全文获取类型
收费全文 | 19144篇 |
免费 | 977篇 |
国内免费 | 1438篇 |
专业分类
化学 | 14628篇 |
晶体学 | 198篇 |
力学 | 409篇 |
综合类 | 10篇 |
数学 | 2743篇 |
物理学 | 3571篇 |
出版年
2023年 | 127篇 |
2022年 | 269篇 |
2021年 | 461篇 |
2020年 | 346篇 |
2019年 | 386篇 |
2018年 | 373篇 |
2017年 | 358篇 |
2016年 | 736篇 |
2015年 | 587篇 |
2014年 | 689篇 |
2013年 | 1593篇 |
2012年 | 1487篇 |
2011年 | 1588篇 |
2010年 | 969篇 |
2009年 | 1148篇 |
2008年 | 1182篇 |
2007年 | 1117篇 |
2006年 | 931篇 |
2005年 | 932篇 |
2004年 | 1212篇 |
2003年 | 865篇 |
2002年 | 791篇 |
2001年 | 401篇 |
2000年 | 330篇 |
1999年 | 246篇 |
1998年 | 228篇 |
1997年 | 205篇 |
1996年 | 206篇 |
1995年 | 167篇 |
1994年 | 125篇 |
1993年 | 145篇 |
1992年 | 120篇 |
1991年 | 82篇 |
1990年 | 84篇 |
1989年 | 77篇 |
1988年 | 69篇 |
1987年 | 59篇 |
1986年 | 67篇 |
1985年 | 95篇 |
1984年 | 104篇 |
1983年 | 69篇 |
1982年 | 58篇 |
1981年 | 62篇 |
1980年 | 58篇 |
1979年 | 39篇 |
1978年 | 32篇 |
1977年 | 38篇 |
1976年 | 29篇 |
1975年 | 26篇 |
1974年 | 32篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Density functional theory (DFT) calculations of nuclear magnetic resonance (NMR) spin–spin coupling constants (SSCCs) provide an important contribution for understanding experimentally observed values. It is known that calculated SSCCs using DFT methods correlate well with those experimentally measured. Unlike most of SSCCs, in fluorine compounds, fluorine–fluorine SSCC JFF shows that the Fermi contact (FC) term is not dominant, particularly for JFF in polyfluorinated organic molecules. In order to devise a DFT approach that would correctly reproduce the variation of SSCCs within a series of fluorine compounds, we test several DFT-based approaches, using different exchange and correlation functionals. Isotropic contributions to NMR fluorine–fluorine coupling constants (FC, spin-dipolar, SD, paramagnetic spin-orbit, PSO, and diamagnetic spin-orbit, DSO) have been calculated. Results show that DFT methods give appropriate values for nJFF (n = 4 to 7), while for geminal and vicinal JFF present large deviations from experimental values. For the latter SSCCs (2JFF and 3JFF), the four contributions (FC, SD, PSO and DSO) are analysed as a function of the local and nonlocal exchange in 1,1- and 1,2-difluoroethylene. Although FC term is not dominant for these SSCCs, the variation of this contribution with exchange is remarkable. On the other hand, SD and PSO contributions can be suitably computed without and with exact exchange, respectively. 相似文献
992.
993.
Diğdem Erdener Çıralı Osman Dayan 《Phosphorus, sulfur, and silicon and the related elements》2013,188(7):1100-1107
994.
Whei Oh Lin Vanderléa De Souza 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Abstract As part of our studies in preparation and physical properties of Potential ligands containing l-phosphoryl(P?O)-3-3-carbonyI(C?X, X?NH, O or S) group, we have investigated the intrdinta molecular hydrogen bonding of diisoproxy- phosphorylquanidine[l] as well as the tautomerism of phosphoryl benzylisothiourea. These are of interest as in interpretation of their chelation behavior as well as in development of other potential ligands for specific metal cations. 相似文献
995.
Sevil Şenkardeş İhsan Han Hakan Hançer Mürüvvet Abbak Özge Çevik Ş. Güniz Küçükgüzel 《Phosphorus, sulfur, and silicon and the related elements》2013,188(12):1164-1170
AbstractA series of thiosemicarbazides were synthesized and structurally characterized by spectroscopic techniques (NMR, FT-IR) besides elemental analysis. These compounds were evaluated for their cytotoxicity against human breast cancer cell line MCF7 and prostate cancer cell line PC3 and nonmalignant fibroblast L929 cell line by MTT assay. Among the compounds, N-[2-(4-chlorophenyl)ethyl]-2-[(4-methylphenyl)sulfonyl]hydrazinecarbothioamide (3d) and 2-[(4-methylphenyl)sulfonyl]-N-[4-(trifluoromethoxy)phenyl]hydrazinecarbothioamide (3f) were found to display significant cytotoxicity with IC50 of 13.87?μM (against PC3 cell line) and 1.47?μM (against MCF7 cell line), respectively. These compounds were non-cytotoxic to normal cell line with IC50>100?μM. Western blotting studies demonstrated that compound 3f induced apoptosis and caused cell death in the MCF7 and PC3 cell lines via an increase in Bax protein expression and a slight decrease in Bcl-2 protein expression. The gene expression ratio Bax/Bcl-2 showed the induction of mitochondrial apoptosis in cancer cell lines. All of synthesized compounds have also been tested for antioxidant activity and all compounds achieved strong inhibition of the DPPH radical. These findings showed that compound 3f, displays potential to be further explored in the development of new anticancer agents. 相似文献
996.
