全文获取类型
收费全文 | 978篇 |
免费 | 20篇 |
国内免费 | 195篇 |
专业分类
化学 | 814篇 |
晶体学 | 86篇 |
力学 | 11篇 |
综合类 | 1篇 |
数学 | 99篇 |
物理学 | 182篇 |
出版年
2023年 | 20篇 |
2022年 | 25篇 |
2021年 | 11篇 |
2020年 | 20篇 |
2019年 | 6篇 |
2018年 | 10篇 |
2017年 | 16篇 |
2016年 | 25篇 |
2015年 | 14篇 |
2014年 | 33篇 |
2013年 | 63篇 |
2012年 | 52篇 |
2011年 | 63篇 |
2010年 | 85篇 |
2009年 | 80篇 |
2008年 | 53篇 |
2007年 | 91篇 |
2006年 | 60篇 |
2005年 | 60篇 |
2004年 | 55篇 |
2003年 | 44篇 |
2002年 | 33篇 |
2001年 | 51篇 |
2000年 | 28篇 |
1999年 | 30篇 |
1998年 | 22篇 |
1997年 | 20篇 |
1996年 | 23篇 |
1995年 | 21篇 |
1994年 | 12篇 |
1993年 | 9篇 |
1992年 | 9篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 5篇 |
1987年 | 8篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 1篇 |
1981年 | 3篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1974年 | 2篇 |
排序方式: 共有1193条查询结果,搜索用时 203 毫秒
61.
62.
Ming-Zhao Wang Ying Li Jin-Jin Ji Gai-Ling Huang Xin Zhang Si-Hui Li Xiao-Jing Yang 《中国化学快报》2013,24(7):593-596
Four Cu2+ complexes of salicylidene-amino acid Schiff base with 1,10-phenanthroline(Phen) or 2,2’- bipyridine(Bipy) were successfully intercalated in interlayer galleries of Mg/Al-NO3-layered double hydroxide(LDH) by the swelling-restored method.The hybrids were characterized by elemental analysis,X-ray diffraction,FT-IR spectra,UV-vis DRS,TG-DTA and SEM observation.Good protection of the complexes by LDH in neutral and weak acidic solutions was revealed by UV spectra,cyclic voltammograms and luminescence spectra. 相似文献
63.
《Journal of Coordination Chemistry》2012,65(22):4102-4116
The tetra α- or β-thiophene substituted metal and metal-free phthalocyanines (Pcs) M[Pc(α-OCH2Thiopen)4] and M[Pc(β-OCH2Thiopen)4] {(α-ThMet-MPc), (β-ThMet-MPc) [ThMet: Thiophene methoxy], M = Zn(II), Co(II) and, 2H} were synthesized from the corresponding 3’-(thiophen-3-ylmethoxy)phthalonitrile or 4’-(thiophen-3-ylmethoxy)phthalonitrile (ThMePN). The structural characterization, spectral, and antioxidant properties of a series of new Pcs were also presented. Both α- and β-substituted Pc complexes increased solubility in polar solvents, such as THF, DMF, and DMSO. FT-IR, 1H-NMR, 13C-NMR, UV–vis, MALDI-TOF/MS spectral, and elemental analysis data were used to characterize the compounds. The aggregation behaviors of 3–8 were also investigated at different concentrations in THF. Antioxidant test methods, α,α-diphenyl-β-picrylhydrazyl radical scavenging activity, metal chelating activity, and reducing power, were used to determine the antioxidant activities. 6 showed very good ferrous ion chelating activity of 81 ± 1%. 6, 5, 4, and 3 showed better reducing power than trolox, ascorbic, acid and butylated hydroxytoluene, commercially used antioxidants. 相似文献
64.
M. R. Kalaee M. H. N. Famili M. Dadgar M. R. Talei Bavil Olyai A. Naderi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):588-594
The kinetics of the condensation polymerization of a novel polysulfide polymer based on methylene dichloride and sodium tetrasulfide is studied. The results of the experiments indicated that the reaction order is two. The activation energy obtained from the Arrhenius plot is 1.879 kcal mol?1, and the pre-exponential frequency factor is A = 27.11 min?1 at temperature range of 40~60°C. The polymer is characterized by using Fourier transform-infrared and CHN analysis. Thermal properties were evaluated by differential scanning calorimetry. The TGA-DTA was used to find out the thermal stability of polymer. The solvent resistance of the polymer was investigated by the swelling method. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. 相似文献
65.
Glutaraldehyde-crosslinked O-carboxymethyl chitosan (O-CMC)–gum Arabic (GA) coacervates were characterized against coacervation acidity. As the coacervation pH increased from 3.0 to 6.0, the crosslinking degree of the coacervates and its sensitivity to glutaraldehyde concentration variation declined gradually, but the elasticity increased markedly. Crosslinking improved the structure compactness and thermal stability of the coacervates and high coacervation pH favored the increase of the two parameters, but a reverse trend was observed regarding swelling ratio in the simulated gastric fluid. It was concluded that glutaraldehyde-crosslinked O-CMC–GA coacervates with required properties could be tailored by selecting an appropriate complexation acidity. 相似文献
66.
