全文获取类型
收费全文 | 4869篇 |
免费 | 359篇 |
国内免费 | 288篇 |
专业分类
化学 | 1922篇 |
晶体学 | 4篇 |
力学 | 491篇 |
综合类 | 85篇 |
数学 | 2595篇 |
物理学 | 419篇 |
出版年
2024年 | 11篇 |
2023年 | 59篇 |
2022年 | 61篇 |
2021年 | 78篇 |
2020年 | 99篇 |
2019年 | 114篇 |
2018年 | 132篇 |
2017年 | 162篇 |
2016年 | 159篇 |
2015年 | 123篇 |
2014年 | 168篇 |
2013年 | 361篇 |
2012年 | 239篇 |
2011年 | 234篇 |
2010年 | 234篇 |
2009年 | 274篇 |
2008年 | 271篇 |
2007年 | 349篇 |
2006年 | 274篇 |
2005年 | 240篇 |
2004年 | 217篇 |
2003年 | 219篇 |
2002年 | 200篇 |
2001年 | 143篇 |
2000年 | 146篇 |
1999年 | 136篇 |
1998年 | 126篇 |
1997年 | 140篇 |
1996年 | 88篇 |
1995年 | 65篇 |
1994年 | 43篇 |
1993年 | 53篇 |
1992年 | 45篇 |
1991年 | 50篇 |
1990年 | 43篇 |
1989年 | 18篇 |
1988年 | 23篇 |
1987年 | 26篇 |
1986年 | 12篇 |
1985年 | 17篇 |
1984年 | 13篇 |
1983年 | 6篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1980年 | 6篇 |
1979年 | 9篇 |
1978年 | 7篇 |
1977年 | 3篇 |
1976年 | 7篇 |
1936年 | 1篇 |
排序方式: 共有5516条查询结果,搜索用时 15 毫秒
141.
An evaluation of the non-boiling evaporation technique for the preconcentration of Pb, Cd, Cu, Zn at the pg g?1 level in water samples is presented. Various improvements were made to allow efficient control of contamination problems at these extremely low concentrations. They include the choice of FEP Teflon for the evaporation containers and the use of sophisticated cleaning, ageing and pre-conditionning procedures. Detailed calibration graphs were obtained down to the sub-pg g?1 level by processing ultra-low concentration standards. This technique was then applied to the determination of these four metals in snow samples collected in Greenland and Antarctica. 相似文献
142.
Anantha Iyengar Gopalan Kwang-Pill Lee Kalayil Manian Manesh Jun Heon Kim Jae Soo Kang 《Talanta》2007,71(4):1774-1781
A modified electrode is fabricated by embedding gold nanoparticles into a layer of electroactive polymer, poly(4-aminothiophenol) (PAT) on the surface of glassy carbon (GC) electrode. Cyclic voltammetry (CV) is performed to deposit PAT and concomitantly deposit Au nanoparticles. Field emission transmission electron microscopic image of the modified electrode, PAT-Aunano-ME, indicates the presence of uniformly distributed Au nanoparticles having the sizes of 8-10 nm. Electrochemical behavior of the PAT-Aunano-ME towards detection of ascorbic acid (AA) and dopamine (DA) is studied using CV. Electrocatalytic determination of DA in the presence of fixed concentration of AA and vice versa, are studied using differential pulse voltammetry (DPV). PAT-Aunano-ME exhibits two well defined anodic peaks at the potential of 75 and 400 mV for the oxidation of AA and DA, respectively with a potential difference of 325 mV. Further, the simultaneous determination of AA and DA is studied by varying the concentration of AA and DA. PAT-Aunano-ME exhibits selectivity and sensitivity for the simultaneous determination of AA and DA without fouling by the oxidation products of AA or DA. PAT and Au nanoparticles provide synergic influence on the accurate electrochemical determination of AA or DA from a mixture having any one of the component (AA or DA) in excess. The practical analytical utilities of the PAT-Aunano-ME are demonstrated by the determination of DA and AA in dopamine hydrochloride injection and human blood serum samples. 相似文献
143.
