全文获取类型
收费全文 | 2176篇 |
免费 | 34篇 |
国内免费 | 10篇 |
专业分类
化学 | 1090篇 |
晶体学 | 18篇 |
力学 | 64篇 |
数学 | 282篇 |
物理学 | 565篇 |
无线电 | 201篇 |
出版年
2023年 | 13篇 |
2022年 | 32篇 |
2021年 | 34篇 |
2020年 | 32篇 |
2019年 | 25篇 |
2018年 | 27篇 |
2017年 | 20篇 |
2016年 | 55篇 |
2015年 | 45篇 |
2014年 | 41篇 |
2013年 | 96篇 |
2012年 | 96篇 |
2011年 | 111篇 |
2010年 | 81篇 |
2009年 | 93篇 |
2008年 | 118篇 |
2007年 | 113篇 |
2006年 | 107篇 |
2005年 | 108篇 |
2004年 | 88篇 |
2003年 | 75篇 |
2002年 | 54篇 |
2001年 | 53篇 |
2000年 | 53篇 |
1999年 | 36篇 |
1998年 | 44篇 |
1997年 | 36篇 |
1996年 | 38篇 |
1995年 | 27篇 |
1994年 | 26篇 |
1993年 | 25篇 |
1992年 | 20篇 |
1991年 | 10篇 |
1990年 | 18篇 |
1989年 | 12篇 |
1988年 | 12篇 |
1987年 | 11篇 |
1986年 | 13篇 |
1985年 | 31篇 |
1984年 | 33篇 |
1983年 | 17篇 |
1982年 | 20篇 |
1981年 | 17篇 |
1980年 | 21篇 |
1979年 | 20篇 |
1978年 | 17篇 |
1977年 | 20篇 |
1976年 | 17篇 |
1974年 | 12篇 |
1973年 | 14篇 |
排序方式: 共有2220条查询结果,搜索用时 31 毫秒
991.
Cristoni S Bernardi LR Gerthoux P Gonella E Mocarelli P 《Rapid communications in mass spectrometry : RCM》2004,18(16):1847-1855
A new ionization method, named surface-activated chemical ionization (SACI), was employed for the analysis of five amphetamines (3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyethylamphetamine (MDE), amphetamine and methamphetamine) by ion trap mass spectrometry. The results so obtained have been compared with those achieved by using atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) using the same instrument, clearly showing that SACI is the most sensitive of the three. The limit of detection and linearity range for SACI were compared with those obtained using APCI and ESI, showing that the new SACI approach provides the best results for both criteria. SACI was used to analyze MDA, MDMA MDE, amphetamine and methamphetamine in four urine samples, and the quantitation results are compared with those achieved using ESI. 相似文献
992.
Roda B Cioffi N Ditaranto N Zattoni A Casolari S Melucci D Reschiglian P Sabbatini L Valentini A Zambonin PG 《Analytical and bioanalytical chemistry》2005,381(3):639-646
Biocompatible methods capable of rapid purification and fractionation of analytes from complex natural matrices are increasingly in demand, particularly at the forefront of biotechnological applications. Field-flow fractionation is a separation technique suitable for nano-sized and micro-sized analytes among which bioanalytes are an important family. The objective of this preliminary study is to start a more general approach to field-flow fractionation for bio-samples by investigation of the correlation between channel surface composition and biosample adhesion. For the first time we report on the use of X-ray photoelectron spectroscopy (XPS) to study the surface properties of channels of known performance. By XPS, a polar hydrophobic environment was found on PVC material commonly used as accumulation wall in gravitational field-flow fractionation (GrFFF), which explains the low recovery obtained when GrFFF was used to fractionate a biological sample such as Staphylococcus aureus. An increase in separation performance was obtained first by conditioning the accumulation wall with bovine serum albumin and then by using the ion-beam sputtering technique to cover the GrFFF channel surface with a controlled inert film. XPS analysis was also employed to determine the composition of membranes used in hollow-fiber flow field-flow fractionation (HF FlFFF). The results obtained revealed homogeneous composition along the HF FlFFF channel both before and after its use for fractionation of an intact protein such as ferritin. 相似文献
993.
