全文获取类型
收费全文 | 4447篇 |
免费 | 145篇 |
国内免费 | 37篇 |
专业分类
化学 | 2817篇 |
晶体学 | 33篇 |
力学 | 161篇 |
数学 | 607篇 |
物理学 | 1011篇 |
出版年
2024年 | 6篇 |
2023年 | 30篇 |
2022年 | 121篇 |
2021年 | 151篇 |
2020年 | 114篇 |
2019年 | 173篇 |
2018年 | 144篇 |
2017年 | 139篇 |
2016年 | 201篇 |
2015年 | 151篇 |
2014年 | 185篇 |
2013年 | 251篇 |
2012年 | 335篇 |
2011年 | 359篇 |
2010年 | 202篇 |
2009年 | 201篇 |
2008年 | 291篇 |
2007年 | 259篇 |
2006年 | 235篇 |
2005年 | 209篇 |
2004年 | 176篇 |
2003年 | 111篇 |
2002年 | 126篇 |
2001年 | 47篇 |
2000年 | 50篇 |
1999年 | 39篇 |
1998年 | 43篇 |
1997年 | 33篇 |
1996年 | 35篇 |
1995年 | 17篇 |
1994年 | 14篇 |
1993年 | 9篇 |
1992年 | 9篇 |
1991年 | 12篇 |
1990年 | 8篇 |
1989年 | 12篇 |
1988年 | 5篇 |
1987年 | 7篇 |
1986年 | 6篇 |
1985年 | 8篇 |
1984年 | 14篇 |
1983年 | 6篇 |
1981年 | 7篇 |
1978年 | 9篇 |
1977年 | 12篇 |
1976年 | 8篇 |
1975年 | 9篇 |
1973年 | 8篇 |
1972年 | 6篇 |
1969年 | 4篇 |
排序方式: 共有4629条查询结果,搜索用时 15 毫秒
61.
Moses Salci Evgeny Yarevsky Sergey B. Levin Nils Elander 《International journal of quantum chemistry》2007,107(2):464-468
A three‐dimensional finite element method is applied to the ground states of the symmetric and asymmetric atomic helium trimers 4He3 and 4He2–3He. Three different He–He interaction potentials of hard‐core nature were studied. Two extrapolation procedures based on the convergence properties of the finite element method are investigated. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
62.
Nataliya A. Sanina Arina A. Starostina Andrey N. Utenyshev Pavel V. Dorovatovskii Nina S. Emelyanova Vladimir B. Krapivin Victor B. Luzhkov Viktoriya A. Mumyatova Anastasiya A. Balakina Alexei A. Terentiev Sergey M. Aldoshin 《Molecules (Basel, Switzerland)》2022,27(20)
In this work a new donor of nitric oxide (NO) with antibacterial properties, namely nitrosyl iron complex of [Fe(C6H5C-SNH2)2(NO)2][Fe(C6H5C-SNH2)(S2O3)(NO)2] composition (complex I), has been synthesized and studied. Complex I was produced by the reduction of the aqueous solution of [Fe2(S2O3)2(NO)2]2− dianion by the thiosulfate, with the further treatment of the mixture by the acidified alcohol solution of thiobenzamide. Based on the structural study of I (X-ray analysis, quantum chemical calculations by NBO and QTAIM methods in the frame of DFT), the data were obtained on the presence of the NO…NO interactions, which stabilize the DNIC dimer in the solid phase. The conformation properties, electronic structure and free energies of complex I hydration were studied using B3LYP functional and the set of 6–31 + G(d,p) basis functions. The effect of an aquatic surrounding was taken into account in the frame of a polarized continuous model (PCM). The NO-donating activity of complex I was studied by the amperometry method using an “amiNO-700” sensor electrode of the “inNO Nitric Oxide Measuring System”. The antibacterial activity of I was studied on gram-negative (Escherichia coli) and gram-positive (Micrococcus luteus) bacteria. Cytotoxicity was studied using Vero cells. Complex I was found to exhibit antibacterial activity comparable to that of antibiotics, and moderate toxicity to Vero cells. 相似文献
63.