Sabry K. Mohamed 《Analytica chimica acta》2006,562(2):204-209
A poly(vinyl chloride)-based membrane of 2,9-dimethyl-4,11-diphenyl-1,5,8,12-tetraazacyclotetradeca-1,4,8,11-tetraene (DDTCT) with sodium tetraphenyl borate (STB) as an anion excluder and dibutyl phthalate (DBP), dibutyl butylphosphonate (DBBP), tris(2-ethylhexyl) phosphate (TEP) and tributyl phosphate (TBP) as plasticizing solvent mediators was prepared and investigated as a Ga(III)-selective electrode. The best performance was observed with the membrane having the ligand-PVC-DBP-STB composition 1:4:1:1, which worked well over a wide concentration range (1.45 × 10−6 to 0.1 mol L−1) with a Nernstian slope of 28.7 mV per decade of activity between pH 4.0 and 10.0. This electrode showed a fast response time of 12 s and was used over a period of 100 days with good reproducibility (s = 0.3 mV). The selectivity coefficients for monovalent, divalent and trivalent cations indicate excellent selectivity for Ga(III) ions over a large number of cations. Anions such as Cl− and SO42− do not interfere and the electrode also works satisfactorily in partially water-alcohol medium. The practical utility of the membrane sensor has also been observed in solutions contaminated with detergents, i.e., cetyltrimethylammonium bromide and sodium dodecyl sulfate and used for the determination of gallium in nickel alloy, fly-ash and biological samples. 相似文献
144.
微波增压溶样-石墨炉原子吸收光谱法同时测定植物性样品中微量铅镉 总被引:7,自引:2,他引:7
使用微波增压溶样法,将样品用HNO3—HClO4溶解后,用石墨炉原子吸收光谱法同时测定植物性样品中铅和镉。以磷酸二氢铵—硝酸镁作为基体改进剂,可使灰化温度大大提高,克服了基体的干扰。铅和镉的回收率分别为95.3%—104.8%和96.2%—105.5%,RSD分别为4.8%-7.2%和4.3%-7.6%。 相似文献
145.
A novel kinetic method for the determination of trace amounts of Co(II) has been developed. The proposed method based on the catalytic effect of Co(II) on the oxidation of xylenol orange tetra sodium salt by H2O2 in the presence of cationic surfactant (N‐dodecylpyridinium chloride). Co(II) at μg.mL?1 was determined spectrophotometrically by measuring the decrease in the absorbance of xylenol orange at 577 nm by the differential method. The method is precise, selective, and sensitive. The detection limit of the procedure was 0.058 μg.mL?1. The relative standard deviation for the replicate determination (n = 6) of 0.7 μg.mL?1 was 1.285%. The results compared satisfactorily with those of atomic absorption spectrometry. The method was successful for the analysis of Co(II) in veterinary and synthetic samples. 相似文献
146.
Kanchi Suvardhan Kailasa Suresh Kumar Dasari Rekha Pantrangam Subrahmanyam Kapuvedi Kiran Bellum Jayaraj Surasura Ramanaiah Kandhukuri Janardhanam Pattium Chiranjeevi 《Mikrochimica acta》2007,157(3-4):237-244
Cloud point extraction was applied as a method for preconcentration of rhodium after formation of a complex with 2-propylpiperidine-1-carbodithioate
(2-PPC), and later determined by flame atomic absorption spectrometry using TritonX-114 as surfactant. Rhodium was complexed
with 2-PPC in an aqueous phase and kept for 15 min in a thermostatted bath at 40 °C. Separation of the two phases was accomplished
by centrifugation for 15 min at 4000 rpm. The chemical variables affecting the cloud point extraction were optimized and successfully
applied to rhodium determination in various water samples. Under optimized conditions, the preconcentration system (100 mL
sample) permitted an enhancement factor of 50. The detection limits obtained under optimal conditions was 0.052 ng mL−1. The extraction efficiency was investigated at different rhodium concentrations (7.0–42.0 μg mL−1), and good recoveries (96.42–99.14%) were obtained using this method. It has been applied to the determination of rhodium
in water and was compared with reported methods in terms of Student’s ‘t’-test and variance ratio ‘f’-test. 相似文献
147.
