首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1950篇
  免费   158篇
  国内免费   233篇
  2023年   32篇
  2022年   42篇
  2021年   55篇
  2020年   60篇
  2019年   91篇
  2018年   72篇
  2017年   84篇
  2016年   65篇
  2015年   82篇
  2014年   80篇
  2013年   183篇
  2012年   80篇
  2011年   78篇
  2010年   67篇
  2009年   109篇
  2008年   105篇
  2007年   125篇
  2006年   102篇
  2005年   97篇
  2004年   64篇
  2003年   74篇
  2002年   61篇
  2001年   46篇
  2000年   45篇
  1999年   50篇
  1998年   34篇
  1997年   29篇
  1996年   24篇
  1995年   20篇
  1994年   18篇
  1993年   23篇
  1992年   25篇
  1991年   29篇
  1990年   21篇
  1989年   8篇
  1988年   13篇
  1987年   10篇
  1986年   12篇
  1985年   15篇
  1984年   19篇
  1983年   13篇
  1982年   18篇
  1981年   6篇
  1980年   9篇
  1979年   13篇
  1978年   7篇
  1977年   4篇
  1976年   5篇
  1975年   5篇
  1974年   3篇
排序方式: 共有2341条查询结果,搜索用时 856 毫秒
71.
Water-soluble corn silk polysaccharides (CSPS) were chemically modified to obtain their sulfated, acetylated and carboxymethylated derivatives. Chemical characterization and bioactivities of CSPS and its derivatives were comparatively investigated by chemical methods, gas chromatography, gel filtration chromatography, scanning electron microscope, infrared spectroscopy and circular dichroism spectroscopy, scavenging DPPH free radical assay, scavenging hydroxyl radical assay, ferric reducing power assay, lipid peroxidation inhibition assay and α-amylase activity inhibitory assay, respectively. Among the three derivatives, carboxylmethylated polysaccharide (C-CSPS) demonstrated higher solubility, narrower molecular weight distribution, lower intrinsic viscosity, a hyperbranched conformation, significantly higher antioxidant and α-amylase inhibitory abilities compared with the native polysaccharide and other derivatives. C-CSPS might be used as a novel nutraceutical agent for human consumption.  相似文献   
72.
73.
Phenylethanolamine N-methyltransferase (PNMT) catalyzes the conversion of norepinephrine (noradrenaline) to epinephrine (adrenaline) while, concomitantly, S-adenosyl-l-methionine (AdoMet) is converted to S-adenosyl-l-homocysteine. This reaction represents the terminal step in catecholamine biosynthesis and inhibitors of PNMT have been investigated, inter alia, as potential antihypertensive agents. At various times the kinetic mechanism of PNMT has been reported to operate by a random mechanism, an ordered mechanism in which norepinephrine binds first, and an ordered mechanism in which AdoMet binds first. Here we report the results of initial velocity studies on human PNMT in the absence and presence of product and dead end inhibitors. These, coupled with isothermal titration calorimetry and fluorescence binding experiments, clearly shown that hPNMT operates by an ordered sequential mechanism in which AdoMet binds first. Although the log V pH-profile was not well defined, plots of log V/K versus pH for AdoMet and phenylethanolamine, as well as the pKi versus pH for the inhibitor, SK&F 29661, were all bell-shaped indicating that a protonated and an unprotonated group are required for catalysis.  相似文献   
74.
A multiple-bile-ion-sensing polyvinyl chloride-based membrane electrode capable of monitoring any of the three common bile ions in humans, namely, cholate, deoxycholate, and chenodeoxycholate, was developed and characterized. Compared to single-bile-ion-sensing electrodes, it showed a sub-Nernstian response. All other electrode properties were, however, similar, making this a successful replacement for three individual electrodes. With appropriate conditioning, this electrode could repeatedly change selectivity without losing membrane activity. It was reproducible, was stable for 5 months, had low response time, and could be used to measure critical micelle concentrations. The lower limit of detection was 10 nM. Selectivity coefficients for various anions with respect to bile ions more or less followed the Hoffmeister series. Plots of R ((Nernst equivalent of slope in the presence of primary ion and a fixed amount of interfering ion)/(slope in the presence of only the primary ion)) vs square root of ionic strength for an interfering ion were linear. One major application of this electrode is its use in kinetics. We have tested its ability to monitor continuously changing bile ion concentrations during their interactions with a biocompatible polymer, polyethylene glycol (6000), and determined rate constants.  相似文献   
75.
Abstract

