全文获取类型
收费全文 | 691篇 |
免费 | 0篇 |
国内免费 | 7篇 |
专业分类
化学 | 456篇 |
晶体学 | 15篇 |
力学 | 7篇 |
数学 | 74篇 |
物理学 | 146篇 |
出版年
2023年 | 8篇 |
2021年 | 8篇 |
2020年 | 7篇 |
2019年 | 6篇 |
2018年 | 10篇 |
2017年 | 10篇 |
2016年 | 3篇 |
2015年 | 5篇 |
2014年 | 8篇 |
2013年 | 16篇 |
2012年 | 31篇 |
2011年 | 45篇 |
2010年 | 28篇 |
2009年 | 23篇 |
2008年 | 57篇 |
2007年 | 47篇 |
2006年 | 54篇 |
2005年 | 44篇 |
2004年 | 50篇 |
2003年 | 39篇 |
2002年 | 31篇 |
2001年 | 10篇 |
2000年 | 10篇 |
1999年 | 9篇 |
1998年 | 5篇 |
1997年 | 8篇 |
1996年 | 8篇 |
1995年 | 4篇 |
1994年 | 13篇 |
1993年 | 3篇 |
1992年 | 7篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 7篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 4篇 |
1978年 | 6篇 |
1977年 | 8篇 |
1976年 | 5篇 |
1975年 | 9篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1954年 | 1篇 |
排序方式: 共有698条查询结果,搜索用时 15 毫秒
101.
Toru Tatsumi Ken-ichi Aketagawa Masayuki Hiroi Junro Sakai 《Journal of Crystal Growth》1992,120(1-4):275-278
The conditions under which selective epitaxial growth (SEG) is achieved in UHV-CVD with Si2H6 are determined by the amount of Si2H6 molecules being supplied, and there is a critical gas supply amount (Fc) beyond which SEG will break down and lose its selectivity. The value of Fc is itself determined by two factors, growth temperature and the material used for masking, i.e. SiO2, Si3N4. We found that this limiting factor of Fc was increased through the addition of a small amount of Cl2, and that after such addition, the resulting decrease in growth rate is minimal. 相似文献
102.
Acyloxymethyl radicals were generated from the corresponding iodomethyl esters and successfully underwent addition to the CN bond of N-Ts, N-PMP, and N-Dpp imines by the action of dimethylzinc or triethylborane. Ethyl acetate, toluene, and benzene as well as dichloromethane were suitable solvents. The utility of acyloxymethyl radicals as a hydroxymethyl anion equivalent was highlighted by the facile hydrolysis of the acyloxy moiety of the adducts to give the corresponding amino alcohol derivatives in good to high yield. 相似文献
103.
Araki Y Mukaisyo K Sugihara H Fujiyama Y Hattori T 《Journal of separation science》2008,31(15):2827-2830
In the present study, we developed a novel, simple, and specific detection method using an RP-HPLC at UV 285 nm for the separation and quantification of N-nitroso-bile acids. First, we found that N-nitroso-bile acids have a specific spectrophotometric absorbance at 285 nm. Using this 285 nm detection system, we could especially measure N-nitroso-bile acids, even in co-existence of non-N-nitroso-bile acids. Next, we observed the decomposition of N-nitroso-glychocholate under alkaline, acidic, and neutral conditions. N-nitroso-glychocholate rapidly decomposed under alkaline conditions (pH 9) (t(1/2) = 0.96 h), but remained fairly stable under acidic (pH 2) (t(1/2) = 12.8 h) and neutral (pH 7) (t(1/2) = 7.8 h) conditions. This study is the first report, which simply and specifically analyzes N-nitroso-bile acids using an RP-HPLC system. 相似文献
104.
The old well-known result of Chartrand, Kaugars and Lick says that every k-connected graph G with minimum degree at least 3k/2 has a vertex v such that G−v is still k-connected. In this paper, we consider a generalization of the above result [G. Chartrand, A. Kaigars, D.R. Lick, Critically n-connected graphs, Proc. Amer. Math. Soc. 32 (1972) 63–68]. We prove the following result:Suppose G is a k-connected graph with minimum degree at least 3k/2+2. Then G has an edge e such that G−V(e) is still k-connected.The bound on the minimum degree is essentially best possible. 相似文献
105.
