全文获取类型
收费全文 | 267篇 |
免费 | 10篇 |
国内免费 | 6篇 |
专业分类
化学 | 170篇 |
晶体学 | 1篇 |
力学 | 12篇 |
数学 | 46篇 |
物理学 | 54篇 |
出版年
2023年 | 1篇 |
2022年 | 4篇 |
2021年 | 5篇 |
2020年 | 5篇 |
2019年 | 2篇 |
2018年 | 6篇 |
2017年 | 6篇 |
2016年 | 14篇 |
2015年 | 12篇 |
2014年 | 11篇 |
2013年 | 23篇 |
2012年 | 24篇 |
2011年 | 19篇 |
2010年 | 15篇 |
2009年 | 20篇 |
2008年 | 15篇 |
2007年 | 19篇 |
2006年 | 16篇 |
2005年 | 7篇 |
2004年 | 13篇 |
2003年 | 7篇 |
2002年 | 3篇 |
2001年 | 2篇 |
2000年 | 5篇 |
1999年 | 3篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 5篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1989年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1971年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有283条查询结果,搜索用时 0 毫秒
81.
Chun‐Ho Wong Lai‐Sheung Choi Sui‐Lung Yim Dr. Kwun‐Ngai Lau Prof. Dr. Hak‐Fun Chow Sin‐Kam Hui Prof. Dr. Kong‐Hung Sze 《化学:亚洲杂志》2010,5(10):2249-2257
Two series of aliphatic hydrocarbon‐based G1–G3 dendritic 2‐ureido‐4‐pyrimidinones (UPy) ( S‐Gn )2 and ( L‐Gn )2, differing from one another by the distance between the branching juncture to the urea end, were prepared and characterized. These hydrocarbon dendrons were also appended to a p‐aminonitrobenzene solvatochromic chromophore in order to probe their microenvironment polarity. While positive solvatochromism was observed which indicated the chromophore was solvent accessible, there was no significant difference between the microenvironment polarities on going from the G1 to the G3 dendrons. The self‐assembling behavior and tautomeric preference of the dendritic UPy derviatives were examined by 1H NMR spectroscopy. The dimerization constants (Kdim*) of the DDAA tautomers were unchanged at 107 M ?1 in CDCl3 at both 25 and 50 °C, which were comparable to those of UPy compounds bearing other nonpolar substitutents. Furthermore, the lower limits on the K′dim* of the DADA tautomeric forms of the ( S‐Gn )2 and ( L‐Gn )2 series were determined to be 106 and 105 M ?1 in CDCl3, respectively. It was found that a closer proximity of the dendron branching juncture to the UPy unit could lead to a destabilization effect on the dimeric states. Hence, the ( L‐Gn )2 dimers are more stable than those of ( S‐Gn )2 in the DDAA form, but the latter are more stable than the former in the tautomeric DADA state. This study showed that both the highly nonpolar microenvironment and the proximity of the dendritic branching juncture to the UPy motif could alter the strength and profile of the hydrogen bond‐mediated self‐assembling process. 相似文献
82.
