全文获取类型
收费全文 | 1860篇 |
免费 | 55篇 |
国内免费 | 6篇 |
专业分类
化学 | 1293篇 |
晶体学 | 14篇 |
力学 | 11篇 |
数学 | 247篇 |
物理学 | 265篇 |
无线电 | 91篇 |
出版年
2024年 | 4篇 |
2023年 | 11篇 |
2022年 | 29篇 |
2021年 | 41篇 |
2020年 | 38篇 |
2019年 | 45篇 |
2018年 | 42篇 |
2017年 | 28篇 |
2016年 | 70篇 |
2015年 | 61篇 |
2014年 | 65篇 |
2013年 | 136篇 |
2012年 | 136篇 |
2011年 | 155篇 |
2010年 | 102篇 |
2009年 | 107篇 |
2008年 | 138篇 |
2007年 | 112篇 |
2006年 | 109篇 |
2005年 | 95篇 |
2004年 | 80篇 |
2003年 | 51篇 |
2002年 | 61篇 |
2001年 | 22篇 |
2000年 | 19篇 |
1999年 | 18篇 |
1998年 | 12篇 |
1997年 | 13篇 |
1996年 | 16篇 |
1995年 | 13篇 |
1994年 | 2篇 |
1993年 | 10篇 |
1992年 | 11篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 8篇 |
1981年 | 2篇 |
1980年 | 8篇 |
1978年 | 5篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 3篇 |
1971年 | 1篇 |
1970年 | 3篇 |
排序方式: 共有1921条查询结果,搜索用时 15 毫秒
111.
Helio Gauze Bonacorso Arci Dirceu Wastowski Nilo Zanatta Marcos Antonio Pinto Martins 《合成通讯》2013,43(8):1457-1465
A convenient method for the synthesis of alkyl[aryl]-substituted 5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-1-methylpyrazole (2) from a new ring transformation reaction of alkyl[aryl]-substituted-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-1-pyrazolethiocarboxyamide (1) with methylhydrazine in THF, and the thermal dehydration of 2, are reported. 相似文献
112.
Silvia Hernández-Ainsa Rafael Alcalá Joaquín Barberá Mercedes Marcos Carlos Sánchez José Luis Serrano 《European Polymer Journal》2011,(3):311-318
A series of codendrimers has been prepared by the grafting of poly(propylene imine) PPI-(NH2)16 (G = 3) with two different carboxylic acids: the aromatic-based 5-[4′-(4-cyanophenylazo)phenyloxy]pentanoic acid (AZO) and the aliphatic 2,2-bis(undecanoyloxymethylene)propionic acid (BUPA) in different proportions. Their thermal properties, liquid crystalline behavior and photoinduced optical anisotropy have been investigated. The formation of the ionic compounds was confirmed by nuclear magnetic resonance (NMR) spectroscopy, and Fourier transform infrared (FT-IR) spectroscopy. The influence of the acid percentage in the liquid crystalline behavior was investigated by means of differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffractometry (XRD). All the resulting co-dendrimers present liquid crystalline properties displaying an evolution from nematic mesophase for the azo-richer dendrimers to smectic A mesophase for the BUPA-richer dendrimers. Only materials with low azobenzene contents up to four AZO units per dendrimer on average were processable by casting from dichloromethane solutions and resulted in transparent thin films appropriate for optical studies. The photoinduced dichroism reached was higher in the dendrimer with higher azo content (four units per dendrimer) being this material a good compromise between processability and optical response. 相似文献
113.
