全文获取类型
收费全文 | 1088篇 |
免费 | 52篇 |
国内免费 | 5篇 |
专业分类
化学 | 895篇 |
力学 | 19篇 |
数学 | 86篇 |
物理学 | 145篇 |
出版年
2024年 | 2篇 |
2023年 | 14篇 |
2022年 | 39篇 |
2021年 | 80篇 |
2020年 | 31篇 |
2019年 | 37篇 |
2018年 | 17篇 |
2017年 | 16篇 |
2016年 | 41篇 |
2015年 | 40篇 |
2014年 | 41篇 |
2013年 | 51篇 |
2012年 | 77篇 |
2011年 | 91篇 |
2010年 | 60篇 |
2009年 | 52篇 |
2008年 | 77篇 |
2007年 | 82篇 |
2006年 | 48篇 |
2005年 | 61篇 |
2004年 | 50篇 |
2003年 | 29篇 |
2002年 | 29篇 |
2001年 | 10篇 |
2000年 | 4篇 |
1999年 | 5篇 |
1998年 | 3篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1995年 | 1篇 |
1994年 | 9篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 6篇 |
1990年 | 2篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 3篇 |
1973年 | 1篇 |
排序方式: 共有1145条查询结果,搜索用时 31 毫秒
171.
Jaroslav Mosná?ek Monica Bertoldo Chiara Cappelli Ivan Luká? 《Polymer Degradation and Stability》2007,92(5):849-858
Various diazo-compounds, 1,2,2,6,6-pentamethylpiperidin-4-yl diazoacetate (PMPDA), 2,2,6,6-tetramethylpiperidin-4-yl diazoacetate (TMPDA), methyl diazoacetate (MDA), 1,2,2,6,6-pentamethylpiperidin-4-yl 2-diazo-3-methyloxycarbonylpropionate (PMPMDS), 1,2,2,6,6-pentamethylpiperidin-4-yl 2-diazo-4-methyloxycarbonylbutanoate (PMPMDP), and one azide, methyl azidocarboxylate (MAC), were successfully prepared and grafted on polyethylene films by UV light (λ > 210 nm) activation. The treated films were characterised by FT-IR spectroscopy and contact angle measurements. Ab-initio quantum mechanical calculations allowed simulating the IR absorption spectra of the polymer grafted species. These last and the related grafting yields are discussed with reference to the diazo-compound structure and concentration. Up to 8.6 mol% of bonded groups (grafted groups/ethylene monomeric unit) were found without affecting the polymer molecular weight distribution, as shown by GPC analysis. All modified films bearing HAS groups showed very high photo-stability. 相似文献
172.
Zoccatelli G Dalla Pellegrina C Mosconi S Consolini M Veneri G Chignola R Peruffo A Rizzi C 《Electrophoresis》2007,28(3):460-466
Wheat proteinaceous alpha-amylase inhibitors (alpha-AIs) are increasingly investigated for their agronomical role as natural defence molecules of plants against the attack of insects and pests, but also for their effects on human health. The wheat genomes code for several bioactive alpha-AIs that share sequence homology, but differ in their specificity against alpha-amylases from different species and for their aggregation states. Wheat alpha-AIs are traditionally classified as belonging to the three classes of tetrameric, homodimeric and monomeric forms, each class being constituted by a number of polypeptides that display different electrophoretic mobilities. Here we describe a proteomic approach for the identification of bioactive alpha-AIs from wheat and, in particular, a 3-D technique that allows to best identify and characterize the dimeric fraction. The technique takes advantage of the thermal resistance of alpha-AIs (resistant to T > 70 degrees C) and consists in the separation of protein mixtures by 2-D polyacrylamide/starch electrophoresis under nondissociating PAGE (ND-PAGE, first dimension) and dissociating (urea-PAGE or U-PAGE second dimension) conditions, followed by in-gel spontaneous reaggregation of protein complexes and identification of the alpha-amylase inhibitory activity (antizymogram, third dimension) using enzymes from human salivary glands and from the larvae of Tenebrio molitor coleopter (yellow mealworm). Dimeric alpha-AIs from Triticum aestivum (bread wheat) were observed to exist as heterodimers. The formation of heterodimeric complexes was also confirmed by in vitro reaggregation assays carried out on RP-HPLC purified wheat dimeric alpha-AIs, and their bioactivity assayed by antizymogram analysis. The present 3-D analytical technique can be exploited for fast, full-fledged identification and characterization of wheat alpha-AIs. 相似文献
173.
