全文获取类型
收费全文 | 303篇 |
免费 | 26篇 |
国内免费 | 5篇 |
专业分类
化学 | 256篇 |
晶体学 | 2篇 |
力学 | 13篇 |
数学 | 22篇 |
物理学 | 41篇 |
出版年
2024年 | 1篇 |
2023年 | 1篇 |
2022年 | 42篇 |
2021年 | 18篇 |
2020年 | 20篇 |
2019年 | 14篇 |
2018年 | 25篇 |
2017年 | 16篇 |
2016年 | 21篇 |
2015年 | 15篇 |
2014年 | 9篇 |
2013年 | 27篇 |
2012年 | 32篇 |
2011年 | 17篇 |
2010年 | 10篇 |
2009年 | 15篇 |
2008年 | 13篇 |
2007年 | 9篇 |
2006年 | 2篇 |
2005年 | 3篇 |
2004年 | 3篇 |
2003年 | 3篇 |
2002年 | 3篇 |
1999年 | 2篇 |
1998年 | 2篇 |
1996年 | 1篇 |
1994年 | 1篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有334条查询结果,搜索用时 156 毫秒
221.
Dr. Haiyan Li Wenbo Lu Jingqi Tian Yonglan Luo Prof. Abdullah M. Asiri Abdulrahman O. Al‐Youbi Prof. Xuping Sun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(27):8508-8514
Nanocomposites of Ag/TiO2 nanowires with enhanced photoelectrochemical performance have been prepared by a facile solvothermal synthesis of TiO2 nanowires and subsequent photoreduction of Ag+ ions to Ag nanoparticles (AgNPs) on the TiO2 nanowires. The as‐prepared nanocomposites exhibited significantly improved cathodic photocurrent responses under visible‐light illumination, which is attributed to the local electric field enhancement of plasmon resonance effect near the TiO2 surface rather than by the direct transfer of charge between the two materials. The visible‐light‐driven photocatalytic performance of these nanocomposites in the degradation of methylene blue dye was also studied, and the observed improvement in photocatalytic activity is associated with the extended light absorption range and efficient charge separation due to surface plasmon resonance effect of AgNPs. 相似文献
222.
223.
An efficient method was developed for plant regeneration and establishment from alginate encapsulated synthetic seeds of Rauvolfia serpentina. Synthetic seeds were produced using in vitro proliferated microshoots upon complexation of 3% sodium alginate prepared in Llyod and McCown woody plant medium (WPM) and 100 mM calcium chloride. Re-growth ability of encapsulated nodal segments was evaluated after storage at 4 °C for 0, 1, 2, 4, 6 and 8 weeks and compared with non-encapsulated buds. Effects of different media viz; Murashige and Skoog medium; Lloyd and McCown woody Plant medium, Gamborg’s B5 medium and Schenk and Hildebrandt medium was also investigated for conversion into plantlets. The maximum frequency of conversion into plantlets from encapsulated nodal segments stored at 4 °C for 4 weeks was achieved on woody plant medium supplement with 5.0 μM BA and 1.0 μM NAA. Rooting in plantlets was achieved in half-strength Murashige and Skoog liquid medium containing 0.5 μM indole-3-acetic acid (IAA) on filter paper bridges. Plantlets obtained from stored synseeds were hardened, established successfully ex vitro and were morphologically similar to each other as well as their mother plant. The genetic fidelity of Rauvolfia clones raised from synthetic seeds following four weeks of storage at 4 °C were assessed by using random amplified polymorphic DNA (RAPD) and inter-simple sequence repeat (ISSR) markers. All the RAPD and ISSR profiles from generated plantlets were monomorphic and comparable to the mother plant, which confirms the genetic stability among the clones. This synseed protocol could be useful for establishing a particular system for conservation, short-term storage and production of genetically identical and stable plants before it is released for commercial purposes. 相似文献
224.
