全文获取类型
收费全文 | 1069篇 |
免费 | 55篇 |
国内免费 | 2篇 |
专业分类
化学 | 935篇 |
晶体学 | 5篇 |
力学 | 15篇 |
数学 | 78篇 |
物理学 | 93篇 |
出版年
2023年 | 9篇 |
2022年 | 25篇 |
2021年 | 36篇 |
2020年 | 25篇 |
2019年 | 18篇 |
2018年 | 11篇 |
2017年 | 9篇 |
2016年 | 37篇 |
2015年 | 39篇 |
2014年 | 43篇 |
2013年 | 60篇 |
2012年 | 71篇 |
2011年 | 105篇 |
2010年 | 61篇 |
2009年 | 48篇 |
2008年 | 77篇 |
2007年 | 65篇 |
2006年 | 64篇 |
2005年 | 60篇 |
2004年 | 65篇 |
2003年 | 57篇 |
2002年 | 38篇 |
2001年 | 14篇 |
2000年 | 10篇 |
1999年 | 8篇 |
1998年 | 8篇 |
1997年 | 17篇 |
1996年 | 15篇 |
1995年 | 6篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1988年 | 2篇 |
1985年 | 2篇 |
1981年 | 1篇 |
1978年 | 1篇 |
1939年 | 2篇 |
1934年 | 1篇 |
1933年 | 3篇 |
1928年 | 1篇 |
排序方式: 共有1126条查询结果,搜索用时 15 毫秒
41.
Bérangère C Caussarieu N Morin P Morin-Allory L Lafosse M 《Journal of separation science》2004,27(12):964-970
An original system which uses Porous Graphitic Carbon as support and a mixture of organic solvents as mobile phase is proposed for the analysis of triterpenic acids by liquid chromatography. The separation of betulinic acid, ursolic acid, oleanolic acid, and 18alpha- and 18beta-glycyrrhetinic acids was carried out within a short time and monitored by evaporative light scattering detection as universal detection method. Molecular modelling studies show that the main contribution to the selectivity comes from the electrostatic interaction characterised by the dipole moment of the products. 相似文献
42.
Mondon M Fontelle N Désiré J Lecornué F Guillard J Marrot J Blériot Y 《Organic letters》2012,14(3):870-873
A flexible synthetic access to six-membered L- and D-iminosugar C-glycosides is reported starting from the easily available 6-azido-6-deoxy-2,3,4-tri-O-benzyl-D-glucopyranose precursor. This methodology involves a highly diastereoselective tandem ring enlargement/alkylation and a stereocontrolled ring contraction. It allows an efficient synthesis of iminosugar C-glycosides displaying structural diversity at both C-1 and C-6. 相似文献
43.
44.
45.
Nawel Cheikh Didier Villemin Nathalie Bar Jean-François Lohier Nourredine Choukchou-Braham Bachir Mostefa-Kara Jana Sopkova 《Tetrahedron》2013,69(3):1234-1247
In the course of our studies on Cerpegin analogues synthesis, a serendipitous reactivity of enaminolactone nitrile has been observed. Instead of expecting iminocerpegins, we have gained new class of substituted 2-aminopyridines. The methodology has been applied on a wide range of primary amines, as aliphatic, aromatic, heteroaromatic and also, diamines, hydrazines and chiral amines. 相似文献
46.
Sophie Danappe Fabien Boeda Christian Alexandre Anne‐Marie Aubertin Nathalie Bourgougnon 《合成通讯》2013,43(21):3225-3239
Synthesis of eight nucleoside analogues 4–11 with a methylenecyclobutane unit is described. Wittig reaction with 2‐hydroxymethylcyclobutanone 12 gave a mixture of Z (13) and E (14) derivatives, which was separated before functional modifications. The heterocyclic moieties were introduced via a Mitsunobu reaction either on the saturated chain or on the unsaturated chain. When adenine was used in this reaction, only the N‐9 substitution products were obtained. Removal of the protecting groups provided the target products. 相似文献
47.
