全文获取类型
收费全文 | 1189篇 |
免费 | 32篇 |
国内免费 | 2篇 |
专业分类
化学 | 841篇 |
晶体学 | 6篇 |
力学 | 10篇 |
数学 | 86篇 |
物理学 | 280篇 |
出版年
2022年 | 5篇 |
2021年 | 13篇 |
2020年 | 9篇 |
2019年 | 16篇 |
2018年 | 11篇 |
2017年 | 15篇 |
2016年 | 18篇 |
2015年 | 22篇 |
2014年 | 30篇 |
2013年 | 61篇 |
2012年 | 53篇 |
2011年 | 76篇 |
2010年 | 45篇 |
2009年 | 45篇 |
2008年 | 58篇 |
2007年 | 66篇 |
2006年 | 76篇 |
2005年 | 78篇 |
2004年 | 60篇 |
2003年 | 62篇 |
2002年 | 48篇 |
2001年 | 23篇 |
2000年 | 23篇 |
1999年 | 14篇 |
1998年 | 13篇 |
1997年 | 12篇 |
1996年 | 18篇 |
1995年 | 8篇 |
1994年 | 10篇 |
1993年 | 11篇 |
1992年 | 9篇 |
1991年 | 8篇 |
1990年 | 8篇 |
1989年 | 6篇 |
1988年 | 9篇 |
1987年 | 13篇 |
1986年 | 7篇 |
1985年 | 12篇 |
1984年 | 22篇 |
1982年 | 12篇 |
1981年 | 12篇 |
1980年 | 16篇 |
1979年 | 12篇 |
1978年 | 11篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 16篇 |
1974年 | 11篇 |
1973年 | 11篇 |
1964年 | 3篇 |
排序方式: 共有1223条查询结果,搜索用时 15 毫秒
91.
Takahashi G Shirakawa E Tsuchimoto T Kawakami Y 《Chemical communications (Cambridge, England)》2005,(11):1459-1461
Alkynes act not as substrates but as co-catalysts in the presence of a nickel catalyst, an organoboronate and an aldehyde to promote the addition reaction between the substrates in combination with H2O. 相似文献
92.
A method for calibration and validation subset partitioning 总被引:13,自引:0,他引:13
This paper proposes a new method to divide a pool of samples into calibration and validation subsets for multivariate modelling. The proposed method is of value for analytical applications involving complex matrices, in which the composition variability of real samples cannot be easily reproduced by optimized experimental designs. A stepwise procedure is employed to select samples according to their differences in both x (instrumental responses) and y (predicted parameter) spaces. The proposed technique is illustrated in a case study involving the prediction of three quality parameters (specific mass and distillation temperatures at which 10 and 90% of the sample has evaporated) of diesel by NIR spectrometry and PLS modelling. For comparison, PLS models are also constructed by full cross-validation, as well as by using the Kennard-Stone and random sampling methods for calibration and validation subset partitioning. The obtained models are compared in terms of prediction performance by employing an independent set of samples not used for calibration or validation. The results of F-tests at 95% confidence level reveal that the proposed technique may be an advantageous alternative to the other three strategies. 相似文献
93.
Inhibition of the mevalonate pathway by an HMG-CoA reductase inhibitor, mevalotin, in Streptomyces prunicolor possessing both mevalonate and MEP pathways resulted in the production of a new metabolite mevashuntin that consisted of conjugated thiazolone and pyranonaphthoquinone moieties. 相似文献
94.
K Kawakami M Yasuda K Ishii Y Kokusenya T Sato 《Chemical & pharmaceutical bulletin》1999,47(7):919-922
To define the mechanism of the protection by ecabet sodium of the gastric mucosa, the characteristics of protein binding of this drug were investigated using a quartz-crystal microbalance (QCM) method. The binding rate constants (kb) and the binding amounts (delta m) were obtained from time courses of the frequency decrease (mass increase) of the QCM. The binding constants to proteins of two ecabet analogues (G1, ecabet type and G2, non-ionic ecabet type) were dependent on the pH, leading to large kb values at the acidic region. Furthermore, the kb values of G1 with the addition of bovine serum albumin (BSA) and bovine serum fibrinogen (BSF) at the acid region were larger than those of G2. The difference in kb values between G1 and G2 for porcine gastric mucin (PGM) is hardly discernible. Ecabet seems to be more heavily distributed in the ulcerous areas than in the intact mucosa, judging from the large binding constants of this drug to BSA and BSF compared with those to PGM. It is suggested that ecabet is bound to proteins by hydrophobic interaction, moreover, the electrostatic interaction between this drug and proteins (BSA and BSF) occurs at acidic pH region. On account of these interactions, ecabet sodium seems to have a more protective effect on an ulcer at intraluminal acidity than sucralfate. Finally, QCM was found to be a useful technique for detecting quantitatively the time course of binding proteins with drug. 相似文献
95.
