全文获取类型
收费全文 | 1262篇 |
免费 | 23篇 |
国内免费 | 3篇 |
专业分类
化学 | 849篇 |
晶体学 | 21篇 |
力学 | 14篇 |
数学 | 118篇 |
物理学 | 286篇 |
出版年
2022年 | 12篇 |
2021年 | 16篇 |
2020年 | 7篇 |
2019年 | 23篇 |
2018年 | 15篇 |
2017年 | 14篇 |
2016年 | 23篇 |
2015年 | 27篇 |
2014年 | 15篇 |
2013年 | 58篇 |
2012年 | 69篇 |
2011年 | 59篇 |
2010年 | 52篇 |
2009年 | 62篇 |
2008年 | 79篇 |
2007年 | 85篇 |
2006年 | 74篇 |
2005年 | 72篇 |
2004年 | 53篇 |
2003年 | 69篇 |
2002年 | 44篇 |
2001年 | 16篇 |
2000年 | 16篇 |
1999年 | 21篇 |
1998年 | 23篇 |
1997年 | 14篇 |
1996年 | 20篇 |
1995年 | 11篇 |
1994年 | 24篇 |
1993年 | 15篇 |
1992年 | 17篇 |
1991年 | 12篇 |
1990年 | 7篇 |
1989年 | 7篇 |
1988年 | 14篇 |
1987年 | 8篇 |
1986年 | 14篇 |
1985年 | 11篇 |
1984年 | 18篇 |
1983年 | 4篇 |
1982年 | 10篇 |
1981年 | 13篇 |
1980年 | 9篇 |
1979年 | 10篇 |
1978年 | 4篇 |
1977年 | 7篇 |
1976年 | 5篇 |
1975年 | 5篇 |
1974年 | 7篇 |
1973年 | 5篇 |
排序方式: 共有1288条查询结果,搜索用时 0 毫秒
51.
Ochiai M Tada N Murai K Goto S Shiro M 《Journal of the American Chemical Society》2006,128(30):9608-9609
Stable aliphatic bromonium ylides (RfSO2)2C--Br+C6H4-p-CF3 (Rf = CF3, CF3(CF2)3) have been synthesized and structurally characterized for the first time. X-ray crystallographic analyses indicated a ylide structure with an sp2 hybridization of the ylide carbanions and with little double-bond character for the ylidic bond. The bromonium ylides selectively undergo transfer of the aryl group to nitrogen heterocycles, such as pyridines, yielding N-arylpyridinium salts. This is in a marked contrast to the reaction of the iodonium ylides, which produces pyridinium ylides through transylidations. 相似文献
52.
A conceptually new strategy for asymmetric catalysis, namely asymmetric activation, in which a chiral activator selectively activates one enantiomer of a racemic chiral catalyst, and a highly efficient screening system for finding the most effective catalysts, namely super high throughput screening (SHTS), by which the reaction can be conducted in parallel and the ee% of the product is allowed to determine within minutes, are summarized in the present account. It is reasonable to believe that SHTS technique combined with asymmetric activation or deactivation principle will provide a very powerful methodology for finding the new catalysts and the best catalyst tuning for asymmetric reactions. 相似文献
53.
To prepare powdered medicines without bitter taste, film coating is required to cover the surface of core particles. In this study, effect of formulation and operating conditions of agitation fluidized bed on the core particle properties was investigated. In order to prevent breakage of the core particles during coating process, which sometimes causes variation of drug dissolution rate, addition of maltose syrup powder during the formulation process of the core particles was investigated. Also, a method for friability test in which the core particles were subjected to strong impact was proposed to evaluate strength of the core particles. The friability of the core particles determined by this test method correlated well with the actual friability of the particles during the coating process. Based on this result, we confirmed this novel friability test method could predict the core particle endurance during the coating process. 相似文献
54.
Norio Kitadai Tadashi Yokoyama Satoru Nakashima 《Journal of colloid and interface science》2009,338(2):395-401
The adsorption behavior of lysine on montmorillonite in aqueous solution was investigated by in situ attenuated total reflectance infrared (ATR-IR) spectroscopy. To distinguish the protonation states of α-amino group, side-chain amino group and carboxyl group in lysine structure using ATR-IR spectra (i.e., NH2 versus and COO− versus COOH), pH-induced spectral changes of dissolved lysine were firstly measured and correlated with the thermodynamically calculated dissociation states of lysine (di-cationic, cationic, zwitterionic and anionic states). The obtained result was applied to interpret the ATR-IR spectra of lysine adsorbed on montmorillonite. We found that the adsorbed lysine was dominantly present as cationic state over the whole range of tested pH (pH = 4.9–9.7). This indicates that the adsorption is mainly driven by electrostatic interaction between the negatively charged montmorillonite surface and positively charged cationic lysine. We also found that lysine interacts with montmorillonite surface through the protonated side-chain amino group. This result suggests that lysine has a preferred vertical orientation, with the side-chain amino group pointing toward the surface. 相似文献
55.
The title intermediate () is produced on photolysis of hexakis(2,6-diethyl-phenyl)cyclotrigermane () or bis(2,6-diethylphenyl)bis(trimethylsilyl)germane () as evidenced by trapping experiments, and thermally dimerizes to tetrakis(2,6-diethyl-phenyl)digermene (). Diarylgermylenes such as do not form stable triethylamine adducts (e.g. ) as has been previously reported. 相似文献
56.