Frazzoli C Dragone R Mantovani A Massimi C Campanella L 《Analytical and bioanalytical chemistry》2007,389(7-8):2185-2194
Toxicological implications of exposure to bioavailable platinum group metals, here Pd, Pt, and Rh, are still to be clarified.
This study obtained by a biosensor-based method preliminary information on potential effects on cellular metabolism as well
as on possible tolerance mechanisms. Aerobic respiration was taken as the toxicological end point to perform tandem tests,
namely functional toxicity test and tolerance test. Cells were suspended in the absence of essential constituents for growth.
The dose–response curves obtained by exposure (2 h) to the metals (nanogram per gram range) suggested the same mechanisms
of action, with Rh showing the greatest curve steepness and the lowest EC50 value. Conservative (95% lower confidence interval) EC10 values were 187, 85 and 51 ng g−1 for Pt, Pd, and Rh respectively. Tolerance patterns were tested during the same runs. The full tolerance obtained after 12 h
of exposure to each metal suggested mitochondrial inhibition of aerobic respiration as a target effect. The hazard rating
of the metals in the tolerance test changed in the Rh EC50 range, where Rh showed the lowest toxicity. The observed tolerance might suggest a protective mechanism such as metallothionein
induction at concentrations around the EC50 values. The performance of the bioassay was satisfactory, in terms of the limit of detection, repeatability, reproducibility,
roboustness, sensibility, and stability; the method’s critical uncertainty sources were identified for improvements.
Figure Respirometric curved 相似文献
174.
Cavaliere C Foglia P Guarino C Nazzari M Samperi R Laganà A 《Rapid communications in mass spectrometry : RCM》2007,21(4):550-556
A liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) method for measurement of aflatoxins B1, B2, G1, and G2 in maize is described. Aflatoxins (AFs) were extracted from 1 g samples by using tri-portions of acetonitrile/water (80:20, v/v) (10 + 7 + 7 mL), and 2/5 of the extract diluted to 500 mL by water was cleaned up with a 100 mg Carbograph-4 cartridge. After the addition of the internal standard AFM1, the final extract was analyzed by LC/ESI-MS/MS in positive ion mode using multiple reaction monitoring with a triple-quadrupole instrument. A C(18) column thermostatted at 45 degrees C with a mobile phase gradient of acetonitrile/water with 2 mmol/L ammonium formate was used. Although the matrix suppression effect was negligible, quantitation was achieved by an external calibration procedure using matrix-matched standard solutions to improve accuracy. Sample recoveries at four spiking levels ranged from 81 to 101% (relative standard deviation (RSD) =12%), and the method quantification limit ranged from 0.1 to 0.6 microg/kg. This method is sensitive, accurate and selective, and can thus be applied as a confirmatory procedure in establishing non-compliance with EU permitted maximum levels (2 microg/kg for aflatoxin B1 and 4 microg/kg for total AFs in corn products). This work also includes an application to samples obtained from retail markets and from experimental trial fields. Of the 48 samples, 15 were found to be contaminated with AFs and, of these, 5 did not comply with European Union legislation (AFB1 =2 microg/kg). 相似文献
175.
