全文获取类型
收费全文 | 3131篇 |
免费 | 252篇 |
国内免费 | 279篇 |
专业分类
化学 | 1781篇 |
晶体学 | 16篇 |
力学 | 302篇 |
综合类 | 15篇 |
数学 | 81篇 |
物理学 | 1467篇 |
出版年
2024年 | 5篇 |
2023年 | 33篇 |
2022年 | 68篇 |
2021年 | 58篇 |
2020年 | 63篇 |
2019年 | 80篇 |
2018年 | 76篇 |
2017年 | 102篇 |
2016年 | 108篇 |
2015年 | 87篇 |
2014年 | 129篇 |
2013年 | 484篇 |
2012年 | 116篇 |
2011年 | 181篇 |
2010年 | 140篇 |
2009年 | 168篇 |
2008年 | 168篇 |
2007年 | 166篇 |
2006年 | 166篇 |
2005年 | 171篇 |
2004年 | 126篇 |
2003年 | 106篇 |
2002年 | 105篇 |
2001年 | 88篇 |
2000年 | 89篇 |
1999年 | 83篇 |
1998年 | 56篇 |
1997年 | 82篇 |
1996年 | 57篇 |
1995年 | 56篇 |
1994年 | 43篇 |
1993年 | 37篇 |
1992年 | 16篇 |
1991年 | 27篇 |
1990年 | 14篇 |
1989年 | 12篇 |
1988年 | 10篇 |
1987年 | 12篇 |
1986年 | 11篇 |
1985年 | 7篇 |
1984年 | 5篇 |
1983年 | 7篇 |
1982年 | 11篇 |
1981年 | 10篇 |
1979年 | 7篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1974年 | 2篇 |
排序方式: 共有3662条查询结果,搜索用时 15 毫秒
961.
Krisztián Horváth Fabrice Gritti Jacob N. Fairchild Georges Guiochon 《Journal of chromatography. A》2010,1217(41):6373-6381
The thickness of the porous shells of superficially porous particles influences the separation power of columns packed with these packing materials. Models of the mass transfer kinetics across porous adsorbents permit the prediction of the HETP curves of columns packed with particles having shells of different thicknesses, for molecules of different sizes. Decreasing the thickness of the porous layer potentially results in lower values of the “C-term” of the HETP curve and of the minimum of these curves. The Poppe plots calculated under isocratic and gradient conditions show that the separation power of columns packed with superficially porous particles increases significantly with decreasing thickness of the porous layer but this increase is more important for larger than for smaller molecules. The resolution between pairs of compounds increases at constant values of their retention factors when the strength of the eluent must be reduced to compensate for the decrease of their retention that is caused by the reduction of the surface area of the stationary phase. Thus, the separation power of columns packed with superficially porous particles increases with decreasing shell thickness. In contrast, if analysts do not compensate for the retention decrease, the resolution between small molecular weight compounds becomes worse with thin than with thick superficially porous particles. Finally, the importance of using instruments providing low extra-column band broadening contributions is stressed. 相似文献
962.
Johan Boman Annemarie Wagner Michael J. Gatari 《Spectrochimica Acta Part B: Atomic Spectroscopy》2010
Ambient aerosol particles smaller than 2.5 µm (PM2.5) are getting more and more attention worldwide. While legal focus is mainly on sample mass, the composition of the particles is an important research field gaining increased interest. The interest is not only connected to possible health effects of the elemental content of the particles, but the elemental determination can also add valuable information for source apportionment. Samples were collected during 20 days in November 2007 at the campus of the Chemistry Department, University of Gothenburg, Gothenburg, Sweden. The particles were collected using a cyclone that separates the PM2.5 particles from the air stream and impacts them on polycarbonate filters. Filters were changed at early afternoon. The samples were analyzed for particulate mass, black carbon (BC) and the elements S, Cl, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, As, Br, Cd and Pb. Several of the elements were above detection limit in only a few of the samples. Total reflection X-ray fluorescence (TXRF) spectrometer based on the Wobi TXRF module supplied by the International Atom Energy Agency (IAEA) has been used for the determination of most trace elements in the samples. A Graphite Furnace Atomic Absorption Spectrometer (GF-AAS) was used for complementary trace element analysis and a reflectometer was used to analyze black carbon. Before elemental analysis the filters were digested using a microwave digestion system with temperature and pressure control. The results showed a large variation in sample mass, BC and analyzed elemental concentrations. The variation of the different constituents did not show the same pattern. This added to the picture of different sources for different pollutants. The highest S concentration was noted on a day when the air masses were determined to come from the southeast, i.e. Poland and some other Eastern European countries. From the results it can be concluded that more work is needed on the TXRF spectrometer to optimize it for determination of the EU legally regulated elements As, Ni, Pb and Cd. Despite this the study shows that there is no problem in meeting the AAQS limits for Cd and Pb in Gothenburg. 相似文献
963.
