全文获取类型
收费全文 | 2499篇 |
免费 | 32篇 |
国内免费 | 1篇 |
专业分类
化学 | 2221篇 |
晶体学 | 4篇 |
力学 | 7篇 |
数学 | 57篇 |
物理学 | 243篇 |
出版年
2023年 | 11篇 |
2022年 | 32篇 |
2021年 | 29篇 |
2020年 | 20篇 |
2019年 | 24篇 |
2018年 | 13篇 |
2017年 | 18篇 |
2016年 | 43篇 |
2015年 | 30篇 |
2014年 | 38篇 |
2013年 | 64篇 |
2012年 | 160篇 |
2011年 | 291篇 |
2010年 | 112篇 |
2009年 | 47篇 |
2008年 | 223篇 |
2007年 | 228篇 |
2006年 | 219篇 |
2005年 | 210篇 |
2004年 | 143篇 |
2003年 | 126篇 |
2002年 | 106篇 |
2001年 | 69篇 |
2000年 | 70篇 |
1999年 | 21篇 |
1998年 | 16篇 |
1997年 | 13篇 |
1996年 | 14篇 |
1995年 | 11篇 |
1994年 | 14篇 |
1993年 | 12篇 |
1992年 | 6篇 |
1991年 | 9篇 |
1990年 | 3篇 |
1989年 | 8篇 |
1988年 | 8篇 |
1987年 | 9篇 |
1986年 | 6篇 |
1985年 | 4篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1980年 | 3篇 |
1978年 | 4篇 |
1976年 | 3篇 |
1974年 | 4篇 |
1971年 | 3篇 |
1969年 | 3篇 |
1967年 | 5篇 |
1966年 | 5篇 |
排序方式: 共有2532条查询结果,搜索用时 15 毫秒
61.
Capillary zone electrophoresis of orotic acid in urine with on-line isotachophoresis sample pretreatment and diode array detection 总被引:1,自引:0,他引:1
Danková M Strasík S Molnárová M Kaniansky D Marák J 《Journal of chromatography. A》2001,920(1-2):143-153
Two hydroxide-selective microbore analytical columns (the Dionex AS11 and AS15) were tested and compared for the quantitation of anionic species in 30% hydrogen peroxide. The ions of interest were fluoride, acetate, formate, chloride, bromide, nitrate, sulfate, and phosphate. Statistically sound calibration and spiking studies were carried out, investigating the range of a blank to 60 ppb. Prior to injection onto the separators, peroxides were loaded without pretreatment onto a concentrator column, which was then washed with deionized water to remove the matrix. Although retention times gradually decreased during the spiking studies, reliable quantitation was still achievable on both columns at the target concentration of 30 ppb. However, various resolution problems meant that the AS11 should not be recommended for this application. 相似文献
62.
Kvasnicková L Glatz Z Sterbová H Kahle V Slanina J Musil P 《Journal of chromatography. A》2001,916(1-2):265-271
Capillary electrochromatography (CEC) using polymer-based monolithic stationary phase has been developed as a promising method for the determination of lignans of Schisandra chinensis. The columns were prepared by in situ copolymerisation of acrylamide, N,N'-methylenebisacrylamide, vinylsulfonic acid and lauryl acrylate in presence of poly(ethylene glycol) as a porogenic agent. The columns [33 cm (24.5 cm effective length) x 75 microm I.D.] were successfully used to analyse and quantify the major lignans in extract of the seeds of Schisandra chinensis. Good separations were achieved in less than 35 min. The calibration graphs were linear in the range 0.025-1.0 mg/ml of given lignan with correlation coefficients between 0.9951 and 0.9996. The inter-day reproducibility of the peak area were below 3.9% and the inter-day reproducibility of the migration time were below 4.2%. The results of quantitative CEC analyses were compared with those obtained by reversed-phase HPLC, the levels of schizandrin, gomisin A, gomisin N and wuweizisu C determined by CEC were in a good agreement with those determined by HPLC. 相似文献
63.