Takahashi Y Nonogawa M Fujita K Yamaguchi R 《Dalton transactions (Cambridge, England : 2003)》2008,(27):3546-3552
Reaction of [Cp*Ir(micro-H)](2) (5) (Cp* = eta(5)-C(5)Me(5)) with bis(dimethylphosphino)methane (dmpm) gives a new neutral diiridium complex [(Cp*Ir)(2)(micro-dmpm)(micro-H)(2)] (3). Treatment of 3 with methyl triflate at -30 degrees C results in the formation of [(Cp*Ir)(H)(micro-dmpm)(micro-H)(Me)(IrCp*)][OTf] (6). Warming a solution of above 0 degrees C brings about predominant generation of 32e(-) Ir(II)-Ir(II) species [(Cp*Ir)(micro-dmpm)(micro-H)(IrCp*)][OTf] (7). Further heating of the solution of 7 up to 30 degrees C for 14 h leads to quantitative formation of a new complex [(Cp*Ir)(H)(micro-Me(2)PCH(2)PMeCH(2))(micro-H)(IrCp*)][OTf] (8), which is formed by intramolecular oxidative addition of the methyl C-H bond of the dmpm ligand. Intermolecular C-H bond activation reactions with 7 are also examined. Reactions of 7 with aromatic molecules (benzene, toluene, furan, and pyridine) at room temperature result in the smooth sp(2) C-H activation to give [(Cp*Ir)(H)(micro-dmpm)(micro-H)(Ar)(IrCp*)][OTf] (Ar = Ph (9); Ar = m-Tol (10a) or p-Tol (10b); Ar = 2-Fur (11)) and [(Cp*Ir)(H)(micro-dmpm)(micro-C(5)H(4)N)(H)(IrCp*)][OTf] (12), respectively. Complex also reacts with cyclopentene at 0 degrees C to give [(Cp*Ir)(H)(micro-dmpm)(micro-H)(1-cyclopentenyl)(IrCp*)][OTf] (13). Structures of 3, 8 and 12 have been confirmed by X-ray analysis. 相似文献
106.
Dr. Ziqian Xue Dr. Jia-Jia Zheng Dr. Yusuke Nishiyama Dr. Ming-Shui Yao Dr. Yoshitaka Aoyama Zeyu Fan Dr. Ping Wang Prof. Takashi Kajiwara Prof. Yoshiki Kubota Prof. Satoshi Horike Prof. Ken-ichi Otake Prof. Susumu Kitagawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2023,135(2):e202215234
Exploring new porous coordination polymers (PCPs) that have tunable structure and conductivity is attractive but remains challenging. Herein, fine pore structure engineering by ligand conformation control of naphthalene diimide (NDI)-based semiconducting PCPs with π stacking-dependent conductivity tunability is achieved. The π stacking distances and ligand conformation in these isoreticular PCPs were modulated by employing metal centers with different coordination geometries. As a result, three conjugated PCPs (Co−pyNDI, Ni−pyNDI, and Zn−pyNDI) with varying pore structure and conductivity were obtained. Their crystal structures were determined by three-dimensional electron diffraction. The through-space charge transfer and tunable pore structure in these PCPs result in modulated selectivity and sensitivity in gas sensing. Zn−pyNDI can serve as a room-temperature operable chemiresistive sensor selective to acetone. 相似文献
107.
Masahiko Matsukata Ken-ichi Sawamura Tsutomu Shirai Mitsuko Takada Yasushi Sekine Eiichi Kikuchi 《Journal of membrane science》2008,316(1-2):18-27
Controlling the growth of zeolite crystals on a porous alumina support is essential for preparing a compact zeolite membarne. First, mordenite seed crystals applied on a nonporous -alumina disk were grown and morphological change of mordenite crystals were observed in the course of growth. Then, mordenite membranes were synthesized on a porous -alumina tube under the same conditions employed in the study using the alumina disks. We found that seed crystal growth was widely controllable by changing water content in reaction solution, which resulted in better control of the morphology of mordenite crystals for synthesizing a thin compact mordenite membrane. Separation properties for mordenite membranes were studied in water–hydrogen binary system at 473 K with 10 kPa of water partial pressure, where no capillary condensation was expected in non-zeolitic pores. Separation factor for a mordenite membrane with a few defects was poor; however, a defect-free mordenite membrane prepared under a suitable condition highly separated steam from hydrogen. 相似文献
108.
