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A new method for regioselective carbomagnesation of alkenes and dienes has been developed by the use of a titanocene catalyst. This reaction proceeds efficiently at 0 degrees C in THF in the presence of Cp(2)TiCl(2) by the combined use of organic halides (R-X; R = alkyl, aryl and vinyl) and n-BuMgCl to afford benzyl, alpha-silylalkyl, or allyl Grignard reagents, which were trapped with various electrophiles. The present reaction involves (i) addition of carbon radicals toward alkenes or dienes in the carbon-carbon bond-forming step and (ii) transmetalation on Ti of benzyl-, alpha-silylalkyl-, or allyltitanocene with n-BuMgCl in the carbon-magnesium bond-forming step. The scope and limitations of this reaction have also been examined. 相似文献
33.
Mixed-metal sulfido cluster [(PdCl2)(Cp*Ir)2(μ3-S)2] (Cp*=η5-C5Me5) dissolved in CH2Cl2 reacted with two equivalent of L (L=nicotinamide, isonicotinamide, or N-methylnicotinamide) in the presence of AgBF4 to give the cationic clusters [(PdL2)(Cp*Ir)2(μ3-S)2][BF4]2. The single-crystal X-ray diffraction studies of these products have disclosed that in the solid state the PdIr2S2 cores are self-assembled to form one-dimensional chains through the intermolecular hydrogen-bonding between the amide groups for L=nicotinamide or two-dimensional sheets via the hydrogen-bonding between the amide groups and the BF4 anions for L=isonicotinamide, whereas no organization of the cluster cores is observed for L=N-methylnicotinamide. 相似文献
34.
An effective method was developed to use an enzyme in ionic liquids; the asymmetric reduction of ketones by Geotrichum candidum in ionic liquids proceeded smoothly with excellent enantioselectivity when the cell was immobilized on water-absorbing polymer containing water, while the reaction without the polymer did not proceed. 相似文献
35.
Sekino E Kumamoto T Tanaka T Ikeda T Ishikawa T 《The Journal of organic chemistry》2004,69(8):2760-2767
(-)-Quinine-catalyzed intramolecular oxo-Michael addition (IMA) of 7-hydroxy-5-methoxy-8-tigloylcoumarins was developed for the enantioselective construction of 2,3-dimethyl-4-chromanone systems in the context of the asymmetric synthesis of anti-HIV-1 active Calophyllum coumarins. Combination of the IMA and MgI(2)-assisted demethylation of the 5-methoxy group along with isomerization of the formed chromanone systems as key steps successfully led to the concise synthesis of (+)-inophyllum B and (+)-calanolide A, possible candidates for AIDS drugs. Further examination of the asymmetric IMA with cinchona alkaloids lacking a methoxy group on the quinoline skeleton suggested the influence of the methoxy substituent on stereoselectivity at the stereogenic centers of the chromanone systems. 相似文献
36.
Kosaka T Yoneyama-Takazawa T Kubota K Matsuoka T Sato I Sasaki T Tanaka Y 《Journal of mass spectrometry : JMS》2003,38(12):1281-1287
We have developed a method for protein identification with peptide mass fingerprinting and sequence tagging using nano liquid chromatography (LC)/Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). To achieve greater sensitivity, a nanoelectrospray (nano-ES) needle packed with reversed-phase medium was used and connected to the nano-ES ion source of the FTICR mass spectrometer. To obtain peptide sequence tag information, infrared multiphoton dissociation (IRMPD) was carried out in nano-LC/FTICR-MS analysis. The analysis involves alternating nano-ES/FTICR-MS and nano-ES/IRMPD-FTICR-MS scans during a single LC run, which provides sets of parent and fragment ion masses of the proteolytic digest. The utility of this alternating-scan nano-LC/IRMPD-FTICR-MS approach was evaluated by using bovine serum albumin as a standard protein. We applied this approach to the protein identification of rat liver diacetyl-reducing enzyme. It was demonstrated that this enzyme was correctly identified as 3-alpha-hydroxysteroid dehydrogenase by the alternating-scan nano-LC/IRMPD-FTICR-MS approach with accurate peptide mass fingerprinting and peptide sequence tagging. 相似文献
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Nobuyuki Otozawa Rio Hamajima Masataka Yoshioka Raito Kato Arisa Tanaka Hiroto Fukuma Toshiki Terao Kei Manabe Syuji Fujii Yoshinobu Nakamura Atsushi Takahara Tomoyasu Hirai 《Journal of polymer science. Part A, Polymer chemistry》2020,58(14):1960-1964
This study investigates the effect of ionic liquids (ILs) on the anionic polymerization of methyl methacrylate (MMA). Polymethyl methacrylate (PMMA), an isotactic polymer, is prepared by anionic polymerization at a high reaction temperature with an IL that acts as both solvent and additive. The most plausible reaction mechanism is determined using 1H NMR and Fourier-transform infrared spectroscopy. The electrostatic interaction between MMA and the IL increases the apparent steric hindrance in MMA, resulting in the isotactic PMMA. 相似文献
40.
Rational Design for Rotaxane Synthesis through Intramolecular Slippage: Control of Activation Energy by Rigid Axle Length
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Hiroshi Masai Dr. Jun Terao Dr. Tetsuaki Fujihara Dr. Yasushi Tsuji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(19):6624-6630
We describe a new concept for rotaxane synthesis through intramolecular slippage using π‐conjugated molecules as rigid axles linked with organic soluble and flexible permethylated α‐cyclodextrins (PM α‐CDs) as macrocycles. Through hydrophilic–hydrophobic interactions and flipping of PM α‐CDs, successful quantitative conversion into rotaxanes was achieved without covalent bond formation. The rotaxanes had high activation barrier for their de‐threading, so that they were kinetically isolated and derivatized even under conditions unfavorable for maintaining the rotaxane structures. 1H NMR spectroscopy experiments clearly revealed that the restricted motion of the linked macrocycle with the rigid axle made it possible to control the kinetic stability by adjusting the length of the rigid axle in the precursor structure rather than the steric bulkiness of the stopper unit. 相似文献