A new application of intact cell MALDI-TOF MS (ICM-MS) methodology is described for monitoring the production of viral proteins and viral like particles using the baculovirus/insect cells expression system. Various MALDI matrices, cell preparation methods, cell/matrix volume ratio and MALDI target application procedures were tested in order to obtain the highest intensity and reproducibility of intact insect cell spectra. The web interface, SPECLUST (http://bioinfo.thep.lu.se/speclust.html), was used to construct dendograms based on MALDI-TOF MS data for evaluation of fingerprint changes.We demonstrate that insect cell mass spectrum fingerprints are characteristic of each viral protein/particle production. Their changes along the time for each production experiment correlate with the intracellular viral protein content determined by Western blot.This work shows that this simple, fast and low cost assay, which requires low sample volume, is a powerful analytical tool that complements the most common analytical methods used for monitoring bioprocesses and has potential application in the biotechnological industry namely, in the production of recombinant proteins. 相似文献
964.
Magnetic silica particles coated with hydroxy-terminated multi-walled carbon nanotubes (MWCNTs-OH) were prepared by sol-gel technology, characterized and used for the convenient, rapid and efficient extraction of several estrogens (including diethylstilbestrol, estrone and estriol) in water followed by sweeping micellar electrokinetic chromatography analysis with UV detection. The results demonstrated that sol-gel technology was a feasible, simple and effective technique for the preparation of MWCNTs-OH functionalized magnetic silica particles. The factors affecting the extraction efficiency of estrogens (the pre-activation of magnetic particles, adsorption time, desorption time and the amount of elution solvent) were carefully investigated. The extraction efficiencies for diethylstilbestrol, estrone and estriol were 95.9%, 93.9%, and 52.4%, respectively, under the optimum conditions. The method detection limits for the three estrogens were less than 0.2 ng mL−1. The developed method was applied for the analysis of tap water, mineral water, Pearl River water and honey. 相似文献
965.
Ali H. Eltmimi Leon Barron Aran Rafferty John P. Hanrahan Olga Fedyanina Ekaterina Nesterenko Pavel N. Nesterenko Brett Paull 《Journal of separation science》2010,33(9):1231-1243
A range of porous carbon‐based monolithic (PCM) rods with flow‐through pore sizes of 1, 2, 5 and 10 μm, were produced using a silica particle template method. The rods were characterised using SEM and energy‐dispersive X‐ray spectroscopy, BET surface area and porous structure analysis, dilatometry and thermal gravimetry. SEM evaluation of the carbon monolithic structures revealed an interconnected rigid bimodal porous structure and energy‐dispersive X‐ray spectroscopy analysis verified the quantitative removal of the embedded silica beads. The specific surface areas of the 1, 2, 5 and 10 μm rods were 178, 154, 84 and 125 m2/g after pyrolysis and silica removal, respectively. Shrinkage of the monolithic rods during pyrolysis is proportional to the particle size of the silica used and ranged from 9 to 12%. Mercury porosimetry showed a narrow distribution of pore sizes, with an average of ~700 nm for the 1 μm carbon monolith. The suitability of bare and surface oxidised PCM rods for the use as a stationary phase for reversed and normal phase LC was explored. The additional modification of PCM rods with gold micro‐particles followed by 6‐mercaptohexanoic acid was performed and ion‐exchange properties were evaluated. 相似文献
966.
