全文获取类型
收费全文 | 1070篇 |
免费 | 25篇 |
国内免费 | 7篇 |
专业分类
化学 | 772篇 |
晶体学 | 21篇 |
力学 | 20篇 |
数学 | 60篇 |
物理学 | 229篇 |
出版年
2022年 | 8篇 |
2021年 | 7篇 |
2020年 | 18篇 |
2019年 | 12篇 |
2018年 | 13篇 |
2017年 | 14篇 |
2016年 | 18篇 |
2015年 | 13篇 |
2014年 | 32篇 |
2013年 | 50篇 |
2012年 | 58篇 |
2011年 | 79篇 |
2010年 | 41篇 |
2009年 | 42篇 |
2008年 | 82篇 |
2007年 | 74篇 |
2006年 | 70篇 |
2005年 | 48篇 |
2004年 | 36篇 |
2003年 | 54篇 |
2002年 | 40篇 |
2001年 | 22篇 |
2000年 | 17篇 |
1999年 | 11篇 |
1998年 | 12篇 |
1997年 | 9篇 |
1996年 | 9篇 |
1995年 | 8篇 |
1994年 | 18篇 |
1993年 | 13篇 |
1992年 | 9篇 |
1991年 | 13篇 |
1990年 | 5篇 |
1989年 | 10篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 11篇 |
1985年 | 17篇 |
1984年 | 11篇 |
1983年 | 9篇 |
1982年 | 10篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 3篇 |
1978年 | 7篇 |
1977年 | 7篇 |
1976年 | 13篇 |
1975年 | 7篇 |
1974年 | 4篇 |
1973年 | 3篇 |
排序方式: 共有1102条查询结果,搜索用时 0 毫秒
71.
Keiji Kinoshita Toru SaitoAkira Ito Takashi KawakamiYasutaka Kitagawa Shusuke YamanakaKizashi Yamaguchi Mitsutaka Okumura 《Polyhedron》2011,30(18):3249-3255
Recently, graphene sheet is one of interesting systems to realize novel electronic properties. Especially, interaction between graphene and adsorbed oxygen molecule is very important to control electronic condition. In this paper, we employed some aromatic hydrocarbons as simple systems of graphene sheet and ab initio MO calculations were carried out to investigate inter-molecular interaction. It is found that not triplet but singlet O2 molecule have potential of chemisorption onto graphene surface. From the calculated potential energy surface (PES) for distance between benzene and O2 molecules, meta-stable structure is found at about 1.5 Å with potential barrier. In the optimized structure of its meta-stable state, structural strain can be relaxed through bending of planer benzene ring. Its energy is estimated at 70.10 kcal/mol for benzene. We also estimated the strain effects for naphthalene and pyrene molecules as larger case of graphene and they were 80.85 and 72.45 kcal/mol, respectively. 相似文献
72.
N Kubodera H Watanabe T Kawanishi M Matsumoto 《Chemical & pharmaceutical bulletin》1992,40(6):1494-1499
Six analogues of 1 alpha,25-dihydroxy-22-oxavitamin D3 (OCT) (2), 26,27-dimethyl OCT (5), 26,27-diethyl OCT (6), 24-norOCT (7), 24-homoOCT (8), 24-dihomoOCT (9), and 24-trihomoOCT (10) were synthesized from the 20(S)-alcohol (11) as the common starting material. In the activity inducing differentiation of human myeloid leukemia cells (HL-60) into macrophages, 26,27-dimethyl OCT (5) and 24-homoOCT (8) showed the highest activities. The binding properties of these analogues to the chick embryonic intestinal 1 alpha,25-dihydroxyvitamin D3 (1) receptor are also described. 相似文献
73.
Saito K Masuyama T Oyaizu K Nishide H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(17):4240-4246
Depolymerization of an engineering plastic, poly(2,6-dimethyl-1,4-phenylene oxide) (PPO), was accomplished by using 2,6-dimethylphenol (DMP) under oxidative conditions. The addition of an excess amount of DMP to a solution of PPO in the presence of a CuCl/pyridine catalyst yielded oligomeric products. When PPO (M(n)=1.0x10(4), M(w)/M(n)=1.2) was allowed to react with a sufficient amount of DMP, the molecular weight of the product decreased to M(n)=4.9x10(2) (M(w)/M(n)=1.5). By a prolonged reaction with the oxidant, the oligomeric product was repolymerized to produce PPO essentially identical to the starting material, making the oligomer useful as a reusable resource. During the depolymerization reaction, an intermediate phenoxyl radical was observed by ESR spectroscopy. Kinetic analysis showed that the rate of the oxidation of PPO was about 10 times higher than that of DMP. These results show that a monomeric phenoxyl radical attacks the polymeric phenoxyl to induce the redistribution via a quinone ketal intermediate, leading to the substantial decrease in the molecular weight of PPO, which is much faster than the chain growth. 相似文献
74.
Removal of phosphate by aluminum oxide hydroxide 总被引:17,自引:0,他引:17
Tanada S Kabayama M Kawasaki N Sakiyama T Nakamura T Araki M Tamura T 《Journal of colloid and interface science》2003,257(1):135-140
The development and manufacture of an adsorbent to remove phosphate ion for the prevention of eutrophication in lakes are very important. The characteristics of phosphate adsorption onto aluminum oxide hydroxide were investigated to estimate the adsorption isotherms, the rate of adsorption, and the selectivity of adsorption. Phosphate was easily adsorbed onto aluminum oxide hydroxide, because of the hydroxyl groups. The adsorption of phosphate onto aluminum oxide hydroxide was influenced by pH in solution: the amount adsorbed was greatest at pH 4, ranging with pH from 2 to 9. The optimum pH for phosphate removal by aluminum oxide hydroxide is 4. The selectivity of phosphate adsorption onto aluminum oxide hydroxide was evaluated based on the amount of phosphate ion adsorbed onto aluminum oxide hydroxide from several anion complex solutions. It is phosphate that aluminum oxide hydroxide can selectively adsorb. The selectivity of phosphate onto aluminum oxide hydroxide was about 7000 times that of chloride. This result indicated that the hydroxyl groups on aluminum oxide hydroxide have selective adsorptivity for phosphate and could be used for the removal of phosphate from seawater. 相似文献
75.