Metal fractionation is a powerful tool for studying the mobility, bioavailability and toxicity of metals in sediments and soils. A seven-step sequential extraction technique was used to determine the potential mobility of selected heavy metals (Fe, Mn, Zn, Cu, Pb, Cd and Ni) in the sediments of Lake Naivasha. Results indicate that residual fraction was the most important phase for the elements Fe, Mn, Cu and Zn. However, Pb and Cd are highly enriched in the non-residual phases. Nickel on the other hand was distributed evenly between the non-residual and the residual fractions.

The total concentrations of the heavy metals suggested a decreasing order of iron ?> manganese ? zinc > nickel > copper ? lead > cadmium. However, the detailed sequential extraction data indicated an order of release or mobility of cadmium > lead ? nickel ? zinc > manganese > copper > iron. The high percentage of Cd and Pb in the mobile fractions suggests high bioavailability of these two elements in the study area and maybe a pointer to anthropogenic input of the two elements in the study area.  相似文献   
76.
Abstract

A five-step sequential extraction procedure was applied to organic-rich soil samples from five soil profiles situated 1–8 km from a zinc smelter. The partitioning of Zn, Cd, Pb, and Cu into five operationally defined fractions (exchangeable, “carbonate’’-bound, reducible, oxidizable, and residual) was studied at different soil depths down to 35cm. In the surface soil (0–1 cm) a major part of Pb and Cu was extracted in the oxidizable fraction, whereas for Zn and Cd slightly more was extracted in the ‘‘carbonate”-fraction than in the other four fractions. Extracted metal proportions in the oxidizable fraction were respectively of the order of 30%, 20%, 50%, and 80% for Zn, Cd, Pb, and Cu in the surface soil for all sites, but these proportions decreased with soil depth. In the surface soil less than 20% of all the elements were extracted in the residual fraction, but the proportions associated with this fraction generally increased with soil depth. In the C-horizon, differences in extracted proportions of Pb and Cu in the residual fraction were probably due to geochemical factors, whereas for Zn the low extracted proportion at a highly contaminated site (20%) may be due to Zn migration to the C-horizon at this site. For Cd the extracted proportions in the C-horizon were lower than for the other elements, generally below 20%, presumably because Cd is weaker in terms of its adsorption to the soil than the other elements studied. Total concentrations of the metals decreased strongly with increasing distance from the smelter, but less systematic differences were observed for their distributions among fractions. Potentially bioavailable metal proportions (exchangeable + “carbonate”-bound fraction) in the surface soil were about 50%, 60%, 20%, and 10% for Zn, Cd, Pb, and Cu, respectively. In C-horizon soil the mobility sequence Cd>Zn>Pb = Cu was generally observed. The present results indicate that the concentrations and chemical fractionation of Zn, Pb, and Cd in these soils represent a considerable risk to natural terrestrial food chains.  相似文献   
77.
Abstract