Alain Valla Nathalie Méheux Dominique Cartier Benoist Valla Laurent Dufossé 《合成通讯》2013,43(2):184-190
A synthesis of a new C-15 phosphorus ylide from a C-14 enaminone is reported. This reagent, which undergoes selective 1,2- or 1,4-additions with saturated and unsaturated aldehydes, may find some synthetic use for the preparation of β-end-group retinoid derivatives. 相似文献
48.
a four-step synthesis of monoalkylated benzidin is reported for immunogen preparation against benzidin dye. Use of 10% H2SO4/ dioxan for N-Boc cleavage avoids the cyclisation of 4-benzidinyl butyric acid into the corresponding lactam observed with the classical TFA/ CH2Cl2 system. 相似文献
49.
Zhang Y Mao J Godbout N Oldfield E 《Journal of the American Chemical Society》2002,124(46):13921-13930
We report the results of a series of density functional theory (DFT) calculations aimed at predicting the (57)Fe M?ssbauer electric field gradient (EFG) tensors (quadrupole splittings and asymmetry parameters) and their orientations in S = 0, (1)/(2), 1, (3)/(2), 2, and (5)/(2) metalloproteins and/or model systems. Excellent results were found by using a Wachter's all electron basis set for iron, 6-311G for other heavy atoms, and 6-31G for hydrogen atoms, BPW91 and B3LYP exchange-correlation functionals, and spin-unrestricted methods for the paramagnetic systems. For the theory versus experiment correlation, we found R(2) = 0.975, slope = 0.99, intercept = -0.08 mm sec(-)(1), rmsd = 0.30 mm sec(-)(1) (N = 23 points) covering a DeltaE(Q) range of 5.63 mm s(-)(1) when using the BPW91 functional and R(2) = 0.978, slope = 1.12, intercept = -0.26 mm sec(-)(1), rmsd = 0.31 mm sec(-)(1) when using the B3LYP functional. DeltaE(Q) values in the following systems were successfully predicted: (1) ferric low-spin (S = (1)/(2)) systems, including one iron porphyrin with the usual (d(xy))(2)(d(xz)d(yz))(3) electronic configuration and two iron porphyrins with the more unusual (d(xz)d(yz))(4)(d(xy))(1) electronic configuration; (2) ferrous NO-heme model compounds (S = (1)/(2)); (3) ferrous intermediate spin (S = 1) tetraphenylporphinato iron(II); (4) a ferric intermediate spin (S = (3)/(2)) iron porphyrin; (5) ferrous high-spin (S = 2) deoxymyoglobin and deoxyhemoglobin; and (6) ferric high spin (S = (5)/(2)) metmyoglobin plus two five-coordinate and one six-coordinate iron porphyrins. In addition, seven diamagnetic (S = 0, d(6) and d(8)) systems studied previously were reinvestigated using the same functionals and basis set scheme as used for the paramagnetic systems. All computed asymmetry parameters were found to be in good agreement with the available experimental data as were the electric field gradient tensor orientations. In addition, we investigated the electronic structures of several systems, including the (d(xy))(2)(d(xz),d(yz))(3) and (d(xz),d(yz))(4)(d(xy))(1) [Fe(III)/porphyrinate](+) cations as well as the NO adduct of Fe(II)(octaethylporphinate), where interesting information on the spin density distributions can be readily obtained from the computed wave functions. 相似文献
50.
Lancelot N Elbayed K Raya J Piotto M Briand JP Formaggio F Toniolo C Bianco A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(6):1317-1323
A tetra- and a hepta-homopeptide from the C(alpha)-tetrasubstituted Aib (alpha-aminoisobutyric acid) residue were covalently linked to the POEPOP resin by the fragment-condensation approach. The conformational preferences of the two model peptides were determined for the first time on a solid support by means of high-resolution magic angle spinning NMR spectroscopy. The results obtained indicate that the Aib homopeptides adopt a regular 3(10)-helical structure even when they are covalently bound to a polymeric matrix, and thus confirm the remarkable conformational stability of the peptides rich in this amino acid. An ATR-FTIR spectroscopic investigation, performed in parallel, also confirmed that these polymer-bound peptides do indeed adopt a helical conformation. The results of this study open the possibility to exploit the peptide-resin conjugates based on C(alpha)-tetrasubstituted alpha-amino acids as helpful, structurally organized templates in molecular recognition studies or as catalysts in asymmetric synthesis. 相似文献