Kiyoshi Tanaka Yasuhiro Yamamoto Hiroto Obara Satoru Iwata 《Supramolecular chemistry》2013,25(4):347-352
5,15- cis -bis(Ureidophenyl)porphyrins have significant recognizing ability for p -benzoquinones through four-point hydrogen bonding. Although an unusual temperature-dependence of the complexation is observed with bis( N '-phenylureidophenyl) porphyrin, bis( N '-ethylureidophenyl)porphyrin shows a satisfactorily linear van't Hoff plot and recognizes an electron-rich p -benzoquinone such as tetramethyl- p -benzoquinone more effectively, which is ascribed to the large enthalpy change in the complex. 相似文献
57.
Kiyoshi Tanaka Tohru Kurushima Satoru Iwata Syunsuke Shimada 《Journal of heterocyclic chemistry》2007,44(2):303-307
2‐(3,4,5,6‐Tetrafluoro‐2‐hydroxyphenyl)imidazo[1,2‐a]pyridine ( 1 ) emits long wavelength light around 540 nm both in polar and in nonpolar solvents. Zn2+ perchlorate in acetonitrile causes the intermediate wavelength emission around 430 nm, which is ascribed to the species where the imidazole nitrogen atom and the phenolate oxygen atom bridge Zn2+. In the presence of Hg2+ and Al3+ perchlorates, short wavelength emission around 370 nm is strongly increased and this fluorescent enhancement is attributable not to the coordination of Hg2+ and Al3+ to 1 but to the formation of the salt of perchloric acid of 1 . 相似文献
58.
Tano T Ertem MZ Yamaguchi S Kunishita A Sugimoto H Fujieda N Ogura T Cramer CJ Itoh S 《Dalton transactions (Cambridge, England : 2003)》2011,40(40):10326-10336
Copper(II) complexes 1a and 1b, supported by tridentate ligand bpa [bis(2-pyridylmethyl)amine] and tetradentate ligand tpa [tris(2-pyridylmethyl)amine], respectively, react with cumene hydroperoxide (CmOOH) in the presence of triethylamine in CH(3)CN to provide the corresponding copper(II) cumylperoxo complexes 2a and 2b, the formation of which has been confirmed by resonance Raman and ESI-MS analyses using (18)O-labeled CmOOH. UV-vis and ESR spectra as well as DFT calculations indicate that 2a has a 5-coordinate square-pyramidal structure involving CmOO(-) at an equatorial position and one solvent molecule at an axial position at low temperature (-90 °C), whereas a 4-coordinate square-planar structure that has lost the axial solvent ligand is predominant at higher temperatures (above 0 °C). Complex 2b, on the other hand, has a typical trigonal bipyramidal structure with the tripodal tetradentate tpa ligand, where the cumylperoxo ligand occupies an axial position. Both cumylperoxo copper(II) complexes 2a and 2b are fairly stable at ambient temperature, but decompose at a higher temperature (60 °C) in CH(3)CN. Detailed product analyses and DFT studies indicate that the self-decomposition involves O-O bond homolytic cleavage of the peroxo moiety; concomitant hydrogen-atom abstraction from the solvent is partially involved. In the presence of 1,4-cyclohexadiene (CHD), the cumylperoxo complexes react smoothly at 30 °C to give benzene as one product. Detailed product analyses and DFT studies indicate that reaction with CHD involves concerted O-O bond homolytic cleavage and hydrogen-atom abstraction from the substrate, with the oxygen atom directly bonded to the copper(II) ion (proximal oxygen) involved in the C-H bond activation step. 相似文献
59.
Watano S Okamoto T Sato Y Ohnishi Y Yasutomo T Osako Y 《Chemical & pharmaceutical bulletin》2005,53(1):18-21
A novel multi-functional vertical high shear kneader has been developed and its performance in wet kneading has previously been reported [Watano et al., Chem. Pharm. Bull., 50(3), 341-345 (2002)]. In this study, scale-up of wet kneading in the novel vertical high shear kneader was conducted. Pharmaceutical excipients composed of lactose, cornstarch and micro-crystalline cellulose were used as powder samples. Kneading operations were conducted under various operating conditions and three different vessel scales. The dried pellets were then prepared by extruding the wet kneaded masses through a dome-type extruder and their drying by a fluidized bed. The physical properties such as strength and disintegration time of the dried pellets were evaluated. It was found that the properties of the dried pellets and their scale-up characteristics were well expressed by an agitation power per unit vessel volume and dimensionless Froude number. 相似文献
60.
Michito Shiotsuka Naoki Nishiko Yasushi Tsuji Noboru Kitamura Satoru Onaka Katsuya Sako 《Transition Metal Chemistry》2010,35(2):129-135
A novel asymmetric dinuclear gold(I) complex with 3,6-diethynylphenanthroline, 3,6-bis{(PPh3)–Au–C≡C}2-phen, has been synthesized from Au(PPh3)Cl (PPh3 = triphenylphosphine) and 3,6-diethynyl-1,10-phenanthroline. The asymmetrical dinuclear gold(I) complex, 3,6-bis{(PPh3)–Au–C≡C}2-phen, demonstrated a weak phosphorescence assignable to the metal-perturbed 3
π–π* transition in the long wavelength region compared to an intense emission of the symmetrical dinuclear complex with 3,8-diethynylphenanthroline,
3,8-bis{(PPh3)–Au–C≡C}2-phen. A similar tendency of phosphorescent bands for the mononuclear gold(I) complexes with 5-ethynylphenanthroline, 5-{(PPh3)–Au–C≡C}-phen, and 3-ethynylphenanthroline, 3-{(PPh3)–Au–C≡C}-phen was observed. The absorption bands assignable to the π–π*(C≡Cphen) transition and phosphorescent emission assignable to the metal-perturbed 3
π–π* transition for these four gold(I) complexes were reasonably consistent with the results calculated by DFT and TD-DFT. 相似文献