The objective of the present work was to investigate the chromatographic behavior of natural phenolic compounds in micellar and aqueous‐organic LC using a short column packed with 1.8 μm particles. Firstly, the effect of ACN and SDS on elution strength and selectivity was examined by isocratic submicellar (0–30% ACN/5% 1‐butanol/1–6 mM SDS) and micellar (0–30% ACN/5% 1‐butanol/40–60 mM SDS) systems. The varied concentrations of two modifiers in the mobile phases revealed different eluting power. Then, the application of organic modifier gradient was discussed in both submicellar and micellar LC using mobile phases of 4 mM SDS/5% 1‐butanol or 50 mM SDS/5% 1‐butanol containing ACN gradient from 0 to 30%, respectively. For micellar system, the separation was found to be better in gradient than isocratic elution. Additionally, the sensitivity of aqueous‐organic LC was examined. The mobile phase was a mixture of ACN and water employing gradient elution at a flow rate of 0.5 mL/min, with analysis time below 9 min. It was found that separation efficiency was significantly better compared with micellar LC. Besides, the aqueous‐organic LC has been applied to separation of various phenolic compounds in Yangwei granule or Radix Astragali samples. 相似文献
967.
Rangam Rajkhowa Eun Seok Gil Jonathan Kluge Keiji Numata Lijing Wang Xungai Wang David L. Kaplan 《Macromolecular bioscience》2010,10(6):599-611
Silk fibroin is a useful protein polymer for biomaterials and tissue engineering. In this work, porogen leached scaffolds prepared from aqueous and HFIP silk solutions were reinforced through the addition of silk particles. This led to about 40 times increase in the specific compressive modulus and the yield strength of HFIP‐based scaffolds. This increase in mechanical properties resulted from the high interfacial cohesion between the silk matrix and the reinforcing silk particles, due to partial solubility of the silk particles in HFIP. The porosity of scaffolds was reduced from ≈90% (control) to ≈75% for the HFIP systems containing 200% particle reinforcement, while maintaining pore interconnectivity. The presence of the particles slowed the enzymatic degradation of silk scaffolds.
968.
The mass transfer mechanisms in columns packed with old (55 μm Zipax and 5 μm Poroshell) and recently commercialized shell particles (2.7 μm Halo-C(18) and Kinetex-C(18)) were investigated from a physico-chemical point of view. Combining a model of diffusion in heterogeneous packed beds (effective medium theory) with values of the heights equivalent to a theoretical plate (HETPs derived from the first and second central moments of the elution profiles) and of the peak variances provided by the peak parking method, we demonstrate that columns packed with current shell particles perform better than those packed with fully porous particles in resolving low molecular weight compounds because the eddy diffusion term of the van Deemter equation of the former is markedly smaller. The calculation of eddy diffusion in column beds suggests that the smaller A terms are due to smaller trans-column velocity bias in columns packed with shell particles. We also show that the mass transfer of large molecules (e.g., proteins) is faster when the internal volume accessible to the analyte increases. Therefore, it is suggested that shell particles made of concentric layers with average pore sizes increasing with increasing diameter would provide columns with higher efficiency. 相似文献
969.
《Physics and Chemistry of Liquids》2012,50(2):95-106
Abstract By means of a toroidal oscillating viscometer, the shear viscosity of some mercury-thallium alloys has been measured in the composition range 28.5–29.5 atomic percent thallium and over the temperature range from 12.5–15.5°C. Some discussion of the experimental results is given in terms of liquid coordination number. 相似文献
970.
冰冻升华极稀溶液制备的iPS超细粉末结晶的结构与性质 总被引:2,自引:0,他引:2
高分子在浓度低于动态接触浓度cs的极稀溶液中以单链形式存在[1,2],用冰冻升华法将极稀溶液中的溶剂除掉可获得高分子的超细粉末.这些超细粒子与普通的聚合物相比,比表面积大,高分子链之间缠结程度小,有可能表现出特殊的物理性质.本文用示差扫描量热计(DS... 相似文献