2-Substituted indoles (5a,b and 7) and fused indoles (9a-c, 11a,b, and 12) have been obtained by the S(RN)1 mechanism from photostimulated reactions of o-iodoaniline (1) and 1-halo-2-naphthalen-2-ylamines (3a,b) with enolate ions of acyclic (acetophenone (6), 2- (4a) and 4-acetylpyridine (4b)) and cyclic ketones (1- (8a) and 2-indanone (10a), 1- (8b) and 2-tetralone (10b) and 1-benzosuberone (8c)) in DMSO and liquid ammonia as solvents. The carbanions derived from 4a,b, 8a, and 10b are novel nucleophiles that form new C-C bonds by the S(RN)1 mechanism. 相似文献
994.
P. F. Rossi 《Journal of Thermal Analysis and Calorimetry》1997,49(2):627-634
A differential microcalorimeter (E. Calvet) was used to study the processes of adsorption of five aliphatic alcohols (C1-C5) on α-Al2O3 at 25, 50, 100, 150 and 200°C. In particular, the importance of the thermokinetic study of the chemisorption of such alcohols at different experimental temperatures was demonstrated, with regard to the variations in the thermokinetic parameters (tmax, t1/2 and t0) and the evolution of the alcohol vapor pressure on the adsorbent during the adsorption process. It was concluded that:
- all the heat emission peaks of alcohol adsorption have the same rounded shape at 25°C;
- on passing from methanol to 1-pentanol, the area of the adsorption peaks increases as the chain length or molecular weight increases;
- on passing from 25 to 200°C, the shape of the adsorption peaks becomes more pointed.
995.
Infrared fluorescence (IRF) from the CH stretch modes of vibrationally excited gas-phase azulene* was observed to depend on Evib according to a simple model. The IRF time/pressure behavior shows that the average energy transferred per collision depends strongly on Evib for azulene* + azulene and azulene* + argon collisions. 相似文献
996.
Cristoni S Cantù M Bernardi LR Gerthoux P Gonella E Brambilla M Cavalca V Zingaro L Guidugli F 《Rapid communications in mass spectrometry : RCM》2005,19(10):1231-1236
Alterations of arginine plasma levels are involved in several disorders of amino acid metabolism such as hurtnup, argininosuccinic aciduria, histidinemia, citrullinuria, and cystinuria. In this work a new liquid ionization source, surface-activated chemical ionization (SACI), has been used to analyze arginine in human and rat plasma samples. Arginine was extracted and diluted ten times through protein precipitation. The diluted arginine samples were then analyzed using an ion-exchange chromatographic column coupled with the SACI source and an ion trap analyzer using MS(3) monitoring in order to increase the sensitivity and specificity of the analysis. The multiple-point standard additions method was used to quantify the arginine. This method was employed to eliminate the matrix effect that affects all liquid ionization sources (APCI, ESI, SACI, etc.), and also does not require use of an internal standard. High-quality results in terms of sensitivity, limit of detection, lower limit of quantitation, linearity and reproducibility, are demonstrated. 相似文献
997.
A series of new 4-aryl-1,3-dihydro-2H-1,5-benzodiazepine-2-thiones ( 3 ) has been synthesized by condensing the 3,3-dimercapto-1-aryl-2-propen-1-ones with o-phenylenediamine. The structure was established by the results of acid cleavage and by nmr spectra. The alkylation of compounds 3 gave 2-alkylthio-4-aryl-3H-1,5 benzodiazepines ( 10 ). 相似文献
998.
