全文获取类型
收费全文 | 532篇 |
免费 | 35篇 |
国内免费 | 2篇 |
专业分类
化学 | 404篇 |
晶体学 | 1篇 |
力学 | 8篇 |
数学 | 29篇 |
物理学 | 127篇 |
出版年
2024年 | 1篇 |
2023年 | 4篇 |
2022年 | 21篇 |
2021年 | 33篇 |
2020年 | 25篇 |
2019年 | 25篇 |
2018年 | 33篇 |
2017年 | 12篇 |
2016年 | 28篇 |
2015年 | 17篇 |
2014年 | 25篇 |
2013年 | 22篇 |
2012年 | 32篇 |
2011年 | 35篇 |
2010年 | 37篇 |
2009年 | 16篇 |
2008年 | 43篇 |
2007年 | 32篇 |
2006年 | 36篇 |
2005年 | 25篇 |
2004年 | 16篇 |
2003年 | 13篇 |
2002年 | 13篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 7篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1991年 | 1篇 |
1988年 | 1篇 |
1984年 | 1篇 |
排序方式: 共有569条查询结果,搜索用时 15 毫秒
91.
Krivdin LB Larina LI Chernyshev KA Rulev AY 《Magnetic resonance in chemistry : MRC》2006,44(2):178-187
Configurational assignment of seven azomethines obtained from the alpha-functionally substituted and nonsubstituted alpha,beta-unsaturated aldehydes has been performed on the basis of experimental measurements and the high-level ab initio calculations of their 1J(C,C) and 1J(C,H), involving the alpha-imino carbon that demonstrated the marked stereochemical dependence of both coupling constants upon the orientation of the nitrogen lone pair in the diverse isomers of the title azomethines. 相似文献
92.
Hoa V. Phan Pradip Chakraborty Meimei Chen Yitzi M. Calm Dr. Kirill Kovnir Lawrence K. Keniley Jr. Jordan M. Hoyt Elisabeth S. Knowles Dr. Céline Besnard Prof. Mark W. Meisel Prof. Andreas Hauser Prof. Catalina Achim Prof. Michael Shatruk 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(49):15805-15815
Three iron(II) complexes, [Fe(TPMA)(BIM)](ClO4)2?0.5H2O ( 1 ), [Fe(TPMA)(XBIM)](ClO4)2 ( 2 ), and [Fe(TPMA)(XBBIM)](ClO4)2 ?0.75CH3OH ( 3 ), were prepared by reactions of FeII perchlorate and the corresponding ligands (TPMA=tris(2‐pyridylmethyl)amine, BIM=2,2′‐biimidazole, XBIM=1,1′‐(α,α′‐o‐xylyl)‐2,2′‐biimidazole, XBBIM=1,1′‐(α,α′‐o‐xylyl)‐2,2′‐bibenzimidazole). The compounds were investigated by a combination of X‐ray crystallography, magnetic and photomagnetic measurements, and Mössbauer and optical absorption spectroscopy. Complex 1 exhibits a gradual spin crossover (SCO) with T1/2=190 K, whereas 2 exhibits an abrupt SCO with approximately 7 K thermal hysteresis (T1/2=196 K on cooling and 203 K on heating). Complex 3 is in the high‐spin state in the 2–300 K range. The difference in the magnetic behavior was traced to differences between the inter‐ and intramolecular interactions in 1 and 2 . The crystal packing of 2 features a hierarchy of intermolecular interactions that result in increased cooperativity and abruptness of the spin transition. In 3 , steric repulsion between H atoms of one of the pyridyl substituents of TPMA and one of the benzene rings of XBBIM results in a strong distortion of the FeII coordination environment, which stabilizes the high‐spin state of the complex. Both 1 and 2 exhibit a photoinduced low‐spin to high‐spin transition (LIESST effect) at 5 K. The difference in the character of intermolecular interactions of 1 and 2 also manifests in the kinetics of the decay of the photoinduced high‐spin state. For 1 , the decay rate constant follows the single‐exponential law, whereas for 2 it is a stretched exponential, reflecting the hierarchical nature of intermolecular contacts. The structural parameters of the photoinduced high‐spin state at 50 K are similar to those determined for the high‐spin state at 295 K. This study shows that N‐alkylation of BIM has a negligible effect on the ligand field strength. Therefore, the combination of TPMA and BIM offers a promising ligand platform for the design of functionalized SCO complexes. 相似文献
93.
The tropolone subunit of the naturally occurring alkaloid rubrolone aglycon is synthesized via a short reaction sequence starting with a 1,3-dipolar cycloaddition of a pyrylium ylide and indenone, followed by enone oxidation, oxygen-bridge elimination and finally hydroxy group oxidation. 相似文献
94.
Atom-economic Approach to the Synthesis of α-(Hetero)aryl-substituted Furan Derivatives from Biomass
Leonid V. Romashov Kirill S. Kozlov Matvey K. Skorobogatko Alexander Y. Kostyukovich Valentine P. Ananikov 《化学:亚洲杂志》2022,17(1):e202101227
An atom-economic ring construction approach to the synthesis of α-(hetero)arylfurans based on renewable furanic platform chemicals has been developed. Corresponding compounds have been prepared in good to excellent yields via [2+2+2] and [4+2] cycloaddition reactions using metal-catalyzed or photoredox protocols. Easily available HMF-based 2-hydroxymethyl-5-ethynylfuran and 2-hydroxymethyl-5-cyanofuran were used as starting materials. A synthetic route with an improved carbon economy factor has been implemented to achieve sustainability aim. The possible application of arylfurans as molecular conductors has been investigated by DFT calculations, which revealed excellent charge transfer properties. As a future perspective, integration of biomass processing strategy into manufacturing of molecular electronics was pointed out to achieve the aim of sustainability. 相似文献
95.
