全文获取类型
收费全文 | 566篇 |
免费 | 32篇 |
国内免费 | 11篇 |
专业分类
化学 | 450篇 |
晶体学 | 2篇 |
力学 | 18篇 |
数学 | 43篇 |
物理学 | 96篇 |
出版年
2024年 | 2篇 |
2023年 | 2篇 |
2022年 | 13篇 |
2021年 | 16篇 |
2020年 | 23篇 |
2019年 | 24篇 |
2018年 | 29篇 |
2017年 | 19篇 |
2016年 | 45篇 |
2015年 | 28篇 |
2014年 | 47篇 |
2013年 | 72篇 |
2012年 | 42篇 |
2011年 | 42篇 |
2010年 | 43篇 |
2009年 | 18篇 |
2008年 | 27篇 |
2007年 | 31篇 |
2006年 | 23篇 |
2005年 | 15篇 |
2004年 | 13篇 |
2003年 | 7篇 |
2002年 | 11篇 |
2001年 | 1篇 |
2000年 | 1篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1986年 | 1篇 |
1981年 | 1篇 |
1978年 | 1篇 |
排序方式: 共有609条查询结果,搜索用时 0 毫秒
41.
The synthesis of several novel three-dentate sulfonamide alcohol ligands is described, starting from camphorsulfonyl chloride. The influence of temperature and ligand structure on the asymmetric addition of dietylzinc to aromatic aldehydes has been studied. Enantioselectivities up to 76% have been obtained. 相似文献
42.
de Campo L Varslot T Moghaddam MJ Kirkensgaard JJ Mortensen K Hyde ST 《Physical chemistry chemical physics : PCCP》2011,13(8):3139-3152
Triphilic star-polyphiles are short-chain oligomeric molecules with a radial arrangement of hydrophilic, hydrocarbon and fluorocarbon chains linked to a common centre. They form a number of liquid crystalline structures when mixed with water. In this contribution we focus on a hexagonal liquid crystalline mesophase found in star-polyphiles as compared to the corresponding double-chain surfactant to determine whether the hydrocarbon and fluorocarbon chains are in fact demixed in these star-polyphile systems, or whether both hydrocarbon and fluorocarbon chains are miscible, leading to a single hydrophobic domain, making the star-polyphile effectively amphiphilic. We report SANS contrast variation data that are compatible only with the presence of three distinct immiscible domains within this hexagonal mesophase, confirming that these star-polyphile liquid crystals are indeed hydrophilic/oleophilic/fluorophilic 3-phase systems. Quantitative comparison with scattering simulations shows that the experimental data are in very good agreement with an underlying 2D columnar (12.6.4) tiling. As in a conventional amphiphilic hexagonal mesophase, the hexagonally packed water channels (dodecagonal prismatic domains) are embedded in a hydrophobic matrix, but that matrix is split into oleophilic hexagonal prismatic domains and fluorophilic quadrangular prismatic domains. 相似文献
43.
Marzieh Mohammadi Akram Zamani Keikhosro Karimi 《Applied biochemistry and biotechnology》2013,171(6):1465-1472
In this study, the effect of phosphorous compound concentration on the production of glucosamine by Mucor indicus was investigated. Changes in the yield of ethanol, the major metabolite of the fungus, were also followed besides. The alkali insoluble material of the biomass of the fungus mainly contained phosphates and polymers of glucosamine and N-acetyl glucosamine, i.e., chitin and chitosan. Yields of glucosamine (78–113 g/kg dry fungal biomass) and ethanol (200–370 g/kg glucose) were significantly affected by the phosphorous concentration. The results showed that lower concentrations of phosphorous favored the production of glucosamine while higher ethanol as well as biomass yields was obtained at higher concentrations. The best concentration was 0.5 g/l where glucosamine yield was 0.37 g/l (11 % of the biomass). At this phosphate concentration, ethanol and biomass yields were 360 and 76 g/kg glucose, respectively. On average, proteins comprised 51.5 % of the biomass. Glycerol was the second important metabolite during the fermentation by the fungus which appeared at lower yields (20–34 g/kg glucose). 相似文献
44.
45.
A novel straightforward synthesis of 3‐(1H‐tetrazol‐5‐yl)coumarins (=3‐(1H‐tetrazol‐5‐yl)‐2H‐1‐benzopyran‐2‐ones) 6 via domino Knoevenagel condensation, Pinner reaction, and 1,3‐dipolar cycloaddition of substituted salicylaldehydes (=2‐hydroxybenzaldehydes), malononitrile (propanedinitrile), and sodium azide in H2O is reported (Scheme 1 and Table 2). This general protocol provides a wide variety of 3‐(1H‐tetrazol‐5‐yl)coumarins in good yields under mild reaction conditions. 相似文献
46.
