全文获取类型
收费全文 | 3659篇 |
免费 | 156篇 |
国内免费 | 19篇 |
专业分类
化学 | 2608篇 |
晶体学 | 23篇 |
力学 | 55篇 |
数学 | 413篇 |
物理学 | 735篇 |
出版年
2023年 | 21篇 |
2022年 | 15篇 |
2021年 | 72篇 |
2020年 | 64篇 |
2019年 | 79篇 |
2018年 | 56篇 |
2017年 | 48篇 |
2016年 | 119篇 |
2015年 | 116篇 |
2014年 | 123篇 |
2013年 | 239篇 |
2012年 | 228篇 |
2011年 | 279篇 |
2010年 | 174篇 |
2009年 | 175篇 |
2008年 | 246篇 |
2007年 | 214篇 |
2006年 | 189篇 |
2005年 | 162篇 |
2004年 | 149篇 |
2003年 | 101篇 |
2002年 | 122篇 |
2001年 | 63篇 |
2000年 | 80篇 |
1999年 | 41篇 |
1998年 | 47篇 |
1997年 | 37篇 |
1996年 | 36篇 |
1995年 | 45篇 |
1994年 | 33篇 |
1993年 | 42篇 |
1992年 | 39篇 |
1991年 | 40篇 |
1990年 | 35篇 |
1989年 | 25篇 |
1988年 | 25篇 |
1987年 | 24篇 |
1986年 | 22篇 |
1985年 | 30篇 |
1984年 | 28篇 |
1983年 | 19篇 |
1982年 | 24篇 |
1981年 | 17篇 |
1980年 | 15篇 |
1978年 | 11篇 |
1977年 | 11篇 |
1976年 | 8篇 |
1975年 | 8篇 |
1974年 | 7篇 |
1970年 | 8篇 |
排序方式: 共有3834条查询结果,搜索用时 734 毫秒
31.
A large number of nanostructures have the potential to be used together with electrophoresis as separation media or separation additive in capillary electrophoresis, micellar electrokinetic chromatography, capillary electrochromatography, and other analytical techniques. Among those structures are nanotubes, nanocavities, nanowires, nanoposts, nanocones, nanospheres, molecular imprints, nanoparachutes (conical monodendrons), and general nanoparticles with random structures. This review is focused only on publications describing experimental works using molecular imprints, nanoposts, and nanospheres that are fabricated and applied for the purpose of separation media in electrophoresis-driven separations. The review follows an approximate chronological order in each section. As shown, the most popular are those resulting from molecular imprinting technologies. These biomimetic receptors are used in a great variety of fields, which includes electrophoresis, micellar electrokinetic chromatography, capillary electrochromatography, and other fields not reviewed in this work. A few examples of these other fields are, e.g., liquid chromatography, membranes, extractor or preconcentration techniques, immunosorbent assays, and sensing devices. The second topic scanned in the present work is the nanostructures that are used as obstacles to replace gels or polymers solutions in electrophoresis. Finally, the nascent field of nanospheres of gold and other materials as separation media is also reviewed. 相似文献
32.
Tomazela DM Gozzo FC Mayer I Engelmann FM Araki K Toma HE Eberlin MN 《Journal of mass spectrometry : JMS》2004,39(10):1161-1167
Ten homologous or isomeric singly, doubly, triply and quadruply charged cationic macrocyclic complexes I-Va, bn+ (n = 1-4) formed by the coordination of [Ru(bipy)2Cl]+ to the pyridyl N-atoms of a series of meso-(phenyl)m-(meta or para-pyridyl)n-porphyrins (m + n = 4) were transferred to the gas phase and structurally characterized by electrospray ionization (ESI) mass (MS) and tandem mass (MS/MS) spectrometry. Previously known to be stable in solution and in the solid state, I-Va, bn+ are found to constitute also a new class of stable, long-lived multiply charged gas-phase ions with spatially separated charge sites. Increasing intramolecular electrostatic repulsion from Ia, b+ to IVa, b3+ facilitates in-source and tandem collision-induced dissociation (CID). However, for the quadruply charged ions Va, b4+, electrostatic repulsion is alleviated mainly by ion pairing with the CF3SO3- counterion forming the salt clusters [Va,b/CF3SO3]3+ and [Va,b/(CF3SO3)2]2+ with reduced charge states. Ion-pairing that yields [IVa,b/CF3SO3]2+ is also observed as a minor ESI process for the triply charged ions IVa, b3+. The gaseous ions I-Va, bn+ (n = 2, 3 or 4) dissociate by sequential 'charge partitioning' with the formation of two cationic fragments by the release of [Ru(bipy)2Cl]+. The meta (a) and para (b) isomers and the positional isomers II2+ and III2+ display nearly identical ESI-MS and ESI-MS/MS spectra. ESI-MS/MS of I-Va, bn+ shows that the Ru-py(P) is, intrinsically, the weakest bond since this bond breaks preferentially upon CID. 相似文献
33.
A simple method for determination of polycyclic aromatic hydrocarbons (PAHs) in water using headspace solid-phase microextraction (HS-SPME) with gas chromatography-flame ionisation detector (GC-FID) was developed. In order to obtain the convenient experimental conditions for HS-SPME extraction an experimental design with two steps was accomplished. A 26-2 fractional factorial design and central composite design (CCD) considering three significant factors were used. Naphthalene, anthracene and fluoranthene were chosen as representatives of two, three and four aromatic rings, and the global response of three PAHs was used for the results, evaluation. The chosen extraction conditions were: 85 μm polyacrylate fibre; 50 °C temperature; 60 min time; 20 mL-dissolution volume (in 40 mL glass vial); without salt addition; and 2 min desorption time. The procedure was extended to other seven PAHs (acenaphthylene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene and benzo(a)anthracene) and the analytical characteristics were checked. The limit of detection (LOD) was from 0.08 (anthracene) to 0.20 μg L?1 (naphthalene). The precision expressed as relative standard deviation (RSD in %) using 50 μg L?1 of each analyte ranged from 6.8 to 17 %. The method was applied to the analysis of the surface waters and leaching waters of contaminated soils from Gipuzkoa (North Spain). The PAHs were not detected in surface water samples. Most of the PAHs were found in the leachates from contaminated soils showing a maximum global value of 75.5 μg L?1. 相似文献
34.
