全文获取类型
收费全文 | 1306篇 |
免费 | 31篇 |
国内免费 | 7篇 |
专业分类
化学 | 1002篇 |
晶体学 | 16篇 |
力学 | 13篇 |
数学 | 58篇 |
物理学 | 255篇 |
出版年
2020年 | 7篇 |
2019年 | 9篇 |
2018年 | 6篇 |
2016年 | 13篇 |
2015年 | 23篇 |
2014年 | 19篇 |
2013年 | 77篇 |
2012年 | 66篇 |
2011年 | 57篇 |
2010年 | 35篇 |
2009年 | 40篇 |
2008年 | 61篇 |
2007年 | 74篇 |
2006年 | 85篇 |
2005年 | 82篇 |
2004年 | 73篇 |
2003年 | 66篇 |
2002年 | 48篇 |
2001年 | 28篇 |
2000年 | 22篇 |
1999年 | 16篇 |
1998年 | 11篇 |
1997年 | 16篇 |
1996年 | 19篇 |
1995年 | 14篇 |
1994年 | 10篇 |
1993年 | 6篇 |
1992年 | 20篇 |
1991年 | 12篇 |
1990年 | 14篇 |
1989年 | 13篇 |
1988年 | 9篇 |
1987年 | 9篇 |
1986年 | 10篇 |
1985年 | 24篇 |
1984年 | 17篇 |
1983年 | 14篇 |
1982年 | 20篇 |
1981年 | 19篇 |
1980年 | 19篇 |
1979年 | 23篇 |
1978年 | 10篇 |
1977年 | 22篇 |
1976年 | 14篇 |
1975年 | 12篇 |
1974年 | 12篇 |
1973年 | 11篇 |
1972年 | 6篇 |
1968年 | 5篇 |
1967年 | 5篇 |
排序方式: 共有1344条查询结果,搜索用时 125 毫秒
41.
2,3-Dideoxy-3-fluoro-α-d-ribose 1-phosphate 2 was stereoselectively synthesized and converted to 2′,3′-dideoxy-3-fluoro-β-d-guanosine 1 by enzymatic reaction using purine nucleoside phosphorylase. This chemo-enzymatic strategy was first applied to the synthesis of 1. 相似文献
42.
Tsuda M Izui N Shimbo K Sato M Fukushi E Kawabata J Katsumata K Horiguchi T Kobayashi J 《The Journal of organic chemistry》2003,68(13):5339-5345
A novel cytotoxic 16-membered macrodiolide, amphidinolide X (1), has been isolated from a marine dinoflagellate Amphidinium sp. (strain Y-42). The gross structure of 1 was elucidated on the basis of spectroscopic data including one-bond and long-range (13)C-(13)C correlations. The relative and absolute stereochemistries were determined by combined analyses of NOESY data and (1)H-(1)H and (1)H-(13)C coupling constants of 1 and NMR data of the degradation products. Amphidinolide X (1) is the first macrodiolide consisting of polyketide-derived diacid and diol units from natural sources. The biosynthetic origins of 1 were investigated by means of feeding experiments with (13)C-labeled acetates. 相似文献
43.
Takeo Iida Motoharu Nakanishi Kunio Got
《Journal of polymer science. Part A, Polymer chemistry》1974,12(4):737-749
Poly(vinyl chloride) (PVC) alone or mixed with 10 wt-% and 50 wt-% TiO2, SnO2, ZnO, and Al2O3 were pyrolyzed by using a pyrolysis gas chromatograph. Benzene, toluene, ethylbenzene, o-xylene, styrene, naphthalene, and various chlorobenzenes were identified. No hydrocarbons could be detected in pyrolysis products of any samples at 200°C. More aromatic hydrocarbons than aliphatic hydrocarbons are released from the PVC–TiO2 system and in preheated PVC. The contrary result is observed in the PVC–ZnO and PVC–SnO2 systems. Aromatics having methyl endgroups are easily released from the PVC–ZnO and PVC–SnO2 systems and at elevated pyrolysis temperature, because methylene groups are easily isolated along the chain by ZnO, SnO2 and the heating. The release of ethylbenzene o-xylene, and chlorobenzenes suggests a repeated dehydrochlorination and recombination of HCl and Cl2 to double bonds along the chain. Possible decomposition mechanisms of PVC are discussed. 相似文献
44.