《高分子科学杂志,A辑:纯化学与应用化学》2013,50(11):1301-1315
Three hyperbranched multi-methacrylates (H20-MMA, H30-MMA and H40-MMA) have been synthesized by reacting Boltorn dendritic polyols with methacrylic anhydride and methacryloyl chloride. Their structures were characterized by FT-IR and NMR (1H and 13C) and molecular weights were measured by GPC. These multi-methacrylates (H-MMAs) mixed well with a variety of monomers such as acrylic acid (AA), methacrylic acid (MA), methyl methacrylate (MMA), 2-hydroxy-ethyl methacrylate (HEMA), tri(ethylene glycol) dimethdimethacrylate (TEGDMA), and bisphenol A glycidyl dimethacrylate (BisGMA). The initial studies on thermal polymerization activities of 10% of H-MMAs with AA, MA, and MMA showed that they gave higher polymerization enthalpy than the corresponding homopolymerization. The resulting materials showed one glass transition temperature, indicating a typical single-phase resin. The H-MMAs can effectively copolymerize with AA, MA, and MMA, with essentially no homopolymers produced, as indicated by acetone extraction studies. This indicated that the hyperbranched multi-methacrylates have the potential to be used as crosslinking agents or modifiers with a number of monomers to produce new thermosets. 相似文献
67.
《高分子科学杂志,A辑:纯化学与应用化学》2013,50(9):1001-1010
Abstract Comb‐like polystyrene grafted silica nanoparticles (c‐PS‐SNs) were prepared by the following steps: (a) methacryloxypropyl silica nanoparticles (MPSNs) were used as macromonomer and free radical copolymerized with 4‐vinyl benzyl chloride (VBC) by a solution polymerization method; (b) the product of (A), poly(4‐vinyl benzyl chloride) grafted silica nanoparticle (PVBC‐SN) was separated and then used as a macroinitiator for the surface‐initiated atom transfer radical polymerization (SI‐ATRP) of styrene catalyzed by the complex of Cu(I)Br and 2,2′‐bipyridyl (bipy) in toluene solutions. The structurally well‐defined polymer chains were grown from the nanoparticle surfaces to yield particles composed of a silica core and a well defined, densely grafted outer comb‐like PS layer. A percentage of grafting (PG%) (the weight ratio of the PS grafted with that of the silica charged) of more than 80% was achieved after a polymerizing time of 5?hr. 相似文献
68.
K. Hanabusa J. Yamasaki T. Koyama H. Shirai T. Hayakawa A. Kurose 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(12):1571-1584
Two esters of L-lysine and L-glutamic acid containing long alkyl groups were synthesized and their polycondensation in monolayers and multilayers was investigated. The pressure-area isotherms of the ester of L-lysine depend markedly on the time of residence at the air-water interface. The change of FT-IR spectra of the deposited film, which can be lifted as a Z-type film, indicates that polycondensation can occur in the monolayer at 10°C without any treatment. The spectrum of the film cast from chloroform hardly changed with time. These results lead to the conclusion that a regular arrangement of monomer molecules in the monolayer, where the amino and ester carbonyl groups are concentrated, is more suitable for the polycondensation. The ester of L-glutamic acid can also form stable monolayers which can be easily deposited on a hydrophobic plate as a Y-type film by the Blodgett technique. The polycondensation of multilayers under an atmosphere of triethylamine was investigated by IR spectroscopy. It indicates that the condensation in multilayers proceeds via intermolecular and intramolecular reactions, by which poly(L-glutamate) derivatives and 2-pyrrolidone derivatives are formed, respectively. The condensation in the bulk crystalline powder gives exclusively the 2-pyrrolidone derivative by intramolecular reaction. These results suggest that the monomer molecules in the multilayers are favorably aligned for the intermolecular reaction, in contrast to the situation in the bulk crystalline powder. 相似文献
69.
Qixin Dong Jiajun Zhu Qiang Sui Chao Tang Xiaomei Wang Yunqiu Yu 《Journal of separation science》2013,36(7):1200-1208
In this study, the objective was to investigate the degradation behavior of Esomeprazole under different recommended stress conditions according to International Conference on Harmonization of Technical Requirements for Registration of Pharmaceuticals for Human Use [1] by HPLC. Our research showed that the effect of mobile phase species on separation was significant for the determination of Esomeprazole and its related compounds. Successful separation of the drug from its related impurities and degradation products formed under different stress conditions was achieved using ammonium acetate buffer/ACN by a gradient elution. Compared with phosphate buffer/ACN, ammonium acetate buffer/ACN under same pH and gradient showed a great improvement in resolution due to the change of elution order. The drug was subjected to stress conditions including acidic, alkaline, oxidative, photolytic, and thermal conditions. Extensive degradation occurred in acidic and oxidative conditions, while mild degradation was observed in alkaline and photolytic conditions. Besides, it turned out the drug was extremely stable under thermal condition. The stability‐indicating LC–UV method was validated with respect to linearity, precision, accuracy, specificity, and robustness. The LC–MS method was also adopted for the characterization of degradation products. Based on the m/z values and fragmentation patterns, the degradation pathway of the drug has been proposed. 相似文献
70.
A high-performance liquid chromatography coupled with photodiode array detection and electrospray ionization tandem mass spectrometry (HPLC-PAD–ESI-MS) method has been developed for the simultaneous identification and quantification of active compounds (rutin and quercetin) contained in Traditional Chinese Medicine (TCM) Euonymus alatus (Thunb.) Siebold (EAS). The herb samples from ten main origins and five medicinal portions (leaf, fruit, stem, pterygium and root) were investigated. The separation was performed on a Shim C18 column at 30 °C with an isocratic elution. Methanol (A) and water (0.5% methanoic acid, v/v) (B) were used as mobile phases. The recoveries of the two compounds were 100.184% and 100.417%, respectively, and all of them showed good linearity (r2 ? 0.9993) in relatively wide concentration ranges. The developed method was applied to identify and quantify the two major active compounds in the collected herb samples, and the results indicated that contents of the two compounds in EAS varied significantly from habitat to habitat. It was demonstrated that the proposed method was helpful for the quality evaluation of EAS. 相似文献