全文获取类型
收费全文 | 858篇 |
免费 | 6篇 |
国内免费 | 3篇 |
专业分类
化学 | 507篇 |
晶体学 | 3篇 |
力学 | 41篇 |
数学 | 139篇 |
物理学 | 177篇 |
出版年
2020年 | 6篇 |
2019年 | 8篇 |
2018年 | 11篇 |
2017年 | 8篇 |
2016年 | 20篇 |
2015年 | 8篇 |
2014年 | 10篇 |
2013年 | 35篇 |
2012年 | 54篇 |
2011年 | 71篇 |
2010年 | 32篇 |
2009年 | 31篇 |
2008年 | 51篇 |
2007年 | 50篇 |
2006年 | 59篇 |
2005年 | 50篇 |
2004年 | 48篇 |
2003年 | 29篇 |
2002年 | 36篇 |
2001年 | 10篇 |
2000年 | 6篇 |
1999年 | 15篇 |
1998年 | 8篇 |
1997年 | 9篇 |
1996年 | 10篇 |
1995年 | 6篇 |
1994年 | 8篇 |
1993年 | 6篇 |
1992年 | 11篇 |
1991年 | 8篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 5篇 |
1986年 | 8篇 |
1985年 | 15篇 |
1984年 | 13篇 |
1983年 | 10篇 |
1982年 | 8篇 |
1981年 | 8篇 |
1980年 | 5篇 |
1979年 | 13篇 |
1978年 | 7篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 5篇 |
1974年 | 12篇 |
1973年 | 8篇 |
1972年 | 2篇 |
1925年 | 2篇 |
排序方式: 共有867条查询结果,搜索用时 15 毫秒
1.
Interactions of Pt‐ttpy with G‐Quadruplexes Originating from Promoter Region of the c‐myc Gene Deciphered by NMR and Gel Electrophoresis Analysis 下载免费PDF全文
2.
Mathieu Boiret Anna de Juan Nathalie Gorretta Yves-Michel Ginot Jean-Michel Roger 《Analytica chimica acta》2015
Raman chemical imaging provides chemical and spatial information about pharmaceutical drug product. By using resolution methods on acquired spectra, the objective is to calculate pure spectra and distribution maps of image compounds. With multivariate curve resolution-alternating least squares, constraints are used to improve the performance of the resolution and to decrease the ambiguity linked to the final solution. Non negativity and spatial local rank constraints have been identified as the most powerful constraints to be used. 相似文献
3.
4.
The photoinduced dynamics of isolated n-hydroxyquinoline (nHQ) molecules (n=6,8) was investigated in femtosecond pump-probe experiments. A qualitative difference was found between 8HQ and 6HQ. After an initial rapid decay corresponding to the departure of the initial wavepacket out of the Franck-Condon region of the excitation, the 8HQ probe signal decays to zero in 0.37 ps whereas a much longer time constant of 10.4 ps is observed in 6HQ. This interrogates on the role played by the intramolecular H-bond N HO which is at play the 8HQ molecule. Ab-initio were performed at the MCSCF/aug-cc-pVDZ level on the 8HQ molecule to help the discussion. A complex energy landscape was found, which includes a conical intersection. 相似文献
5.
Florent Monie Dr. Bruno Grignard Dr. Jean-Michel Thomassin Dr. Raphael Mereau Dr. Thierry Tassaing Prof. Dr. Christine Jerome Dr. Christophe Detrembleur 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17181-17189
Polyurethane (PU) foams are indisputably daily essential materials found in many applications, notably for comfort (for example, matrasses) or energy saving (for example, thermal insulation). Today, greener routes for their production are intensively searched for to avoid the use of toxic isocyanates. An easily scalable process for the simple construction of self-blown isocyanate-free PU foams by exploiting the organocatalyzed chemo- and regioselective additions of amines and thiols to easily accessible cyclic carbonates is described. These reactions are first validated on model compounds and rationalized by DFT calculations. Various foams are then prepared and characterized in terms of morphology and mechanical properties, and the scope of the process is illustrated by modulating the composition of the reactive formulation. With impressive diversity and accessibility of the main components of the formulations, this new robust and solvent-free process could open avenues for construction of more sustainable PU foams, and offers the first realistic alternative to the traditional isocyanate route. 相似文献
6.
