全文获取类型
收费全文 | 323篇 |
免费 | 31篇 |
国内免费 | 1篇 |
专业分类
化学 | 283篇 |
晶体学 | 3篇 |
力学 | 3篇 |
数学 | 31篇 |
物理学 | 35篇 |
出版年
2023年 | 2篇 |
2022年 | 1篇 |
2021年 | 8篇 |
2020年 | 6篇 |
2019年 | 7篇 |
2018年 | 8篇 |
2017年 | 5篇 |
2016年 | 16篇 |
2015年 | 15篇 |
2014年 | 18篇 |
2013年 | 20篇 |
2012年 | 43篇 |
2011年 | 35篇 |
2010年 | 16篇 |
2009年 | 13篇 |
2008年 | 19篇 |
2007年 | 26篇 |
2006年 | 13篇 |
2005年 | 14篇 |
2004年 | 19篇 |
2003年 | 24篇 |
2002年 | 5篇 |
2001年 | 1篇 |
1999年 | 1篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1994年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有355条查询结果,搜索用时 15 毫秒
61.
Audrey Boutonnet Arnaud Morin Pierre Petit Patricia Vicendo Véréna Poinsot François Couderc 《Analytica chimica acta》2016
Pulsed lasers are widely used in capillary electrophoresis (CE) studies to provide laser induced fluorescence (LIF) detection. Unfortunately pulsed lasers do not give linear calibration curves over a wide range of concentrations. While this does not prevent their use in CE/LIF studies, the non-linear behavior must be understood. Using 7-hydroxycoumarin (7-HC) (10–5000 nM), Tamra (10–5000 nM) and tryptophan (1–200 μM) as dyes, we observe that continuous lasers and LEDs result in linear calibration curves, while pulsed lasers give polynomial ones. The effect is seen with both visible light (530 nm) and with UV light (355 nm, 266 nm). In this work we point out the formation of byproducts induced by pulsed laser upon irradiation of 7-HC. Their separation by CE using two Zeta LIF detectors clearly shows that this process is related to the first laser detection. All of these photodegradation products can be identified by an ESI-/MS investigation and correspond to at least two 7HC dimers. By using the photodegradation model proposed by Heywood and Farnsworth (2010) and by taking into account the 7-HC results and the fact that in our system we do not have a constant concentration of fluorophore, it is possible to propose a new photochemical model of fluorescence in LIF detection. The model, like the experiment, shows that it is difficult to obtain linear quantitation curves with pulsed lasers while UV-LEDs used in continuous mode have this advantage. They are a good alternative to UV pulsed lasers. An application involving the separation and linear quantification of oligosaccharides labeled with 2-aminobezoic acid is presented using HILIC and LED (365 nm) induced fluorescence. 相似文献
62.
Nanometer‐sized metal particles constitute an unavoidable family of catalysts, combining the advantages of molecular complexes in regards to their catalytic performances and the ones of heterogeneous systems in terms of easy recycling. As part of this research, our group aims at designing well‐defined metal nanoparticles based‐catalysts, in non‐conventional media (ionic liquids or water), for various catalytic applications (hydrogenation, dehalogenation, carbon‐carbon coupling, asymmetric catalysis) in mild reaction conditions. In the drive towards a more eco‐responsible chemistry, the main focuses rely on the search of highly active and selective nanocatalysts, in association with an efficient recycling mainly under pure biphasic liquid‐liquid conditions. In this Personal Account, we proposed our almost fifteen‐years odyssey in the world of metal nanoparticles for a sustainable catalysis.
63.
