全文获取类型
收费全文 | 2846篇 |
免费 | 132篇 |
国内免费 | 13篇 |
专业分类
化学 | 2153篇 |
晶体学 | 10篇 |
力学 | 126篇 |
数学 | 327篇 |
物理学 | 375篇 |
出版年
2023年 | 31篇 |
2022年 | 59篇 |
2021年 | 59篇 |
2020年 | 67篇 |
2019年 | 65篇 |
2018年 | 43篇 |
2017年 | 36篇 |
2016年 | 89篇 |
2015年 | 81篇 |
2014年 | 94篇 |
2013年 | 147篇 |
2012年 | 217篇 |
2011年 | 256篇 |
2010年 | 124篇 |
2009年 | 142篇 |
2008年 | 218篇 |
2007年 | 203篇 |
2006年 | 208篇 |
2005年 | 196篇 |
2004年 | 169篇 |
2003年 | 134篇 |
2002年 | 115篇 |
2001年 | 51篇 |
2000年 | 28篇 |
1999年 | 20篇 |
1998年 | 20篇 |
1997年 | 20篇 |
1996年 | 22篇 |
1995年 | 6篇 |
1994年 | 8篇 |
1993年 | 8篇 |
1992年 | 14篇 |
1991年 | 4篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有2991条查询结果,搜索用时 11 毫秒
1.
Johann Guilleminot Christian Soize Djimedo Kondo Christophe Binetruy 《International Journal of Solids and Structures》2008,45(21):5567-5583
Many engineering materials exhibit fluctuations and uncertainties on their macroscopic mechanical properties. This randomness results from random fluctuations observed at a lower scale, especially at the meso-scale where microstructural uncertainties generally occur. In the present paper, we first propose a complete theoretical stochastic framework (that is, a relevant probabilistic model as well as a non-intrusive stochastic solver) in which the volume fraction at the microscale is modelled as a random field whose statistical reduction is performed using a Karhunen–Loeve expansion. Then, an experimental procedure dedicated to the identification of the parameters involved in the probabilistic model is presented and relies on a non-destructive ultrasonic method. The combination of the experimental results with a micromechanical analysis provides realizations of the volume fraction random field. In particular, it is shown that the volume fraction can be modelled by a homogeneous random field whose spatial correlation lengths are determined and may provide conditions on the size of the meso-volumes to be considered. 相似文献
2.
Iron-catalyzed homo-coupling of simple and functionalized arylmagnesium reagents is described. The reaction is highly chemoselective (CN, COOEt and NO(2) groups are tolerated). The procedure was used to perform intramolecular couplings. This cyclization reaction is the key step of the total synthesis of the N-methylcrinasiadine. 相似文献
3.
Mahesh Attimarad Katharigatta Narayanaswamy Venugopala Muhammad S. Chohan Marysheela David Efren II Plaza Molina Nagaraja Sreeharsha Anroop Balachandran Nair Christophe Tratrat Abdulrahman Ibrahim Altaysan Abdulmalek Ahmed Balgoname 《Molecules (Basel, Switzerland)》2022,27(10)
A rapid and reproducible hydrophilic liquid chromatography (HILIC) process was established for concomitant determination of remogliflozin etabonate (RE), vildagliptin (VD), and metformin (MF) in a formulation. A face-centered central composite experimental design was employed to optimize and predict the chromatographic condition by statistically studying the surface response model and design space with desirability close to one. A HILIC column with a simple mobile phase of acetonitrile (65% v/v) and 20 mM phosphate buffer (35% v/v, pH 6, controlled with orthophosphoric acid) was used to separate RE, VD, and MF. RE, VD, and MF were separated in 3.6 min using an isocratic mode mobile phase flow at a flow rate of 1.4 mL at room temperature, and the analytes were examined by recording the absorption at 210 nm. The developed HILIC method was thoroughly validated for all parameters recommended by ICH, and linearity was observed in the ranges 20–150 µg/mL, 10–75 µg/mL, and 50–750 µg/mL for RE, VD, and MF, respectively, along with excellent regression coefficients (r2 > 0.999). The calculated percentage relative deviation and relative error ascertained the precision and accuracy of the method. The selectivity and accuracy were further confirmed by the high percentage recovery of added standard drugs to the formulation using the standard addition technique. The robustness of the HILIC processes was confirmed by developing a half-normal probability plot and Pareto chart, as the slight variation of a single factor had no significant influence on the assay outcomes. Utilization of the optimized HILIC procedure for concurrent quantification of RE, VD, and MF in solid dosage forms showed accurate and reproducible results. Hence, the fast HILIC method can be regularly employed for the quality assurance of pharmaceutical preparations comprising RE, VD, and MF. 相似文献
4.