The L-dopa is the immediate precursor of the neurotransmitter dopamine. Unlike dopamine, L-dopa easily enters the central nervous system and is used in the treatment of Parkinson’s disease. A sensitive and selective method is presented for the voltammetric determination of L-dopa in pharmaceutical formulations using a carbon paste electrode modified with trinuclear ruthenium ammine complex [(NH3)5RuIIIORuIV(NH3)4ORuIII(NH3)5]6+ (Ru-red) incorporated in NaY zeolite. The parameters which influence on the electrode response (paste composition, potential scan rate, pH and interference) were also investigated. The optimum conditions were found to an electrode composition (m/m) of 25% zeolite containing 6.7% Ru, 50% graphite and 25% mineral oil in acetate buffer at pH 4.8. Voltammetric peak currents showed a linear response for L-dopa concentration in the range between 1.2×10−4 and 1.0×10−2 mol l−1 (r=0.9988) with a detection limit of 8.5×10−5 mol l−1. The variation coefficient for a 1.0×10−3 mol l−1 L-dopa (n=10) was 5.5%. The results obtained for L-dopa in pharmaceutical formulations (tablet) was in agreement with compared official method. In conclusion, this study has illustrated that the proposed electrode modified with Ru-red incorporated zeolite is suitable valuable for selective measurements of L-dopa. 相似文献
114.
Rezende MC Flores P Guerrero J Villarroel L 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(7):1637-1640
The 13C NMR of two solvatochromic dyes derived from a barbituric acid acceptor and dimethylaminophenyl donor fragments, compound 1 and the related merocyanine 2, were recorded in various solvents. The observed chemical-shift variations were used to interpret their structural differences and solvatochromic behavior in solution. 相似文献
115.
de Souza BM Marques MR Tomazela DM Eberlin MN Mendes MA Palma MS 《Rapid communications in mass spectrometry : RCM》2004,18(10):1095-1102
The social wasp P. paulista is relatively common in southeast Brazil causing many medically important stinging incidents. The seriousness of these incidents is dependent on the amount of venom inoculated by the wasps into the victims, and the characteristic envenomation symptoms are strongly dependent on the types of peptides present in the venom. In order to identify some of these naturally occurring peptides available in very low amounts, an analytical protocol was developed that uses a combination of reversed-phase and normal-phase high-performance liquid chromatography (HPLC) of wasp venom for peptide purification, with matrix-assisted laser desorption/ionization time-of-flight post-source decay mass spectrometry (MALDI-Tof-PSD-MS) and low-energy collision-induced dissociation (CID) in a quadrupole time-of-flight tandem mass spectrometry (QTof-MS/MS) instrument for peptide sequencing at the sub-picomole level. The distinction between Leu and Ile was achieved both by observing d-type fragment ions obtained under CID conditions and by comparison of retention times of the natural peptides and their synthetic counterparts (with different combinations of I and/or L at N- and C-terminal positions). To distinguish the isobaric residues K and Q, acetylation of peptides was followed by Q-Tof-MS analysis. The primary sequences obtained were INWLKLGKMVIDAL-NH(2) (MW 1611.98 Da) and IDWLKLGKMVMDVL-NH(2) (MW 1658.98 Da). Micro-scale bioassay protocols characterized both peptides as presenting potent hemolytic action, mast cell degranulation, and chemotaxis of polymorphonucleated leukocyte (PMNL) cells. The primary sequences and the bioassay results suggest that these toxins constitute members of a new sub-class of mastoparan toxins, directly involved in the occurrence of inflammatory processes after wasp stinging. 相似文献
116.
Daniel G. Cummings James D. Sommers Mary L. Adamic Marcos Jimenez Jeffrey J. Giglio Kevin P. Carney Karl Grimm 《Journal of Radioanalytical and Nuclear Chemistry》2009,282(3):923-928
A radioactive 137Cs source has been analyzed for the radioactive parent 137Cs and stable decay daughter 137Ba. The ratio of the daughter to parent atoms is used to estimate the date when Cs was purified prior to source encapsulation
(an “age” since purification). The isotopes were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) after chemical
separation. In addition, Ba was analyzed by isotope dilution ICP-MS (ID-ICP-MS). A detailed error analysis of the mass spectrometric
work has been undertaken to identify areas of improvement, as well as quantifying the effect the errors have on the “age”
determined. This paper reports an uncertainty analysis to identifying areas of improvement and alternative techniques that
may reduce the uncertainties. In particular, work on isotope dilution using ICP-MS for the “age” determination of sealed sources
is presented. The results will be compared to the original work done using external standards to calibrate the ICP-MS instrument. 相似文献
117.
