全文获取类型
收费全文 | 140篇 |
免费 | 3篇 |
专业分类
化学 | 115篇 |
晶体学 | 1篇 |
数学 | 20篇 |
物理学 | 7篇 |
出版年
2023年 | 1篇 |
2022年 | 3篇 |
2021年 | 7篇 |
2018年 | 1篇 |
2017年 | 3篇 |
2016年 | 5篇 |
2015年 | 8篇 |
2014年 | 11篇 |
2013年 | 10篇 |
2012年 | 10篇 |
2011年 | 11篇 |
2010年 | 5篇 |
2009年 | 6篇 |
2008年 | 11篇 |
2007年 | 7篇 |
2006年 | 6篇 |
2005年 | 4篇 |
2004年 | 6篇 |
2003年 | 4篇 |
2002年 | 2篇 |
2001年 | 3篇 |
2000年 | 1篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有143条查询结果,搜索用时 15 毫秒
21.
Carboxyl groups in pre-treated regenerated cellulose fibres 总被引:1,自引:1,他引:0
Lidija Fras Zemljič Zdenka Peršin Per Stenius Karin Stana Kleinschek 《Cellulose (London, England)》2008,15(5):681-690
The influence of peroxide bleaching and slack-mercerization on the amount of acidic groups in regenerated fibres (viscose,
modal and lyocell) were studied. Conductometric titration was used to determine the total content of acidic carboxylic groups.
Polyelectrolyte titration was used for surface and total charge determination, and to obtain information about the charge
distribution and accessibilities of charged groups. Changes in fibre crystallinity to pre-treatment processes were characterized
using iodine sorption (Schwertassek method) and correlated to treatments and the amount of carboxylic groups. For all three
types of fibres the amount of accessible carboxyl groups was lowered by an increase in the degree of crystallinity. Bleaching
with hydrogen peroxide causes some oxidative cellulose damage and, therefore, a larger amount of carboxyl groups (presumably
formed at the end of cellulose chains). Slack-mercerization did not significantly change the total amount of acidic groups
in the fibres, but their accessibility to cationic polyelectrolytes, in particular to polymers with high molecular weight
was substantially lowered.
Lidija Fras Zemljič, Zdenka Peršin, and Karin Stana Kleinschek are the members of the European Polysaccharide Network of Excellence
(EPNOE). 相似文献
22.
Jovana Šakota Rosić Jelena Munćan Ivana Mileusnić Boris Kosić Lidija Matija 《Soft Materials》2016,14(4):264-271
The aim of this study was to determine if it is possible to distinguish between the groups of spoiled and unspoiled soft contact lenses using near-infrared spectroscopy and new analytical approach – Aquaphotomics. Using the principal component analysis, it was established that the absorbance spectra of worn and new contact lenses are differed at water absorption band related to hydration of proteins. Detection of proteins thus was performed indirectly by using vibrations of water molecules. This exploratory study showed that near-infrared spectroscopy and Aquaphotomics have potential for non-invasive, chemical-free detection of protein deposits on hydrated soft contact lenses. 相似文献
23.
Lidija Posavec Jesper T. N. Knijnenburg Florentine M. Hilty Frank Krumeich Sotiris E. Pratsinis Michael B. Zimmermann 《Journal of nanoparticle research》2016,18(10):310
Rapid calcium (Ca) dissolution from nanostructured Ca phosphate and carbonate (CaCO3) powders may allow them to be absorbed in much higher fraction in humans. Nanosized Ca phosphate and CaCO3 made by flame-assisted spray pyrolysis were characterized by nitrogen adsorption, X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy. As-prepared nanopowders contained both CaCO3 and CaO, but storing them under ambient conditions over 130 days resulted in a complete transformation into CaCO3, with an increase in both crystal and particle sizes. The small particle size could be stabilized against such aging by cation (Mg, Zn, Sr) and anion (P) doping, with P and Mg being most effective. Calcium phosphate nanopowders made at Ca:P ≤ 1.5 were XRD amorphous and contained γ-Ca2P2O7 with increasing hydroxyapatite content at higher Ca:P. Aging of powders with Ca:P = 1.0 and 1.5 for over 500 days gradually increased particle size (but less than for CaCO3) without a change in phase composition or crystallinity. In 0.01 M H3PO4 calcium phosphate nanopowders dissolved ≈4 times more Ca than micronsized compounds and about twice more Ca than CaCO3 nanopowders, confirming that nanosizing and/or amorphous structuring sharply increases Ca powder dissolution. Because higher Ca solubility in vitro generally leads to greater absorption in vivo, these novel FASP-made Ca nanostructured compounds may prove useful for nutrition applications, including supplementation and/or food fortification. 相似文献
24.