Janis V. Musso Jordan De Jesus Silva Mathis J. Benedikter Jonas Groos Wolfgang Frey Christophe Copret Michael R. Buchmeiser 《Chemical science》2022,13(29):8649
Cationic d0 group 6 olefin metathesis catalysts have been recently shown to display in most instances superior activity in comparison to their neutral congeners. Furthermore, their catalytic performance is greatly improved upon immobilization on silica. In this context, we have developed the new family of molecular cationic molybdenum oxo alkylidene complexes stabilized by N-heterocyclic carbenes of the general formula [Mo(O)(CHCMe3)(IMes)(OR)[X−]] (IMes = 1,3-dimesitylimidazol-2-ylidene; R = 1,3-dimesityl-C6H3, C6F5; X− = B(3,5-(CF3)2C6H3)4−, B(ArF)4, tetrakis(perfluoro-t-butoxy)aluminate (PFTA)). Immobilization of [Mo(O)(CHCMe3)(IMes)(O-1,3-dimesityl-C6H3)+B(ArF)4−] on silica via surface organometallic chemistry yields an active alkene metathesis catalyst that shows the highest productivity towards terminal olefins amongst all existing molybdenum oxo alkylidene catalysts.The first cationic molybdenum oxo complexes were synthesized and immobilized on partially dehydroxylated silica. Vastly enhanced catalytic activity for terminal olefins was found compared to their neutral congeners. 相似文献
5.
Floraine Collette Régis Delatouche Christophe Blanquart Fabien Gueugnon Marc Grégoire Philippe Bertrand Valérie Héroguez 《Journal of polymer science. Part A, Polymer chemistry》2013,51(1):176-189
In this contribution, a versatile approach for the synthesis of functionalized particles for drug delivery is presented, using two nonaggressive standardized procedures. The first procedure considered is the functionalization of an azido‐terminated α‐norbornenyl poly(ethylene oxide) (PEO) macromonomer with an alkyne‐containing active molecule via the copper catalyzed azide alkyne cycloaddition, click type reaction. The functionalized macromonomer is then polymerized by Ring‐Opening Metathesis Polymerization (ROMP) in dispersion to form functionalized particles. The second procedure consists in synthesizing particles by ROMP in dispersed media of norbornene with azido‐terminated α‐norbornenyl PEO macromonomer. The ROMP was initiated by the first generation Grubbs catalyst. Such functionalized core‐shell particles have stealthy properties due to their PEO shell and can be viewed as universal nanocarriers on which any alkyne‐modified active molecule can be grafted by click chemistry. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献
6.
7.
The analysis of changes in the vibrational spectrum of infrared active molecules adsorbed on a ionic surface containing point or extended defects can be an efficient method to determine the nature and density of surface defects. We study the infrared response of ammonia molecules deposited on a ionic surface of MgO containing charge vacancies and dipolar defects in various concentrations and distributions and show significant changes assigned to the defects signature. A Monte Carlo approach is used to randomly deposit the probe molecules on the surface displaying random or regularly arranged defects at low temperature. 相似文献
8.
9.
Christophe Bliard Pal Herczegh Alain Olesker Gabor Lukacs 《Journal of carbohydrate chemistry》2013,32(1):103-113
Abstract L-Oleandrose is the carbohydrate constituent of the potent anthelmintic agents the avermectins. Diethylaminosulfur tri-fluoride treatment of appropriate uloses did not give gem-difluoro sugars. Trifluorofluoroxymethane or xenon difluoride addition to the double bond of 4-O-benzoyl-6-deoxy-2-fluoro-3-O-methyl-L-glucal produced protected 2,2-difluorooleandrose derivatives activated at their anomeric center and ready for glycosidation. 相似文献
10.