全文获取类型
收费全文 | 888篇 |
免费 | 15篇 |
国内免费 | 11篇 |
专业分类
化学 | 547篇 |
晶体学 | 27篇 |
力学 | 47篇 |
数学 | 179篇 |
物理学 | 114篇 |
出版年
2023年 | 8篇 |
2022年 | 19篇 |
2021年 | 24篇 |
2020年 | 22篇 |
2019年 | 13篇 |
2018年 | 16篇 |
2017年 | 9篇 |
2016年 | 37篇 |
2015年 | 12篇 |
2014年 | 33篇 |
2013年 | 64篇 |
2012年 | 43篇 |
2011年 | 44篇 |
2010年 | 34篇 |
2009年 | 42篇 |
2008年 | 57篇 |
2007年 | 35篇 |
2006年 | 42篇 |
2005年 | 30篇 |
2004年 | 29篇 |
2003年 | 30篇 |
2002年 | 35篇 |
2001年 | 11篇 |
2000年 | 18篇 |
1999年 | 12篇 |
1998年 | 12篇 |
1997年 | 10篇 |
1996年 | 15篇 |
1995年 | 15篇 |
1994年 | 9篇 |
1993年 | 6篇 |
1992年 | 11篇 |
1991年 | 5篇 |
1990年 | 7篇 |
1989年 | 9篇 |
1988年 | 7篇 |
1987年 | 3篇 |
1985年 | 11篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 10篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 6篇 |
1976年 | 7篇 |
1975年 | 4篇 |
1965年 | 2篇 |
1916年 | 4篇 |
排序方式: 共有914条查询结果,搜索用时 0 毫秒
11.
Andrzej Maączyński Marian Góral Barbara Wiśniewska-Gocłowska Adam Skrzecz David Shaw 《Monatshefte für Chemie / Chemical Monthly》2003,134(5):633-653
Summary. The evaluation of mutual solubility data for systems water with n-alkanes, isoalkanes, and cycloalkanes along the three phase line is reported and a formula for the prediction of solubility
of alkanes in water is developed. Then a cubic equation of state with an added term, which accounts for hydrogen bonding is
used for correlation of liquid–liquid equilibrium data and for prediction of solubility of water in hydrocarbons using alkane
in water solubility data. Comparison of the predicted and experimental solubilities is performed using all accessible experimental
data. With this approach it is possible to predict the solubilities of water in alkanes with good accuracy over the temperature
range up to about 20 K below critical temperature. Solubility of alkanes in water can also be calculated using experimental
data for solubility of water in alkanes but results of these calculations are more sensitive to experimental errors of the
data.
Corresponding author: E-mail: macz@ichf.edu.pl
Received August 5, 2002; accepted (revised) September 13, 2002
Published online March 13, 2003
RID="a"
ID="a" Dedicated to Prof. Dr. H. Gamsj?ger on the occasion of his 70th birthday anniversary 相似文献
12.
Measurement of resistant starch by enzymatic digestion in starch and selected plant materials: collaborative study 总被引:11,自引:0,他引:11
Interlaboratory performance statistics was determined for a method developed to measure the resistant starch (RS) content of selected plant food products and a range of commercial starch samples. Food materials examined contained RS (cooked kidney beans, green banana, and corn flakes) and commercial starches, most of which naturally contain, or were processed to yield, elevated RS levels. The method evaluated was optimized to yield RS values in agreement with those reported for in vivo studies. Thirty-seven laboratories tested 8 pairs of blind duplicate starch or plant material samples with RS values between 0.6 (regular maize starch) and 64% (fresh weight basis). For matrixes excluding regular maize starch, repeatability relative standard deviation (RSDr) values ranged from 1.97 to 4.2%, and reproducibility relative standard deviation (RSDR) values ranged from 4.58 to 10.9%. The range of applicability of the test is 2-64% RS. The method is not suitable for products with <1% RS (e.g., regular maize starch; 0.6% RS). For such products, RSDr and RSDR values are unacceptably high. 相似文献
13.