Firas Awaja Michael Gilbert Minoo Naebe Georgina Kelly Bronwyn Fox Russell Brynolf Paul J. Pigram 《Polymer Degradation and Stability》2013
Thermoplastic polyolefin panels were treated with a flame, flame & water, and accelerated thermo molecular adhesion process (ATmaP) treatment. XPS, contact angle and adhesion test (pull off) results were acquired over a one year period to determine the changes in the elemental composition, surface energy and adhesion strength respectively over time. All surface-treated thermoplastic polyolefin samples showed a sharp decline in adhesion strength up to an ageing period totalling 6 months. The decline in adhesion strength was correlated with a decline in the nitrogen-containing constituents and C–O functional groups at the surface and a decline in surface energy for the flame & water-treated sample. There was no significant change in adhesion strength for all samples for ageing periods greater than 6 months. ATmaP-treated thermoplastic polyolefin outperformed the other two surface treatments in adhesion strength tests due to ATmaP retaining nitrogen-based functional groups (mainly nitrogen oxides) over the year long study. This retention of functionality allowed for a slower ageing process for ATmaP-treated surfaces in comparison to the other surface treatments. 相似文献
47.
48.
Mostafa Hosseini Ali Asghar Karkhane Bagher Yakhchali Mehdi Shamsara Saeed Aminzadeh Dena Morshedi Kamahldin Haghbeen Ibrahim Torktaz Esmat Karimi Zahra Safari 《Applied biochemistry and biotechnology》2013,169(3):773-785
Lipases are one of the highest value commercial enzymes as they have broad applications in detergent, food, pharmaceutical, and dairy industries. To provide chimeric Bacillus thermocatenulatus lipase (BTL2), the completely conserved pentapeptide (112Ala-His-Ser-Gln-Gly116) was replaced with similar sequences (207Gly-Glu-Ser-Ala-Gly211) of Candida rugosa lipase (CLR) at the nucleophilic elbow region. For this purpose, three mutations including A112G, H113E, and Q115A were inserted in the conserved pentapeptide sequence of btl2 gene. Based on the crystal structures of 2W22, the best structure of opened form of the chimeric lipases were garnered using the MODELLER v9.10 software. The native and chimeric lipases were docked to a set of ligands, and a trial version of Molegro Virtual Docker (MVD) software was used to obtain the energy values. Docking results confirmed chimeric lipase to be better than the native lipase. Following the in silico study, cloning experiments were conducted and expression of native and chimeric btl2 gene in Pichia pastoris was performed. The native and chimeric lipases were purified, and the effect of these mutations on characteristics of chimeric lipase studied and then compared with those of native lipase. Chimeric lipase exhibited 1.6-fold higher activity than the native lipase at 55 °C. The highest percentage of both lipases activity was observed at 60 °C and pH of 8.0. The ion Ca2+ slightly inhibited the activity of both lipases, whereas the organic solvent enhanced the lipase stability of chimeric lipase as compared with the native lipase. According to the results, the presence of two glycine residues at the conserved pentapeptide region of this chimeric lipase (112 Gly-Glu-Ser-Ala-Gly 116) may increase the flexibility of the nucleophilic elbow region and affect the enzyme activity level. 相似文献
49.
Alkyl halides are efficiently converted to their corresponding nitroalkanes under mild and nonaqueous conditions by using polymer supported nitrites. The polymeric reagent is regenerable. 相似文献
50.
Reza Karimi Shervedani Saied Mohsen Siadat‐Barzoki Mojtaba Bagherzadeh 《Electroanalysis》2010,22(9):969-977
A new sensor, gold‐6‐amino‐2‐mercaptobenzothiazole (6A2MBT), was fabricated via a self‐assembly procedure. Electrochemical properties of the monolayer were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The modified electrode showed excellent antifouling property against the oxidation products of DA, allowed us to construct a dynamic calibration curve with two linear parts, 1.00×10?6 to 3.72×10?4 and 3.72×10?4 to 6.42×10?4 M DA, with correlation coefficients of 0.997 and 0.992 and a detection limit of 1.57×10?7 M DA by using differential pulse voltammetry (DPV), respectively. Finally, the performance of the Au‐6A2MBT modified electrode was successfully tested for electrochemical detection of DA in a pharmaceutical sample. 相似文献