For a set of 32 selected free radicals, energy minimum structures, harmonic vibrational wave numbers ωe, principal moments of inertia IA, IB, and IC, heat capacities C°p(T), entropies S°(T), thermal energy contents H°(T) ? H°(0), and standard enthalpies of formation ΔfH°(T) were calculated at the G3MP2B3 level of theory in the temperature range 200–3000 K. In this article, thermodynamic functions at T = 298.15 K are presented and compared with recent experimental values. The mean absolute deviation between calculated and experimental ΔfH°(298.15) values resulted in 3.91 kJ mol?1, which is close to the average experimental uncertainty of ± 3.55 kJ mol?1. The influence of hindered rotation on thermodynamic functions is studied for isopropyl and tert‐butyl radicals. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 550–560, 2002 相似文献
999.
Imidacloprid is a new insecticide with a wide range of action. Because honeybees are very sensitive to this substance, two techniques (HPLC–UV and GC–MS) which enable its detection in several matrices of both animal and vegetable origin were used to monitor its possible presence in cultivated land. In the first method quantification of imidacloprid in honeybees was achieved by use of the external standard method; the detection limit was 50 mg kg–1, the linear range 0.05–1 mg mL–1, recovery 60–83%, and the imprecision (coefficient of variation) 8.6% for repeatability and 11.8% for reproducibility. Recovery from pollen was 71–98% in the range 0.05–0.5 mg kg–1. The repeatability was 9.2–13.9%. Imidacloprid can often be found in the environment, not as a simple molecule but as a group of degradation products. The GC–MS method could be used to quantify all these species as oxidation products and to determine the initial quantity of imidacloprid by use of a conversion factor. The liquid chromatographic analysis could be used to detect, in a standard solution, 10 ng mL–1 derivatized 6-chloronicotinic acid. The linearity was good (R=0.999) over a wide concentration range (10 g mL–1–10 ng mL–1). Several samples with different matrices (filter paper placed on an pneumatic corn seed drill, grass, flowers, honeybees, etc.) obtained during the sowing period for imidacloprid-treated corn were analyzed. The quantification limit (LOQ) was 0.005 mg kg–1 for grass and flowers, 0.002 mg kg–1 for honeybees, and 0.024 mg kg–1 for paper filters. 相似文献
1000.
Berti E Caneschi A Daiguebonne C Dapporto P Formica M Fusi V Giorgi L Guerri A Micheloni M Paoli P Pontellini R Rossi P 《Inorganic chemistry》2003,42(2):348-357
The basicity behavior and ligational properties of the ligand 2-((bis(aminoethyl)amino)methyl)phenol (L) toward Ni(II), Cu(II), and Zn(II) ions were studied by means of potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, l = 0.15 mol dm-3). The anionic L-H- species can be obtained in strong alkaline solution; this species behaves as tetraprotic base (log K1 = 11.06, log K2 = 9.85, log K3 = 8.46, log K4 = 2.38). L forms mono- and dinuclear complexes in aqueous solution with all the transition metal ions examined; the dinuclear species show a [M2(L-H)2]2+ stoichiometry in which the ligand/metal ratio is 2:2. The studies revealed that two mononuclear [ML-H]+ species self-assemble, giving the dinuclear complexes, which can be easily isolated from the aqueous solution due to their low solubility. This behavior is ascribed to the fact that L does not fulfill the coordination requirement of the ion in the mononuclear species and to the capacity of the phenolic oxygen, as phenolate, to bridge two metal ions. All three dinuclear species were characterized by determining their crystal structures, which showed similar coordination patterns, where all the single metal ions are substantially coordinated by three amine functions and two oxygen atoms of the phenolate moieties. The two metals in the dinuclear complexes are at short distance interacting together as shown by magnetic measurements performed with Ni(II) and Cu(II) complexes, which revealed an antiferromagnetic coupling between the two metal ions. The [Cu2(L-H)2]2+ cation shows a phase transition occurring by the temperature between 100 and 90 K; the characterization of the compounds existing at different temperatures was investigated using X-ray single-crystal diffraction, EPR, and magnetic measurements. 相似文献