Narayani Ramakrishnan Nancy L. Oleinick Marian E. Clay Min-Fen Horng Antonio R. Antunez Helen H. Evans 《Photochemistry and photobiology》1989,50(3):373-378
Two closely related strains of mouse lymphoma L5178Y cells, LY-R and LY-S, have been found to differ in their sensitivity to the cytotoxic effects of photodynamic treatment (PDT) with chloroaluminum phthalocyanine (CAPC) and red light. Strain LY-R is more sensitive to photodynamic cell killing than strain LY-S. Differences in uptake of CAPC could not account for the differences in cytotoxic effects. There was no marked difference between the two strains in the induction of single-strand breaks (which includes frank single-strand breaks and alkali-labile lesions), but substantially more DNA-protein cross-links were formed in strain LY-R by CAPC and light. Repair of single-strand breaks proceeded with similar kinetics in both strains for the first 30 min post-irradiation, suggesting that these lesions are not responsible for the differential sensitivity of the two strains to the lethal effects of photodynamic treatment. Thereafter, alkaline elution revealed the presence of increasing DNA strand breakage in strain LY-R. DNA degradation, as measured by the conversion of prelabeled [14C] DNA to acid-soluble radioactivity, was more rapid and extensive in strain LY-R. 相似文献
14.
Some cis,cis,cis-RuX(2)(Me(2)SO)(2)(1,2-Me(2)Im)L complexes [L = 1,2-Me(2)Im (1,2-dimethylimidazole) or Me(3)Bzm (1,5,6-trimethylbenzimidazole), X = Cl or Br, and Me(2)SO = S-bonded DMSO] have been synthesized and their rotamers studied in CDCl(3). From 2D NMR data, cis,cis,cis-RuCl(2)(Me(2)SO)(2)(1,2-Me(2)Im)(Me(3)Bzm) has 1,2-Me(2)Im in position "a" (cis to both Me(2)SO's and cis to "b") and Me(3)Bzm in position "b" (trans to one Me(2)SO and cis to the other). There are two stable atropisomers [head-to-tail (HT, 84%) and head-to-head (HH, 16%), defining the aromatic H of Ru-N-C-H as head for both ligands]. Me(3)Bzm has the same orientation in both atropisomers. In this orientation, the unfavorable interligand steric interactions of Me(3)Bzm with the Me(2)SO and 1,2-Me(2)Im ligands appear to be countered by favorable electrostatic attraction between the delta+ N(2)CH moiety of Me(3)Bzm and the delta- cis Cl ligands. The 1,2-Me(2)Im lacks a delta+ N(2)CH group, and its orientation is dominated by steric effects of the 2-Me group. The NMR spectrum of cis,cis,cis-RuCl(2)(Me(2)SO)(2)(1,2-Me(2)Im)(2) is consistent with four rotamers in restricted rotation about both Ru-N bonds: two HH and two HT. 2D NMR techniques (NOESY and ROESY) afforded complete proton signal assignments. The ligand disposition could be assessed from the large chemical shift dispersion of some 1,2-Me(2)Im ligand signals (Delta 0.86-1.52 ppm) arising from cis-1,2-Me(2)Im shielding modulated by deshielding influences of the cis halides. The relative stability of the four rotamers correlates best with steric interactions between the 2-Me groups and the Me(2)SO ligands. The most favorable conformer (46%) is the HH rotamer with both 2-Me groups pointing away from the Me(2)SO ligands. The least favorable conformer (14%) was also HH, but the methyl groups in this case point toward the Me(2)SO ligands. In the HT conformers of intermediate stability ( approximately 20%), one 2-Me group is toward and the other is away from the Me(2)SO ligands. The exchange cross-peaks in the 2D spectra are unusually informative about the dynamic processes in solution; the spectra provide evidence that the rotamers interchange in a definite pattern of succession. Thus, all conceivable exchange pathways are not available. 1,2-Me(2)Im "b" can rotate regardless of the orientation of 1,2-Me(2)Im "a". 1,2-Me(2)Im "a" can rotate only when "b" has the orientation with its 2-Me group directed away from "a". Thus, 1,2-Me(2)Im "b" can switch 1,2-Me(2)Im "a" rotation on or off. 相似文献
15.