Lottmann A Cadé E Geagea ML Delhomme O Grand C Veilleraud C Rizet AL Mirabel P Millet M 《Analytical and bioanalytical chemistry》2007,387(5):1855-1861
In to order increase sensitivity and to reduce the background induced by matrix effects, a method was developed that uses
flash chromatography to separate various compounds present in atmospheric aerosol samples prior to their analysis with different
analytical techniques (GC–MS, GC–FID, HPLC). For this purpose, flash chromatography using a 4 g silica gel column crossed
by eluent at a flow rate of 20 mL min−1 was used. An eluent with enhanced polarity is needed to separate nonpolar (linear and branched alkanes), semipolar (PAH,
nitro-PAH and cholesterol) and polar (methoxyphenols, alkanoic acids, and levoglucosan) compounds. Three combinations of solvents
were used: hexane for the nonpolar fraction (F1), toluene/hexane for the semipolar fraction (F2) and dimethylformamide for
the polar fraction (F3). The use of different eluents for each fraction allows separation of the sample to be accomplished
with good repeatability and satisfying yields [85 ± 5% for F1, 81 ± 8% (PAHs), 89 ± 6% (nitro-PAHs) and 74 ± 7% (cholesterol)
for F2 and 79 ± 7% (n-alkanoic acids), 40 ± 11% (methoxyphenols) and 77 ± 6% (levoglucosan) for F3]. The methoxyphenol yields were low due to losses
during the concentration/evaporation step. This method was then applied to analyse the organic composition of particles collected
at an urban site in Strasbourg (France). 相似文献
64.
A series of experiments in a novel quench flow reactor was used to study the influence of the means of adding TEA to the catalyst, the reaction temperature and the hydrogen concentration on the kinetics and morphology of the nascent phase of the polymerisation of ethylene in heptane slurry. It was shown that regardless of the way in which the alkyl was added, an extremely rapid reaction rate was observed for the first few fractions of a second, but that precontacting the catalyst and the TEA cocatalyst led to a slightly higher initial rate. On the other hand, the nascent morphology of the particle/support complex was strongly influenced by the means of adding the alkyl, with precontacting of the two components leading to a better defined product. The influence of the temperature was found to be less significant; however, this was attributed to the particular catalyst.
65.
Martin AN Farquar GR Jones AD Frank M 《Rapid communications in mass spectrometry : RCM》2007,21(22):3561-3568
Single over-the-counter medication tablets were analyzed in real time using Single Particle Aerosol Mass Spectrometry (SPAMS). Dual-polarity time-of-flight mass spectra were obtained for micrometer-sized single particles dislodged from a single tablet without destroying the shape or markings of each tablet. The solid tablet was placed in a modified-top glass vial and shaken to dislodge and introduce micrometer-sized particles into the SPAMS system. Unique spectra from these particles were obtained in less than 1 s for single tablets of aspirin, ibuprofen, pseudoephedrine, phenylephrine, loratadine, or diphenhydramine. The signals obtained allowed the non-destructive identification of an individual tablet in seconds. SPAMS presents an ideal system for high-throughput analysis of solid drugs. 相似文献
66.
Artzner F Geiger S Olivier A Allais C Finet S Agnely F 《Langmuir : the ACS journal of surfaces and colloids》2007,23(9):5085-5092
Poloxamers F88 (EO97PO39EO97) and P85 (EO27PO39EO27) are triblock copolymers of ethylene oxide (EO) and propylene oxide (PO), which have the same hydrophobic PO block. We studied aqueous solutions of these two copolymers by the conjoint use of differential scanning calorimetry (DSC), rheology, and small-angle X-ray scattering (SAXS). The results showed that the temperature-induced micellization of aqueous solutions of F88 and P85 was a progressive process followed by gelation for sufficiently concentrated samples. Gelation was due to the ordered packing of micelles under a hexagonal compact (HC) structure for P85 and a body-centered cubic (BCC) phase for F88. Importantly, the phase diagram of F88/P85 mixtures in water was elucidated and showed the destabilization of the HC phase upon addition of small amounts of F88. 相似文献
67.
Audrey S. C. Lim David H. Solomon Xiaoqing Zhang 《Journal of polymer science. Part A, Polymer chemistry》1999,37(9):1347-1355
The reactions between hexamethylenetetramine (HMTA) and compounds which model novolac resins have been studied by 13C‐ and 15N‐NMR techniques. The dimer and tetramer compounds vary in molecular size and structure and react with HMTA to yield benzylamines and benzoxazine as the major initial‐formed intermediates and convert to methylene linked compounds at increased temperatures. The reaction of the compounds with only ortho reactive sites paralleled the 2,4‐xylenol–HMTA case reported by us previously; however, increasing molecular weight favored the formation of benzylamines and not benzoxazines. Those compounds with only para reactive sites paralleled the 2,6‐xylenol–HMTA case. The reactivity of the systems containing both ortho and para reactive sites depends on the ratio of ortho/para sites and various aspects such as the chemical structure and molecular weight of the compound, the HMTA level, and the melting point and pH of the system. These results parallel those obtained from novolac/HMTA systems. The xylenol/HMTA reactions formed similar products but showed quite different relative reaction rates by varying the HMTA ratio and structures of the materials. The importance of careful selection of model systems is also discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1347–1355, 1999 相似文献
68.