In the presence of CuCN, reaction of γ,γ-dialkoxyallylic zirconium species 1 with imines proceeded at the γ-position of 1 to give gem-dialkoxyhomoallylic amines 3 in high yield. In this reaction, γ,γ-dialkoxyallylic zirconium species 1 acts as an α,β-unsaturated acyl anion equivalent. 相似文献
45.
Noboru Oyama Takeo Ohsaka Takeyoshi Okajima Tomoaki Hirokawa Tsuyoshi Maruyama Yukio Ohnuki 《Journal of Electroanalytical Chemistry》1985,187(1):79-96
Liquid crystalline/polymer composite membrane-coated electrodes were prepared by casting a 1,2-dichloroethane solution of N-(4-ethoxybenzylidene)-4′-n-butylaniline (EBBA) and polycarbonate (PC) on an electrode surface. The temperature-dependence of the permeability of the EBBA/PC composite membrane on electrodes to Fe(CN)3?6 ion as a solution-phase redox ion was investigated by means of hydrodynamic voltammetry at a rotating disk electrode. The permeability changed with temperature over the range of the crystalline-nematic-phase transition temperature of EBBA. It is demonstrated that the observed temperature-dependence of the permeability reflects the thermotropic properties of EBBA in the EBBA/PC composite membrane. Furthermore, the dependence of the limiting current of the steady-state current-potential curves for the reduction of Fe(CN)—6 at the EBBA/PC composite membrane-coated electrode upon the membrane thickness, the blend ratio of EBBA and PC and the concentration of Fe(CN)3?6 in a bulk solution was examined in order to understand the transport process of Fe(CN)?36 through the EBBA/PC composite membrane from the membrane/solution interface to the electrode/membrane interface. The transport process of Fe(CN)3?6 within the membrane was found to obey Fick's Law. 相似文献
46.
D'Souza F Chitta R Gadde S Zandler ME McCarty AL Sandanayaka AS Araki Y Ito O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(15):4416-4428
Two types of structurally well-defined, self-assembled zinc porphyrin-fullerene conjugates were formed by "two-point" binding strategies to probe the effect of axial ligation or pi-pi-type interactions on the photochemical charge stabilization in the supramolecular dyads. To achieve this, meso-tetraphenylporphyrin was functionalized to possess one or four [18]crown-6 moieties at different locations on the porphyrin macrocycle while fullerene was functionalized to possess an alkyl ammonium cation, and a pyridine or phenyl entities. As a result of the crown ether-ammonium cation complexation, and zinc-pyridine coordination or pi-pi-type interactions, stable zinc porphyrin-fullerene conjugates with defined distance and orientation were formed. Evidence for the zinc-pyridine complexation or pi-pi-type interactions was obtained from the spectral and computational studies. Steady-state and time-resolved emission studies revealed efficient quenching of the zinc-porphyrin singlet excited state in these dyads, and the measured rates of charge separation, k(CS) were found to be slightly better in the case of the dyads held by axial coordination and crown ether-cation complexation. Nanosecond transient absorption studies provided evidence for the electron transfer reactions, and these studies also revealed charge stabilization in these dyads. The lifetimes of the radical ion pairs were found to depend upon the type of porphyrins utilized to form the dyads, that is, porphyrin possessing the crown ether moiety at the ortho position of one of the phenyl rings yielded prolonged charge stabilized states. Addition of pyridine to the supramolecular dyads eliminated the zinc-pyridine coordination or pi-pi-type interactions of the "two-point" bound systems due to the formation of a new zinc-pyridine axial bond thus giving a unique opportunity to probe the effect of axial coordination or pi-pi interactions on k(CS) and k(CR). Under these conditions, the measured electron transfer rates revealed faster k(CS) and slower k(CR) as compared to those obtained in the absence of added pyridine. The evaluated lifetimes of the radical ion-pairs were found to be hundreds of nanoseconds and were longer in the presence of pyridine. 相似文献
47.