Koichiro Yonetake Kunio Maruyama Jun-Ichi Sugiyama Toru Masuko Mitsuru Ueda 《Journal of polymer science. Part A, Polymer chemistry》1994,32(8):1415-1421
Poly[4-(4-hydroxyphenoxy) benzoic acid] was prepared by the bulk polycondensation of 4-(4-acetoxyphenoxy) benzoic acid. Polycondensation was conducted at 350°C for 3 h under a reduced pressure of 0.1 mmHg and gave a polymer with X?n of 255. The polymer was characterized by elemental analysis, IR spectroscopy, differential scanning calorimetry, and wide-angle X-ray measurement. The crystal/nematic and nematic/isotropic phase transition temperatures of polymer, which depend on the molecular weight, were observed at about 300°C and 410°C, respectively. The polymers with low molecular weights showed nematic textures above 300°C. This nematic/isotropic phase transition temperature is lower than that of poly (4-hydroxybenzoic acid). This thermal behavior of polymer comes from ether units, which increase the flexibility (the rotation or torsion of skeletal bonds) of the polymer chain. © 1994 John Wiley & Sons, Inc. 相似文献
76.
UV rays in sunlight are an important factor in the degradation of chemicals. In this study, we investigated the degradation of nonionic surfactants, nonylphenol polyethoxylates (NPEOs) with 10 or 70 ethylene oxide (EO) units using UVA, B and C, and their genotoxic change based on phosphorylation of histone H2AX (γ‐H2AX), a marker of DNA damage. NPEOs were degraded dependent on the energy of UV, that is, UVC having the highest energy was most effective, whereas UVA having the lowest energy caused little change. The EO side chain of NPEO(70) was broken near the benzene ring by UV, producing NPEOs with a shortened EO chain (around 10 units). The generation of γ‐H2AX reflected the pattern of degradation; shortening of the EO chain changed NPEO(70) into an inducer for γ‐H2AX, and degradation of NPEO(10) attenuated the genotoxicity. The γ‐H2AX generated by NPEO(10) and UV‐degraded NPEO(70) was independent of the cell cycle. The formation of DNA double strand breaks detected by gel electrophoresis was consistent with the results for γ‐H2AX. These results suggested that UV rays can make NPEOs harmless or genotoxic according to the degradation of the EO side chain, the effects being dependent on wavelength. 相似文献
77.
Takahiro Hosokawa Takanori Kono Toru Shinohara Shun-Ichi Murahashi 《Journal of organometallic chemistry》1989,370(1-3):C13-C16
The oxidative cyclization of 2-(3-pentenyl)phenol catalyzed by [(η3-pinene)PdOAc]2 gives optically active (+)-2-vinylchroman (25% e.e.), while (−)-2-(1-hydroxyethyl)chroman (56% e.e.) is formed as a single diastereomer upon treatment with t-BuOOH in the presence of Ti(OiPr)4 and
-(+)-diethyl tartrate. 2-(2-Butenyl)phenol also undergoes the Ti-promoted asymmetric cyclization to give (2S,1′R)-(−)-2-(1-hydroxyethyl)-2,3-dihydrobenzofuran (29% e.e.). 相似文献
78.
Murahashi S Imada Y Kawakami T Harada K Yonemushi Y Tomita N 《Journal of the American Chemical Society》2002,124(12):2888-2889
A chiral titanium complex, Ti(O-i-Pr)(4)/BINOL/tert-butylcatechol, catalyzes enantioselective addition reaction of ketene silyl acetals to nitrones to give optically active beta-amino acid derivatives which are biologically active compounds and useful synthetic intermediates of natural products and pharmaceuticals such as beta-lactam antibiotics. The combined process of catalytic oxidation of secondary amines and enantioselective carbon-carbon bond formation of nitrones thus obtained with ketene silyl acetals provides a useful two-step method for the synthesis of optically active beta-amino acid derivatives and related nitrogen compounds. 相似文献
79.
Separation of polar and non-polar analytes using dimethyl sulfoxide-modified subcritical water 总被引:1,自引:0,他引:1
Separations using methanol–water or acetonitrile–water mixtures at different temperatures have been well investigated in reversed-phase liquid chromatography. However, reversed-phase separation with dimethyl sulfoxide (DMSO)–water mixtures is much less studied. In this work, separations of polyhydroxybenzenes, phenol derivatives, benzene, toluene, ethylbenzene, and xylenes (BTEX), and polycyclic aromatic hydrocarbons (PAHs) with DMSO-modified subcritical water were performed at several temperatures to evaluate the effect of temperature on the elution strength of DMSO–water mixtures. The column efficiency obtained by using DMSO-modified subcritical water was also studied. Finally, the resolution of ethylbenzene and p-xylene was investigated. 相似文献
80.
Water-soluble constituents of dill 总被引:1,自引:0,他引:1
From the water-soluble portion of the methanol extract of dill (fruit of Anethum graveolens L.), which has been used as a spice and medicine, thirty-three compounds, including a new monoterpenoid, six new monoterpenoid glycosides, a new aromatic compound glucoside and a new alkyl glucoside were obtained. Their structures were clarified by spectral investigation. 相似文献