The authors study the large time asymptotics of a solution of the Fisher-KPP reaction-diffusion equation,with an initial condition that is a compact perturbation of a step function.A well-known result of Bramson states that,in the reference frame moving as 2t-(3/2) log t+x∞,the solution of the equation converges as t-→ +o∞ to a translate of the traveling wave corresponding to the minimal speed c* =2.The constant x∞ depends on the initial condition u(0,x).The proof is elaborate,and based on probabilistic arguments.The purpose of this paper is to provide a simple proof based on PDE arguments. 相似文献
7.
Ahmad Sarakbi Zeynep AydogmusAngela Dago Dominique MertensJean-Yves Dewert Jean-Michel Kauffmann 《Analytica chimica acta》2013
Liquid chromatography coupled to a silver electrode based flow-through amperometric detector (LC-EC-Ag) was developed for the determination of aminothiols in white wines. The C18 reversed phase LC system operated in the isocratic mode at 0.7 mL min−1 and used an acidic mobile phase composed of formic acid, EDTA, sodium nitrate, sodium hydroxide, and methanol 1% (v/v) at pH 4.5. The working electrode operated at 0.08 V vs Ag/AgCl, 3 M KCl and its manual cleaning was realized once a month by smoothing on a polishing cloth. The analyzed aminothiols were resolved and eluted within 4 min, and all standard curves were linear in the range 2 × 10−7–2 × 10−5 M. The analyzed wine samples needed no preparation other than dilution with the mobile phase. The concentration of cysteine (CYS), homocysteine (HCYS), glutathione (GSH) and N-acetylcysteine (NAC) in bottled white wines, determined by the method of standard addition, was found to be in the low μM range (0.2–2 mg L−1) depending on the wine type and its age. 相似文献
8.
9.
Our efforts in construction the 1,2-dioxane ring of plakortolides through two approaches are described. The first one involved as a key step an acid catalyzed 6-endo ring closure of β-hydroperoxy trans-epoxides directed by a vinyl group adjacent to the epoxide function. By this route, an advanced intermediate of plakortolides was obtained in six steps and 35% overall yield. The second approach featured a 1,2-dioxane ring forming by a double opening of bis-epoxides by ethereal hydrogen peroxide. This reaction did not proceed in the expected sense and exclusive formation of hydroperoxy tetrahydropyran derivatives was observed via a tandem oxacyclization–hydroperoxidation sequence. 相似文献
10.
Frédéric Daems Jean-Michel Romnee Catherine Rasse Éric Froidmont 《Analytical letters》2017,50(14):2189-2216
Many studies have been conducted on the impact of animal feed on isoflavones and their metabolite concentrations in bovine milk, but few studies have focused on the development and validation of analytical protocols for quantifying these compounds in biological matrices other than milk and plants. The purpose of this study was to develop a method that would enable four isoflavones and equol in cows’ feces and digestive fluids to be quantified simultaneously. The method is based on aglycones released by methanolic ultrasound-assisted extraction, followed by enzymatic hydrolysis and high-performance liquid chromatography tandem–mass spectrometry analysis. The sample preparation was optimized using the Box–Behnken design. The selected extraction conditions were 80°C, 10?min, and 50% methanol for digestive fluids and 70°C, 35?min, and 60% methanol for feces. For hydrolysis, the selected conditions were 37°C, 1?h, and a pH of 6 for both matrices. The analytical method showed a good linear regression model ranging from 5 to 125?ng?mL?1. Both inter- and intraday accuracy (≤8.5 and ≤12.3%) and precision (≤11.1 and ≤15.2%) were suitable. No matrix effects were found. There was good repeatability and extract stability for at least 4 days of storage at???20 and 6°C. All recoveries were in the acceptable range of 70–120% for both matrices, except for biochanin A in feces, where the value was approximately 43%. This sensitive and reliable method will be useful for monitoring the passage of isoflavones and equol in the digestive system of ruminants. 相似文献