Ohsaka T Tian Y Shioda M Kasahara S Okajima T 《Chemical communications (Cambridge, England)》2002,(9):990-991
A superoxide dismutase (SOD)-modified electrode, in which SOD is oriented on the gold electrode via a self-assembled monolayer of cysteine so as to allow its direct electrode reaction, possesses a bi-directional electrocatalysis for both the oxidation of superoxide ion (O2-) to O2 and the reduction of O2- to H2O2 and functions as a third generation O2- biosensor. 相似文献
48.
The unstable species aminoborane, BH2NH2, has been identified as a reaction product of ammonia with diborane by microwave spectroscopy. The rotational constants determined are A = 138212 ± 4 MHz, B = 27487.83 ± 0.10 MHz and C = 22878.44 ± 0.11 MHz for 11BH2NH2 and A = 138199 ± 6 MHz, B = 28420.36 ± 0.11 MHz and C = 23520.78 ± 0.12 MHz for 10BH2NH2. The dipole moment is 1.844 ± 0.015 D. 相似文献
49.
Koji Yagi Veronica Garcia Ma. E. Rivas Javier Salas Andres Camargo Takeo Tabata 《Journal of inclusion phenomena and macrocyclic chemistry》1984,2(1-2):179-184
Some crown ethers were found to show significant antifungal activity against some wood-decay fungi, phytopathogenic fungi and eumycetes,Trichophytons for dermatomycosis. Their toxicity was evaluated by the paper disc method as well as by determining the values of ED50, i.e., the concentration which inhibits the mycelium growth by 50%. The fungi examined areTyromyces palustris, Picnoporous coccineus, Coriolous versicolor, Pyricularia filamentosa, Fusarium sp., Trichophyton rubrum, Trichophyton sp., etc. Among the 26 crown ethers tested, 3,5-di-t-butyl-benzo-15-crown-5 showed relatively high activity, the highest ED50 value of which being 8 M or 3 ppm. Other alkylbenzocrown ethers, dicyclohexyl crown ethers and Kryptofix 22DD also showed considerable activity. On the other hand, unsubstituted crown ethers, benzocrown ethers with a polar substituent, Kryptofix 222B and Kryptofix 221 were inactive. 相似文献
50.
Takeo Araki Shuzi Hayase Akira Nakamura 《Journal of polymer science. Part A, Polymer chemistry》1983,21(6):1671-1679
Based on our recent discovery of the isomerization polymerization of β-(2-acetoxyethyl)-β-propiolactone into poly-δ-ester,1,2 we examined the generality of this phenomenon by using two related monomers. The catalysts were (EtAlO)n and Et(ZnO)2ZnEt. The side-chains in the monomers selected were the (CH3)2CHCOO? CH2CH2? (2) and (CH3)CICHCOO? CH2CH2? (3) groups in which steric effects are almost identical but electronic effects are in opposition. The monomers yielded isomerized poly-δ-ester units, depending on the terminal substituent groups in the side-chain. These observations can be interpreted with the bicyclic intermediate proposed in the earlier work. Monomer (2) was reactive and produced a poly-δ-ester structure most readily, probably because of the higher electron density at the side-chain ester group which coordinated with the catalyst. In contrast, monomer (3) was less reactive, and the probability of isomerization was the lowest, i.e., the electron deficient side-chain ester group apparently interfered with the formation of the intermediate, especially in the Zn-catalysis. Equibinary random copolymers were prepared from (2) and (3) according to the catalyst and polymerization conditions chosen. 相似文献