全文获取类型
收费全文 | 558篇 |
免费 | 27篇 |
国内免费 | 1篇 |
专业分类
化学 | 425篇 |
晶体学 | 12篇 |
力学 | 8篇 |
数学 | 38篇 |
物理学 | 103篇 |
出版年
2022年 | 3篇 |
2021年 | 3篇 |
2020年 | 5篇 |
2018年 | 12篇 |
2017年 | 6篇 |
2016年 | 8篇 |
2015年 | 15篇 |
2014年 | 11篇 |
2013年 | 34篇 |
2012年 | 19篇 |
2011年 | 31篇 |
2010年 | 19篇 |
2009年 | 14篇 |
2008年 | 52篇 |
2007年 | 29篇 |
2006年 | 33篇 |
2005年 | 27篇 |
2004年 | 24篇 |
2003年 | 23篇 |
2002年 | 25篇 |
2001年 | 8篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1998年 | 5篇 |
1997年 | 3篇 |
1996年 | 7篇 |
1995年 | 5篇 |
1994年 | 3篇 |
1993年 | 6篇 |
1992年 | 7篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 7篇 |
1985年 | 7篇 |
1984年 | 8篇 |
1983年 | 7篇 |
1982年 | 11篇 |
1981年 | 12篇 |
1980年 | 12篇 |
1979年 | 7篇 |
1978年 | 10篇 |
1977年 | 13篇 |
1976年 | 7篇 |
1975年 | 6篇 |
1974年 | 5篇 |
1973年 | 3篇 |
1962年 | 2篇 |
排序方式: 共有586条查询结果,搜索用时 0 毫秒
561.
The benzyloxymethyl (BOM) group has been utilized widely in syntheses of a variety of natural and non-natural products. The BOM group is also one of few choices to protect uridine ureido nitrogen. However, hydrogenolytic cleavage of the BOM group of uridine derivatives has been unreliably performed via heterogeneous conditions using Pd catalysts. One of the undesirable by-products formed by Pd-mediated hydrogenation conditions is the over-reduced product in which the C5-C6 double bond of the uracil moiety was saturated. To date, we have generated a wide range of uridine-containing antibacterial agents, where the BOM group has been utilized in their syntheses. In screening of deprotection conditions of the BOM group of uridine ureido nitrogen under Pd-mediated hydrogenation conditions, we realized that the addition of water to the iPrOH-based hydrogenation conditions can suppress the formation of over-reduced uridine derivatives and the addition of HCO2H (0.5%) dramatically improve the reaction rate. An optimized hydrogenation condition described here can be applicable to the BOM-deprotections of a wide range of uridine derivatives. 相似文献
562.
Xiao F Davidsavor KJ Park S Nakayama M Phillips BR 《Journal of colloid and interface science》2012,368(1):505-511
Amberlite XAD resins have been employed to a great extent as the sorbent for removing or concentrating organic compounds from different matrices. We present for the first time a systematic study on the sorption of perfluorochemical (PFC) surfactants, an emerging class of environmental contaminants, by XAD-7HP (moderately polar) and XAD-2 (nonpolar). The results show that XAD-7HP can strongly sorb PFCs at circumneutral pH; the isotherm-determined linear sorption coefficient can reach 10(6)L/kg. On the other hand, the sorption coefficient for XAD-2 was two orders of magnitude lower than that for XAD-7HP. PFC sorption on XAD-7HP increased with an increase of the perfluorocarbon chain length of PFC and a decrease of the solution pH, indicating the importance of hydrophobic and electrostatic effects. The sorption coefficient for XAD-7HP reduced markedly with increasing fraction of the organic cosolvent (methanol) in the water-cosolvent mixture; however, the trend could not be predicted by a log-linear cosolvency model. Furthermore, the statistical analysis of column test results showed that after regeneration XAD-7HP can be used at least eight times without significant loss of performance. Finally, the experimental results imply that XAD-7HP sorption of shorter-chained PFCs (≤5 perfluorinated carbons) from water can be thermodynamically favorable. 相似文献
563.