Seraglia R Molin L Tonidandel L Pucciarelli S Agostini M Urso ED Bedin C Quaia M Nitti D Traldi P 《Journal of mass spectrometry : JMS》2007,42(12):1606-1612
In an investigation devoted to the search for plasma markers for colorectal cancer (CRC), carried out by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry, a series of overexpressed peptides were identified in the plasma of patients. Among them the peptide with molecular weight 903 Da was the most abundant one, with a mean +/- (SD) relative abundance of 37 +/- 17% and a frequency over 60%. Interestingly, also in plasma samples of ten subjects affected by familial adenomatous polyposis (FAP), the peptide with molecular weight 903 was overexpressed. In this investigation, MALDI/MS/MS experiments were carried out on the ion at m/z 904 detected in the MALDI mass spectra of CRC and FAP patients. The data analysis by SwissProt.2007.01.09 indicates that this peptide is due to the sequence RPPGFSPF, found in the kininogen-1 precursor, which is an alpha-2-thiol proteinase inhibitor. In the case of subjects affected by a particular FAP syndrome, the MALDI/MS/MS spectra were quite different from those obtained from CRC and FAP patients. In fact, two sequences have been evidenced: RPPGFSPF belonging to kininogen-1 precursor, and PRKSSSSR belonging to Forkhead box protein 01A. 相似文献
176.
Bacaloni A Cavaliere C Foglia P Nazzari M Samperi R Laganà A 《Rapid communications in mass spectrometry : RCM》2007,21(7):1123-1130
A liquid chromatography/electrospray ionization tandem mass spectrometric method for analyzing organophophorus flame retardants and plasticizers in drinking and environmental waters was developed. Five alkyl phosphates, three chlorinated alkyl phosphates, two aryl phosphate and triphenylphosphine oxide were selected for this study. These compounds were extracted from water samples by a hydrophilic polymeric solid-phase extraction cartridge. Accuracy and precision were evaluated analyzing 0.5 L of water samples spiked at concentrations of 10 and 100 ng/L for drinking water and at 300 and 1000 ng/L for river water. Except for trimethyl phosphate, analyte recoveries were better than 80%, and were not dependent on the type of aqueous matrix in which they were dissolved. At the spike levels considered, within-day precision was between 3 and 12% for tap water and between 4 and 14% for river water, and estimated method quantification limits ranged from 0.2 to 3.9 ng/L. A short survey conducted by analyzing some river water samples (River Tiber) ascertained the presence of ten organophosphorus compounds at concentration levels ranging from a few nanograms per liter to 323 ng/L for tris(2-butoxyethyl) phosphate. 相似文献
177.
Stefania?Gaudino Chiara?Galas Maria?Belli Sabrina?Barbizzi Paolo?de?Zorzi Radojko?Ja?imovi? Zvonka?Jeran Alessandra?Pati Umberto?SansoneEmail author 《Accreditation and quality assurance》2007,12(2):84-93
The measurement of trace-element concentration in soil, sediment and waste, is generally a combination of a digestion procedure
for dissolution of elements and a subsequent measurement of the dissolved elements. “Partial” and “total” digestion methods
can be used in environmental monitoring activities. To compare measurement results obtained by different methods, it is crucial
to determine and to maintain control of the bias of the results obtained by these methods. In this paper, ICP-MS results obtained
after matrix digestion with modified aqua regia (HCl+HNO3+H2O2) method and two “total” digestion methods (microwave aqua regia+HF and HNO3+HF) are compared with those obtained by instrumental neutron activation analysis, a non-destructive analytical method for
the determination of the total mass concentrations of inorganic components in environmental matrices. The comparison was carried
out on eight agricultural soil samples collected in one test area and measured by k0-INAA and ICP-MS to determine As, Co, Cr, Sb and Zn mass concentration. The bias of results for As, Cd, Co, Cr, Cu, Ni, Pb,
Sb and Zn of the three digestion methods were assessed using selected measurement standards. This paper highlights that the
digestion procedure is an integral part of the measurement and can affect the measurement result in environmental analysis. 相似文献
178.
Costa JS Balde C Carbonera C Denux D Wattiaux A Desplanches C Ader JP Gütlich P Létard JF 《Inorganic chemistry》2007,46(10):4114-4119
A comprehensive study of the photomagnetic behavior of the [Fe(L222N5)(CN)2].H2O complex has been carried out. This complex is characterized by a low-spin (LS) iron(II)-metal center up to 400 K and exhibits at 10 K the well-known Light-Induced Excited Spin State Trapping (LIESST) effect. The critical LIESST temperature (T(LIESST)) has been measured to be 105 K. The kinetics of the transition from the metastable high-spin (HS) state to the low-spin state have been determined and used for reproducing the experimental T(LIESST) curve. This study represents a second example of a fully low-spin iron(II)-metal complex up to 400 K, which can be photoexcited at low temperature with an atypical long-lived metastable HS state. This underlines the preponderant role of the inner coordination sphere for stabilizing the lifetime of the photoinduced HS state. 相似文献
179.