SA Al-Issa 《Molecules (Basel, Switzerland)》2012,17(9):10902-10915
The reaction of 4-methyl-2-phenyl-1,2-dihydro-6-oxo-5-pyridine- carbonitrile (1) with arylidene malononitrile afforded isoquinoline derivatives 2a,b. 6-Chloro-4-methyl-2-phenyl-5-pyridinecarbonitile (3) obtained by chlorination of compound 1 with phosphoryl chloride was converted into 6-amino-4-methyl-2-phenyl-5-pyridinecarbonitrile (4) and 6-hydrazido-4-methyl-2-phenyl-5-pyridinecarbonitrile (5) in good yield, through reactions with ammonium acetate and hydrazine hydrate, respectively. Treatment of 4 with ethyl acetoacetate, acetic anhydride, formic acid, urea and thiourea gave the corresponding pyrido [2,3-d] pyrimidine derivatives 7-10a,b. A new series of 6-substituted-4-methyl-2-phenyl-5-pyridine carbonitriles 11-13 has been synthesized via reaction of 4 with phenyl isothiocyanate, benzenesulphonyl chloride and acetic anhydride. Treatment of 4 with malononitrile gave 1,8-naphthyridine derivative 14. The reactivity of hydrazide 5 towards acetic acid, phenylisothiocyanate and methylacrylate to give pyrazolo-[3,4-b]-pyridine derivatives 15-17 was studied. Treatment of 5 with acetic anhydride, phthalic anhydride and carbon disulphide gave pyridine derivatives 18,19 and 1,2,4-triazolo-[3,4-a]-pyridine derivative 20. 相似文献
225.
The superposition of chiral states of chiral molecules, as delocalized quantum states of a many-particle system, can be used for the experimental investigations of decoherence theory. In this regard, a great challenge is the precise quantification of the robustness of these superpositions against environmental effects. The methods so far proposed need the detailed specification of the internal states of the molecule, usually requiring heavy numerical calculations. Here, by using the linearized quantum Boltzmann equation and by borrowing ideas employed for analyzing other quantum systems, we present a general and simple approach, of wide applicability, which can be used to compute the dominant contribution to the decoherence rate for the superpositions of chiral states of chiral molecules, due to environmental scattering. 相似文献
226.
Phosphorus oxychloride efficiently promoted the synthesis of sulfonamides and sulfonic esters from thiols with hydrogen peroxide in the presence of Amberlite IRA-400 (OH?). This method has been applied to a variety of substrates including nucleophilic and sterically hindered amines, and also phenols with excellent yields of sulfonamides and sulfonic esters. In most cases these reactions are highly selective, simple, and clean, affording products in excellent yields and high purity. 相似文献
227.
Negar Saedi Abdulrahman Bahrami Farshid Ghorbani Shahna Majid Habibi Mohraz Maryam Farhadian Saber Alizadeh 《Biomedical chromatography : BMC》2020,34(4):e4800
The aim of this study was to develop a new method for the determination of benzene, toluene, ethylbenzene and xylene isomers (BTEXs) in urine samples. In this method, MIL-100(Fe)@Fe3O4@SiO2 metal–organic framework was synthesized, characterized and packed inside a needle trap device (NTD) as a sorbent for headspace extraction of unmetabolized BTEXs from urine samples followed by gas chromatography (GC) analysis. The GC device was equipped with a flame ionization detector (FID). The results showed that the optimal extraction time, extraction temperature and salt content were 60 min, 30°C and 5%, respectively. Also, the optimal desorption time and temperature were determined to be 1 min and 250°C, respectively. The limits of detection and quantification of the analytes of interest were in the ranges 0.0001–0.0005 and 0.0003–0.0014 μg ml−1, respectively. The intra- and inter-day repeatability were <7.6%. The accuracy of the measurements in urine samples was in the range 7.1–11.4%. The results also demonstrated that the proposed NTD offered various advantages such as having high sensitivity and being inexpensive, reusable, user friendly, environmentally friendly and compatible for use with the GC device. Therefore, it can be efficiently used as a MIL–NTD for the extraction and analysis of unmetabolized BTEXs from urine samples. 相似文献
228.