Stephen Sin‐Yin Chui Dr. Kam‐Hung Low Dr. Jun Lu Dr. V. A. L. Roy Dr. Sharon Lai‐Fung Chan Dr. Chi‐Ming Che Prof. Dr. 《化学:亚洲杂志》2010,5(9):2062-2074
Homoleptic d8‐metal organothiolates and phenylselenolates [M(EC6H5)2]∞ (E=S, M=Pt 1 , M=Pd 2 , M=Ni 5 ; E=Se, M=Pt 3 , M=Pd 4 ) were prepared as crystalline solids under solvothermal conditions. Their structures were solved using powder X‐ray diffraction data. In each case, the EC6H5 (E=S, Se) ligand binds to two metal ions (M=Pt, Pd, and Ni) to form chain‐like structures with planar (in 1 ) or zig‐zag (in 2 , 3 , 4 , 5 ) conformations. The [M(SR)2]∞ complexes (M=Pt, R=4‐tert‐butylphenyl 6 ; R=2‐naphthyl 8 ; R=4‐nitrophenyl 10 and M=Pd, R=4‐tert‐butylphenyl 7 ; R=2‐naphthyl 9 ; R=4‐nitrophenyl 11 ) were prepared under similar solvothermal conditions. Based on the XPS binding energies and elemental analyses, complexes 6 , 7 , 8 , 9 , 10 , 11 have the same [M(SR)2]∞ formulation as 1 and 2 . The cyclic complex [Pd6(SCH3)12] 12 was prepared as a crystalline solid by solvothermal annealing treatment of the amorphous precipitate. A chain‐like polymer structure is proposed for both [Pd(SC12H25)2]∞ 13 and [Pd(SC16H33)2]∞ 14 ; these polymeric chains self‐assemble to give layer‐like structures. Solid‐state diffuse reflectance spectra reveal that the optical band gap Eg (eV) of complexes 1 , 6 , 8 , 10 and of 2 , 7 , 9 , 11 are in the range of 2.10–3.00 eV and 2.10–2.63 eV, respectively, and 5 has the lowest Eg value (1.72 eV). Heating solid samples of 4 and 13 under solvothermal conditions afforded phase‐pure Pd17Se15 and PdS nanocrystals, respectively. Field‐effect transistors fabricated with a drop‐cast thin film made from Pd17Se15 nanocrystals prior treated with an ethanolic solution of 1‐hexadecanethiol displayed ambipolar charge transporting properties with hole and electron mobility being 7×10?2 cm2 V?1 s?1 and 6×10?2 cm2 V?1 s?1, respectively. 相似文献
83.
84.
85.
Ming‐Sheng Hsu Yi‐Wei Cao Hsuang‐Wen Wang Ya‐Sin Pan Bo‐Hong Lee Cheng‐Liang Huang Prof. 《Chemphyschem》2010,11(8):1742-1748
Herein, we find that the surface plasmon resonance (SPR) spectra of silver nanoprisms in the presence of halide ions change gradually with reaction time. The changes in the spectra correspond to the shape transformation of silver nanoprisms. There are threshold concentrations of halide ions that initiate the shape‐transformation reaction. The threshold concentrations for Cl?, Br?, and I? are about 3×10?4 M , 1×10?6 M , and 1.5×10?6 M , respectively. Any concentrations of the added halide ions above these thresholds can eventually etch the silver nanoprisms into nanodisks if the reaction time is long enough. The higher the concentration of the halide ions, the higher the etching rate will be. The kinetics of the shape transformation of the silver nanoprisms can be studied by recording their time‐dependent surface plasmon resonance (SPR) spectra on a commercial UV/Vis–NIR spectrometer. The peak positions of in‐plane dipole SPR bands of silver colloids in the presence of chloride and bromide ions can be fitted very well with the biexponential functions. We propose that the fast components of the biexponential behaviors should correlate to the truncating effect on the corners of silver nanoprisms, and the slow component should correlate to the redeposition of the truncated residues onto the basal plane of the nanoplates. 相似文献
86.
Copper indium disulfide (CuInS2; CIS) films were deposited on various substrates by two-stage metal-organic chemical vapor deposition (MOCVD) at relatively mild conditions, using Cu- and In/S-containing precursors without toxic H2S gas: first, a pure Cu thin film was prepared on glass or indium/tin oxide glass substrates by using a single-source precursor, bis(ethylbutyrylacetato)copper(II) or bis(ethylisobutyrylacetato)copper(II); second, on the resulting Cu film, tris(N,N-ethylbutyldithiocarbamato)indium(III) was treated to produce CIS films by a MOCVD method at 430 degrees C. In this process, their thicknesses and stoichiometries were found to be elaborately controlled on demand by adjusting the process conditions. The optical band gap of the stoichiometric CIS film was about 1.41 eV, which is in the near-optimal range for harvesting solar radiation energy. 相似文献
87.
88.
