全文获取类型
收费全文 | 1111篇 |
免费 | 32篇 |
国内免费 | 10篇 |
专业分类
化学 | 693篇 |
晶体学 | 16篇 |
力学 | 49篇 |
综合类 | 1篇 |
数学 | 140篇 |
物理学 | 254篇 |
出版年
2023年 | 3篇 |
2022年 | 6篇 |
2021年 | 17篇 |
2020年 | 17篇 |
2019年 | 17篇 |
2018年 | 41篇 |
2017年 | 34篇 |
2016年 | 45篇 |
2015年 | 34篇 |
2014年 | 55篇 |
2013年 | 104篇 |
2012年 | 65篇 |
2011年 | 74篇 |
2010年 | 48篇 |
2009年 | 41篇 |
2008年 | 70篇 |
2007年 | 38篇 |
2006年 | 49篇 |
2005年 | 41篇 |
2004年 | 41篇 |
2003年 | 33篇 |
2002年 | 21篇 |
2001年 | 15篇 |
2000年 | 18篇 |
1999年 | 12篇 |
1998年 | 17篇 |
1997年 | 7篇 |
1996年 | 17篇 |
1995年 | 12篇 |
1994年 | 10篇 |
1993年 | 8篇 |
1992年 | 5篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 8篇 |
1987年 | 7篇 |
1986年 | 10篇 |
1985年 | 12篇 |
1984年 | 7篇 |
1983年 | 6篇 |
1982年 | 10篇 |
1981年 | 4篇 |
1979年 | 4篇 |
1977年 | 4篇 |
1976年 | 6篇 |
1975年 | 7篇 |
1974年 | 7篇 |
1971年 | 4篇 |
1969年 | 3篇 |
排序方式: 共有1153条查询结果,搜索用时 15 毫秒
61.
Regioselective formation of β‐(E)‐ and α‐alkenylsilane moiety attached to silsesquioxane core via Pt‐ and Ru‐based hydrosilylation
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
The first attempts to use ethynylsiloxysilsesquioxanes as reagents for hydrosilylation in the presence of Pt‐ and Ru‐based catalysts are reported. The results obtained strongly depend on the catalytic system used. The catalysts are proved to promote regioselective introduction of β‐(E)‐ and α‐fragments of the alkenylsilane group to the silsesquioxane core. The favourable features of these catalytic systems are their high selectivity and the requirement for relatively mild conditions. This methodology was also successfully applied to dihydro‐substituted organosilicon compounds to obtain a new class of silsesquioxane‐based compounds. 相似文献
62.
Piotr Frąckiewicz 《Physics letters. A》2018,382(48):3463-3469
The Li–Du–Massar quantum duopoly model is one of the generally accepted quantum game schemes. It has applications in a wide range of duopoly problems. Our purpose is to study Stackelberg's duopoly with incomplete information in the quantum domain. The result of Lo and Kiang has shown that the correlation of players' quantities caused by the quantum entanglement enhances the first-mover advantage in the game. Our work demonstrates that there is no first-mover advantage if the players' actions are maximally correlated. Furthermore, we proved that the second mover gains a higher equilibrium payoff than the first one. 相似文献
63.
64.
Łukasz Woźniak Krystian Marszałek Sylwia Skąpska Renata Jędrzejczak 《Chromatographia》2017,80(10):1527-1533
Triterpenic acids are a group of secondary plant metabolites which are part of the cuticular waxes covering fruits, leaves, and flowers. To date, quantitative analysis of these compounds has often been conducted using high-performance liquid chromatography coupled with spectrophotometric detection or mass spectrometry; however, these methods have some major drawbacks. This paper reports a new method of analysis implementing derivatization with 9-anthryldiazomethane and fluorescence detection. The method consists of the extraction of analytes from a matrix, purification with anion exchanging SPE columns, and an optional step of the alkaline hydrolysis of triterpenic acid esters. The paper also describes a fast and easy method for the synthesis of the derivatization agent. The detection limits of the method presented are approximately 100-fold lower than in a similar method using ultraviolet spectrophotometry as the mode of detection. The recovery and repeatability of the method are at satisfactory levels. 相似文献
65.
D. F. Parra P. L. Forster R. Łyszczek A. Ostasz A. B. Lugao Z. Rzączyńska 《Journal of Thermal Analysis and Calorimetry》2013,114(3):1049-1056
The aim of this study has been to gain a fundamental understanding of the mechanisms governing thermal degradation of luminescent poly(3-hydroxybutyrate) (PHB). PHB was doped with diaquatris(thenoyltrifluoroacetonate) europium(III) complex, [Eu(tta)3(H2O)2], and different luminescent systems were obtained. The thermal-stability of the luminescent films was discussed and the products of decomposition were analyzed. Thermal degradation of PHB:Eu(tta)3 x % systems (x = 0, 1, 5, 10, and 15 %) was elucidated by means of thermogravimetric analysis (TG), the thermal-stability decreases with the increase of europium complex concentration. The PHB polymer decomposed with evolution of carbon dioxide and 2-butenoic acid molecules. The TG–FTIR results, of the gaseous degradation products of PHB in nitrogen atmosphere, indicated that the polymer is stable at temperatures up to 200 °C. Polymer matrix at concentrations above 5 % decomposed with evolution of water molecules among the other gaseous products, which implied the presence of a hydrated complex in the system. The luminescent films showed more flexibility due to a loss in crystallinity, which suggested a potential usefulness in technical applications. 相似文献
66.
