全文获取类型
收费全文 | 8090篇 |
免费 | 323篇 |
国内免费 | 16篇 |
专业分类
化学 | 6573篇 |
晶体学 | 47篇 |
力学 | 134篇 |
数学 | 795篇 |
物理学 | 880篇 |
出版年
2023年 | 54篇 |
2022年 | 150篇 |
2021年 | 187篇 |
2020年 | 122篇 |
2019年 | 144篇 |
2018年 | 119篇 |
2017年 | 122篇 |
2016年 | 249篇 |
2015年 | 234篇 |
2014年 | 243篇 |
2013年 | 464篇 |
2012年 | 595篇 |
2011年 | 609篇 |
2010年 | 357篇 |
2009年 | 336篇 |
2008年 | 530篇 |
2007年 | 532篇 |
2006年 | 495篇 |
2005年 | 529篇 |
2004年 | 412篇 |
2003年 | 339篇 |
2002年 | 310篇 |
2001年 | 142篇 |
2000年 | 134篇 |
1999年 | 100篇 |
1998年 | 78篇 |
1997年 | 86篇 |
1996年 | 78篇 |
1995年 | 54篇 |
1994年 | 55篇 |
1993年 | 46篇 |
1992年 | 46篇 |
1991年 | 45篇 |
1990年 | 40篇 |
1989年 | 35篇 |
1988年 | 28篇 |
1987年 | 36篇 |
1986年 | 26篇 |
1985年 | 43篇 |
1984年 | 37篇 |
1983年 | 25篇 |
1982年 | 22篇 |
1981年 | 10篇 |
1980年 | 21篇 |
1979年 | 14篇 |
1978年 | 11篇 |
1977年 | 9篇 |
1976年 | 12篇 |
1975年 | 9篇 |
1974年 | 8篇 |
排序方式: 共有8429条查询结果,搜索用时 31 毫秒
81.
Sanches-Silva A Rodríguez-Bernaldo de Quirós A López-Hernández J Paseiro-Losada P 《Journal of chromatography. A》2004,1032(1-2):7-15
A reversed-phase high performance liquid chromatographic (RP-HLPC) method was compared with a gas chromatography-flame ionization detection (GC-FID) method for determining fatty acids in potato crisps. Different extraction procedures were used. Fatty acids were quantified by linear regression. Both methods presented good precision (R.S.D. < or = 5.88%) and recovery (> or = 82.31%). The precision using HPLC method was slightly better than for GC-FID method. There was good agreement between the fatty acid composition of potato crisps analysed by both methods. For most purposes the HPLC method would be better. However, when more fatty acids need to be analysed, GC is a more suitable method. 相似文献
82.
Carmen Moscoso-Pérez Purificación López-Mahía Soledad Muniategui-Lorenzo Esther Fernández-Fernández Darío Prada-Rodríguez 《Analytica chimica acta》2004,526(2):185-192
A highly sensitive and simple method, based on hydride generation and atomic fluorescence detection, has been developed for the determination of As, Bi, Sb, Se(IV) and Te(IV) in aqua regia extracts from atmospheric particulate matter samples. Atmospheric particulates matter was collected on glass fiber filters using a medium volume sampler (PM1 particulate matter). Two-level factorial designs have been used to optimise the hydride generation atomic fluorescence spectrometry (HG-AFS) procedure. The effects of several parameters affecting the hydride generation efficiency (hydrochloric acid, sodium tetrahydroborate and potassium iodide concentrations and flow rates) have been evaluated using a Plackett-Burman experimental design. In addition, parameters affecting the hydride measurement (delay, analysis and memory times) have been also investigated. The significant parameters obtained (sodium tetrahydroborate concentration, sodium tetrahydroborate flow rate and analysis time for As; hydrochloric acid concentration and sodium tetrahydroborate flow rate for Se(IV); and sodium tetrahydroborate concentration and sodium tetrahydroborate flow rate for Te(IV)) have been optimized by using 2n + star central composite design. Hydrochloric acid concentration and sodium tetrahydroborate flow rate were the significant parameters obtained for Sb and Bi determination, respectively. Using a univariate approach these parameters were optimized. The accuracy of methods have been verified by using several certified reference materials: SRM 1648 (urban particulate matter) and SRM 1649a (urban dust). Detection limits in the range of 6 × 10−3 to 0.2 ng m−3 have been achieved. The developed methods were applied to several atmospheric particulate matter samples corresponding to A Coruña city (NW Spain). 相似文献
83.