Song YF van Albada GA Tang J Mutikainen I Turpeinen U Massera C Roubeau O Costa JS Gamez P Reedijk J 《Inorganic chemistry》2007,46(12):4944-4950
The very unusual case of copper-mediated chlorination of phenol rings under mild conditions at room temperature is reported. Reaction of the ligand 1,7-bis(2-hydroxyphenyl)-2,6-diaza-4-hydroxylheptane (H3L1) with CuCl2 in acetonitrile leads to either the formation of a tetranuclear copper(II) complex [Cu4(HL3)2(mu-Cl)2Cl2](CH3CN) (1) or a linear trinuclear complex [Cu3(HL1)2Cl2(CH3CN)2](CH3CN)2 (2), depending on the reaction conditions. Both compounds have been fully characterized, including the determination of their 3D structures by X-ray diffraction. The unprecedented tetranuclear compound 1 is constituted of a dichlorido-bridged dimer of di-mu-phenoxido-dinuclear species, whereas the trinuclear complex 2 presents a linear array of copper(II) ions, held together through di-mu-phenoxido bridges of the central and external ions. The magnetic susceptibility of the two compounds was investigated, revealing either very strong (J<-500 cm-1) or strong (J value around -370(1) cm-1) antiferromagnetic dominant interactions among the CuII ions for 1 and 2, respectively. The tetranuclear complex 1 is obtained, under dry conditions, through the in situ formation of ligand HL3 (H3L3=1,7-bis(2-hydroxy-5-chlorophenyl)-2,6-diaza-4-hydroxylheptane) by oxidative chlorination of (HL1)2-. In the presence of traces of water, 1 is partially hydroxylated at the ortho position of one of the phenyl rings. The use of trimethylorthoformate as the dehydrating agent prevents the formation of hydroxylated ligands. Several partly chlorinated/hydroxylated products (identified as H3L2) have also been obtained through slight variations of the synthetic procedures (presence or absence of water and/or triethylamine in the reaction mixtures). These partially chlorinated and/or hydroxylated coordination species are mutually isomorphous to either 1 or 2. Several "modified" ligands have been isolated and characterized by 1H NMR and MS, after reaction with sodium sulfide of the complexes formed. 相似文献
180.
Cavaliere C Foglia P Guarino C Nazzari M Samperi R Laganà A 《Analytica chimica acta》2007,596(1):141-148
A liquid chromatography-tandem mass spectrometric with electrospray ionization (LC/ESI-MS/MS) method for determining the four naturally occurring aflatoxins (AFs) B1, B2, G1, and G2 in olive oil is proposed. AFs were extracted from oil sample by means of matrix solid phase dispersion (MSPDE), utilizing C18 as dispersing material. No further purification step, such as lipid removal, was performed. Aflatoxin M1, the hepatic metabolite of AFB1, was employed as internal standard. Olive oil extract was analyzed by LC/ESI-MS/MS in positive ionization mode, with multireaction monitoring acquisition. Due to a signal suppression ranging between 4 and 23%, quantitation was performed by matrix-matched calibration curves. The regression line coefficients of determination were above 0.9991. Sample recoveries ranged from 92 to 107%, with relative standard deviations below 13% for spiking levels between 0.5 and 5 ng g−1; method quantification limits ranged between 0.04 and 0.12 ng g−1. The developed LC/ESI-MS/MS method, although not as sensitive as LC coupled to fluorescence detection, is rapid, selective, accurate and precise, thus it can be used as confirmatory assay. The MSPDE appears suitable for application to other oleaginous matrices and for multiresidue investigation. 相似文献