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31.
A facile and practical synthetic route of unsymmetrical 1,3‐diynes via the PdCl/CuI catalyzed oxidative coupling of two different terminal alkynes has been developed by using 3‐(diphenylphosphino)propanoic acid as a ligand in the presence of oxygen. This system is suitable for not only aromatic alkynes but also heteroaromatic and aliphatic alkynes which were transformed into the corresponding unsymmetrical 1,3‐diynes in moderate to good yields at room temperature. Moreover, the unsymmetrical 1,3‐diynes were also obtained on a multi‐gram scale. Mechanistic studies suggest that oxygen plays a key role in the catalytic cycles. 相似文献
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变厚度正交各向异性矩形板非线性非对称弯曲问题的基本方程 总被引:1,自引:1,他引:0
在不计体力,考虑了薄膜力引起在z方向的分力,导出了厚度线性变化的正交各向异性矩形板非线性非对称弯曲问题的本构方程;在引进无量纲变量和引入三个小参数的条件下,给出了挠度函数W(x,y)和应力函数Φ(x,y)的无量纲化的支配方程形式. 相似文献
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Micha Kosno Tomasz Laskowski Joanna E. Frackowiak Agnieszka Potga Agnieszka Kurdyn Witold Andraoj Julia Borzyszkowska-Bukowska Katarzyna Szwarc-Karabyka Zofia Mazerska 《Molecules (Basel, Switzerland)》2022,27(13)
Unsymmetrical bisacridines (UAs) represent a novel class of anticancer agents previously synthesized by our group. Our recent studies have demonstrated their high antitumor potential against multiple cancer cell lines and human tumor xenografts in nude mice. At the cellular level, these compounds affected 3D cancer spheroid growth and their cellular uptake was selectively modulated by quantum dots. UAs were shown to undergo metabolic transformations in vitro and in tumor cells. However, the physicochemical properties of UAs, which could possibly affect their interactions with molecular targets, remain unknown. Therefore, we selected four highly active UAs for the assessment of physicochemical parameters under various pH conditions. We determined the compounds’ pKa dissociation constants as well as their potential to self-associate. Both parameters were determined by detailed and complex chemometric analysis of UV-Vis spectra supported by nuclear magnetic resonance (NMR) spectroscopy. The obtained results indicate that general molecular properties of UAs in aqueous media, including their protonation state, self-association ratio, and solubility, are strongly pH-dependent, particularly in the physiological pH range of 6 to 8. In conclusion, we describe the detailed physicochemical characteristics of UAs, which might contribute to their selectivity towards tumour cells as opposed to their effect on normal cells. 相似文献
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通过解析的方法分析了储存环在部分填充情况下的纵向耦合不稳定性,给出了不稳定性增长率和同步振荡频移的表达式.得到了一个有趣的结果:虚部阻抗对不稳定性的增长率也有贡献.这一点和均匀填充情况是不一样的. 相似文献
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Pseudo‐atranes have a significant role in catalysis; however, obtaining chiral pseudo‐atranes for covalent functionalization of heterogeneous catalytic surfaces is very challenging. Herein, synthesis of a chiral tripodal amine [N{CH (CH2Ph)CH2OH}{CH2(4? Br? C6H3OH)}{CH2(2? CHO? 4? Me? C6H2OH)}] ( 1 ) and a dichiral [4.4.3.01,5]tridecane copper(II) cluster, that is, (Cu[N{CH (CH2Ph)CH2OH}{CH2(4? Br? C6H3O)}{CH2(2? CHO? 4? Me? C6H2O)}])2 ( 2 ) is described. The compounds are characterized by elemental analyses, Fourier transform infrared (FT‐IR) spectroscopy, mass spectrometry and single‐crystal X‐ray crystallography (for 2 ). The compound 2 is the first example of chiral pseudo‐copper(II)atrane in which three unsymmetrical arms (two phenolic and a chiral ethanolic arm) are fused via Cu? N transannular bond. The free ? CHO group present in one of the tricyclic arms of the 2 is tested as a linker to load it on 3‐aminopropyltriethoxysilane‐functionalized magnetic nanosilica for catalytic applications. The loading of 2 on magnetic nanosilica through ? CHO was confirmed by FT‐IR spectroscopy, and the 2 ‐loaded magnetic nanosilica ( Fe 3 O 4 @SiO 2 /2 ) was characterized by powder X‐ray diffraction, vibrating sample magnetometry, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy and elemental mapping. The Fe 3 O 4 @SiO 2 /2 was found highly efficient, retrievable, eco‐friendly and green catalyst for obtaining β‐amino alcohols in excellent yields in an aqueous medium. Overall, present work is the first report on synthetic, structural and catalytic aspects of dichiral cluster of copper(II)atrane possessing unsymmetrical tricyclic arms. 相似文献
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David H. Wang John K. Riley Scott P. Fillery Michael F. Durstock Richard A. Vaia Loon‐Seng Tan 《Journal of polymer science. Part A, Polymer chemistry》2013,51(23):4998-5011
A new unsymmetrical diamine, 2‐(3‐aminophenoxy)‐6‐(4‐aminophenoxy)benzonitrile (3,4‐APBN), is synthesized via two consecutive SNAr reactions and the temperature‐dependent reactivity of the fluorides in 2,6‐difluorobenzonitrile, whose first SNAr reaction occurs at 70 °C and second, at 100 °C, allowing timing control of reaction sequence and circumventing the transetherification side reaction. Thus, a series of polyimides (PIs) is prepared from the polymerization of 3,4‐APBN with five common dianhydrides (6FDA, DSDA, OPDA, BTDA, and PMDA). For comparison, a second series is also prepared from two symmetrical diamines ([2,6‐bis(3‐aminophenoxy)benzonitrile (3,3‐APBN) and 2,6‐bis(4‐aminophenoxy)benzonitrile (4,4‐APBN)] and 6FDA or PMDA. The processability of the poly(amic acids) (PAAs), for the first series is greatly improved since their solution viscosities are much lower than PAAs based on symmetrical diamines. Besides having high glass‐transition temperatures (249–332 °C), and thermal stability [5% weight loss in the range of 505–542 °C (air) and 512–546 °C (nitrogen)], these PIs form tough, transparent and flexible films that have a tensile‐strength range of 82.1–121.3 MPa, elongations‐at‐break of 5.33–9.81%, and tensile moduli of 2.11–2.97 GPa. Their film dielectric constants are 3.08–3.62 at 10 kHz, moderately higher than that (2.92) of analogous PI (CP2) without nitrile groups. Overall, we found that the reduction of structural symmetry in repeat units can improve the polymer processibility as well as increasing their dielectric constants. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4998–5011 相似文献