Natarajan Arumugam Abdulrahman I. Almansour Raju Suresh Kumar Vagolu Siva Krishna Dharmarajan Sriram Ramanathan Padmanaban 《Arabian Journal of Chemistry》2021,14(2):102938
A stereo- and regioselective synthesis of hitherto unexplored novel class of β-lactam embedded spirooxindolopyrrolidine hybrid heterocycles have been accomplished via ionic liquid accelerated [3 + 2]-cycloaddition reaction process. The expected unusual lactonization/lactamization product could not be observed even in traces. The in vitro antimycobacterium tubercular activity of the synthesized spiroheterocyclic hybrids were assessed against Mycobacterium tuberculosis H37Rv. Among them, the compounds with no substitution and chlorosubstitution on the oxindole ring showed the most potent activity with a MIC 0.78 μg/mL and 1.56 μg/mL, respectively which were two-fold and equal activity than the standard drug, ethambutol (MIC = 1.56 μg/mL). 相似文献
229.
The Theoretical and Experimental Studies on Oxidation of Straight Chain Amino Acids in Moderately Concentrated Sulfuric Acid Medium 下载免费PDF全文
Homayoon Bahrami Gholamreza Jaferian Mehdi D. Davari Mansour Zahedi Ali Akbar Moosavi‐Movahedi 《国际化学动力学杂志》2016,48(11):647-659
The kinetics of the permanganic oxidation process of some straight chain amino acids in moderately concentrated sulfuric acid medium have been investigated using a spectrophotometric technique. Conclusive evidences have proven autocatalytic activity of Mn(II) for these reactions. It is determined that even and odd effects of the number carbon atom in a carbon chain are annihilated when it's the number of carbon atoms is increased more than of three in a noncatalytic oxidation pathway. Thus, rate constants belonging to glycine, l ‐α‐amino‐n‐butyric acid, l ‐norleucine, and l ‐α‐amino‐n‐heptanoic acid satisfy Taft's equation involving the induction factor in the noncatalytic pathway, whereas l ‐α‐amino‐n‐heptanoic acid has an odd number of carbon atom in its chain carbon. On the other hand, in the catalytic pathway, rate constants satisfy Taft' equation including inductive and steric factors, when rate constants belonging to amino acids with an even number of carbon atoms are separated from those with an odd number of carbon atoms. The oxidation process of amino acids in the noncatalytic pathway and those with the even number of carbon atoms in the carbon chain in the catalytic pathway speeds up by an increase in the length of chain that is accompanied with an increase in the carbon chain's electron‐donating characteristic. On the other hand, an increase in the length of the carbon chain is accompanied with more steric hindrance, which counteracts its electron‐donating character, thereby decreasing reaction rate in the catalytic pathway. Finally, amino acid–Mn(II) complexes were studied using a density functional theory method. Results obtained show that such a complex is less stable than reactants, namely it is formed in an endothermic reaction. The number and strength of hydrogen bonding belonging to amino acid is more than those of the amino acid–Mn(II) complex. Besides, it has been illustrated that natural bond orbital analysis and molecular orbital calculations satisfy the findings. 相似文献
230.
Sodium hexafluorosilicate (Na2SiF6) powder has been used as a silicon source for formation of Si3N4 coatings by the hybrid precursor system‐chemical vapor deposition (HYSY‐CVD) route. The quantitative effect of processing time, temperature, gas flow rate, and process atmosphere (N2 and N2:5% NH3) upon the fractional weight loss during the decomposition of Na2SiF6 was studied using a standard L9 Taguchi experimental design and analysis of variance. The decomposition kinetics of Na2SiF6(s) was studied theoretically and experimentally in the temperature range of 550–650ºC by applying the shrinking core model. It was found that regardless of atmosphere type, the reaction order is n ≈ 0.12 and that a two‐stage mixed mechanism consisting of chemical reaction and boundary layer gas transfer controls the decomposition rate. The determined fractional weight loss during Na2SiF6 decomposition in nitrogen atmosphere is about 1.05–1.5 orders of magnitude greater than that in N2:NH3. The gas flow rate affects the dissociation activation energy, being of 121, 109, and 94 kJ/mol in N2 and of 140, 120, and 115 kJ/mol in N2:NH3, for the flow rates of 20, 60, and 100 cm3/min, respectively, in both atmosphere types. A good agreement is observed by comparing experimental weight loss data with model predictions. 相似文献