β-Cyclodextrin-polyurethane polymer as solid phase extraction material for the analysis of carcinogenic aromatic amines 总被引:1,自引:0,他引:1
β-Cyclodextrin-polyurethane (β-CDPU) polymer was synthesized by the reaction of β-cyclodextrin with hexamethylene diisocyanate in dry dimethylformamide and used as a sorbent for the solid phase extraction (SPE) of carcinogenic aromatic amines from water. The polymers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and particle size analysis. The separation and quantification was performed by Liquid chromatography with RP-C18 column and diode array detection using standard arylamines for quantification. When compared with commercially available sorbents, β-CDPU gave better recovery for the aromatic amines. From the variation of pH of the extractant from 4.0 to 8.5 recovery was highest at pH 8.5. The breakthrough volume has been ascertained to be 100 ml for 200 mg of the resin. The new SPE material offers better recovery and estimation of banned arylamines. 相似文献
148.
We study asymptotic properties of discrete and continuous time generalized simulated annealing processesX(·) by considering a class of singular perturbed Markov chains which are closely related to the large deviation of perturbed diffusion processes. Convergence ofX(t) in probability to a setS
0 of desired states, e.g., the set of global minima, and in distribution to a probability concentrated onS
0 are studied. The corresponding two critical constants denoted byd and withd are given explicitly. When the cooling schedule is of the formc/logt, X(t) converges weakly forc>0. Whether the weak limit depends onX(0) or concentrates onS
0 is determined by the relation betweenc, d, and . Whenc>, the expression for the rate of convergence for each state is also derived. 相似文献
149.
A system has been developed for online preconcentration and determination of Cd using thermospray flame furnace atomic absorption
spectrometry (TS-FF-AAS). It is based on the solid-phase extraction of Cd in an Amberlite XAD-2 minicolumn loaded with 2-(2-thiazolylazo)-5-dimethylaminophenol
(TAM), and the metal ion is eluted with 1 mol L−1 hydrochloridric acid, followed by its determination. The online system allows determining Cd with a detection limit of 8.0 ng L−1 and a quantification limit of 25.0 ng L−1. The precision (repeatability), calculated as the relative standard deviation (% RSD) in sample solutions containing 0.5
and 3.0 μg L−1 of Cd, was 6.1 and 4.5%, respectively. The preconcentration factor obtained was 24. The system’s accuracy was confirmed by
analyzing the following certified reference materials (CRMs): Rice flour NIES 10b, Apple leaves NIST 1515 and Orchard leaves
NBS 1571. This procedure was applied to the determination of Cd in cabbage and powdered guarana samples. 相似文献
150.
This paper reviews derivatisation processes applied in chromatographic determination of acidic herbicides (with carboxyl and phenol groups), mainly in aqueous environmental samples. The discussion focuses on the basic derivatisation reactions used to convert herbicides to derivatives to make them analysable by gas chromatography, and possibly to reduce detection limits and/or increase extraction recovery from aqueous samples. The reactions are transesterification, esterification, silylation, alkylation, and extractive and pyrolytic alkylation. The reagents used to conduct the reactions are numerous. Diazomethane is a very efficient methylation reagent but explosive and toxic. Methyl iodide also ensures rapid and efficient methylation. Benzyl bromide can be used directly in water but derivatisation yield is low and reproducibility is poor. Butyl chloroformate and dimethyl sulfite can also be used for derivatisation in water, and acetic anhydride can be used for in-situ derivatisation of phenolic herbicides. For increasing selectivity of GC detection pentafluorobenzyl bromide (for ECD) and (2-cyanethyl)dimethyl(diethylamino)silane (for NPD) have been applied. Very characteristic ions are produced in mass spectra if silyl groups are introduced, e.g. by using bis(trimethylsilyl)trifluoroacetamide. Tetramethylammonium, trimethylphenylammonium, tetraalkylammonium, and trimethylsulfonium hydroxides and salts can by used for derivatisation at elevated temperature in the GC injection port. Extractive alkylation is relatively efficient if tetraalkylammonium salts with long chain alkyl groups are used. 相似文献