全文获取类型
收费全文 | 8500篇 |
免费 | 755篇 |
国内免费 | 225篇 |
专业分类
化学 | 9106篇 |
晶体学 | 24篇 |
力学 | 3篇 |
综合类 | 23篇 |
数学 | 4篇 |
物理学 | 320篇 |
出版年
2024年 | 6篇 |
2023年 | 88篇 |
2022年 | 241篇 |
2021年 | 226篇 |
2020年 | 277篇 |
2019年 | 215篇 |
2018年 | 210篇 |
2017年 | 186篇 |
2016年 | 312篇 |
2015年 | 302篇 |
2014年 | 359篇 |
2013年 | 684篇 |
2012年 | 458篇 |
2011年 | 433篇 |
2010年 | 390篇 |
2009年 | 432篇 |
2008年 | 441篇 |
2007年 | 508篇 |
2006年 | 450篇 |
2005年 | 448篇 |
2004年 | 457篇 |
2003年 | 353篇 |
2002年 | 494篇 |
2001年 | 184篇 |
2000年 | 157篇 |
1999年 | 125篇 |
1998年 | 128篇 |
1997年 | 118篇 |
1996年 | 103篇 |
1995年 | 103篇 |
1994年 | 66篇 |
1993年 | 69篇 |
1992年 | 66篇 |
1991年 | 54篇 |
1990年 | 45篇 |
1989年 | 34篇 |
1988年 | 42篇 |
1987年 | 29篇 |
1986年 | 14篇 |
1985年 | 20篇 |
1984年 | 35篇 |
1983年 | 13篇 |
1982年 | 22篇 |
1981年 | 15篇 |
1980年 | 15篇 |
1979年 | 19篇 |
1978年 | 8篇 |
1972年 | 5篇 |
1969年 | 4篇 |
1968年 | 3篇 |
排序方式: 共有9480条查询结果,搜索用时 15 毫秒
81.
Alkyl ketene dimer (AKD) sizing of paper involves the redistribution of the wax over the fibre surface upon heating. The two
major mechanisms widely studied so far are the spreading of an autophobic precursor of molten AKD and AKD vapour transport
and re-deposition on the fibre surface. All previous work assumed that the transport of AKD vapour could be expressed by the
change of water contact angle with substrates that were exposed to the vapour. Information regarding the chemical composition
of the vapour phase above the AKD wax has not been found in the literature. In this work, a simple method for analysing the
chemical composition of the vapour is established. Our preliminary results indicated that the chemical composition of AKD
vapour in the temperature range of 75–80 °C is dominantly fatty acids. This suggests that the sizing effect by actual AKD
molecules via the vapour deposition mechanism is likely to be insignificant in this temperature range. This also implies that
fatty acids play a positive role in AKD sizing. The chemical stability of AKD in this temperature range is also studied. 相似文献
82.
S. A. Rod’kina 《Chemistry of Natural Compounds》2007,43(5):515-518
The fatty-acid (FA) composition of total lipids from the Okhotsk sea marine sponge Forcepia uschakowi was studied. A total of 56 acids were identified by GC and GC—MS. The principal saturated acids were 16∶0 and 18∶0. The main
monoene acid was 15-Me-24∶1(14), which was observed for the first time in sponge lipids. Polyunsaturated acids represented
of 64.1% of the total FA of F. uschakowi. Of these, the principal ones were non-methylene-separated acids 26∶2(5,9) and 26∶3(5,9,19), which are typical of sponges,
and bromo-acid 6-Br-26∶2(5,9).
__________
Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 422–424, September–October, 2007. 相似文献
83.
The reaction of carbonyl-substituted phenylboronic acids with diethanolamine has been investigated. For compounds containing carbonyl groups at the meta or para positions the reaction occurs exclusively at the boronic acid. Different reactivities were observed for ortho-substituted acetyl- and formylphenylboronic acids where the reaction occurred at both the boronic acid and at the carbonyl group. X-ray studies revealed the presence of a polycyclic structure with tetravalent boron and nitrogen atoms. 相似文献
84.
The Wittig—Horner reaction of CbzNHCH(CO2Me)P(O)(OMe)2 (1) with ArCHO (2) in the presence of Et3N as a base affords methyl (Z)-3-aryl-2-(carbobenzoxyamino)acrylates (3) with high degrees of diastereoselectivity (Z)/(E) > 101. One recrystallization of the crude product is sufficient to obtain isomerically and chemically pure (Z)-3.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2218-2220, November, 1995.The authors are grateful to the Dupont company (USA) for financing this study 相似文献
85.
