全文获取类型
收费全文 | 317篇 |
免费 | 16篇 |
国内免费 | 4篇 |
专业分类
化学 | 235篇 |
力学 | 2篇 |
数学 | 56篇 |
物理学 | 44篇 |
出版年
2024年 | 3篇 |
2023年 | 2篇 |
2022年 | 7篇 |
2021年 | 11篇 |
2020年 | 14篇 |
2019年 | 12篇 |
2018年 | 8篇 |
2017年 | 10篇 |
2016年 | 12篇 |
2015年 | 10篇 |
2014年 | 15篇 |
2013年 | 27篇 |
2012年 | 26篇 |
2011年 | 28篇 |
2010年 | 21篇 |
2009年 | 15篇 |
2008年 | 15篇 |
2007年 | 24篇 |
2006年 | 11篇 |
2005年 | 14篇 |
2004年 | 10篇 |
2003年 | 6篇 |
2002年 | 5篇 |
2001年 | 2篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 4篇 |
1996年 | 1篇 |
1994年 | 4篇 |
1993年 | 1篇 |
1990年 | 2篇 |
1988年 | 3篇 |
1987年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
排序方式: 共有337条查询结果,搜索用时 312 毫秒
1.
Kinetics and concentration profile associated with the regulated radiodegradation of bilirubin in an organic solvent were
assessed. The pure unconjugated specimen was prepared in chloroform (40.0 μM). The depletion of bilirubin was almost linear
with dose, and complete degradation was accomplished with doses in excess of 100 Gy. The method was also evaluated for the
explicit production of the long-wavelength isomer of biliverdin, which was characterized spectrometrically by an absorbance
band in the region 600–650 nm. Results including differences in air, N2 and O2 purged samples are presented to identify the atmospheric medium for optimum production of biliverdin. The process was regulated
by controlling the dose. The general rate constant of the depletion process was estimated at a dose rate of 5.67·10−2Gy·s−1. The method is a convenient substitute for light illumination studies of bilirubin.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
2.
Taxifolin 3-O-glucoside isomers, [(2R, 3R)-, (2R, 3S)-, (2S, 3R)- and (2S, 3S)-] were isolated from leaves of Chamaecyparis obtuse (Cupressaceae). Their structures were elucidated on the basis of UV, MS, CD, 1H- and 13C-NMR spectral data, including 2D shift correlation. It was found that the compounds could be distinguished by the use of 1H- and 13C-NMR spectral data. 相似文献
3.
Alkali Blue 6B-attached poly(2-hydroxyethyl methacrylate) (poly(HEMA)) microporous films were investigated as chelate forming sorbents for heavy metal removal. Poly(HEMA) microporous films were prepared by UV-initiated photo-polymerization of HEMA in the presence of an initiator (azobisisobutyronitrile (AIBN)). Alkali Blue 6B was attached covalently. These films with a swelling ratio of 58%, and carrying 14.8 mmol Alkali Blue 6B m(-2) which were then used in the removal of Cd(II), Zn(II) and Pb(II) from aqueous media. Adsorption rates were very high, equilibrium was achieved in about 30 min. The maximum adsorption of heavy metal ions onto the Alkali Blue 6B-attached films were 41.4 mmol m(-2) for Cd(II), 52.4 mmol m(-2) for Zn(II), and 64.5 mmol m(-2) for Pb(II). When the heavy metal ions competed during the adsorption from a mixture the adsorption values for Cd(II), Zn(II) and Pb(II) were quite close. Heavy metal ions were desorbed by using 0.1 M HNO(3). A significant amount of the adsorbed heavy metal ions (up to 95%) could be desorbed in 30 min. Repeated adsorption/desorption cycles showed the feasibility of these novel dye-attached microporous films for heavy metal removal. 相似文献
4.
Poly(p-chloromethylstyrene-ethyleneglycoldimethacrylate) polymeric microbeads, poly(p-CMS-EGDMA), were synthesized and 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (S4HD) was attached chemically onto the polymeric microbeads. Characterization of all microbeads was done by Fourier transform-infrared spectrometry (FT-IR) and elemental analyzer. The amount of attached 1,5,9,13-tetrathiacyclohexadecane-3,11-diol to the polymer was found to be 2.23 mmol g−1 polymers. The ligand attached microbeads, poly(p-CMS-EGDMA-S4HD), were used to examine the adsorption capacity of Pb(II), Cd(II), Hg(II) and Cr(II) ions for recovery, pre-concentration and the matrix elimination by changing the pH and the initial metal ion concentrations and also adsorption kinetics of the studied metal ions was determined. Pre-concentration factors for the studied toxic metal ions were found to be more than 500-fold and recovery was between 92 and 106%. In the drinking, lake, tap and sea-water samples from water lands, ultra-trace toxic metal ion concentrations were determined easily by using ligand modified microbeads after pre-concentration because of the high pre-concentration factor and easily matrix elimination using ligand modified microbeads. Reference sea-water material was used for the validation of the method and it was found that recovery, pre-concentration and the matrix elimination were performed perfectly. For the desorption of the toxic metal ions, 3 M HCl containing 0.8 M thiourea was used and desorption ratio was obtained more than 96%. 相似文献
5.