118.
Silva MM Vale MG Damin IC Welz B Mandaji M Fett JP 《Analytical and bioanalytical chemistry》2003,377(1):165-172
The amount of sample that is available for analysis in laboratory plant cultivation experiments is usually very limited. Highly sensitive analytical techniques are therefore required, even for elements that are present in the plants at mg g–1 concentrations, and graphite furnace atomic absorption spectrometry (GFAAS) was chosen in this work because of its micro-sampling capability, and its relatively simple operation. Four micro-methods were investigated for the determination of iron in roots and leaves of rice plants: i) a micro-digestion with nitric and hydrochloric acids, ii) a slurry procedure using tetramethylammonium hydroxide (TMAH) tissue solubilizer, iii) a slurry prepared in 1.4 mol L–1 nitric acid, and treated in an ultrasonic bath, and iv) the direct analysis of solid samples. The micro-digestion was suffering from high blank values and contamination problems, so that it could not be recommended for routine purposes. The TMAH method exhibited poor precision and occasional low recoveries, particularly for real samples. Direct solid sampling analysis gave results similar to those obtained with the slurry technique with ultrasonic agitation for the determination of iron in certified reference materials with iron content up to about 100 g g–1, but was too sensitive for the investigated rice plants, which had an iron content up to several mg g–1. The slurry technique with ultrasonic treatment of the samples, suspended in dilute nitric acid, was finally adopted as the method of choice.The method was then applied for the determination of iron in the leaves and in different compartments of the roots of two rice cultivars, one sensitive to iron toxicity, an important nutritional disorder, and the other one resistant to iron toxicity. The results suggest that the higher resistance to iron toxicity of the second cultivar is due to a smaller uptake of iron from the soil, resulting in lower iron levels in all compartments of the plant. 相似文献
119.
Wanderson Romão Marcos F. Franco Gustavo B. Sanvido Fabio C. Gozzo Marcos N. Eberlin 《Polymer Degradation and Stability》2010,95(4):666-2666
Matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) has been shown to provide a valuable technique to study the thermomechanical degradation of poly(ethylene terephthalate) (PET). MALDI-MS has been tested to monitor both the admixture of post-consumption bottle-grade PET (PETpc-btg) with virgin bottle-grade PET (PETv-btg) and the thermomechanical degradation effects on the chemical properties of PETv-btg. Principal component analysis of MALDI-MS data classify the samples into groups with specific features: a) PET-btg with intrinsic viscosities of 0.80 or 0.65-0.60 dL g−1); b) processed or virgin PET with the same intrinsic viscosity; c) PETv-btg from PET containing PETpc-btg; and d) PETv-btg from different manufacturers. MALDI-MS data is therefore able to reveal the quality of PET-btg resins preventing frauds and illegal use of recycled PET-btg. 相似文献
120.
A. Martínez-de la Cruz S. Obregón Alfaro S. M. G. Marcos Villarreal 《Research on Chemical Intermediates》2010,36(8):925-936
Nanoparticles of α-Bi2Mo3O12 were prepared by the Pechini method. The process of formation of the bismuth molybdate was followed by simultaneous thermogravimetric and differential thermal analysis (TGA/DTA). Different samples of α-Bi2Mo3O12 were obtained at 400, 450, and 500 °C, and characterized by X-ray powder diffraction (XRD), nitrogen physisorption (BET), and scanning electron microscopy (SEM). When observed by SEM, the morphology of the sample obtained at the lowest temperature consisted of semi-spherical particles with an average diameter of 150 nm. On the other hand, the highest calcination temperature led to the formation of sintered particles of 500–600 nm. The photocatalytic activity of α-Bi2Mo3O12 was tested by photodegradation of the organic dyes rhodamine B (rhB) and indigo carmine (IC) under visible-light irradiation. The bismuth molybdate nanoparticles were able to bleach aqueous solutions of both organic dyes. The sample obtained at 400 °C was the best photocatalyst with half-lives, t 1/2, of 108 and 154 min for rhB and IC, respectively. 相似文献