96.
H Kawakami 《Radioisotopes》1990,39(6):281-290
97.
This paper proposes a novel wavelet denoising method, which exploits the statistics of individual scans acquired in the course of a coaveraging process. The proposed method consists of shrinking the wavelet coefficients of the noisy signal by a factor that minimizes the expected square error with respect to the true signal. Since the true signal is not known, a sub-optimal estimate of the shrinking factor is calculated by using the sample statistics of the acquired scans. It is shown that such an estimate can be generated as the limit value of a recursive formulation. In a simulated example, the performance of the proposed method is seen to be equivalent to the best choice between hard and soft thresholding for different signal-to-noise ratios. Such a conclusion is also supported by an experimental investigation involving near-infrared (NIR) scans of a diesel sample. It is worth emphasizing that this experimental example concerns the removal of actual instrumental noise, in contrast to other case studies in the denoising literature, which usually present simulations with artificial noise. The simulated and experimental cases indicate that, in classic denoising based on wavelet coefficient thresholding, choosing between the hard and soft options is not straightforward and may lead to considerably different outcomes. By resorting to the proposed method, the analyst is not required to make such a critical decision in order to achieve appropriate results. 相似文献
98.
T Nakao M Obata M Kawakami K Morita H Tanaka Y Morimoto S Takehara T Yakushiji T Tahara 《Chemical & pharmaceutical bulletin》1991,39(10):2556-2563
A series of 2-aryl-5,6-dihydro-(1)benzothiepino[5,4-c]pyridazin-3(2H)- ones and related compounds were synthesized and evaluated for their ability to displace 3H-diazepam from rat brain membranes in vitro, and to prevent bicuculline induced convulsions in mice in vivo. Compounds with a 4'-methoxyphenyl (36) or 4'-chlorophenyl group (37, 39--42) as 2-aryl substituents showed prominent activities in both the in vitro and in vivo tests. Among them, 2-(4'-chlorophenyl)-5,6-dihydro- (37) and 2-(4'-chlorophenyl)-5,6-dihydro-10-fluoro-(1)benzothiepino[5,4-c]+ ++pyridazin- 3(2H)-one 7-oxides (41) showed activity twice as potent as diazepam in an anticonflict test (Vogel type, rats) while exhibiting less muscle relaxation (rotarod test, mice) and augmentation of gamma-aminobutyric acid-induced chloride current (Icl) in isolated frog sensory neurones than diazepam. Compound 37 (Y-23684) was selected from this series as a candidate for further development. The structure-activity relationships are discussed. 相似文献
99.
Michael Andreas Tandiary Masashi Asano Taiki Hattori Satoshi Takehira Yoichi Masui Makoto Onaka 《Tetrahedron letters》2017,58(20):1925-1928
The solid acid, tin hydroxide-embedded montmorillonite, catalyzes the unprecedented alkylation of various silicon enolates with primary, secondary and tertiary benzylic alcohols as well as secondary allylic alcohols. The acid catalysis of Sn-Mont was not only higher than that of the other ion-exchanged montmorillonites (M-Mont; M = H, Ti, Fe and Al), but also higher than that of the typical homogeneous acid catalysts such as BF3·OEt2, TMSOTf and TfOH. 相似文献
100.
Dr. Yoichi Hoshimoto Keita Ashida Yukari Sasaoka Dr. Ravindra Kumar Prof. Dr. Ken Kamikawa Prof. Dr. Xavier Verdaguer Prof. Dr. Antoni Riera Prof. Dr. Masato Ohashi Prof. Dr. Sensuke Ogoshi 《Angewandte Chemie (International ed. in English)》2017,56(28):8206-8210
The nickel(0)-catalyzed carbonylative cycloaddition of 1,5- and 1,6-ene-imines with carbon monoxide (CO) is reported. Key to this reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO)3L]. A variety of tri- and tetracyclic γ-lactams were thus prepared in excellent yields with 100 % atom efficiency. Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic γ-lactams. 相似文献