全文获取类型
收费全文 | 725篇 |
免费 | 27篇 |
国内免费 | 17篇 |
专业分类
化学 | 521篇 |
晶体学 | 4篇 |
力学 | 41篇 |
数学 | 93篇 |
物理学 | 110篇 |
出版年
2024年 | 5篇 |
2023年 | 3篇 |
2022年 | 16篇 |
2021年 | 30篇 |
2020年 | 34篇 |
2019年 | 44篇 |
2018年 | 39篇 |
2017年 | 35篇 |
2016年 | 72篇 |
2015年 | 39篇 |
2014年 | 47篇 |
2013年 | 101篇 |
2012年 | 56篇 |
2011年 | 47篇 |
2010年 | 44篇 |
2009年 | 29篇 |
2008年 | 25篇 |
2007年 | 33篇 |
2006年 | 8篇 |
2005年 | 16篇 |
2004年 | 9篇 |
2003年 | 8篇 |
2002年 | 7篇 |
2001年 | 3篇 |
2000年 | 1篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1980年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有769条查询结果,搜索用时 15 毫秒
661.
Graphene quantum dots were synthesized by control carbonization of citric acid and utilized for selective determination of dopamine in the presence of ascorbic and uric acids. The prepared graphene quantum dots were characterized by X-ray diffraction, transmission electron microscopy, and Fourier transform infrared, ultraviolet–visible and fluorescence spectroscopy. The results revealed that dopamine could quench the fluorescence of graphene quantum dots through a dynamic quenching mechanism. Under the optimized conditions, the linear concentration range was obtained within 0.01–50.0 µM, with the correlation coefficient of 0.9983 and a limit of detection of 8.2 nM. This method does not show any interference with respect to coexisting foreign substances, even at the presence of 500-fold of ascorbic acid and uric acid. 相似文献
662.
Javad Beheshtian Hadi Behzadi Mehdi D. Esrafili Bahram B. Shirvani Nasser L. Hadipour 《Structural chemistry》2010,21(5):903-908
The effect of water molecule adsorption on the surface of (5,0) zigzag boron nitride nanotube was studied by density functional
theory calculations. Geometrical optimizations were carried out at the B3LYP/6-31+G* level of theory. Six different configurations
of water molecule(s) adsorption process including monomer (1WB and 1WN), dimer (2WB, 2WNN, and 2WBN), and trimer (3WB) clusters
were obtained. The strengths of interactions were analyzed by the equilibrium geometries, binding energies, and charge transfer.
The natural bonding analysis was also performed to investigate electronic properties. The results reveal that the adsorption
of water is more favorable as the water cluster size increases. 相似文献
663.
664.
The present study introduces Robinia tree leaves as a novel and efficient biosorbent for removing Pb(II) from aqueous solutions. In order to reduce the large number of experiments and find the highest removal efficiency of Pb(II), a set of full 2(3) factorial design with two blocks were performed in duplicate (16 experiments). In all experiments, the contact time was fixed at 25 min. The main interaction effects of the three factors including sorbent mass, pH and initial concentration of metal-ion were considered. By using Student's t-test and analysis of variances (ANOVA), the main factors, which had the highest effect on the removal process, were identified. Twenty-six experiments were designed according to Doehlert response surface design to obtain a mathematical model describing functional relationship between response and main independent variables. The most suitable regression model, that fitted the experimental data extremely well, was chosen according to the lack-of-fit-test and adjusted R(2) value. Finally, after checking for possible outliers, the optimum conditions for maximum removal of Pb(II) from aqueous solution were obtained. The best conditions were calculated to be as: initial concentration of Pb(II)=40 mg L(-1), pH 4.6 and concentration of sorbet equal to 27.3 g L(-1). 相似文献
665.
Ghasemi Y Rasoul-Amini S Morowvat MH Raee MJ Ghoshoon MB Nouri F Negintaji N Parvizi R Mosavi-Azam SB 《Molecules (Basel, Switzerland)》2008,13(10):2416-2425
A unicellular microalga, Chlamydomonas reinhardtii, was isolated from rice paddy-field soil and water samples and used in the biotransformation of hydrocortisone (1). This strain has not been previously tested for steroid bioconversion. Fermentation was carried out in BG-11 medium supplemented with 0.05% substrate at 25 degrees C for 14 days of incubation. The products obtained were chromatographically purified and characterized using spectroscopic methods. 11b,17 beta-Dihydroxyandrost-4-en-3-one (2), 11 beta-hydroxyandrost-4-en-3,17-dione (3), 11 beta,17 alpha,20 beta,21-tetrahydroxypregn-4-en-3-one (4) and prednisolone (5) were the main products of the bioconversion. The observed bioreaction features were the side chain degradation of the substrate to give compounds 2 and 3 and the 20-ketone reduction and 1,2-dehydrogenation affording compounds 4 and 5, respectively. A time course study showed the accumulation of product 2 from the second day of the fermentation and of compounds 3, 4 and 5 from the third day. All the metabolites reached their maximum concentration in seven days. Microalgal 18S rRNA gene was also amplified by PCR. PCR products were sequenced to confirm their authenticity as 18S rRNA gene of microalgae. The result of PCR blasted with other sequenced microalgae in NCBI showed 100% homology to the 18S small subunit rRNA of two Chlamydomonas reinhardtii spp. 相似文献
666.