Richard K. Johnson Audrey Zink-Sharp Scott H. Renneckar Wolfgang G. Glasser 《Cellulose (London, England)》2009,16(2):227-238
Utilization of TEMPO-oxidized celluloses in bio-based nanocomposites is reported for the first time. TEMPO-oxidized wood pulps
(net carboxylate content 1.1 mmol/g cellulose) were fibrillated to varying degrees using a high intensity ultrasonic processor.
The degree of fibrillation was controlled by varying sonication time from 1 to 20 min. The sonication products were then characterized
independently and as fillers (5 wt% loading) in hydroxypropyl cellulose nanocomposite films. Nanofibril yields ranging from
11 to 98 wt% (on fiber weight basis) were obtained over the range of sonication times used. Suspension viscosities increased
initially with sonication time, peaked with gel-like behavior at 10 min of sonication and then decreased with further sonication.
The thermal degradation temperature of unfibrillated oxidized pulps was only minimally affected (6 °C decrease) by the fibrillation
process. Dynamic mechanical analysis of the nanocomposites revealed strong fibril-matrix interactions as evidenced by remarkable
storage modulus retention at high temperatures and a suppression of matrix glass transition at “high” (~5 wt%) nanofibril
loadings. Creep properties likewise exhibited significant (order of magnitude) suppression of matrix flow at high temperatures.
It was also believed, based on morphologies of freeze-fracture surfaces that the nanocomposites may be characterized by high
fracture toughness. Direct fracture testing will however be necessary to verify this suspicion. 相似文献
69.
Audrey Sassolas Loïc J. Blum Béatrice D. Leca-Bouvier 《Analytical and bioanalytical chemistry》2009,394(4):971-980
Performant reagentless electrochemiluminescent (ECL) (bio)sensors have been developed using polymeric luminol as the luminophore.
The polyluminol film is obtained by cyclic voltammetry (CV) on a screen-printed electrode either in a commonly used H2SO4 medium or under more original near-neutral buffered conditions. ECL responses obtained after performing polymerization either
at acidic pH or at pH 6 have been compared. It appears that polyluminol formed in near-neutral medium gives the best responses
for hydrogen peroxide detection. Polymerization at pH 6 by cyclic voltammetry gives a linear range extending from 8 × 10−8 to 1.3 × 10−4 M H2O2 concentrations. Based on this performant sensor for hydrogen peroxide detection, an enzymatic biosensor has been developed
by associating the polyluminol film with an H2O2-producing oxidase. Here, choline oxidase (ChOD) has been chosen as a model enzyme. To develop the biosensor, luminol has
been polymerized at pH 6 by CV, and then an enzyme-entrapping matrix has been formed on the above modified working electrode.
Different biological (chitosan, agarose, and alginate) and chemical (silica gels, photopolymers, or reticulated matrices)
gels have been tested. Best performances have been obtained by associating a ChOD-immobilizing photopolymer with the polyluminol
film. In this case, choline can be detected with a linear range extending from 8 × 10−8 to 1.3 × 10−4 M.
This paper is based on the results presented in a poster that received a Poster Award on the occasion of XIII International
Symposium on Luminescence Spectrometry in Bologna, Italy, on September, 7th-11th, 2008. 相似文献
70.
Kuethe JT Marcoux JF Wong A Wu J Hillier MC Dormer PG Davies IW Hughes DL 《The Journal of organic chemistry》2006,71(19):7378-7390
A highly efficient synthesis of the potent and selective NK-1 receptor antagonist 1 is described. The key transformation involved the etherification reaction between cyclopentanol 12 and chiral imidate 30 which was catalyzed by HBF4 to initially give ether 14 as a 17:1 mixture of diastereomers and in 75% combined yield. The diastereoselectivity was upgraded to 109:1 by crystallization of the triethylamine solvate 44 which was isolated in 54% yield from 12. Mechanistic studies confirmed that the etherification reaction proceeds through an unprecedented S(N)2 reaction pathway under typical S(N)1 reaction conditions. 相似文献