全文获取类型
收费全文 | 1430篇 |
免费 | 39篇 |
国内免费 | 7篇 |
专业分类
化学 | 597篇 |
晶体学 | 20篇 |
力学 | 68篇 |
数学 | 294篇 |
物理学 | 497篇 |
出版年
2023年 | 11篇 |
2022年 | 19篇 |
2021年 | 31篇 |
2020年 | 35篇 |
2019年 | 41篇 |
2018年 | 41篇 |
2017年 | 33篇 |
2016年 | 58篇 |
2015年 | 38篇 |
2014年 | 60篇 |
2013年 | 89篇 |
2012年 | 90篇 |
2011年 | 107篇 |
2010年 | 92篇 |
2009年 | 74篇 |
2008年 | 64篇 |
2007年 | 78篇 |
2006年 | 39篇 |
2005年 | 49篇 |
2004年 | 29篇 |
2003年 | 28篇 |
2002年 | 25篇 |
2001年 | 13篇 |
2000年 | 21篇 |
1999年 | 19篇 |
1998年 | 10篇 |
1997年 | 13篇 |
1996年 | 26篇 |
1995年 | 17篇 |
1994年 | 12篇 |
1993年 | 19篇 |
1992年 | 10篇 |
1991年 | 11篇 |
1990年 | 5篇 |
1989年 | 11篇 |
1988年 | 11篇 |
1987年 | 7篇 |
1986年 | 12篇 |
1985年 | 15篇 |
1984年 | 12篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 14篇 |
1980年 | 10篇 |
1979年 | 8篇 |
1978年 | 6篇 |
1977年 | 8篇 |
1976年 | 6篇 |
1974年 | 6篇 |
1973年 | 6篇 |
排序方式: 共有1476条查询结果,搜索用时 15 毫秒
131.
Three new Mn(II) coordination compounds {[Mn(NCNCN)(2)(azpy)]·0.5azpy}(n) (1), {[Mn(NCS)(2)(azpy)(CH(3)OH)(2)]·azpy}(n) (2), and [Mn(azpy)(2)(H(2)O)(4)][Mn(azpy)(H(2)O)(5)]·4PF(6)·H(2)O·5.5azpy (3) (where azpy = 4,4'-azobis(pyridine)) have been synthesized by self-assembly of the primary ligands, dicyanamide, thiocyanate, and hexafluorophosphate, respectively, together with azpy as the secondary spacer. All three complexes were characterized by elemental analyses, IR spectroscopy, thermal analyses, and single crystal X-ray crystallography. The structural analyses reveal that complex 1 forms a two-dimensional (2D) grid sheet motif. These sheets assemble to form a microporous framework that incorporates coordination-free azpy by host-guest π···π and C-H···N hydrogen bonding interactions. Complex 2 features azpy bridged one-dimensional (1D) chains of centrosymmetric [Mn(NCS)(2)(CH (3)OH)(2)] units which form a 2D porous sheet via a CH(3)···π supramolecular interaction. A guest azpy molecule is incorporated within the pores by strong H-bonding interactions. Complex 3 affords a 0-D motif with two monomeric Mn(II) units in the asymmetric unit. There exist π···π, anion···π, and strong hydrogen bonding interactions between the azpy, water, and the anions. Density functional theory (DFT) calculations, at the M06/6-31+G* level of theory, are used to characterize a great variety of interactions that explicitly show the importance of host-guest supramolecular interactions for the stabilization of coordination compounds and creation of the fascinating three-dimensional (3D) architecture of the title compounds. 相似文献
132.
Biswas S Maichle-Mössmer C Bettinger HF 《Chemical communications (Cambridge, England)》2012,48(38):4564-4566
Treatment of 9-chloro-9-borafluorene with N,O-bis(trimethylsilyl)hydroxylamine results in 10-trimethylsilyloxy-9-aza-10-boraphenanthrene 6b. NMR spectroscopy shows that the expected antiaromatic 9-(trimethylsilyloxyamino)-9-borafluorene 5b rearranges to the formally aromatic phenanthrene 6b at room temperature. 相似文献
133.
A Sarkar N Biswas S Kapoor H S Mahal C K K Nair T Mukherjee 《Research on Chemical Intermediates》2005,31(9):857-866
The oxidation of flavonoids is of great interest because of their action as antioxidants with the ability to scavenge radicals
by means of electron-transfer processes. The redox reactions of the flavonoid derivative troxerutin, (2-[3,4-bis-(2-hydroxyethoxy)
phenyl]-3[[6-deoxy-α-L-manno-pyranosyl)-β-(D-glucopyranosyl]-oxy]-5-hydroxy-7-(2-hydroxyethoxy)-4H-1-benzo-pyran-4-one), were investigated over a wide range of conditions,
using pulse radiolysis and cyclic voltammetry. The oxidation mechanism proceeds in sequential steps. One-electron redox potentials
for troxerutin were found to be +1.196, +0.846 and −0.634 V vs. NHE. 相似文献
134.