Selected heavy metals Fe, Cd, Ni and Cr were studied in contaminated soil samples collected from south-eastern Nigeria. Geochemical differentiation into different chemical fractions, using Ma and Rao six-step sequential chemical extraction procedure, was carried out to assess the potential mobility and bioavailability of the heavy metals in the soil profiles. The residual fraction was the most important phase for the four heavy metals with the following average percentage values 74.43 for Fe, 37.69 for Cd, 70.11 for Ni and 62.47 for Cr. The carbonate fraction contained an appreciable proportion of Fe, Cd and Ni with the average percentage values of 16.29, 14.86 and 10.47 respectively, while organic fraction was of next importance for Cr with an average percentage value of 27.14. The Fe-Mn oxide fraction also contained 15.86% of Cd. Relatively low amounts of the metals were associated with water soluble and exchangeable fractions. The mobility factors for the metals in all the sites ranged from 8.55 to 40.04 for Fe, 8.66 to 56.58 for Cd, 12.74 to 30.19 for Ni and 0.82 to 7.22 for Cr. The generally low values of mobility factors coupled with significantly high levels of association of the metals with the residual fraction, indicate that the metals do not pose any environmental risk nor hazard.  相似文献   
78.
Abstract

This article documents and interprets stratigraphical changes in fractionation of Fe, Mn, Mg, K, Pb, Cu and Zn in the Sa1/2 sediment core from a coastal freshwater lake, Lake Sarbsko (northern Poland). The elements were sequentially extracted from the samples to distinguish five geochemical fractions: exchangeable, acid-extractable, reducible, oxidisable and residual. The analyses revealed substantial variations in geochemical partitioning of the elements and showed no correlation between the fractionation patterns and lithology of the sediments. In the sediments of Lake Sarbsko, iron is mainly bound to sulfides. Potassium occurs in its residual form. Magnesium and zinc are associated with carbonates and aluminosilicates, while copper occurs in compounds with organic matter and sulfides. Lead is found in connection with aluminosilicates and, to a lesser extent, with sulfides and organic matter. Manganese is partitioned between the oxidisable, acid-extractable, and exchangeable fractions. Heavy metals and potassium display the overall tendency to reduce the contents of their residual forms towards the top of the depositional sequence. Fe, Mn, Mg and Zn were found to be the most susceptible to post-sedimentary mobilisation.  相似文献   
79.
ABSTRACT

EDTA is useful to assess mobile metal pools in polluted soils and sediments. There is a need to enhance our understanding of the significance of metal fractions released. The impact of single reagent extraction with 0.05 mol L?1 EDTA on the solid phase distribution of trace metals in surface soils sampled from confined dredged sediment disposal sites was investigated. Not extracted and EDTA extracted soils were subjected to sequential extraction to fractionate the total contents into: (1) easily exchangeable and carbonate bound fraction; (2) reducible fraction; (3) oxidisable fraction; and (4) residual fraction. With EDTA, significant portions of metals associated with the acid extractable and reducible fractions were released. The oxidisable and residual fractions remained unaffected for most of the investigated metals except for the organic matter associated metals (Cu and Pb). A decrease in the residual fraction after EDTA-extraction for Cu and Pb was attributed to artifacts of the sequential extraction procedure.  相似文献   
80.
Diary     
Abstract

The formation of sparingly soluble Ca2+-phytate (Phy) species was studied using several techniques (potentiometry, calorimetry, thermoanalysis, ICP, SEM). Species with empirical formula CaxH(12_2x)Phy, (6 ≤ x ≤ 4.5) were formed in experiments performed at pH = 5.0, 7.5 and 10.5; at pH = 10.5 and in excess of Na+ the species Ca5Na2Phy was also found. Solubilities (s = 1.0 x 10-9and 1.1 x 10-10mol L-1 for the species Ca6Phy and Ca5Na2Phy respectively, at l = 0 mol L-1), thermogravimetric profiles (dehydratation, monohydrogen-phosphate and final pyrophosphate formation), and formation enthalpies (ΔΗ = 7.6 ± 1 and 3.7 ± 0.8 kJ mol-1for the equilibria 6Ca2+ + H3L9- = Ca6L0 + 3 H+ and 5Ca2+ + 2Na+ + H3L9- = Ca5Na2L0 + 3 H+, respectively), were obtained.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号