Effect of Cold Atmospheric Pressure Plasma on Maize Seeds: Enhancement of Seedlings Growth and Surface Microorganisms Inactivation 总被引:1,自引:0,他引:1
Anna Zahoranová Lucia Hoppanová Juliana Šimončicová Zlata Tučeková Veronika Medvecká Daniela Hudecová Barbora Kaliňáková Dušan Kováčik Mirko Černák 《Plasma Chemistry and Plasma Processing》2018,38(5):969-988
Cold atmospheric pressure ambient air plasma generated by Diffuse Coplanar Surface Barrier Discharge (DCSBD) was investigated for inhibition of native microbiota and potentially dangerous pathogens (Aspergillus flavus, Alternaria alternata and Fusarium culmorum) on the maize surface. Moreover, the improvement of germination and growth parameters of maize seeds was evaluated. Maize (Zea mays L.; cv. Ronaldinio), one of the most important cultivated crops worldwide, was selected as the research material. Electrical measurements confirmed the high volume power density (80 W cm?3) of DCSBD plasma. Non-equilibrium plasma state evaluated using optical emission spectroscopy showed values of vibrational and rotational temperature (2700?±?300) K and (370?±?75) K, respectively. Changes on the plasma treated seeds surface were studied by water contact angle measurement, scanning electron microscope analysis and Fourier transform infrared spectroscopy. A complete devitalisation of native microbiota on the surface of seeds was observed after a short treatment time of 60 s (bacteria) and 180 s (filamentous fungi). The plasma treatment efficiency of artificially contaminated maize seeds was estimated as a reduction of 3.79 log (CFU/g) in F. culmorum after a 60-s plasma treatment, 4.21 log (CFU/g) in A. flavus and 3.22 log (CFU/g) in A. alternata after a 300-s plasma treatment. Moreover, the obtained results show an increase in wettability, resulting in a better water uptake and in an enhancement of growth parameters. The investigated DCSBD plasma source provides significant technical advantages and application potential for seed surface finishing without the use of hazardous chemicals. 相似文献
64.
Fast Exfoliation and Functionalisation of Two‐Dimensional Crystalline Carbon Nitride by Framework Charging 下载免费PDF全文
Dr. Jingjing Jia Dr. Edward R. White Dr. Adam J. Clancy Dr. Noelia Rubio Theo Suter Dr. Thomas S. Miller Kit McColl Prof. Paul F. McMillan Dr. Veronika Brázdová Prof. Furio Corà Dr. Christopher A. Howard Robert V. Law Dr. Cecilia Mattevi Prof. Milo S. P. Shaffer 《Angewandte Chemie (International ed. in English)》2018,57(39):12656-12660
Two‐dimensional (2D) layered graphitic carbon nitride (gCN) nanosheets offer intriguing electronic and chemical properties. However, the exfoliation and functionalisation of gCN for specific applications remain challenging. We report a scalable one‐pot reductive method to produce solutions of single‐ and few‐layer 2D gCN nanosheets with excellent stability in a high mass yield (35 %) from polytriazine imide. High‐resolution imaging confirmed the intact crystalline structure and identified an AB stacking for gCN layers. The charge allows deliberate organic functionalisation of dissolved gCN, providing a general route to adjust their properties. 相似文献
65.
del Mar Graciani M Rodríguez A Muñoz M Moyá ML 《Journal of colloid and interface science》2001,235(2):260-264
The reaction of dehydrobromination of 2-(p-nitrophenyl)ethyl bromide with hydroxide ions has been studied in aqueous micellar solutions of N-tetradecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate, SB3-14. The kinetic effects of added salts (NaF, NaCl, NaBr, and NaNO(3)) on the reaction rate in SB3-14 aqueous micellar solutions have also been studied. They were rationalized by considering the binding of the anions, which come from the salt, to the sulfobetaine micelles and their competition with the reactive hydroxide ions for the micellar surface. The equilibrium binding constant of the 2-(p-nitrophenyl)ethyl bromide to the sulfobetaine micelles was estimated by recording the changes in the spectra of the organic substrate when the SB3-14 concentration in the micellar medium changed. This value was in agreement with that obtained from fitting of kinetic data. The second-order rate constant in the micellar pseudophase revealed that the reaction is faster in SB3-14 micelles than in water. This acceleration seems independent of the presence of added salts and can be explained by considering that SB3-14 micelles favor reactions in which charge is delocalized in the transition state. Copyright 2001 Academic Press. 相似文献
66.
Muchová L Jirsa M Kuroki M Dudková L Benes MJ Marecek Z Smíd F 《Biomedical chromatography : BMC》2001,15(6):418-422
Carcinoembryonic cell adhesion molecule 1 (CEACAM1) is a human membrane glycoprotein belonging to the carcinoembryonic antigen (CEA) family and to the immunoglobulin superfamily. It is expressed in apical membranes of many epithelial cells in gastrointestinal and urogenital tract and also in granulocytes and lymphocytes, and its biological effect in human tissues has recently been discussed in literature. The purpose of this study was to isolate CEACAM1 glycoprotein from bile and characterize its purity and recovery which has not been described before. Affinity chromatography of CEACAM1 on hydrazide-activated cellulose with immobilized monoclonal anti-CEA F34-187 antibody is described. The immunoglobulin carbohydrate moiety was oxidized by periodate and then bound to hydrazide-activated matrix. Crude protein fraction from bile was applied on the affinity column and after extensive washing of non-bound proteins CEACAM1 was eluted with 6 M guanidine-HCl. A single immunopositive 85 kDa band was detected on Western blots with anti-CEA antibody after SDS-PAGE. We found out that CEACAM1 was not stainable with any common method of protein staining and the only non-specific method which could detect the 85 kDa band was a lectin staining. 相似文献
67.
