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151.
Hirofumi Kuroda Ikuyoshi Tomita Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1996,34(8):1597-1604
Tri-n-butylphosphine-catalyzed polyadditions of activated internal diynes (bifunctional β-substituted propiolate, 1B and 1C ) with diols are described. Although a terminal bispropiolate ( 1A ) could not produce soluble polymers, with secondary diols, the polyaddition of 1B or 1C with primary as well as secondary diols gave corresponding polymers ( 3 , only composed of E isomeric units) in high yield. The rate of the present polyaddition was estimated by a model reaction of benzyl alcohol with methyl 2-heptynoate ( 4 ), from which the introduction of alkyl groups at the β-position of propiolate moieties was found to decrease the rate of the reaction by 80 times. Furthermore, the rate-determining step on this polymerization system was speculated to be a protonation step of zwitterionic intermediates with protons from diols. © 1996 John Wiley & Sons, Inc. 相似文献
152.
Tadashi Okazaki Fumio Sanda Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1996,34(10):2029-2035
Synthesis and radical ring-opening polymerization of vinylcyclopropane bearing six-membered cyclic acetal moiety, 1-vinyl-4,8-dioxaspiro[2.5]octane (1), were carried out. 1 was prepared by the reaction of 1,1-dichloro-2-vinylcyclopropane and 1,3-propanediol in DMF in the presence of a base. Radical polymerization of 1 was carried out in the presence of an appropriate initiator (3 mol % vs. 1) at 60 and 120°C in degassed sealed ampoules for 20 h. A colorless transparent viscous polymer was obtained by the isolation with preparative HPLC. The structure of poly(1) was determined to consist of two 1,5-ring-opened units and a unit bearing no olefinic moiety. The difference of the activation energies for the ring-opening reaction of the cyclopropane ring calculated by the molecular orbital method could explain the selectivity in the direction of the cleavage of the cyclopropane ring. Acid hydrolysis of poly(1) afforded the corresponding polyketone in quantitative conversion. © 1996 John Wiley & Sons, Inc. 相似文献
153.
Fumio Sanda Toru Abe Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1996,34(10):1969-1975
Syntheses and radical polymerizations of vinyl and isopropenyl carbamates having L -leucine methyl ester structures, N-vinyloxycarbonyl-L -leucine methyl ester (VOC-L-M) and N-isopropenyloxycarbonyl-L -leucine methyl ester (IOC-L-M), were carried out. VOC-L-M and IOC-L-M were prepared by the reactions of L -leucine methyl ester with vinyl and isopropenyl chloroformates in the presence of sodium hydrogen carbonate. The radical polymerization of VOC-L-M with AIBN (1 mol %) in bulk, chlorobenzene, methanol, and N,N-dimethylformamide afforded the corresponding polymer (poly(VOC-L-M)) with M n 7,400–19,000. Meanwhile, IOC-L-M afforded no polymer with AIBN at 60°C but afforded a polymer having low molecular weight with BPO at 80°C. The glass transition temperatures of poly(VOC-L-M) and poly(IOC-L-M) were 53 and 65°C, respectively. The 10% weight loss temperatures of poly(VOC-L-M) and poly(IOC-L-M) under nitrogen were 255 and 173, respectively. The copolymerization parameters of VOC-L-M (M1) and vinyl acetate (M2) were evaluated as r1 = 0.92 and r2 = 0.63. © 1996 John Wiley & Sons, Inc. 相似文献
154.
A combined ion chromatography (IC) with inductively coupled plasma mass spectrometry (ICP—MS) system as an element-selective detector has been used for the determination of arsenic compounds. Seven arsenic compounds were separated by cation-exchange chromatography. Subsequently, the separated arsenic compounds were directly introduced into the ICP—MS and were detected at m/z =75. Detection limits for the seven arsenic compounds ranged from 0.8 to 3.8 μg As/l. The IC–ICP–MS system was applied to the determination of arsenic compounds in the urine of dimethylarsinic acid (DMAA)-exposed rats. DMAA was the most abundant arsenic compound detected. Arsenous acid, monomethylarsonic acid and trimethylarsine oxide were also detected. 相似文献
155.
Ir(III)‐Catalyzed C7‐Position‐Selective Oxidative CH Alkenylation of Indolines with Alkenes in Air
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An efficient method for C7‐position‐selective alkenylation of N‐substituted indolines with alkenes is reported. Various 7‐alkenylindolines were obtained in moderate to excellent yields in air in the presence of catalytic amounts of [Cp*IrCl2]2, AgOTf, and Cu(OAc)2. The protocol relies on the use of a carbonyl or carbamoyl group on the nitrogen atom of indoline as a directing group and is potentially applicable to the synthesis of 7‐alkenylindoles and 7‐alkylindoles. 相似文献
156.
157.
Masanori Miura Takanori Koike Tsukasa Ishihara Fukushi Hirayama Shuichi Sakamoto Minoru Okada 《合成通讯》2013,43(24):3809-3820
A one‐pot synthetic procedure for 2,2′‐disubstituted biaryls was developed via a Suzuki cross‐coupling reaction of aryl triflates in a biphasic solvent system. The effects of various bases and solvents were investigated. Results showed that the Na2CO3–toluene/H2O combination gave the highest yields. 相似文献
158.
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160.
Takahiro Miyata Kozo Matsumoto Takeshi Endo Shigeaki Yonemori Shoji Watanabe 《Journal of polymer science. Part A, Polymer chemistry》2012,50(15):3046-3051
A styrene‐based monomer having a five‐membered cyclic carbonate structure, 4‐vinylbenzyl 2,5‐dioxoran‐3‐ylmethyl ether (VBCE), was prepared by lithium bromide‐catalyzed addition of carbon dioxide to 4‐vinylbenxyl glycidyl ether (VBGE). Radical polymerization of the obtained VBCE was carried out using 2,2′‐azobisisobutyronitrile as an initiator. PolyVBCE with number‐averaged molecular weight higher than 13,800 was obtained by a solution polymerization in N,N‐dimethylformamide, N,N‐dimethylacetamide, dimethyl sulfoxide, and methyl ethyl ketone. The glass transition temperature and 5 wt % decomposition temperature of the polyVBCE were determined to be 52 and 305 °C by differential scanning calorimetry and thermal gravimetry analysis, respectively. It was confirmed that a polymer consisting of the same VBCE repeating unit can be also obtained via chemical modification of polyVBGE, that is, a lithium‐bromide‐catalyzed addition of carbon dioxide to a polyVBGE prepared from a radical polymerization of VBGE. Further copolymerization of VBCE with styrene gave the corresponding copolymer in a high yield. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献