Anton V. Makarenkov Sergey S. Kiselev Elena G. Kononova Fedor M. Dolgushin Alexander S. Peregudov Yurii A. Borisov Valentina A. Olshevskaya 《Molecules (Basel, Switzerland)》2022,27(21)
An efficient one-pot synthesis of carborane-containing high-energy compounds was developed via the exploration of carbon–halogen bond functionalization strategies in commercially available 2,4,6-trichloro-1,3,5-triazine. The synthetic pathway first included the substitution of two chlorine atoms in s-triazine with 5-R-tetrazoles (R = H, Me, Et) units to form disubstituted tetrazolyl 1,3,5-triazines followed by the sequential substitution of the remaining chlorine atom in 1,3,5-triazine with carborane N- or S-nucleophiles. All new compounds were characterized by IR- and NMR spectroscopy. The structure of four new compounds was confirmed by single crystal X-ray diffraction analysis. The density functional theory method (DFT B3LYP/6-311 + G*) was used to study the geometrical structures, enthalpies of formation (EOFs), energetic properties and highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO) energies and the detonation properties of synthesized compounds. The DFT calculation revealed compounds processing the maximum value of the detonation velocity or the maximum value of the detonation pressure. Theoretical terahertz frequencies for potential high-energy density materials (HEDMs) were computed, which allow the opportunity for the remote detection of these compounds. 相似文献
64.
Reliable information about isobaric heat capacities CP is necessary to determine the energies of organic compounds and chemical processes at an arbitrary temperature. In this work, the possibility of theoretical estimation of CP by the homodesmotic method is analyzed. Three cases of CP calculation applying the methodology of the complete set of homodesmotic reactions (CS HDRs) are considered: the gas- and liquid-phase CP of organic compounds of various classes at 298 K (the mean absolute value of reaction heat capacity, MA ΔCP = 1.44 and 2.83 J/mol·K for the gas and liquid phase, correspondingly); and the gas-phase CP of n-alkanes C2–C10 in the temperature range of 200–1500 K with an average error in calculating the heat capacity of 0.93 J/mol·K. In the latter case, the coefficients of the Shomate equation are determined for all n-alkanes that satisfy the homodesmoticity condition. New values of gas- and liquid-phase heat capacities are obtained for 41 compounds. The CS HDRs-based approach for estimating the CP of organic compounds is characterized by high accuracy, which is not inferior to that of the best CP-additive schemes and allows us to analyze the reproducibility of the calculation results and eliminate unreliable reference data. 相似文献
65.
Kseniya Maryunina Gleb Letyagin Galina Romanenko Artem Bogomyakov Vitaly Morozov Sergey Tumanov Sergey Veber Matvey Fedin Evgeniya Saverina Mikhail Syroeshkin Mikhail Egorov Victor Ovcharenko 《Molecules (Basel, Switzerland)》2022,27(21)
The 2-imidazoline nitroxide derivatives of cymantrene—2-(η5-cyclopentadienyl)tricarbonylmanganese(I)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (NNMn) and 2-(η5-cyclopentadienyl)tricarbonylmanganese(I)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyl (INMn) were synthesized. It was shown that NNMn and INMn exhibit a sufficiently high kinetic stability both in solids and in solutions under normal conditions. Their structural characteristics, magnetic properties and electrochemical behavior are close to Re(I) analogs. This opens the prospect of using paramagnetic cymantrenes as prototypes in the design of Re(I) half-sandwiched derivatives for theranostics, where therapy is combined with diagnostics by magnetic resonance imaging due to the contrast properties of nitroxide radicals. 相似文献
66.
Daria V. Vorobyeva Dmitry A. Petropavlovskikh Ivan A. Godovikov Fedor M. Dolgushin Sergey N. Osipov 《Molecules (Basel, Switzerland)》2022,27(23)
A convenient pathway to a new series of α-CF3-substituted α-amino acid derivatives bearing pharmacophore isoquinolone core in their backbone has been developed. The method is based on [4+2]-annulation of N-(pivaloyloxy) aryl amides with orthogonally protected internal acetylene-containing α-amino carboxylates under Rh(III)-catalysis. The target annulation products can be easily transformed into valuable isoquinoline derivatives via a successive aromatization/cross-coupling operation. 相似文献
67.