The quenching of the fluorescence of three anthropogenic fulvic acids (FA) provoked by Cu(II) (pH 6.0), Fe(III) (pH 4.0) and UO22+ (pH 3.5), was analyzed by a non-linear method and by Stern-Volmer plots. The FA samples were extracted from composted sewage sludges (csFA), composted municipal wastes (mwFA) and composted livestock wastes (lsFA). Synchronous-scan fluorescence (SyF) spectra were collected as a function of metal ion concentration. Spectral data were treated by a self-modeling mixture analysis method (SIMPLISMA) to detect the SyF spectral band with the strongest quenching and to calculate the corresponding quenching profile. The analysis of these profiles by a non-linear method allowed the estimation of conditional stability constants (K) and of the percentage of non-complexing fluorophores. The same quantitative information was obtained by the modified Stern-Volmer equation taking into account the existence of fluorophores that do not participate in the complexation. Good agreement was found between the results of the two procedures. The log K calculated by the non-linear method were (standard deviation in parenthesis): csFA, Cu(II), 4.22 (5); Fe(III), 5.0 (1); UO22+, 5.2 (2); mwFA, Cu(II), 4.21 (3); Fe(III), 5.6 (2); UO22+, 4.7 (3); lsFA, Cu(II), 4.51 (8); Fe(III), 5.5 (2); UO22+, 3.6 (2). 相似文献
86.
The enantiomers of some amino acids have been separated on commercial chiral TLC plates in reversed-phase mode. The effect
of the pH* of the aqueous-organic mobile phase on the retention and mobility of the enantiomers and on selectivity was investigated.
It was shown that for most of the amino acids investigated the highest enantioselectivity was obtained at pH* 3–4 or 6–7.
The drift and disturbance of the baseline on the chromatograms were also much smaller at pH* 3–4 and 6–7. 相似文献
87.
V. Z. Shirinian M. M. Krayushkin D. M. Nikalin A. A. Shimkin 《Russian Chemical Bulletin》2005,54(3):738-742
The reaction of alkyl 4-(2-acetylhydrazino)-2-methyl-3-thiophenecarboxylates with 3-methylbutan-2-one was carried out under the Fischer reaction conditions. The influence of Lewis acids and solvents on the process was studied. A convenient method for the synthesis of thieno [3.2-b]pyrrolenine derivatives was proposed.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 725–729, March, 2005. 相似文献
88.
Krishna Bisetty Francesc J. Corcho Josep Canto Hendrik G. Kruger Juan J. Perez 《Journal of Molecular Structure》2006,770(1-3):221-228
In this paper, we report on the conformational profile of the pentacyclo-undecane (PCU) cage tripeptide carried out by molecular dynamics (MD) simulation using water as an explicit solvent. The MD solution phase studies carried on the model peptide analogues (A)=Ac–Ala–Ala–Ala–NHMe; (B)=Ac–Cage–Cage–Cage–NHMe; (C)=Ac–Ala–Cage–Ala–NHMe and (D)=Ac–Ala–Pro–Ala–NHMe, are used as a complimentary technique to the corresponding gas phase simulated annealing (SA) study previously carried out in our laboratory. No significant structural changes were observed over the MD trajectories. However, the results reported here provide further evidence that the (PCU) cage amino acid exhibits C7eq, C7aq, R and L conformations, and the theoretical results suggest that the PCU cage amino acid is a strong β-turn inducer. These results support the prediction that when the PCU cage residues are in the (i) and (i+2) positions, the β-turn can be extended in either direction to form anti-parallel β-pleated sheets, thereby forming the basis of the mechanism for the folding back of the chain in a cross-β-turn structure. 相似文献
89.
M. Heber Chr Liedtke H. Korte E. Hoffmann-Posorske A. Donella-Deana L. A. Pinna J. Perich E. Kitas R. B. Johns H. E. Meyer 《Chromatographia》1992,33(7-8):347-350
Summary Capillary electrophoresis is a novel technique in the non-radioactive determination of phosphoamino acids. The main advantage of the method presented is the high selectivity and the ability to separate all phosphoamino acid derivatives. Non-radioactive determination of PTH or dabsyl phosphoamino acids by capillary electrophoresis provides a fast and simple screening procedure for all O-phosphorylated amino acids in protein and peptides in the low picomolar range. 相似文献
90.
Zhang JJ Sheng TL Hu SM Xia SQ Leibeling G Meyer F Fu ZY Chen L Fu RB Wu XT 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(16):3963-3969
The first successful attempt to construct 3D supramolecular frameworks with high-nuclear 3d-4f heterometallic clusters as a node is reported. The self-assembly of Ln3+, Cu2+ and amino acid in solution leads to the formation of two polymers, 35-nuclear complex [Sm6Cu29] 1 with a primitive cubic net-like structure and 36-nuclear complex [Nd6Cu30] 2 with a face-centred cubic network type structure. Glycine and L-proline, respectively, were used as ligands. It should be noted that 2 has a chiral framework. X-ray structure analyses show that 1 crystallizes in the triclinic P1 space group (a=19.6451(8), b=20.4682(8), c=20.7046(8) A, alpha=89.453(1), beta=66.290(1), gamma=68.572(1) degrees, V=7003.0(5) A3 and Z=1) and 2 belongs to the cubic P2(1)3 space group (a=b=c=32.4341(3) A, V=34 119.7(5) A3 and Z=4). Both complexes utilize Ln6Cu24 octahedral clusters as nodes and trans-Cu(amino acid)2 groups as bridges. Electrical conductivity measurements reveal that both polymers behave as semiconductors. 相似文献