Marian Mikolajczyk Slawomir Grzejszczak Katarzyna Korbacz 《Tetrahedron letters》1981,22(32):3097-3100
A convenient synthesis of vinylphosphonates which involves addition of elemental selenium to phosphonate carbanions followed by alkylation and selenoxide elimination is described. A general approach to 1,4-dicarbonyl systems based on diethyl α-methylthiovinylphosphonate is also reported. 相似文献
16.
17.
Absolute rate constants and approximate product distributions are presented for the reactions of He+, Ne+, Ar+, Kr+, Xe+, CO+ and CO+2 with NH3 and PH3. In all cases, electron transfer is the dominant reaction channel. Hydrogen atom transfer is observed in several systems, but only as a minor product, even when this channel is very exothermic. The magnitude of the absolute rate constants can be correlated with the Franck-Condon factors associated with the reactions in most cases. Several exceptions to this general rule are observed that could not be readily predicted a priori. It is speculated that these reactions proceed via a collision complex. 相似文献
18.
Eugen Jóna Marian Koman Anton Sirota 《Journal of inclusion phenomena and macrocyclic chemistry》1998,30(1):1-12
The stoichiometry and spectral properties of [Ni(4-Etpy)4(NCS)2]nG clathrates have been studied where n = 2 for G = 1-BrN (N = naphthalene), n = 1 or 2 for G = 1-MeN, and n = 0.5 for 2-MeN and 2-BrN. The complexes under study show electronic absorption spectra typical of an octahedral environment of the Ni(II) central atom. The differences found in IR spectra for the (CN) and (Ni–-NNCS) vibrations are discussed. The crystal structure of [Ni(4-Etpy)4(NCS)2]1-MeN was determined by X-ray diffraction and refined to R = 0.0586. Discrete non-centrosymmetric [Ni(4-Etpy)4(NCS)2] molecules form layers of a host structure and the space between the layers is occupied by 1-MeN. The relationship between interatomic distances in the host complex of similar clathrates are discussed. 相似文献
19.
Extraction and analysis of phenolics in food 总被引:11,自引:0,他引:11
Phenolics are ubiquitous compounds found in all plants as their secondary metabolites. These include simple phenols, hydroxybenzoic acid and cinnamic acid derivatives, flavonoids, coumarines and tannins, among others. The extraction of phenolics from source materials is the first step involved in their analysis. While chemical methods are used for determination of total content of phenolics, chromatographic and spectrometric analyses are employed for identification and quantification of individual compounds present. This paper provides a summary of background information and methodologies used for the analysis of phenolics in foods and nutraceuticals. 相似文献
20.
Teh-Chang Chou Holger Lange Rolf Gleiter Tibor Ggh Miroslav Krí Max H. Pfenninger Marian Valentíny Camille Ganter 《Helvetica chimica acta》1995,78(8):2011-2025
Three 1,4-dimethylidenecyclohexanes, bridged in the 2,6- and 3,5-positions by two ethano ( 4 ), one ethano and one propano ( 5 ), and two propano bridges ( 6 ) have been synthesized. The interaction of the two exocyclic methylidene groups has been investigated by He(I) photoelectron (PE) spectroscopy. It revealed a slightly larger energy difference (0.8 eV) for 4 and 5 as compared to the parent 1,4-dimethylidenecyclohexane ( 7 ) (0.7 eV). The interpretation of the PE spectra was based on the comparison with PE data of related systems and with the results of semiempirical calculations on 4–6 . 相似文献