Mori Y Hirokawa T Aoki K Satomi H Takeda S Aburada M Miyamoto K 《Chemical & pharmaceutical bulletin》2008,56(5):682-687
We previously reported a quinoxalin-2-one compound (Compound 1) that had inhibitory activity equivalent to existing platelet-derived growth factor-beta receptor (PDGFbeta R) inhibitors. Lead optimization of Compound 1 to increase its activity and selectivity, using structural information regarding PDGFbeta R-ligand interactions, is urgently needed. Here we present models of the PDGFbeta R kinase domain complexed with quinoxalin-2-one derivatives. The models were constructed using comparative modeling, molecular dynamics (MD) and ligand docking. In particular, conformations derived from MD, and ligand binding site information presented by alpha-spheres in the pre-docking processing, allowed us to identify optimal protein structures for docking of target ligands. By carrying out molecular modeling and MD of PDGFbeta R in its inactive state, we obtained two structural models having good Compound 1 binding potentials. In order to distinguish the optimal candidate, we evaluated the structural activity relationships (SAR) between the ligand-binding free energies and inhibitory activity values (IC50 values) for available quinoxalin-2-one derivatives. Consequently, a final model with a high SAR was identified. This model included a molecular interaction between the hydrophobic pocket behind the ATP binding site and the substitution region of the quinoxalin-2-one derivatives. These findings should prove useful in lead optimization of quinoxalin-2-one derivatives as PDGFb R inhibitors. 相似文献
109.
Uekusa Y Sugimoto N Sato K Yun YS Kunugi A Yamazaki T Tanamoto K 《Chemical & pharmaceutical bulletin》2007,55(11):1643-1646
A novel crocetin glycosyl ester, neocrocin A (2), was isolated from gardenia yellow. The structure of 2 was elucidated as that of an all-trans-crocetin beta-D-gentiobiosyl beta-D-glucopyranosyl-(1-->6)-D-2-deoxy-glucopyranos-2-yl diester based on chemical and spectral data. The findings provide evidence that the binding system of crocetin glycosides is not limited to the anomeric position. 相似文献
110.
Hatano Y Watanabe K Livshits A Busnyuk A Alimov V Nakamura Y Hashizume K 《The Journal of chemical physics》2007,127(20):204707
Nonmetallic impurities segregated onto metal surfaces are able to drastically decrease the chemical reactivity of metals. In the present paper, effects of bulk impurities on the reactivity of metallic surfaces were investigated in a wide temperature range on an example of the sticking of hydrogen molecules and atoms to Nb [polycrystalline, with mainly (100)] containing solute oxygen. At all the investigated surface temperatures, T(S) (300-1400 K), we found the bulk oxygen concentration C(O) to have a strong effect on the integral probability, alpha(H(2) ), of dissociative sticking of H(2) molecules followed by hydrogen solution in the metal lattice: alpha(H(2) ) monotonically decreased by orders of magnitude with increasing C(O) from 0.03 to 1.5 at. %. The sticking coefficient alpha(H(2) ) was found to depend on T(S) but not on the gas temperature. The effect of C(O) on alpha(H(2) ) is explained by the presence of oxygen-free sites (holes in coverage) serving as active centers of the surface reaction in the oxygen monolayer upon Nb. In contrast to H(2) molecules, H atoms were found to stick to, and be dissolved in, oxygen-covered Nb with a probability comparable to 1, depending neither on C(O) nor on T(S). This proves that, unlike H(2) molecules, H atoms do stick to be dissolved mainly through regular surface sites covered by oxygen and not through the holes in coverage. 相似文献