Toshiyuki Kodaira Quing-Quing Liu Michio Urushisaki 《Journal of polymer science. Part A, Polymer chemistry》1995,33(16):2681-2690
N,N-Diallylmethacrylamide (DAMA) was synthesized and its radical cyclopolymerizability was investigated. Polymerizations of DAMA were found to proceed according to the standard kinetic equation for radical polymerization except for the diffusion controlled termination reactions owing to higher viscosity of DAMA, in spite of the fact that it contains two allyl groups. DAMA yields polymers with slightly higher degree of cyclization than 50% in dilute solution polymerization. With increasing monomer concentration, the degree of cyclization decreases gradually and it becomes slightly lower value than 50% in concentrated solution polymerizations. It was found that about 86% of pendant unsaturations is allyl group and the rest is methacryloyl group. Structural studies on repeating units showed that possibility for the presence of bicyclic structures (those formed with consumption of three double bonds involved in DAMA) and structural units with two pendant unsaturations (those formed with one double bond in DAMA participated in polymerization) is extremely small. Main repeating cyclic unit was assigned to five-membered monocyclic lactam with an allyl group on its nitrogen, the content of which is estimated to be approximately 86% based on the allyl content. The main fraction of the rest of repeating cyclic structures was attributed to monocyclic pirolidine ring with a methacryloyl group on its nitrogen. These structural investigations and ESR studies of DAMA revealed that the methacryloyl group of DAMA is less reactive than its allyl group as in the case of N-methyl-N-allylmethacrylamide which has already been reported. © 1995 John Wiley & Sons, Inc. 相似文献
564.
Tamotsu Hashimoto Hiroyuki Meiji Michio Urushisaki Toshikazu Sakaguchi Kazumasa Kawabe Chihiro Tsuchida Keiichi Kondo 《Journal of polymer science. Part A, Polymer chemistry》2012,50(17):3674-3681
Four sorts of epoxy resins containing degradable acetal linkages were synthesized by the reaction of bisphenol A (BA) or cresol novolak (CN) resin with vinyl ethers containing a glycidyl group [4‐vinlyoxybutyl glycidyl ether (VBGE) and cyclohexane dimethanol vinyl glycidyl ether (CHDMVG)] and cured with known typical amine‐curing agents. The thermal and mechanical properties of the cured resins were investigated. Among the four cured epoxy resins, the CN‐CHDMVG resin (derived from CN and CHDMVE) exhibited relatively high glass transition temperature (Tg = ca. 110 °C). The treatment of these cured epoxy resins with aqueous HCl in tetrahydrofuran (THF) at room temperature for 12 h generated BA and CN as degradation main products in high yield. Carbon fiber‐reinforced plastics (CFRPs) were prepared by heating the laminated prepreg sheets with BA‐CHDMVG (derived from BA and CHDMVE) and CN‐CHDMVG, in which strands of carbon fibers are impregnated with the epoxy resins containing conventional curing agents and curing accelerators. The obtained CFRPs showed good appearance and underwent smooth breakdown with the aqueous acid treatment in THF at room temperature for 24 h to produce strands of carbon fiber without damaging their surface conditions and tensile strength. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
565.
Yutaka Maeda Prof. Dr. Satoru Sato Koji Inada Hidefumi Nikawa Michio Yamada Dr. Naomi Mizorogi Dr. Tadashi Hasegawa Prof. Dr. Takahiro Tsuchiya Dr. Takeshi Akasaka Prof. Dr. Tatsuhisa Kato Prof. Dr. Zdenek Slanina Dr. Shigeru Nagase Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(7):2193-2197
The first regioselective functionalization of La@C82 by two different groups has been performed. Bis‐adducts of La@C82 with Cp* and adamantylidene were synthesized by using two different routes and characterized. Spectroscopic analysis and theoretical calculations reveal that the addition position is controlled by the charge density and p‐orbital axis vector value of the fullerene cage. 相似文献
566.
A novel method for the preparation of oligopeptides with a PS-ammonium fluoride in the solution phase is reported. The synthesis of lipid II pentapeptide is efficiently synthesized via a PS-ammonium fluoride without chromatographic purifications. The method reported here is very convenient to synthesize a relatively large amount of oligopeptides with abundantly available Fmoc-protected amino acids in a time efficient manner. 相似文献
567.
The WXYZA'B'C' ring system ( 1) of maitotoxin (MTX) was synthesized in a convergent manner via successive coupling of the W, Z, and C' ring fragments through construction of the XY and A'B' ring systems. The synthetic segment 1 blocked the hemolytic activity elicited by MTX. 相似文献
568.
