全文获取类型
收费全文 | 1926篇 |
免费 | 54篇 |
国内免费 | 9篇 |
专业分类
化学 | 1458篇 |
晶体学 | 6篇 |
力学 | 40篇 |
数学 | 315篇 |
物理学 | 170篇 |
出版年
2024年 | 1篇 |
2023年 | 21篇 |
2022年 | 105篇 |
2021年 | 92篇 |
2020年 | 75篇 |
2019年 | 56篇 |
2018年 | 39篇 |
2017年 | 32篇 |
2016年 | 62篇 |
2015年 | 74篇 |
2014年 | 47篇 |
2013年 | 114篇 |
2012年 | 122篇 |
2011年 | 157篇 |
2010年 | 84篇 |
2009年 | 77篇 |
2008年 | 129篇 |
2007年 | 138篇 |
2006年 | 107篇 |
2005年 | 103篇 |
2004年 | 83篇 |
2003年 | 77篇 |
2002年 | 73篇 |
2001年 | 19篇 |
2000年 | 12篇 |
1999年 | 11篇 |
1998年 | 3篇 |
1997年 | 10篇 |
1996年 | 13篇 |
1995年 | 11篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 7篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
排序方式: 共有1989条查询结果,搜索用时 15 毫秒
71.
Pezzatini G Midili I Toti G Loglio F Innocenti M 《Analytical and bioanalytical chemistry》2004,380(4):650-657
The chlorite ion is an unavoidable by-product of the disinfection of drinking water by means of chlorine dioxide. The maximum concentration values of chlorite accepted in many countries regulations range from 0.2 to 1.0 mg L–1. A simple, inexpensive and quickly set up voltammetric procedure for the on-site determination of chlorite in drinking water networks is described. This procedure is suitable for the whole range of applications in drinking water plants. A useful cell for on-field analysis has been developed. Surface morphology and behaviour of carbon-based working electrodes have been investigated by voltammetry and atomic force microscopy (AFM). Actual samples of different types of water networks have been analysed for chlorite concentration. 相似文献
72.
Angela LaBella Francesca Leonelli Ilse DeSalve LuisaM. Migneco Rinaldo MariniBettolo 《Helvetica chimica acta》2004,87(8):2120-2124
A new preparation and the isolation and spectroscopic characterization of 1,3,3‐trimethylbicyclo[2.2.2]octan‐2,6‐dione ( 3 ), a so far elusive key intermediate in the Liu–Ralitsch total synthesis of (+)‐norpatchoulenol ((+)‐ 1a ), is described. The preparation of 3 constitutes also a formal total synthesis of (±)‐iso‐norpatchoulenol ((±)‐ 1b ), since 3 is correlated to an intermediate in the Monti and co‐workers synthesis of (±)‐ 1b . 相似文献
73.
Valensin D Luczkowski M Mancini FM Legowska A Gaggelli E Valensin G Rolka K Kozlowski H 《Dalton transactions (Cambridge, England : 2003)》2004,(9):1284-1293
Potentiometric and spectroscopic data have shown that octarepeat dimer and tetramer are much more effective ligands for Cu(II) ions than simple octapeptide. Thus, the whole N-terminal segment of prion protein due to cooperative effects, could be more effective in binding of Cu(II) than simple peptides containing a His residue. The gain of the Cu(II) binding by longer octarepeat peptides derives from the involvement of up to four imidazoles in the coordination of the first Cu(II) ion. This type of binding increases the order of the peptide structure, which allows successive metal ions for easier coordination. 相似文献
74.
Pucci V Bugamelli F Mandrioli R Ferranti A Kenndler E Raggi MA 《Biomedical chromatography : BMC》2004,18(1):37-44
An accurate and precise high-performance liquid chromatographic method using diode array detection for the determination of the novel antiepileptic, Levetiracetam, has been developed. Three clean-up procedures for the analysis of Levetiracetam in human plasma were implemented and evaluated, namely solid-phase extraction, deproteinization by addition of organic solvents and formation of insoluble salts. Adenosine was used as the internal standard for all three sample pretreatment procedures. Among the several cartridges used for solid-phase extraction, the hydrophilic-lypophilic balance (Oasis) HLB) phase provides the best extraction yield of Levetiracetam, together with high precision. With the two other clean-up procedures involving plasma deproteinization by addition of methanol or zinc sulphate, lower sensitivity and precision of the assays were obtained. However, they are cheaper and faster when compared with the solid-phase extraction procedure. 相似文献
75.
Graham SF Ruiz-Aracama A Lommen A Cannizzo FT Biolatti B Elliott CT Mooney MH 《Analytical and bioanalytical chemistry》2012,403(2):573-582
Detection of growth-promoter use in animal production systems still proves to be an analytical challenge despite years of
activity in the field. This study reports on the capability of NMR metabolomic profiling techniques to discriminate between
plasma samples obtained from cattle treated with different groups of growth-promoting hormones (dexamethasone, prednisolone,
oestradiol) based on recorded metabolite profiles. Two methods of NMR analysis were investigated—a Carr–Purcell–Meiboom–Gill
(CPMG)-pulse sequence technique and a conventional 1H NMR method using pre-extracted plasma. Using the CPMG method, 17 distinct metabolites could be identified from the spectra.