Marfisi S Rodríguez MP Alvarez G Celis MT Forgiarini A Lachaise J Salager JL 《Langmuir : the ACS journal of surfaces and colloids》2005,21(15):6712-6716
Commercial ethoxylated nonionic surfactant mixtures containing alcohol cosurfactant exhibit a three-phase behavior whose formulation strongly varies with the water/oil ratio. As a consequence, a change in water/oil ratio can result in a sequence of up to three different emulsion inversion processes, through a combination of formulation and composition effects. 相似文献
84.
Rodríguez JL Souto RM Fernández-Mérida L Pastor E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(9):2134-2142
Spectroelectrochemical studies on the reactivity of butanol isomers on Pt electrodes in perchloric acid medium led to the observation of structural effects that result from the different arrangements of atoms in the organic molecules. The use of differential electrochemical mass spectrometry (DEMS) to detect volatile products showed that all four isomers react on the electrode, though different product yields were observed for each compound. In spite of the differences in the electrochemical behaviour of the butanol isomers, a series of general processes accounts for the results obtained. The formation of strongly adsorbed residues by a dehydration process leading to the formation of a C=C bond was proposed for all isomers. Electroreduction of the adsorbates produces C(4) and C(3) alkanes, and the latter reveal the existence of a fragmentation process. The C(4) hydrocarbons can be formed by hydrogenation of these residues and by hydrogenolysis of alcohol molecules in the bulk solution which react at the electrode with adsorbed hydrogen. On the other hand, CO(2) is formed during electrooxidation of the adsorbed species. Partial-oxidation products containing a carbonyl group were detected from 0.2 M solutions of 1-butanol, isobutyl alcohol and sec-butyl alcohol. The tertiary alcohol tert-butyl alcohol only reacts in its adsorbed state. 相似文献
85.
Gutiérrez L Alzuet G Borrás J Castiñeiras A Rodríguez-Fortea A Ruiz E 《Inorganic chemistry》2001,40(13):3089-3096
New Cu(II) complexes of sulfamethazine (4-amino-N-[4,6-dimethyl-2-pyrimidinyl]benzenesulfonamide, HL) [Cu(2)(CH(3)COO)(2)(L)(2)].2dmf (1) and ([Cu(L)(2)].2H(2)O)(infinity) (2) were prepared and structurally characterized. Compound 1 crystallizes in the monoclinic system, space group P2(1)/n, with a = 8.9486(9) A, b = 15.0956(12) A, c = 16.542(3) A, beta = 105.584(15) degrees, and Z = 2. Compound 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 13.8097(8) A, b = 14.5765(4) A, c = 13.7853(15) A, beta = 96.033(9) degrees, and Z = 1. In compound 1 two copper ions are linked by two syn-syn acetates and two nonlinear NCN bridging groups pertaining to the deprotonated sulfamethazine ligands. Each copper center presents a nearly square planar geometry. Magnetic susceptibility data for 1 show a strong antiferromagnetic coupling with 2J = -216.7 cm(-)(1). The EPR spectra at the X- and Q-band frequencies present the signals corresponding to the dinuclear entity, being the zero-field splitting parameter, D = 0.265 cm(-)(1). The antiferromagnetic exchange coupling is discussed using DFT calculations on some model compounds with NCN bridging ligands and also on model structures with mixed mu-acetato and NCN bridges. The copper in the polymeric compound 2 is five coordinate. The CuN(5) chromophore has a highly distorted square pyramidal geometry with small axial N-Cu-N angles of 65.53(14) and 59.90(13) degrees. In the structure a sulfamethazinate anion binds to one copper through the sulfonamido and pyrimidine N atoms and to an adjacent copper via the amino N atom. 相似文献
86.
Margarita Valero Brígida Esteban Rafael Peläez Licesio J. Rodrïguez 《Journal of inclusion phenomena and macrocyclic chemistry》2004,48(3-4):157-163
The aim of the present study was to investigate the effect of the presence of thewater-soluble polymer polyvinylpyrrolidone (PVP) MW = 24000 g/mol, on thecomplexation of the phototoxic anti-inflammatory drug naproxen, in its sodiumsalt form, with hydroxypropil-β-cyclodextrin (HP-β-CD). The datashown that the polymer interacts with the free naproxen and with thenaproxen:HP-β-CD inclusion complex. The presence of different proportions of PVP, in the 0–1%(w/w) rangesystematically increased the Kapp of the naproxen:HP-β-CD inclusioncomplex formation. The cause of this increase is that the polymer interactswith the HP-β-CD with a binding constant of K2 = 29000 ± 53 M-1; and with the naproxen:HP-β-CD inclusion complex, to givea ternary complex naproxen:HP-β-CD:PVP. The binding constant of thisprocess was K3 = 5350 ± 1 M-1. NMR data revealed that in the ternary system, PVP is outside of the cyclodextrin, and therefore must be wholly or partially recovering the naproxen:HP-β-CD inclusion complex. 相似文献
87.