The development of piezoelectric immunosensors for human serum albumin (HSA) is reported. The piezoelectric crystals were modified either with monoclonal antibody AL-01 (direct assay) or with HSA (competitive assay). Measurements were carried out in the flow-through mode. Affinity interaction between albumin and the antibody was characterised. With immobilised antibody and HSA in solution, the kinetic association rate constant k(a) was 18 100 l mol(-1) s(-1) and the dissociation constant k(d) was 0.00369 s(-1). For the opposite arrangement (immobilised HSA), a slower dissociation was observed, k(d) was 0.00085 s(-1). A competitive assay for HSA was developed with working range of 1-5 mug ml(-1) and a total time for one analysis equal to 17 min. Samples of urine were analysed after tenfold dilution. The developed system was successfully evaluated on real samples from diabetic patients and the obtained results correlated well with the standard reflectometric assay of proteins in urine. 相似文献
68.
Mineralization procedures for arsenic and selenium analysis are usually limited to wet digestion methods owing to high volatility of these analytes. On the other hand, variable amounts of silicon in some types of samples imply elaborated mineralization procedures to liberate analytes which may be retained in an insoluble residue. Consequently, methods for such material generally include an hydrofluoric step followed by an evaporation to dryness. This type of mineralization is most easily accomplished using a dry ashing procedure. For plant analysis, a well validated and readily applicable dry ashing method is used for a long time in several laboratories but up today one could suppose that As and Se determinations cannot be performed after such a type of mineralization. Surprisingly, it has been observed that for plant samples these analytes are detected even after a calcination at 450 degrees C. The general usefulness of a dry ashing method for analysis of all other analytes (main, minor and trace elements) incitates us to also verify As and Se recoveries. Results obtained in this work indicate clearly that plants of terrestrial origin may be mineralized using dry ashing procedure without As and Se losses. This statement was confirmed by analyses of several reference terrestrial plant samples (RMs) and laboratory control samples. Another confirmation was given by the direct graphite furnace analysis of the same plant samples but in slurried form (SS-ETAAS). As a direct consequence, As and Se analysis in terrestrial plants no more necessitates a separate preparation methodology. On the other hand, significant losses of As and Se were observed for aquatic plants, e.g. algaes. For the analysis of this type of samples, a separate wet digestion procedure remains unavoidable if the determination of As and Se has to be considered. Also some preparation procedures were tested for As and Se-analysis of soil and sediment reference samples. In these cases the wet digestion with a mixture of nitric, perchloric and hydrofluoric acids seems to remain the best alternative. 相似文献
69.
Boca R Boca M Dlhán L Falk K Fuess H Haase W Jarosciak R Papánková B Renz F Vrbová M Werner R 《Inorganic chemistry》2001,40(13):3025-3033
The spin crossover system, [Fe(bzimpy)(2)](ClO(4))(2).0.25H(2)O, was reinvestigated above room temperature (bzimpy = 2,6-bis(benzimidazol-2-yl)pyridine). The system exhibits an abrupt low-spin to high-spin transition at T(c) = 403 K. Liberation of a fractional amount of water does not affect the spin crossover: the system is perfectly reversible with a hysteresis width of DeltaT = 12 K. The existence of the hysteresis at such high temperature determines that the lowest limit of the solid-state cooperativity parameter is J/k > 403 K despite long iron(II) separations (10 A). The high cooperativeness has been assigned to a perfect pi-stacking of the benzimidazole rings in the crystal lattice at a distance as short as 3.6 A. Variable-temperature IR data and the heat capacity measurements match well the magnetic data. The thermodynamic properties are DeltaH = 17 kJ mol(-)(1), DeltaS = 43 J K(-)(1) mol(-)(1), so that the entropy of the spin transition shows a considerable contribution from the molecular vibrations. A theoretical model has been applied in fitting the magnetic data along the whole hysteresis path. A statistical distribution of the cooperativity parameter led to the feature that angled walls of the hysteresis loop are well reproduced. 相似文献
70.
Stable cyclotriphosphazenes 4 and 5, incorporating one and two carbon radical centers, respectively, have been easily prepared and characterized. EPR spectroscopic studies in fluid solution at room temperature were carried out for both compounds and also for diradical 5 in frozen solvent matrixes. Spectral results are consistent with a triplet or degenerate singlet triplet ground state for 5. Reductive cyclic voltammetry shows a redox couple, being monoelectronic for 4 and bielectronic for 5. 相似文献