Mitra Ghassemzadeh Samira Bahemmat Javad Malakootikhah Bernhard Neumüller Alexander Rothenberger 《无机化学与普通化学杂志》2007,633(8):1178-1182
The reactions of AMTTO = 4‐amino‐6‐methyl‐1,2,4‐triazine‐thione‐5‐one (AMTTO, 1 ) with 2‐hydroxybenzaldehyde (salicylaldehyde) and 4‐hydroxybenzaldehyde in methanol under reflux conditions led to the corresponding Schiff‐bases ( H2L1 and H2L2 ). The reaction of H2L1 with palladium acetate in ethanol and additional recrystallization from toluene gave the tetrameric complex [Pd(L)]4·2C7H8 ( 2 ). All compounds were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for H2L1 at ?80 °C: space group P21/c with a = 1285.4(1), b = 707.7(1), c = 1348.2(1) pm, β = 109.32(1)°, Z = 4, R1 = 0.0328, H2L2 at ?80 °C: space group P43212 with a = 762.5(1), b = 762.5(1), c = 4038.9(2) pm, Z = 8, R1 = 0.025 and for 2 at ?103 °C: space group C2/c with a = 2862.5(6), b = 2847.6(6), c = 1727.8(4) pm, β = 105.18(3)°, Z = 8, R1 = 0.0704. 相似文献
667.
Javad Azizian Mohammad R. Mohammadizadeh Ali A. Mohammadi Ali R. Karimi Fatemeh Teimouri 《Heteroatom Chemistry》2007,18(1):16-18
A novel one‐pot procedure for preparation of some new condensed pyrido[2,3‐d]pyrimidine(1H,3H)‐2,4‐diones based on condensation of ninhydrin, alkyl cyanoacetate, and 6‐aminouracil derivatives has been reported. The reactions were carried out in refluxed ethanol and were completed in less than 2 h. © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:16–18, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20242 相似文献
668.
Theoretical calculation and prediction for experimental design to obtain spin crossover complexes
下载免费PDF全文

Farsheed Shahbazi‐Raz Maryam Adineh Nasser Safari Mansour Zahedi 《International journal of quantum chemistry》2016,116(15):1179-1186
DFT methods were utilized to study SCO complexes. [Fe(2btz)2(NCX)2] (2btz = 2,2′‐bithiazoline, X = S ( 1 ) and Se ( 2 )), [Fe(phen)2(NCX)2] (phen = 1,10‐phenantroline, X = S ( 3 ) and Se ( 4 )), and [Fe(bpy)2(NCS)2] ( 5 ) (bpy = 2,2′‐bipyridine) compounds, which have experimentally shown SCO behavior, were calculated. B3LYP, B3LYP*, OPBE, and OLYP with 6‐31G* and 6‐311 + G** basis sets were employed to calculate the ΔEHS/LS energy gap as a clue to find complexes with SCO behavior. It is found that calculated result by B3LYP* with c3 = 0.14 and OPBE methods and 6‐31G* basis set are in agreement with experimentally observed SCO complexes. Then, newly designed Fe(N‐N)2(X)2 complexes, where N‐N are bidentate nitrogen donor chelating ligands and X= SCN‐, SeCN‐, Cl‐, Br‐, I‐, were chosen to see their potential to be SCO compounds. ΔEHS/LS for potential SCO complexes are estimated from 0.8 to 6.5 kcal/mol in B3LYP* and 0.6–5.7 kcal/mol in OPBE. These calculations suggest [Fe(bpy)2(NCSe)2], [Fe(5dmbpy)2(NCS)2], and [Fe(3‐BrPhen)2(NCSe)2] compounds have the ability to show SCO behavior. © 2016 Wiley Periodicals, Inc. 相似文献
669.
Magnetic carbon nanotube‐supported imidazolium ionic liquid (CNT‐Fe3O4‐IL) was synthesized and investigated using various characterization techniques, including Fourier transform infrared and Raman spectroscopies, X‐ray diffraction, vibrating sample magnetometry, scanning and transmission electron microscopies, and thermogravimetric and differential thermal analyses. In order to synthesize the CNT‐Fe3O4‐IL nanocomposites, Fe3O4‐decorated multi‐walled CNTs were modified with 1‐methyl‐3‐(3‐trimethoxysilylpropyl)‐1H‐imidazol‐3‐ium chloride. This catalytic system was found to be a highly stable, active, reusable and solid‐phase catalyst for the synthesis of 2‐aminothiazoles via the one‐pot reaction of ketone, thiourea and N‐bromosuccinimide under mild conditions. Immobilized magnetic ionic liquid catalysis combines the advantages of ionic liquid media with magnetic solid support nanomaterials which enables the application of nanotechnology and green chemistry in chemical processes. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
670.
Javad Safari Soheila Gandomi-Ravandi Saeedeh Shariat 《Journal of the Iranian Chemical Society》2016,13(8):1499-1507
In the present investigation, we have developed a novel technique to prepare azines using nano-WCl6 loaded on Montmorillonite K10 clay as a highly active catalyst. A variety of aldehydes and ketones were efficiently converted to the corresponding azines using catalytic amounts of nanosized WCl6/Mont. K10 under mild conditions. The nanostructures of WCl6 loaded on Mont. K10 as solid acid catalyst have been prepared by solid dispersion method. The advantages of this catalyst are rapid completion of the reactions, simplicity of performance, lack of pollution and mild and green reaction conditions. The morphologies, structure, and chemical components of parent and modified clay were successfully characterized using SEM, FT-IR, CV, XRD and EDX measurements. 相似文献