全文获取类型
收费全文 | 291篇 |
免费 | 15篇 |
国内免费 | 2篇 |
专业分类
化学 | 230篇 |
晶体学 | 3篇 |
力学 | 2篇 |
数学 | 11篇 |
物理学 | 62篇 |
出版年
2024年 | 3篇 |
2023年 | 3篇 |
2022年 | 6篇 |
2021年 | 9篇 |
2020年 | 12篇 |
2019年 | 11篇 |
2018年 | 11篇 |
2017年 | 12篇 |
2016年 | 14篇 |
2015年 | 15篇 |
2014年 | 25篇 |
2013年 | 28篇 |
2012年 | 33篇 |
2011年 | 30篇 |
2010年 | 10篇 |
2009年 | 6篇 |
2008年 | 11篇 |
2007年 | 8篇 |
2006年 | 9篇 |
2005年 | 8篇 |
2004年 | 6篇 |
2003年 | 6篇 |
2002年 | 6篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1987年 | 1篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1981年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有308条查询结果,搜索用时 31 毫秒
131.
Limi Goswami Pranjal Gogoi Junali Gogoi Ashwini Borah Manash R. Das Romesh C. Boruah 《Tetrahedron letters》2014
A mild and selective protocol has been developed for the palladium-catalyzed phosphine-free Suzuki cross-coupling reaction of aryl bromides with arylboronic acids in aqueous tea extract at room temperature. It is noteworthy that the aqueous tea extract plays an important role in the reaction, and various functional groups are tolerated under the optimized conditions. The reactions proceeded with very good chemoselectivity in favor of the bromo instead of the chloro group even at higher temperatures. Furthermore, this protocol could be applied to the cross-coupling of 4-bromoindole without protecting the base sensitive amine group with arylboronic acids in moderate to excellent yields. 相似文献
132.
Sachin B. Baravkar Mahendra A. Wagh Debasish Paul Manas Santra Gangadhar J. Sanjayan 《Tetrahedron letters》2018,59(38):3473-3476
Herein, we report synthesis and in vitro anticancer activity of conformationally constrained Smac mimetics containing reverse turn inducing motifs “Ant-Pro” and “sAnt-Pro”. The synthesis of Smac analogs with diverse hydrophobic groups at the C-terminus was carried out using solution phase peptide synthesis. The synthesis of Ant-Pro containing analogs 3a–j was carried out by ring opening of benzoxazinones 7a–c, whereas, their sulfonamide counterparts 4a–h were synthesized by using routine acid-amine coupling reaction. In vitro anticancer studies against breast cancer cell line MDA-MB-231 revealed that some of the new analogs had better anticancer activity than the standard AVPI Smac tetrapeptide. 相似文献
133.
Manjit Borah Dambarudhar Mohanta 《Applied Physics A: Materials Science & Processing》2014,115(3):1057-1067
We report on the structural, optical and dielectric characterization of solid state derived, pseudo-cubic nanoscale barium titanates (BTs) with gadolinium (Gd3+) as substitutional dopant. Referring to X-ray diffractograms, apart from the BT peaks related to perovskite structure, the non-existence of any additional peaks due to byproducts has revealed that Gd3+ has undergone substitutional doping into the BT host lattice. The well-separated BT nanoparticles of typical size ~10–15 nm were observed through electron microscopy studies. Following a direct, allowed type carrier transition (n=1/2), a reduction in the optical band gap value (from 3.28 to 3.255 eV) was observed when the Gd-doping level was varied within 0–7 %. Conversely, the Urbach energy followed an increasing trend, from a value of 0.741 to 1.879 eV. Furthermore, the dielectric constant showed a decreasing tendency with doping content and with increasing frequency. However, in the low-frequency region, the loss tangent (tanδ), which is the combined result of orientational polarization and electrical conduction, was found to be quite high in the doped samples as compared to their un-doped counterpart. The frequency-dependent electrical data were also analyzed in the framework of conductivity and impedance formalisms. In particular, the ac conductivity which varies as ~ω s approaches ideal Debye behavior (s→1) for a low Gd level and a higher doping concentration did not show improved dielectric feature of the host. The incorporation of rare-earth (Gd3+) ions into the BT host system could greatly manifest dielectric relaxation and carrier conduction mechanisms, in a given frequency range, and thus can find immense scope in miniaturized nanoelectronic elements including ceramic capacitors and transducers. 相似文献
134.
Using IR and Raman spectra, it is shown that the sytidinium cation hydrogen bonds to cytidine to form a stable 1:1 complex, in both aqueous solution (pH ~ 3.3) and as a solid. The spectra indicate that the proton is located asymmetrically in the NH?N bond of the complex, on the vibrational time scale, in both solution and the solid. The perdeuterated systems were also examined; their spectra support these conclusions. 相似文献
135.
There is a growing interest in the development of new materials through utilization of natural resources. This paper describes evaluation of water leached and alkali treated chopped grass fiber reinforced phenol formaldehyde composite. Here alkali treatment of grass fiber was carried out by varying the concentration of sodium hydroxide. The thermal stability of the composite was assessed by thermogravimetric analysis (TGA). Fourier transformation infrared spectroscopic study of both water leached and alkali treated grass fiber‐phenolic resin composite was also performed. Water absorption and swelling behavior of grass fiber phenolic resin composites in water were studied and the alkali treated grass fiber‐resin composite showed less water absorption and swelling. A composite prepared from 1% alkali treated grass fiber and 55% resin, showed the highest tensile strength whereas a composite prepared from 5% alkali treated grass fiber and 55% resin, showed maximum flexural properties. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
136.
