全文获取类型
收费全文 | 1408篇 |
免费 | 107篇 |
国内免费 | 2篇 |
专业分类
化学 | 1220篇 |
晶体学 | 19篇 |
力学 | 19篇 |
数学 | 42篇 |
物理学 | 217篇 |
出版年
2023年 | 16篇 |
2022年 | 24篇 |
2021年 | 44篇 |
2020年 | 40篇 |
2019年 | 60篇 |
2018年 | 51篇 |
2017年 | 26篇 |
2016年 | 47篇 |
2015年 | 54篇 |
2014年 | 62篇 |
2013年 | 103篇 |
2012年 | 138篇 |
2011年 | 145篇 |
2010年 | 60篇 |
2009年 | 48篇 |
2008年 | 90篇 |
2007年 | 75篇 |
2006年 | 57篇 |
2005年 | 62篇 |
2004年 | 51篇 |
2003年 | 37篇 |
2002年 | 32篇 |
2001年 | 10篇 |
2000年 | 12篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1995年 | 7篇 |
1994年 | 8篇 |
1993年 | 6篇 |
1992年 | 3篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1988年 | 10篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 9篇 |
1984年 | 8篇 |
1982年 | 3篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1975年 | 9篇 |
1974年 | 6篇 |
1969年 | 5篇 |
1967年 | 7篇 |
1966年 | 4篇 |
排序方式: 共有1517条查询结果,搜索用时 15 毫秒
1.
Joji Ohshita Ryosuke Taketsugu Yuki Nakahara Atsutaka Kunai 《Journal of organometallic chemistry》2004,689(20):3258-3264
Selective dehydrogenative coupling of di- and trihydrosilanes with alcohols catalyzed by PdCl2 or NiCl2 afforded alkoxyhydro- and dialkoxyhydrosilanes in good yield. Further treatment of the resulting alkoxyhydrosilanes with carbon tetrachloride or allyl bromide in the presence of the same catalyst led to the formation of alkoxychloro- and alkoxybromosilanes, respectively. Similar reactions of dialkoxyhydrosilanes with carbon tetrachloride afforded dialkoxychlorosilanes in good yield, although contamination of small amounts of trialkoxysilanes and alkoxydichlorosilanes was detected in the products. Selective substitution of the alkoxyhalosilanes with nucleophiles is also reported. 相似文献
2.
Hideyuki Yoshida Yuki Ohno Kenichiro Yoshikuni Kenichiro Todoroki Hitoshi Nohta Masatoshi Yamaguchi 《Analytical sciences》2003,19(2):317-319
A simple and sensitive fluorometric high-performance liquid chromatographic method was developed for the determination of midodrine in human plasma. After liquid-liquid extraction from plasma, the drug and 2-phenylglycinol (internal standard) were convened into the corresponding fluorescent derivatives by reaction with 3,4-dihydro-6,7-dimethoxy-4-methyl-3-oxoquinoxaline-2-carbonyl chloride, a fluorescence derivatization reagent for amines. The derivatives were separated within 30 min on a reversed-phase column using isocratic elution with acetonitrile-methanol-water (10:30:60, v/v) and were detected spectrofluorometrically at 485 nm with excitation at 400 nm. The detection limit for midodrine was 0.3 pmol (76 pg) per mL plasma at a signal-to-noise ratio of 3. 相似文献
3.
Hidenori Hanaoka Yuka Imamoto Takahiro Hino Tetsuya Kohno Kazunori Yanagi Yoshiaki Oda 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3668-3676
Chromium catalysts combined with phosphorous‐bridged bisphenoxy ligands were found to be highly active for ethylene polymerization. The most efficient catalyst precursor among them, generated by combining bis[3‐tert‐butyl‐5‐methyl‐2‐hydroxyphenyl](phenyl)phosphine hydrochloride ( 1a ) and CrCl3(THF)3, was characterized. X‐ray analysis of (3‐tert‐butyl‐5‐methyl‐2‐phenoxy)(3‐tert‐butyl‐5‐methyl‐ 2‐hydroxyphenyl)(phenyl)phosphine bis(tetrahydrofuran)chromium dichloride ( 6 ), obtained by the reaction of 1a and CrCl3(THF)3 in the presence of NaH, revealed a unique structure in which one phenol moiety of the bisphenol did not coordinate to the chromium center. Complex 6 showed higher activities than those observed in the in situ catalyst system. Polyethylene of various molecular weights was obtained with differing activators. The highest activity (113.5 kg mmol (cat)?1 h?1) was observed when TIBA/TB was used as a cocatalyst. A medium molecular weight polymer with narrow molecular weight distribution (Mw = 128,700, Mw/Mn = 1.8) was obtained using a 6 ‐TIBA/B(C6F5)3 system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3668–3676, 2007 相似文献
4.
5.