Thomas S Biswas N Venkateswaran S Kapoor S Naumov S Mukherjee T 《The journal of physical chemistry. A》2005,109(44):9928-9934
The surface-enhanced Raman scattering (SERS) studies of 5-amino tetrazole (5AT), a tetrazole derivative, in aqueous silver sol at pH approximately 9 and on deposited colloidal silver films were carried out and compared with the normal Raman spectrum of the molecule. The experimentally observed Raman bands along with their corresponding infrared bands were assigned based on the results of density functional theory (DFT) calculations. The significant changes evidenced between the SERS and the normal Raman spectra combined with the theoretical data obtained for Ag-5AT system demonstrated that the molecule is adsorbed on colloidal Ag particles through the lone pair of electrons of the nitrogen atom. The contribution of the chemical mechanism for the SERS enhancement was proved by the behavior of the electronic absorption spectrum of the Ag colloid upon addition of 5AT. This is further supported by the theoretical calculations that show that the favorable interaction of the frontier orbitals localized on Ag(+) and the negatively charged nitrogen from the tetrazole ring leads to the formation of the stable (up to 130 kJ mol(-1)) charge-transfer complex. The orientation of the adsorbed species with respect to the metal surface was also predicted by applying the "surface selection rule". In addition, the feasibility of the formation of the polymeric species has also been discussed. 相似文献
135.
Herein the present article reports the fabrication of ZnO/reduced graphene oxide (ZnG) nanohybrid following a reduction-based process using a non-hazardous material, i.e., ascorbic acid. The morphology, structure, and bonding in the nanohybrid were analyzed using different techniques. Atomic force microscopy and scanning electron microscopy images show spherical particles of ZnO distributed over reduced graphene oxide (rGO). The X-ray diffraction analysis gives calculated values of crystallite size for ZnO as 15.62 nm. The successful incorporation of ZnO nanoparticles into rGO was confirmed using energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy analyses. The electrochemical studies were performed using an electrolyte (0.5 M H2SO4). The calculated value of specific capacitance for the nanohybrid was 345 Fg-1, which was found to be almost double as compared to that of rGO, which is having a value of only 190.5 Fg-1 at the same scan rate. The nanohybrid also showed excellent capacitance retention after 1,000 cycles. 相似文献
136.
137.
The structure and phase behavior of liquid crystalline polymers (LCPs) having a common chiral side chain mesogen but different main chain structures have been investigated using small-angle X-ray scattering (SAXS). While the low molecular weight chiral side chain mesogen by itself exhibits ferroelectricity, the SAXS data of the side chain LCP with a flexible polyacrylate backbone contains a bilayered superstructure peak that is indicative of antiferroelectric order. The combined LCP with a nonpolar main chain mesogen also has a bilayered superstructure, but has a different structural organization in the proposed antiferroelectric phase compared to the side chain LCP. Further changes in the phase behavior and structural organization occur when a polar group is introduced into the main chain mesogen. A ferrielectric phase has been proposed to explain the observation of a trilayered superstructure in the corresponding SAXS data. The influence of the chemical structure and connectivity on the phase behavior and superstructure formation in the chiral LCPs is discussed. 相似文献
138.
139.
Satchidanand S. Biswas Achamkulangara Sethumadhavan Pappu S. Murty 《Mikrochimica acta》1991,103(1-2):71-77
Inductively coupled plasma atomic emission spectrometry (ICP-AES) was employed to determine Y, Sm, Eu, Gd, Dy, Ho and Er in high purity terbium oxide. Terbium oxide was dissolved in 0.5 mol/l HNO3 and nebulized into the plasma generated by a 56 MHz RF generator at 1.5 kW output power. Using a Jobin-Yvon 1-m Czenry-Turner high resolution, high dispersion scanning monochromator, lines mutually interference-free as well as free of interference from the matrix Tb were chosen for the seven analytes. A set of standards containing the analytes in the concentration range 0.01–1.0 gmg/ml with 1 mg/ml Tb was used for calibration. It was necessary to apply background correction to the gross analyte line intensities in order to obtain linear calibration plots for the analytes. 相似文献
140.