Bondarenko L Hentschel S Greiving H Grunenberg J Hopf H Dix I Jones PG Ernst L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(14):3950-3963
A selection of pseudo-geminally substituted [2.2]paracyclophanes, the alkynes 6, 7, 10, 11 a, and 11 b and the alkenes 8 and 9 were prepared for the study of intraannular reactions between functional groups in direct juxtaposition. Whereas 9 and 10 provide the corresponding cyclobutane and cyclobutene derivatives on irradiation (12 and 13, respectively), the bis-alkynes 7 and 11 b do not lead to a cyclobutadiene intermediate. In the latter case the "half-closed" butadiene derivative 17 was isolated. A Paterno-Büchi reaction took place on irradiation of 8 and 6, although the oxetene intermediate 21 produced in the second example did not survive the reaction conditions (ring-opening to 22). Bromine addition to 9, 10, and 7 occurred with high stereoselectivity (formation of the dibromides 27, 30, and 33, respectively), and is rationalized by postulating the formation of the cationic intermediates 26, 29, and 32, respectively. To study the interaction of a carbocation with a facing triple bond, the alcohol 34 was prepared from 6. On acid treatment ring closure to the triply-bridged phane 38 took place, accompanied by the hydration of the triple bond to the ketoalcohol 37. In an interesting intraannular [2+3]cycloaddition reaction the bis-acetylene 11 a, on treatment with n-butyl lithium, provided the cyclopentadiene derivative 42. That the two triple bonds of a pseudo-geminal diacetylene can engage in a cyclization reaction leading to the cyclopentadienone complex 44 was also shown by treating 11 b with iron pentacarbonyl. 相似文献
25.
Regina Janciene Ausra Vektariene Zita Stumbreviciute Lidija Kosychova Algirdas Klimavicius Benedikta D. Puodziunaite 《Heteroatom Chemistry》2004,15(5):363-368
The novel 4H‐thiazolo[3,2‐d][1,5]benzodiazepinium salts have been synthesized in a single step by the reaction of the variously substituted 2,3,4,5‐tetrahydro‐1,5‐benzodiazepine‐2(1H)‐thiones and bromoacetaldehyde diethyl acetal. Cyclization is obviously influenced by the nature of the substituents in the benzodiazepine system. Theoretical modeling and B3LYP DFT computational studies are presented. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:363–368, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20026 相似文献
26.
27.
Using a fixed point relation of the square-root type and the basic fourth-order method, improved methods of fifth and sixth order for the simultaneous determination of simple zeros of a polynomial are obtained. An increase in convergence is achieved without additional numerical operations, which points to high computational efficiency of the accelerated methods. The main aim of this work is the convergence analysis of improved simultaneous methods given under computationally verifiable initial conditions in the spirit of Smale’s point estimation theory. 相似文献
28.
In this paper the method of conditional moments is developed for the case of a two–component matrix composite with randomly distributed unidirectional and arbitrarily oriented ellipsoidal inclusions. The algorithm for determination of the effective elastic properties of composites from the given elastic constants of the components and geometrical parameters and orientation of inclusions is discussed. It is assumed that the components of the composite show orthotropic symmetry of thermoelastic properties. As a numerical example arbolite (straw particle inclusions in a cement matrix) is considered. The dependencies of Young's moduli, Poisson's ratios and shear moduli from the concentration of inclusions and for certain orientations of the inclusions are predicted and discussed. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
29.
Hu W Blecking C Kralj M Šuman L Piantanida I Schrader T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(12):3589-3597
A new class of potent DNA binding agents is presented. Dimeric calix[4]arenes with cationic groups at their upper rims and flexible alkyl bridges can be synthesized from triply acyl-protected calix[4]arene tetramines in relatively short synthetic sequences (3-5 steps). The compounds attach themselves to double-stranded nucleic acids in a noncovalent fashion, with micro- to nanomolar affinities. Guanidinium headgroups with their extended hydrogen-bonding "fingers" are more powerful than ammonium groups, and the benzylamine series is superior to the anilinium series (see below). The new ligands easily distinguish between RNA and various DNA types, and produce characteristic changes in UV/Vis, fluorescence, CD, as well as NMR spectra. Especially extended oligonucleotides of more than 100 base pairs are bound with affinities increasing from RNA (10?μM K(d))相似文献
30.
A polymeric resin material was chosen as the model system to visualise the ageing-induced chemical surface changes with molecular
spectroscopic imaging techniques and correlate these results to physical properties such as colour changes. The influence
of light radiation, temperature and humidity on the polymeric surfaces was analysed by means of attenuated total reflection
infrared imaging, Raman imaging spectroscopy and scanning electron microscopy. Samples were analysed before, during and after
the weathering/ageing tests. From these combined data, the mechanisms for the damaging of the resin surface under the various
environmental conditions (as applied in the accelerated ageing tests) were deduced. Photo-oxidative decay of the resin leading
to a degradation of the uppermost surface layers as well as hydrolysis of the aged surface was identified. The combination
of the spectral and spatial data as obtained from spectroscopic imaging with the morphological and elemental information of
scanning electron microscopic mapping experiments turned out to be highly advantageous for the elucidation of ageing processes.
A correlation between the molecular spectroscopic data and the results from the macroscopic colour difference measurements
was found. 相似文献