H Fujita Y Sasaki H Kohno Y Ohkubo A Ambo K Suzuki M Hino 《Chemical & pharmaceutical bulletin》1990,38(8):2197-2200
Nine analogs based on a structure of Tyr-D-Arg-Phe-X (X = alkylamides or alkylhydrazide containing electron-withdrawing atoms or groups) were newly synthesized and their biological properties were examined by the opioid receptor binding properties of mu-, delta- and kappa-receptors, guinea-pig ileum (GPI) assay and analgesic activity in the tail pinch test after subcutaneous administration in mice. Analogs with X = NHCF2CF3, Sar-ol, or NH(CH2)2CN showed potent activities in the GPI and analgesic assays and high affinity for mu-receptor. An analog with X = taurinamide was found to possess 4-fold higher mu-receptor selectivity than that of [D-Ala2, MePhe4, Gly-ol5]enkephalin (DAGO). The receptor binding properties of previously reported analogs [Chem. Pharm. Bull., 33, 1528 (1985); ibid., 33, 4865 (1985); ibid., 36, 4834 (1988)] were also examined for overall discussion of the structure-activity relationships of this series of tripeptide amides. 相似文献
6.
The polymerization of isobutyl vinyl ether was studied in a heterogeneous system using iron (II) sulfate calcined in air at various temperatures as a catalyst. The maximum activity was shown by the catalyst calcined at 700°C, which effected the polymerization at room temperature in a few seconds, while the sulfate treated at 750°C was totally inactive. Poly(vinyl ethyl ether) was also obtained by the FeSO4 (700°C) catalyst at room temperature. This catalyst formed the crystalline polymer (melting temperature 135–138°C) when the reaction was performed in toluene as solvent at room temperature. Poisoning experiments with Hammett indicators were carried out with the FeSO4 (700°C) catalyst. The treatment with n-butylamine rendered it inactive in the reaction of isobutyl vinyl ether, while its catalytic activity was little affected by dicinnamalacetone. On the basis of the observed results, the nature of active sites of catalyst is discussed. 相似文献
7.
8.
Wright RJ Phillips AD Hino S Power PP 《Journal of the American Chemical Society》2005,127(13):4794-4799
The synthesis and characterization of three new organothallium(I) compounds are reported. Reaction of (Ar'Li)(2) (Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)) and Ar"Li (Ar" = C(6)H(3)-2,6-(C(6)H(3)-2,6-Me(2))(2)) with TlCl in Et(2)O afforded (Ar'Tl)(2) (1) and (Ar' 'Tl)(3) (2). The "dithallene" 1 is the heaviest group 13 dimetallene and features a planar, trans-bent structure with Ar'Tl-Tl = 119.74(14) degrees and Tl-Tl = 3.0936(8) A. Compound 2 is the first structurally characterized neutral, three-membered ring species of formula c-(MR)(3) (M = Al-Tl; R = organo group). The Tl(3) ring has Tl-Tl distances in the range ca. 3.21-3.37 A as well as pyramidal Tl geometries. The Tl-Tl bonds in 1 and 2 are outside the range (2.88-2.97 A) of Tl-Tl single bonds in R(2)TlTlR(2) compounds. The weak Tl-Tl bonding in 1 and 2 leads to their dissociation into Ar'Tl and Ar' 'Tl monomers in hexane. The Ar'Tl monomer behaves as a Lewis base and readily forms a 1:1 donor-acceptor complex with B(C(6)F(5))(3) to give Ar'TlB(C(6)F(5))(3), 3. Adduct 3 features an almost linear thallium C(ipso)-Tl-B angle of 174.358(7) degrees and a Tl-B distance of 2.311(2) A, which indicates strong association. Treatment of 1 with a variety of reagents resulted in no reactions. The lower reactivity of 1 is in accord with the reluctance of Tl(I) to undergo oxidation to Tl(III) due to the unreactive character of the 6s(2) electrons. 相似文献
9.
We apply the singular value decomposition to compress the degrees of freedom of T3 amplitude for the CCSDT-1 method (compressed CCSDT-1). This method enables us to make the number of the T3 amplitudes less than that of the T2 amplitudes, making CCSDT-1 calculations much less expensive without losing accuracy. We perform test calculations on some atoms and molecules to investigate the applicability of this method. Computational results for the electronic energies as well as timings of these calculations are presented. 相似文献
10.
Shigeyama M Ohgaya O Takeuchi H Hino T Kawashima Y 《Chemical & pharmaceutical bulletin》2001,49(2):129-133
We intended to develop a desired ointment base suitable for treatment of bedsores including the proliferation of granulation and epidermis. The main bedsore bacteria detected in our hospital were S. aureus in gram-positive coccus and P. aeruginosa in gram-negative bacillus. As the macrogol ointment (MO) was found to have bactericidal effects on these bacteria, MO was adopted as the base for the objective ointment. To improve the properties of the ointment base such as regulating the humidity of the exudation and controlling the release of antibiotics formulated in the ointment, co-formulating effects of various additives to MO were evaluated. The sustained release function of the ointment base was obtained by adding hydrophilic petrolatum (HP) to MO. However, the resultant ointment was found to have a poor humidity regulating property. On the other hand, MO containing 5% of hydroxypropyl cellulose (HPC) showed both the humidity regulating and the controlled drug releasing properties. It was considered that HPC particles dispersed in the ointment could be swelled by absorbing water to form a gel network. The curd tension meter tests for the ointments prepared with the various polymers showed that the MO-HPC base, which showed the highest sustained drug releasing property, was found to have the highest hardness. This result means that HPC formulated into the base forms the most rigid gel structure to resist the erosion of the ointment and to control the drug release. 相似文献