Volonterio A Bellosta S Bravin F Bellucci MC Bruché L Colombo G Malpezzi L Mazzini S Meille SV Meli M Ramírez De Arellano C Zanda M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4510-4522
Partially modified retro- (PMR) and retro-inverso (PMRI) psi[NHCH(CF(3))]Gly peptides, a conceptually new class of peptidomimetics, have been synthesized in wide structural diversity and variable length by aza-Michael reaction of enantiomerically pure alpha-amino esters and peptides with enantiomerically and geometrically pure N-4,4,4-trifluorocrotonoyl-oxazolidin-2-ones. The factors underlying the observed moderate to good diastereocontrol have been investigated. The conformations of model PMR-psi[NHCH(CF(3))]Gly tripeptides have been studied in solution by (1)H NMR spectroscopy supported by MD calculations, as well as in the solid-state by X-ray diffraction. Remarkable stability of turn-like conformations, comparable to that of parent malonyl-based retropeptides, was evidenced, as a likely consequence of two main factors: 1) severe torsional restrictions about sp(3) bonds in the [CO-CH(2)-CH(CF(3))-NH-CH(R)-CO] module, which is biased by the stereoelectronically demanding CF(3) group and the R side chain; 2) formation of nine-membered intramolecularly hydrogen-bonded rings, which have been clearly detected both in CHCl(3) solution and in some crystal structures. The former factor seems to be more important, as turn-like conformations were found in the solid-state even in the absence of intramolecular hydrogen bonding. The relative configuration of the -C*H(CF(3))NHC*H(R)- stereogenic centers has a major effect on the stability of the turn-like conformation, which seems to require a syn stereochemistry. X-ray diffraction and ab initio computational studies showed that the [-CH(CF(3))NH-] group can be seen as a sort of hybrid between a peptide bond mimic and a proteolytic transition state analogue, as it combines some of the properties of a peptidyl -CONH- group (low NH basicity, CH(CF(3))-NH-CH backbone angle close to 120 degrees, C-CF(3) bond substantially isopolar with the C=O) with some others of the tetrahedral intermediate [-C(OX)(O(-))NH-] involved in the protease-mediated hydrolysis reaction of a peptide bond (high electron density on the CF(3) group, tetrahedral backbone carbon). 相似文献
88.
Reaction conditions and structure of the starting enamines (cyclic or open-chain) determine greatly the final products of the title reactions. Whereas in benzene and acetonitrile, DMAD and 1 give a mixture of the diastereoisomeric dienamines 5, in methanol they afford pirrolizine 3. Enaminofuranones 2 and 10 furnish the corresponding “Michael adducts” 7a,b,c and 11a,b,c but fail to yield pirrolizines. It has been demonstrated that above b and c adducts differ exclusively on the arrangement of groups around a chiral axis. 相似文献
89.
Aránzazu Espina Enrique Jaimez Sergei A. Khainakov Camino Trobajo José R. García Julio Rodríguez 《Journal of inclusion phenomena and macrocyclic chemistry》1998,30(4):333-352
The intercalation of some amines (aniline, benzylamine, cyclohexylamine,piperidine, pyridine, pyrazine and piperazine) into -titaniumphosphate, Ti(HPO4)2×H2O,has been investigated by the batch method and/or by exposing the host to thevapour of the amines. The changes in the interlayer distance of the solidduring the intercalation process was followed by X-ray powder diffraction.The new intercalates were characterised by chemical and thermal analysis.Materials with a monolaminar and/or bilaminar arrangement of amine moleculesin the phosphate interlayer region are obtained depending on the nature ofthe amine. Due to steric hindrance, saturated phases are not obtained forall amines studied. The thermal decomposition of the intercalates (nitrogenatmosphere), takes place in three stages: dehydration, removal of amines andcondensation of the hydrogenphosphate to pyrophosphate groups. 相似文献
90.
A new family of polyoxygenated stilbenophanes has been synthesized as conformationally restricted analogues of antimitotic combretastatins. By means of the McMurry olefination process, compounds derived from diethyleneglycol and 1,6-hexanediol were obtained, whereas Grubbs' catalyst failed in producing the ring-closing metathesis to this kind of macrocyclic products. 相似文献