Intersalation reactions of the complexes [Ni(L-L)(3)]SO(4) and [Ni(L-L)(3)]Cl(2) (L-L=1,10-phenanthroline (phen), 2,2'-bipyridyl (bpy)), with Na-montmorillonite carried out under different dynamic conditions such as ultrasonic irradiation, refluxing, autoclaving, and vigorous stirring showed that under ultrasonic irradiation, maximum adsorption of the metal complexes occurred within a period of 30 min. Metal complexes containing the phen ligand showed higher adsorption than those containing bpy. Maximum adsorption up to about three times the cation exchange capacity (CEC) of the clay was observed. Aggregated (basal spacing d(001) 12.5 ?) Na-montmorillonite, in treatment with a higher amount (>CEC) of metal complexes, formed monolayered (basal spacing d(001) 17.6 ?) species, while with predispersed clay, bilayered (basal spacing d(001)>28 ?) or pseudo-trilayer (basal spacing d(001)>32 ?) species were formed. The bilayered species were thermally stable up to 250 degrees C and above this temperature monolayered species were formed. The thermal stability of the intersalated species was higher than that of the intercalated ones. X-ray diffraction, UV-visible, IR-spectroscopy, thermal analyses, and surface area measurements were used for characterization of the products. Copyright 2001 Academic Press. 相似文献
137.
The viscosities of solutions of tetrapropylammonium bromide (Pr4NBr), tetrabutylammonium bromide (Bu4NBr), tetrapentylammonium bromide (Pen4NBr), tetrahexylammonium bromide (Hex4NBr), tetraheptylammonium bromide (Hep4NBr), tetraoctylammonium bromide (Oct4NBr), tetrabutylammonium tetraphenylborate (Bu4NBPh4), sodium tetraphenylborate (NaBPh4), and potassium tetraphenylborate (KBPh4) in N,N-dimethylacetamide are reported at 25°C. The viscosity data havebeen analyzed by the Jones-Dole equation for associated electrolytes to evaluate the viscosity B coefficients of the electrolytes. These data have also been analyzed by the transition-state theory to obtain the contribution of the solutes to the free energy of activation for viscous flow of the solution. The ionic contribution to the viscosity B coefficient and the free energy of activation for viscous flow have been estimated using of the reference electrolyte Bu4NBPh4. The bromide, tetraphenylborate, and tetraalkylammonium ions are found to be weakly solvated in N,N-dimethylacetamide, whereas significant solvation has been detected for sodium and potassium ions. The viscosity of the solvent is greatly modified by the presence of all the ions investigated here with the exception of the bromide ion. 相似文献
138.
The n-job, single-machine total tardiness problem is considered in this paper. A branching algorithm based on three theorems is proposed to generate a reduced set of candidate sequences. The computational results indicate that the proposed algorithm provides a smaller set of candidate sequences than the DP algorithm of Schrage and Baker. 相似文献
139.
Adsorption kinetics, adsorption isotherms and surface complexation of trimesic acid onto alpha-alumina surfaces were investigated. Adsorption kinetics of trimesic acid with an initial concentration of 0.5 mM onto alpha-alumina surfaces were carried out in batch method in presence of 0.05 mM NaCl (aq) at pH 6 and 298.15, 303.15 and 313.15 K. Adsorption isotherms were carried out at 298.15 K, pH 5-9, and 0.05 mM NaCl (aq) by varying trimesic acid concentration from 0.01 to 0.6 mM. Three kinetics equations such as pseudo-first-order, pseudo-second-order and Ho equations were used to estimate the kinetics parameters of the adsorption of trimesic acid on the alpha-alumina surfaces. Ho equation fits the experimental kinetics data significantly better and the estimated equilibrium concentration is in excellent agreement with the experimental value. The adsorption data were fitted to Freundlich and Langmuir adsorption model and the later best fits the adsorption isotherms. Comparison of adsorption density of trimesic acid with that of benzoic and phthalic acids follows the sequence: benzoic acid < trimesic acid < phthalic acid. The negative activation energy and the Gibbs free energy for adsorption indicate that the adsorption of trimesic acid onto alpha-alumina is spontaneous and facile. DRIFT spectroscopic studies reveal that trimesate forms outer-sphere complexes with the surface hydroxyl groups that are generated onto alpha-alumina surfaces in the pH range of the study. 相似文献
140.
Macitentan (MCT) is an endothelin receptor antagonist used for the treatment of pulmonary arterial hypertension. In the present study, MCT was subjected to forced degradation as per ICH guidelines. The drug degraded extensively in acidic, basic as well as neutral hydrolytic conditions and seven degradation products (DPs) were formed. All these DPs were selectively separated using high-performance liquid chromatography (HPLC) with a stationary phase of Inertsil C18 column (150 × 4.6 mm, 5 μm) and a mobile phase consisting of gradient mixture of 0.02% trifluoroacetic acid (TFA) and acetonitrile (ACN). The developed HPLC method was transferred to LC–ESI–QTOF–MS/MS for identification of DPs. The final mass spectrometric conditions were optimized for better ionization of drug and DPs with optimum mass signal sensitivity. All the formed DPs were new and well separated with sufficient resolution. The developed HPLC method was validated as per ICH-guidelines and can be used in drug testing labs for determination of quality of MCT in bulk and finished formulations. 相似文献