Paweł K. Zarzycki Magdalena M. Ślączka Elżbieta Włodarczyk Michał J. Baran 《Chromatographia》2013,76(19-20):1249-1259
In this work we demonstrated analytical capability of micro-planar (micro-TLC) technique comprising one and two-dimensional (2D) separation modes to generate fingerprints of environmental samples originated from sewage and ecosystems waters. We showed that elaborated separation and detection protocols are complementary to previously invented HPLC method based on temperature-dependent inclusion chromatography and UV-DAD detection. Presented 1D and 2D micro-TLC chromatograms of SPE (solid-phase extraction) extracts were optimized for fast and low-cost screening of water samples collected from lakes and rivers located in the area of Middle Pomerania in northern part of Poland. Moreover, we studied highly organic compounds loaded in the treated and untreated sewage waters obtained from municipal wastewater treatment plant “Jamno” near Koszalin City (Poland). Analyzed environmental samples contained number of substances characterized by polarity range from estetrol to progesterone as well as chlorophyll-related dyes previously isolated and pre-purified by simple SPE protocol involving C18 cartridges. Optimization of micro-TLC separation and quantification protocols of such samples were discussed from the practical point of view using simple separation efficiency criteria including total peaks number, log(product ΔhR F), signal intensity and peak asymmetry. Outcomes of the presented analytical approach, especially using detection involving direct fluorescence (UV366/Vis) and phosphomolybdic acid (PMA) visualization are compared with UV-DAD HPLC-generated data reported previously. Chemometric investigation based on principal components analysis revealed that SPE extracts separated by micro-TLC and detected under fluorescence and PMA visualization modes can be used for robust sample fingerprinting even after long-term storage of the extracts (up to 4 years) at subambient temperature (?20 °C). Such approach allows characterization of wide range of sample components that are present in given extract in high and middle concentration range. Due to protocol simplicity and low cost of analysis this method can be useful for preliminary sample screening. 相似文献
67.
Protocols for the synthesis of cage-substituted 1-vinylsilatranes have been developed and updated. The 1-vinylsilatranes with organic substituents attached to silatrane cage were functionalized in ruthenium-catalyzed trans-silylation with olefins, leading to novel styrylsilatranes in high yields. 相似文献
68.
Formation, crystal structure, polymorphism, and transition between polymorphs are reported for M(thd)3, (M = Al, Cr, Mn, Fe, Co, Ga, and In) [(thd)– = anion of H(thd) = C11H20O2 = 2, 2, 6, 6‐tetramethylheptane‐3, 5‐dione]. Fresh crystal‐structure data are provided for monoclinic polymorphs of Al(thd)3, Ga(thd)3, and In(thd)3. Apart from adjustment of the M–Ok bond length, the structural characteristics of M(thd)3 complexes remain essentially unaffected by change of M. Analysis of the M–Ok, Ok–Ck, and Ck–Ck distances support the notion that the M–Ok–Ck–Ck–Ck–Ok– ring forms a heterocyclic unit with σ and π contributions to the bonds. Tentative assessments according to the bond‐valence or bond‐order scheme suggest that the strengths of the σ bonds are approximately equal for the M–Ok, Ok–Ck, and Ck–Ck bonds, whereas the π component of the M–Ok bonds is small compared with those for the Ok–Ck, and Ck–Ck bonds. The contours of a pattern for the occurrence of M(thd)3 polymorphs suggest that polymorphs with structures of orthorhombic or higher symmetry are favored on crystallization from the vapor phase (viz. sublimation). Monoclinic polymorphs prefer crystallization from solution at temperatures closer to ambient. Each of the M(thd)3 complexes subject to this study exhibits three or more polymorphs (further variants are likely to emerge consequent on systematic exploration of the crystallization conditions). High‐temperature powder X‐ray diffraction shows that the monoclinic polymorphs convert irreversibly to the corresponding rotational disordered orthorhombic variant above some 100–150 °C (depending on M). The orthorhombic variant is in turn transformed into polymorphs of tetragonal and cubic symmetry before entering the molten state. These findings are discussed in light of the current conceptions of rotational disorder in molecular crystals. 相似文献
69.
Glenn Mangelinckx Jeroen Beeckman Olga Chojnowska Jungsoon Shin James D.K. Kim Roman Dąbrowski 《Liquid crystals》2013,40(11):1553-1558
This paper describes a novel implementation of a dual-frequency liquid crystal optical shutter of the guest–host type. The transmissive state of the filter is obtained by applying a low-frequency electric field that brings the dichroic dye in a homeotropic orientation. The light-absorbing state is realised by a twisted planar configuration for which the absorption is quasi-independent of the polarisation. Switching between the two states occurs in about 1 ms and the devices show no scattering for wavelengths inside or outside the absorption band of the dichroic dye. Simulations and experiments reveal how a twisted state is obtained through the backflow phenomenon. 相似文献
70.
The results of dielectric studies performed in a broad frequency range for two compounds, 4-cyanophenyl 4-n-heptylbenzoate (7BBCN) and 4-(4-cyanobutyloxy)phenyl 4- n-heptylbenzoate (7BB4CN), are compared. They have the same molecular core whereas the strongly polar CN group is attached to the benzene ring in 7BBCN or is separated from it by the butyloxy chain in 7BB4CN. 7BBCN has a nematic phase, whereas 7BB4CN exhibits a monotropic nematic and smectic A2 polymorphism. Large differences in the dielectric properties of the two substances were found. The analysis of the results led to the conclusion that the antiparallel dipole-dipole associations are considerably stronger in the substance with a decoupled CN group. 相似文献