Determination and on-line clean-up of (fluoro)quinolones in bovine milk using column-switching liquid chromatography fluorescence detection 总被引:1,自引:0,他引:1
A simple, cost-effective, and high throughput method using on-line column-switching liquid chromatography fluorescence detection was developed and validated for analysing five (fluoro)quinolones (FQs)--enrofloxacin (ENRO), ciprofloxacin (CIPR), sarafloxacin (SARA), oxolinic acid (OXOL), and flumequine (FLUM) in bovine milk. Norfloxacin (NORF) and nalixidic acid (NALI) were used as internal standards. After simple deproteination of milk sample with 5% (w/v) metaphosphoric acid, the supernatant was subject to on-line column clean-up and direct analysis by LC-FLD. The extraction cartridge was prepared in-house by slurry packing with hydrophilic-lipophilic polymer sorbent. The accuracy of measurement for each (fluoro)quinolone at different maximum residue limits (MRL) was 101-103% (ENRO), 92.8-97.4% (CIPR), 89.8-92.8% (SARA), 116-121% (OXOL), and 81.3-85.5% (FLUM), whilst the precision was 2.9-6.1% (ENRO), 2.5-5.1% (CIPR), 2.3-5.0% (SARA), 3.1-5.9% (OXOL), and 5.6-6.5% (FLUM). The decision limits, detection capabilities, specificity and analytes stability during storage were also investigated. 相似文献
89.
Abstract— Dianthracene is efficiently photodissociated, forming anthracene with a quantum yield of about 0.63. Like anthracene, tetracene undergoes a reversible photochemical reaction, the product of which appears to be di-tetracene. In dilute, deoxygenated solutions the of quantum yeild for the formation of di-tetracene is directly proportional to the concentration of the monomer ødim = 2.2 (). The quantum yield for the reverse reaction is approximately 0.74
When dilute deaerated solutions of anthracene are irradiated with the unfiltered radiation from a quartz-mercury arc, a degradation product is formed. Unlike the dimer, this product cannot be converted into anthracene either by heating it to 200C or by irradiating it in solution with light of 254 nm. This degradation product appears to be the compound or compounds which Birks et al. believed to be dianthracene. Irradiation of deaerated solutions of anthracene (or tetracene) with light of wavelenghts longer than 300 nm produces only the dimer, which has an absorption spectrum similar to that reported by Coulson et al. 相似文献
When dilute deaerated solutions of anthracene are irradiated with the unfiltered radiation from a quartz-mercury arc, a degradation product is formed. Unlike the dimer, this product cannot be converted into anthracene either by heating it to 200C or by irradiating it in solution with light of 254 nm. This degradation product appears to be the compound or compounds which Birks et al. believed to be dianthracene. Irradiation of deaerated solutions of anthracene (or tetracene) with light of wavelenghts longer than 300 nm produces only the dimer, which has an absorption spectrum similar to that reported by Coulson et al. 相似文献
90.
Jin‐Hee Park Yoo‐Sin Park Si‐Youn Rhim Hyun‐Jin Kim Ok‐Hwa Jhee Yun‐Sik Lee Min‐Ho Lee Leslie M. Shaw Ju‐Seop Kang 《Biomedical chromatography : BMC》2009,23(12):1350-1356
A rapid and validated method for analysis of levosulpiride in human plasma using liquid chromatography coupled to tandem mass spectrometry was developed. Levosulpiride and tiapride (IS, internal standard) were extracted from alkalized plasma samples with ethylacetate and separation by RP‐HPLC. Detection was performed by positive ion electrospray ionization in multiple‐reaction monitoring mode, monitoring the transitions m/z 342.1 → m/z 112.2 and m/z 329.1 → m/z 213.2, for quantification of levosulpiride and IS, respectively. The standard calibration curves showed good linearity within the range of 2–200 ng/mL (r2 ≥ 0.9990). The lower limit of quantitation was 2 ng/mL. The retention times of levosulpiride (0.63 min) and IS (0.66 min) presented a significant time saving benefit of the proposed method. No significant metabolic compounds were found to interfere with the analysis. This method offered good precision and accuracy and was successfully applied for the pharmacokinetic and bioequivalence study of a 25 mg of levosulpiride tablet in 24 healthy Korean volunteers. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献