[reaction, structure: see text] We report a unimolecular system functioning as a combinatorial logic circuit for half-subtractor. The emission characteristics can be modulated by chemical inputs, and when followed at two different wavelengths, two functionally integrated logic gates XOR and INHIBIT are obtained. Both logic gates function in the emission mode, and with very large differences in the signal intensity allowing unequivocal assignment of logic-0 and logic-1. 相似文献
6.
We report a novel dimeric boradiazaindacene dye which can be converted in one step to an efficient resonance energy transfer (RET) dyad. In addition, if this modification is done with appropriate ligands, RET can be coupled to ion sensing. The utility of this approach is demonstrated in a highly selective, emission ratiometric chemosensor for Ag(I). 相似文献
7.
4-Morpholinoacetophenone thiosemicarbazone, MAPT, and its nickel(Ⅱ) and copper(Ⅱ) complexes have been prepared and characterized by elemental analysis, magnetic susceptibility, spectral methods (FT-IR, ^1H NMR) and cyclic voltammetry. Electrochemical behaviors of the complexes have been studied by cyclic voltammetry in DMF media showing metal centered reduction processes for both of them. The redox properties, nature of the electrode processes and the stability of the complexes were discussed. [Cu(MAPT)2]Cl2 complex shows Cu(Ⅱ)/Cu(Ⅰ) couple and quasi-reversible wave associated with the Cu(Ⅲ)/Cu(Ⅱ) process. The reduction/oxidation potential values depend on the structures of complexes. Also, the antimicrobial activities of these complexes were determined against S. aureus, E. coli and B. subtilis. 相似文献
8.
Zuhair S. Salih Peter Stegmüller Wolfgang Pfleiderer 《Journal of heterocyclic chemistry》1988,25(5):1443-1447
Acylations of 1,3-dimethyl- ( 1 ) and 1,3,7-trimethylpyrrolo[2,3-d]pyrimidine-2,4-dione ( 2 ) with anhydrides in the presence of trifluoroacetic acid proceed well to give in good yields the corresponding 7-acyl derivatives 3–11 . The 6-trichloroacetyl derivatives 5 and 6 are sensitive towards nucleophiles, which displace the trichloromethyl group easily by formation of the corresponding 6-carboxylic acid derivatives 12–23. The newly synthesized compounds have been characterized by elemental analysis, uv and 1H nmr spectra and pKa, determinations. 相似文献
9.
C. S. Erdurak-Kiliç B. Uslu B. Dogan U. Ozgen S. A. Ozkan M. Coskun 《Journal of Analytical Chemistry》2006,61(11):1113-1120
Ascorbic acid is the most common electroactive biological compound found in some plant species (e.g., Citrus species, Rosa species). The electrochemical oxidation of ascorbic acid was investigated by cyclic, linear sweep, differential pulse (DPV),
and square wave (SWV) voltammetry. For analytical purposes, a very well-resolved diffusion-controlled voltammetric peak was
obtained in acetate buffer at pH 3.50 for DPV and SWV. The linear response was obtained in the range of 3.52–176.1 μg/mL with
a detection limit of 0.88 μg/mL for DPV and 0.52 μg/mL for SWV. Based on this study, simple, rapid, selective, and sensitive
voltammetric methods were developed for the determination of ascorbic acid in pharmaceutical dosage forms and Rosa species (R. dumalis ssp. boissieri var. boissieri, R. canina, R. pulverulenta, R. heckeliana ssp. vanheurckiana, and R. montana subsp. woronowii). The results obtained are compared with the HPLC data. The developed methods enable the extracts to be analyzed without
the necessity of any time-consuming separation.
The text was submitted by the authors in English. 相似文献
10.
Kusano G Orihara S Tsukamoto D Shibano M Coskun M Guvenc A Erdurak CS 《Chemical & pharmaceutical bulletin》2002,50(2):185-192
Investigation of the constituents of the fruits of Morus alba LINNE (Moraceae) afforded five new nortropane alkaloids (1-5) along with nor-psi-tropine (6) and six new amino acids, morusimic acids A-F (7-12). The structures of the new compounds were determined to be 2alpha,3beta-dihydroxynortropane (1), 2beta,3beta-dihydroxynortropane (2), 2alpha,3beta,6exo-trihydroxynortropane (3), 2alpha,3beta,4alpha-rihydroxynortropane (4), 3beta,6exo-dihydroxynortropane (5), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (7), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid (8), (3R)-3-hydroxy-12-1(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (9), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid (10), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-hydroxymethyl-piperidin-1-yl]-dodecanoic acid-3-O-beta-D-glucopyranoside (11), and (3R)-3-hydroxy-12-[(1R,4S,5S)-4-hydroxy-5-methyl-piperidin-1-yl]-dodecanoic acid (12) on the basis of spectral and chemical data. 相似文献