Dmitriy S. Yambulatov Stanislav A. Nikolaevskii Mikhail A. Kiskin Kirill V. Kholin Mikhail N. Khrizanforov Yulia G. Budnikova Konstantin A. Babeshkin Nikolay N. Efimov Alexander S. Goloveshkin Vladimir K. Imshennik Yurii V. Maksimov Evgeny M. Kadilenko Nina P. Gritsan Igor L. Eremenko 《Molecules (Basel, Switzerland)》2021,26(10)
The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)FeIII2] (1). Molecular structure of 1 was determined by the single crystal X-ray diffraction analysis. The spin state of the iron cation in complex 1 at room temperature and the magnetic behavior of 1 in the temperature range of 2–300 K were studied using Mossbauer spectroscopy and magnetic susceptibility measurements, respectively. The neutral character of dpp-BIAN in 1 was confirmed by IR and UV spectroscopy. The electrochemistry of 1 was studied in solution and solid state using cyclic voltammetry. The generation of the radical anion form of the dpp-BIAN ligand upon reduction of 1 in a CH2Cl2 solution was monitored by EPR spectroscopy. 相似文献
96.
Kirill V. Kholin Mikhail N. Khrizanforov Vasily M. Babaev Guliya R. Nizameeva Salima T. Minzanova Marsil K. Kadirov Yulia H. Budnikova 《Molecules (Basel, Switzerland)》2021,26(18)
A selective noble-metal-free molecular catalyst has emerged as a fruitful approach in the quest for designing efficient and stable catalytic materials for CO2 reduction. In this work, we report that a sodium pectate complex of copper (PG-NaCu) proved to be highly active in the electrocatalytic conversion of CO2 to CH4 in water. Stability and selectivity of conversion of CO2 to CH4 as a product at a glassy carbon electrode were discovered. The copper complex PG-NaCu was synthesized and characterized by physicochemical methods. The electrochemical CO2 reduction reaction (CO2RR) proceeds at −1.5 V vs. Ag/AgCl at ~10 mA/cm2 current densities in the presence of the catalyst. The current density decreases by less than 20% within 12 h of electrolysis (the main decrease occurs in the first 3 h of electrolysis in the presence of CO2). This copper pectate complex (PG-NaCu) combines the advantages of heterogeneous and homogeneous catalysts, the stability of heterogeneous solid materials and the performance (high activity and selectivity) of molecular catalysts. 相似文献
97.
Simon Smolders Tom Willhammar Andra Krajnc Kadir Sentosun Michael T. Wharmby Kirill A. Lomachenko Sara Bals Gregor Mali Maarten B. J. Roeffaers Dirk E. DeVos Bart Bueken 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(27):9258-9263
While titanium‐based metal–organic frameworks (MOFs) have been widely studied for their (photo)catalytic potential, only a few TiIV MOFs have been reported owing to the high reactivity of the employed titanium precursors. The synthesis of COK‐47 is now presented, the first Ti carboxylate MOF based on sheets of TiIVO6 octahedra, which can be synthesized with a range of different linkers. COK‐47 can be synthesized as an inherently defective nanoparticulate material, rendering it a highly efficient catalyst for the oxidation of thiophenes. Its structure was determined by continuous rotation electron diffraction and studied in depth by X‐ray total scattering, EXAFS, and solid‐state NMR. Furthermore, its photoactivity was investigated by electron paramagnetic resonance and demonstrated by catalytic photodegradation of rhodamine 6G. 相似文献
98.
99.
Tolkacheva Anna S. Shkerin Sergey N. Zemlyanoi Kirill G. Reznitskikh Olga G. Pershina Svetlana V. Khavlyuk Pavel D. 《Journal of Thermal Analysis and Calorimetry》2019,136(3):1003-1009
Calcium vanadates Ca5Mg4−xZnx(VO4)6 (0 ≤ x ≤ 4) have been studied for the first time using a set of high-temperature methods of analysis. The onset of melting process determined from differential scanning calorimetry decreases from 1158 to 881 °C (± 1.5 °C) with increasing of x (dopant’s content). CTE temperature dependence is found to show a hysteresis. Electrical transport properties measured by impedance spectroscopy in air of different humidity are also discussed. The value of electrical conductivity does not depend on air humidity. It is found to equal to 1.5 × 10−6 S cm−1 at 720 °C for Ca5Mg4(VO4)6 which is specific for garnet-related crystals.
相似文献100.
Kirill F. Sheberstov Eduard Sistaré Guardiola Damien Jeannerat 《Magnetic resonance in chemistry : MRC》2020,58(5):376-389
The fundamental concept of phase discussed in this tutorial aimed at providing students with an explanation of the delays and processing parameters they may find in nuclear magnetic resonance (NMR) pulse programs. We consider the phase of radio-frequency pulses, receiver, and magnetization and how all these parameters are related to phases and offsets of signals in spectra. The impact of the off-resonance effect on the phase of the magnetization is discussed before presenting an overview of how adjustment of the time reference of the free induction decay avoids first-order correction of the phase of spectra. The main objective of this tutorial is to show how the relative phase of a pulse and the receiver can be used to change the reference frequency along direct and indirect dimensions of NMR experiments. Unusual of phase incrementation with non-90° angles will be illustrated on one- and two-dimensional NMR spectra. 相似文献