Artemiy A. Samarov Stanislav O. Kondratev Sergey P. Verevkin 《Molecules (Basel, Switzerland)》2022,27(23)
Benzophenone derivatives exhibit not only biological activity but also act as photo initiator and UV blocker. We carried out experimental and theoretical thermochemical studies of hydroxy- and methoxy-substituted benzophenones. Standard molar enthalpies of vaporisation were obtained from the temperature dependence of vapour pressures measured by the transpiration method. The thermodynamic data on phase transitions available in the literature (crystal–gas, crystal–liquid, and liquid–gas) were also collected and evaluated. High-level quantum chemical methods G3MP2 and G4 were used to estimate the standard molar enthalpies of formation of substituted benzophenones in the gas phase and establish agreement between experimental and theoretical results. The application of the “centrepiece” group-contribution approach to hydroxy- and methoxy-substituted benzophenones was demonstrated. A quantitative assessment of the hydrogen bond was carried out using various approaches based on experimental data and quantum chemical calculations. 相似文献
68.
Eugeny Nikolaevich Zapolotsky Sergey Pavlovich Babailov Gennadiy Alexandrovich Kostin 《Molecules (Basel, Switzerland)》2022,27(14)
1H NMR measurements are reported for the CD2Cl2/CDCl3 solutions of the Co(II) calix[4]arenetetraphosphineoxide complex (I). Temperature dependences of the 1H NMR spectra of I have been analyzed using the line shape analysis, taking into account the temperature variation of paramagnetic chemical shifts, within the frame of the dynamic NMR method. Conformational dynamics of the 2:1 Co(II) calix[4]arene complexes was conditioned by the pinched cone ↔pinched cone interconversion of I (with activation Gibbs energy ΔG≠(298K) = 40 ± 3 kJ/mol. Due to substantial temperature dependence of paramagnetic shifts, complex I can be used as model compound for designing an NMR thermosensor reagent for local temperature monitoring. 相似文献
69.
Yuriy G. Denisenko Victor V. Atuchin Maxim S. Molokeev Alexander E. Sedykh Nikolay A. Khritokhin Aleksandr S. Aleksandrovsky Aleksandr S. Oreshonkov Nikolai P. Shestakov Sergey V. Adichtchev Alexey M. Pugachev Elena I. Salnikova Oleg V. Andreev Illaria A. Razumkova Klaus Müller-Buschbaum 《Molecules (Basel, Switzerland)》2022,27(13)
Praseodymium sulfate was obtained by the precipitation method and the crystal structure was determined by Rietveld analysis. Pr2(SO4)3 is crystallized in the monoclinic structure, space group C2/c, with cell parameters a = 21.6052 (4), b = 6.7237 (1) and c = 6.9777 (1) Å, β = 107.9148 (7)°, Z = 4, V = 964.48 (3) Å3 (T = 150 °C). The thermal expansion of Pr2(SO4)3 is strongly anisotropic. As was obtained by XRD measurements, all cell parameters are increased on heating. However, due to a strong increase of the monoclinic angle β, there is a direction of negative thermal expansion. In the argon atmosphere, Pr2(SO4)3 is stable in the temperature range of T = 30–870 °C. The kinetics of the thermal decomposition process of praseodymium sulfate octahydrate Pr2(SO4)3·8H2O was studied as well. The vibrational properties of Pr2(SO4)3 were examined by Raman and Fourier-transform infrared absorption spectroscopy methods. The band gap structure of Pr2(SO4)3 was evaluated by ab initio calculations, and it was found that the valence band top is dominated by the p electrons of oxygen ions, while the conduction band bottom is formed by the d electrons of Pr3+ ions. The exact position of ZPL is determined via PL and PLE spectra at 77 K to be at 481 nm, and that enabled a correct assignment of luminescent bands. The maximum luminescent band in Pr2(SO4)3 belongs to the 3P0 → 3F2 transition at 640 nm. 相似文献
70.
Asanbaeva Nargiz B. Rychkov Denis A. Tyapkin Pavel Yu. Arkhipov Sergey G. Uvarov Nikolay F. 《Structural chemistry》2021,32(3):1261-1267
Structural Chemistry - The crystal and molecular structure of tris(tetrabutylammonium) pentanitratoplumbate(II) was determined and characterized by single-crystal and powder X-ray diffraction and... 相似文献