Relative mass transport efficiencies of near infrared (λ = 795 nm) femtosecond laser generated brass aerosols in helium were measured by ICP-MS applying different ablation cells with short and long washout times. It was found that the transport efficiencies are independent of the cell used within the mutual experimental uncertainties. This finding was confirmed by additional measurements providing the absolute particle mass transport efficiencies of femtosecond laser ablation in He. Here, the transport efficiencies were determined by weighing the samples before and after ablation with a micro-balance, collecting the particles by low-pressure impaction, and evaluating the impacted masses quantitatively by total reflection X-ray fluorescence. Within the experimental uncertainties (± 9–19%) the same absolute transport efficiency (about 77%) was found for all cells applied. This efficiency value can be regarded as a lower limit of the absolute mass transport efficiency since mass losses in the impactor are difficult to quantify. 相似文献
35.
Summary A new technique is described for the identification of the chloride ion through the formation of chromyl chloride, based on the extraction of the latter with carbon tetrachloride. The identification limit is 2g of chloride. It is possible to carry out the test in the presence of many other anions, including fluoride, which cannot be present when the traditional distillation technique is employed.
Zusammenfassung Vorgeschlagen wird eine neue Technik zum Chloridnachweis durch Bildung von Chromylchlorid. Dieser Nachweis beruht auf der Extraktion des Chromylchlorids mit Tetrachlorkohlenstoff. Die Nachweisgrenze liegt bei 2g Chlorid, wobei die Möglichkeit besteht, den Test auch in Gegenwart von Fluorid durchzuführen, das bei Anwendung der üblichen Destillationsmethoden nicht anwesend sein darf.相似文献
36.
Ivette Garcia CastroAnnegret Tillack Christian G HartungMatthias Beller 《Tetrahedron letters》2003,44(15):3217-3221
The one-pot synthesis of several branched secondary aliphatic amines is described. Hydroamination of terminal alkynes with aliphatic primary amines in the presence of Cp2Ti(η2-Me3SiCCSiMe3) gives the corresponding aldimines as intermediates. Reaction of these in situ produced aldimines with organolithium reagents (n-BuLi, PhLi) provides the α-branched amines in an easy way in upto 78% overall yield. 相似文献
37.
For determination of phosphorus in samples of vegetable origin (leaves and wheat flour) decomposition by means of molten alkali is proposed. Two procedures have been studied, one with dry reagents including an auxiliary oxidant, and the other with initially moist alkali with no extra oxidant. The fusion product is easily soluble and produces a solution suitable for elemental analysis. The phosphorus is determined by the molybdenum blue method. The suggested mineralization is rapid, accurate and precise. 相似文献
38.
An electrochemical method for the simultaneous determinations of HgII concentration and total AsIII and AsV concentration has been developed. The method does not require the additional preliminary step of the chemical reduction of AsV to AsIII, or oxidation of AsIII to AsV before stripping analysis takes place. Also, the method for the simultaneous determination of HgII concentration and AsIII concentration is described. Measurements were performed in 0.1 M HCl using a gold-plated graphite electrode as sensor. Detection limits for both methods are below 0.4 ppb. Relative standard deviation did not exceed 15%. The possible interference by other trace metals was investigated. Analyses of natural water and industrial solutions were made using proposed methods and AAS. The t-test demonstrates that there was no significant difference between the results obtained with these methods. Proposed methods decrease the time of analysis because concentrations of the HgII and arsenic ions were measured simultaneously. Also, the removal of the additional step of chemical reduction of AsV to AsIII or oxidation of AsIII to AsV decreases analysis time, and also reduces the chance of contamination due to the use of additional reagents. 相似文献
39.
Adsorption of the cationic polymers poly(methacrylamidopropyltrimethyl ammonium chloride) (PMAPTAC) and poly(1,1-dimethylpiperidinium-3,5-diallylmethylene chloride) (PDMPDAMC) on human hair was studied by measurements of the amount of polymer adsorbed and by the streaming potential method. Results reflect the amphoteric nature of the keratin surface and show that the excess of anionic sites at pH values above 4 is the main driving force for the adsorption of cationic polyelectrolytes. Lowering the pH below 4 or addition of neutral salt (KCl) reduces the amount of adsorbed polymer. It was shown that the adsorption of cationic polymer in the concentration range 0.01 to 0.1 % and at neutral pH reverses the overall character of the surface from anionic to cationic. Keratin fibers modified in this manner do not exhibit amphoteric character and bear excess positive charge in the pH range 2–9.5. The value of the amount of the polymer adsorbed at saturation concentration (2 mg/g) as well as the lack of molecular weight effect in the range (5 · 104 – 106) on the amount of polymer adsorbed suggest that polymer chains adopt a rather extended conformation on the fiber surface. Some data concerning the formation of a complex between adsorbed cationic polymer and anionic detergents or polyelectrolytes are also presented. 相似文献
40.
Garcia Ruano JL Alcudia A del Prado M Barros D Maestro MC Fernandez I 《The Journal of organic chemistry》2000,65(10):2856-2862
The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported. 相似文献