Takano Y Yomogida A Nikawa H Yamada M Wakahara T Tsuchiya T Ishitsuka MO Maeda Y Akasaka T Kato T Slanina Z Mizorogi N Nagase S 《Journal of the American Chemical Society》2008,130(48):16224-16230
The thermal reaction of La@C(82)(C(2v)) with 3-triphenylmethyl-5-oxazolidinone (1) in toluene affords benzyl monoadducts La@C(82)(C(2v))(CH(2)C(6)H(5)) (2a-2d). The same monoadducts are also obtained by the photoirradiation of La@C(82)(C(2v)) in toluene without the existence of 1. These reactions are applicable to paramagnetic metallofullerenes, such as La@C(82)(C(s)) and Ce@C(82)(C(2v)). The photoirradiation of La@C(82)(C(2v)) in 1,2-dichlorobenzene in the presence of alpha,alpha,2,4-tetrachlorotoluene also affords the monoadducts La@C(82)(C(2v))(CHClC(6)H(3)Cl(2)) (3a-3d). The monoadducts are fully characterized by spectroscopic analyses. Single-crystal X-ray structure analysis for 3d reveals the unique structure. Theoretical calculations show that the cage carbons having high spin densities are selectively attacked by radical species to form the monoadducts linked by a carbon-carbon single bond. The thermal reaction of La@C(82)(C(2v)) with 1 in benzene affords metallofulleropyrrolidine La@C(82)(C(2v))(C(2)H(4)NCPh(3)) (5), unlike the reaction in toluene. 相似文献
569.
Michio Sorai Corresponding author Kazuya Saito Corresponding author Tadahiro Nakamoto Mayumi Ikeda Yuri G. Galyametdinov Irina Galyametdinova 《Liquid crystals》2013,40(7):861-869
The heat capacity of the cubic mesogen ACBC(16) was measured between 16 and 500?K by adiabatic calorimetry. As well as the known condensed phases, a new crystalline phase was found to undergo a glass transition at around 165?K. Phase transitions between crystal, SmC, cubic, and isotropic liquid phases took place at 399.16, 431.15, and 474.30?K, respectively. As in the case of ANBC, a broad hump was observed in the heat capacity of the isotropic liquid phase. The first order nature of the SmC–cubic phase transition was confirmed for the first time by the observation of supercooling of the cubic phase. The broad hump in the isotropic liquid phase was shown to extend to a low temperature side if the isotropic liquid was supercooled, suggesting that the event occurring at the hump is not directly related to the cubic–isotropic liquid phase transition. 相似文献
570.
Kitano M Funatsu K Matsuoka M Ueshima M Anpo M 《The journal of physical chemistry. B》2006,110(50):25266-25272
Nitrogen-substituted TiO2 (N-TiO2) thin film photocatalysts have been prepared by a radio frequency magnetron sputtering (RF-MS) deposition method using a N2/Ar mixture sputtering gas. The effect of the concentration of substituted nitrogen on the characteristics of the N-TiO2 thin films was investigated by UV-vis absorption spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM) analyses. The absorption band of the N-TiO2 thin film was found to shift smoothly to visible light regions up to 550 nm, its extent depending on the concentration of nitrogen substituted within the TiO2 lattice in a range of 2.0-16.5%. The N-TiO2 thin film photocatalyst with a nitrogen concentration of 6.0% exhibited the highest reactivity for the photocatalytic oxidation of 2-propanol diluted in water even under visible (lambda > or = 450 nm) or solar light irradiation. Moreover, N-TiO2 thin film photocatalysts prepared on conducting glass electrodes showed anodic photocurrents attributed to the photooxidation of water under visible light, its extent depending on wavelengths up to 550 nm. The absorbed photon to current conversion efficiencies reached 25.2% and 22.4% under UV (lambda = 360 nm) and visible light (lambda = 420 nm), respectively. UV-vis and photoelectrochemical investigations also confirmed that these thin films remain thermodynamically and mechanically stable even under heat treatment at 673 K. In addition, XPS and XRD studies revealed that a significantly high substitution of the lattice O atoms of the TiO2 with the N atoms plays a crucial role in the band gap narrowing of the TiO2 thin films, enabling them to absorb and operate under visible light irradiation as a highly reactive, effective photocatalyst. 相似文献