bond interactions, topological analysis of electron density at bond critical points (BCP) is executed using Bader's atoms‐in‐molecules (AIM) theory. Natural bond orbital (NBO) analysis has also been performed to study the orbital interactions and change of hybridization. Theoretical calculations show that there is no essential difference between the blue‐shift H‐bond and the conventional one. In H3C…HNC complex, rehybridization is responsible for shortening of the N? H bond. The hyperconjugative interaction between the single electron of the methyl radical and N? H antibonding orbital is up to 7.0 kcal/mol, exceeding 3.0 kcal/mol, the upper limit of hyperconjugative n(Y)→σ*(X–H) interaction to form the blue‐shifted H‐bond according to Alabugin's theory. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献