Alma Viso Roberto Fernández de la Pradilla Ana García Carlos Guerrero-Strachan Marta Alonso Mariola Tortosa 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5-6):1229-1234
Abstract Readily available p-tolylsulfinimines undergo highly stereoselective [3 + 2] cycloadditions with azomethine ylides generated from α -iminoesters and LDA to produce N-sulfinylimidazolidines. In the presence of Lewis acids, p-tolylsulfinimines react with glycine iminoester enolates to produce N-sulfinylimidazolidines, after cyclization of open chain intermediates. These mechanistically diverse processes take place with excellent regio-, stereo-, and facial selectivities, and the latter is opposite to most known reactions involving sulfinimines. Some of the resulting imidazolidines have been transformed into examples of a novel class of nonsymmetrical vicinal diamines using reductive and/or hydrolytic protocols. 相似文献
997.
998.
The free-radical initiated copolymerization of 2-(4-chloro-1-naphtyloxy)-2-oxoethyl methacrylate (ClNOEMA) with 2-(diethylamino) ethyl methacrylate (DEAEMA) was carried out in 1,4-dioxane solution at 70 ± 1°C using 2,2′-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios (ranging from 0.15 to 0.85) in the feed. The copolymer composition obtained by elemental analysis led to the determination of reactivity ratios employing Fineman-Ross (F-R) and Kelen-Tüdös (KT) linearization methods. These parameters were also estimated using a non-linear computational fitting procedure, known as reactivity ratios error in variable model (RREVM). The prepared homo and copolymers were tested for their antimicrobial activity against bacteria and yeast. These copolymers have been converted into novel salts by reaction with the iodemethane (CH3I). The copolymers and the corresponding salts have been characterized fully by a range of spectroscopic analysis techniques. The electrical conductivity dependence of temperature of the polymers were measured and the polymers exhibit the semi-conducting behavior, confirming that the electrical conductivity increases with increasing temperature. The poly(CINOEMA-co-DEAEMA) polymer doped by CH3I for 15 min shows the highest conductivity. The optical band gap, activation energy and room temperature conductivity values of these polymers were obtained. These electronic parameters suggest that the poly(CINOEMA-co-DEAEMA)s doped by CH3I for 15 min is an organic semiconductor with the thermally activated conduction mechanism. 相似文献
999.
Electrically conductive composite systems based on polyvinyl chloride (PVC) and polymethyl methacrylate (PMMA) filled with metal powders of Al and Cu have been studied. The composite preparation conditions allow the formation of a random distribution of metallic particles in the polymer matrix. Dependence of the dielectric and conductivity properties of the PVC and PMMA/fillers was studied over a broad range of frequency and volume fraction of metal fillers. The experimental results could be explained by means of the conductivity of fillers and the interface polarization between polymers and fillers. Percolation was also seen in this study when the volume fraction of conducting fillers was close to critical value, in which the composites undergo an insulator‐conductor transition. The relation among the dielectric property and the fillers with different conductivity was proposed. 相似文献
1000.
Conductive polythiophene (PTh)/poly(ethylene terephthalate) (PET) composite fibers were prepared by polymerization of thiophene in the presence of PET fibers in acetonitrile medium using FeCl3. The effects of polymerization conditions such as oxidant/monomer mol ratio and polymerization temperature and time on PTh content and surface electrical resistivity of PTh/PET composite fiber were investigated in detail. It was observed that the usage of preswelled PET fibers in dichloromethane increased the PTh content and decreased surface resistivity of composite fiber. Composite fiber having the highest PTh content (5.7%) and the lowest surface resistivity (80 kΩ) was obtained at 20°C with 1.25 M FeCl3 and 0.42 M thiophene concentrations. The washing effects of laundering detergent and dry cleaning liquid on surface resistivity of composite fibers were investigated. The electromagnetic shielding effectiveness (EMSE) and relative shielding efficiency by absorption and reflection of composite fibers were measured in the radio and microwave frequency range. The results show that the EMSE values decreased with increasing frequency from radio waves to microwaves with an attenuation of 21 dB to 4 dB. 相似文献