1H NMR analysis of extracted plasma facilitated identification of 23 metabolites—six more than the alternative method and all
within the aromatic region. Multivariate statistical analysis of acquired data from both forms of NMR analysis separated the
plasma metabolite profiles into distinct sample cluster sets representative of the different animal study groups. Samples
from both sets of corticosteroid-treated animals—dexamethasone and prednisolone—were found to be clustered relatively closely
and had similar alterations to identified metabolite panels. Distinctive metabolite profiles, different from those observed
within plasma from corticosteroid-treated animal plasma, were observed in oestradiol-treated animals and samples from these
animals formed a cluster spatially isolated from control animal plasma samples. These findings suggest the potential use of
NMR methodologies of plasma metabolite analysis as a high-throughput screening technique to aid detection of growth promoter
use. 相似文献
76.
Francesca Benedini Giorgio Bertolini Francesco Ferrario Angelo Motti Alberto Sala Flavio Somenzi 《Journal of heterocyclic chemistry》1995,32(1):103-107
The preparation and the physico-chemical characterization of 2H-pyrido[2,3-e]-1,3-oxazine-2,4(3H)-diones, 2H-pyrido[4,3-e]-1,3-oxazine-2,4(3H)-diones, 2H-pyrido[4,3-e]-1,3-oxazin-4(3H)-ones, 2H-thieno[2,3-e]-1,3-oxazin-4(3H)-ones and 2H-thieno[3,4-e]-1,3-oxazine-2,4(3H)-diones are reported. 相似文献
77.
Adhesives used in food packaging to glue different materials can provide several substances as potential migrants, and the identification of potential migrants and migration tests are required to assess safety in the use of adhesives. Solid-phase microextraction in headspace mode and gas chromatography coupled to mass spectrometry (HS-SPME-GC-MS) and ChemSpider and SciFinder databases were used as powerful tools to identify the potential migrants in the polyurethane (PU) adhesives and also in the individual plastic films (polyethylene terephthalate, polyamide, polypropylene, polyethylene, and polyethylene/ethyl vinyl alcohol). Migration tests were carried out by using Tenax(?) and isooctane as food simulants, and the migrants were analyzed by gas chromatography coupled to mass spectrometry. More than 63 volatile and semivolatile compounds considered as potential migrants were detected either in the adhesives or in the films. Migration tests showed two non-intentionally added substances (NIAS) coming from PU adhesives that migrated through the laminates into Tenax(?) and into isooctane. Identification of these NIAS was achieved through their mass spectra, and 1,6-dioxacyclododecane-7,12-dione and 1,4,7-trioxacyclotridecane-8,13-dione were confirmed. Caprolactam migrated into isooctane, and its origin was the external plastic film in the multilayer, demonstrating real diffusion through the multilayer structure. Comparison of the migration values between the simulants and conditions will be shown and discussed. 相似文献
78.
Fabris F De Lucchi O Nardini I Crisma M Mazzanti A Mason SA Lemée-Cailleau MH Scaramuzzo FA Zonta C 《Organic & biomolecular chemistry》2012,10(12):2464-2469
(+)-syn-Benzotriborneol forms stable complexes with one molecule of water. This is due to the ability of the host to form three hydrogen bonds with water, to act simultaneously as a hydrogen-bond acceptor and donor, and to a perfect geometrical match between the pair. We report experimental (X-ray and neutron diffraction, VT NMR, DSC, TGA) and stereochemical studies carried out to elucidate and quantify the molecular and thermodynamic aspects of this supramolecular complex. 相似文献
79.
Ikpo N Hoffmann C Dawe LN Kerton FM 《Dalton transactions (Cambridge, England : 2003)》2012,41(22):6651-6660
A series of lithium complexes were prepared from 2(N-piperazinyl-N'-methyl)-2-methylene-4-R'-6-R-phenols ([ONN](RR')) and characterized through elemental analysis, (1)H and (13)C{(1)H} NMR spectroscopy, and X-ray crystallography. Treatment of the ligands with n-butyllithium afforded {Li[ONN](RR')}(3) [R = Me, R' = (t)Bu, (1); R = R' = (t)Bu (2); R = R' = (t)Am, (3), (t)Am = C(CH(3))(2)CH(2)CH(3)], with trimetallic structures in the solid-state as shown by single-crystal X-ray diffraction. The reactivity of these complexes in the ring-opening polymerization of ε-caprolactone (ε-CL), as well as the influences of monomer concentration, monomer/Li molar ratio, polymerization temperature and time, was studied. Rates of polymerization were first order with respect to both monomer and lithium concentrations, and activation energies for the reactions were determined. MALDI-TOF MS analysis revealed that transesterification had occurred during the polymerization. 相似文献
80.
The synthesis of the methyl esters of optically pure trans and cis 4-guanidinocyclohexylglycine as rigid analogues of D-arginine methyl ester are described. 相似文献