全文获取类型
收费全文 | 53106篇 |
免费 | 1523篇 |
国内免费 | 28篇 |
专业分类
化学 | 31645篇 |
晶体学 | 280篇 |
力学 | 911篇 |
综合类 | 1篇 |
数学 | 10385篇 |
物理学 | 11435篇 |
出版年
2023年 | 372篇 |
2022年 | 328篇 |
2021年 | 550篇 |
2020年 | 753篇 |
2019年 | 712篇 |
2018年 | 1097篇 |
2017年 | 1014篇 |
2016年 | 1962篇 |
2015年 | 1600篇 |
2014年 | 1574篇 |
2013年 | 3554篇 |
2012年 | 3229篇 |
2011年 | 3119篇 |
2010年 | 2040篇 |
2009年 | 1690篇 |
2008年 | 2655篇 |
2007年 | 2378篇 |
2006年 | 2095篇 |
2005年 | 2137篇 |
2004年 | 1844篇 |
2003年 | 1569篇 |
2002年 | 1399篇 |
2001年 | 1046篇 |
2000年 | 1023篇 |
1999年 | 743篇 |
1998年 | 588篇 |
1997年 | 518篇 |
1996年 | 662篇 |
1995年 | 472篇 |
1994年 | 550篇 |
1993年 | 501篇 |
1992年 | 527篇 |
1991年 | 440篇 |
1990年 | 489篇 |
1989年 | 406篇 |
1988年 | 421篇 |
1987年 | 385篇 |
1986年 | 374篇 |
1985年 | 516篇 |
1984年 | 482篇 |
1983年 | 387篇 |
1982年 | 387篇 |
1981年 | 394篇 |
1980年 | 331篇 |
1979年 | 334篇 |
1978年 | 326篇 |
1977年 | 322篇 |
1976年 | 327篇 |
1974年 | 311篇 |
1973年 | 326篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Study of the effects of operational parameters on multiresidue pesticide analysis by LC-MS/MS 总被引:2,自引:0,他引:2
In this paper, the influence of several operational parameters on a well established multiresidue LC-MS/MS method has been studied in relation to the analysis of 150 pesticides commonly present in vegetable samples. The operational parameters investigated are: (i) the influence of different modifiers (0.1% formic acid; 5 mM ammonium formiate; 5 mM ammonium acetate in aqueous phase) - both on the retention time and on the analytical response of the studied compounds; (ii) the effect of the analytical column's temperature on the retention time and on the analytical response of the pesticides investigated; (iii) the effects of co-elution in mixture containing 150 pesticides and, additionally, (iv) the carrying out of a study about the common transitions obtained by LC-MS/MS. Various common transitions were found among the 150 pesticides, but there were only two problematic cases, the pairs diuron-fluometuron and prometryn-terbutryn, which have common scanned transitions and have very close retention times. The use of ammonium salts as modifier instead of formic acid reports enhancement or suppression of the response depending on the pesticides. No great influence on the retention time or on the response of the pesticides and commodities studied was observed with relation to the column temperature. Two different columns: an HPLC (5 μm particle size) and an UHPLC analytical column (1.8 μm particle size) have been used. As was expected, shorter run times and lower peak width was achieved with the UHPLC column.In this paper, the effect of the compounds on each other in the MS analysis when the number of co-eluting compounds is quite high is also described. Mainly small suppression or enhancement co-elution effect was observed, but some particular pesticides presented high sensitivity (>±60% effect) when they elute together with others. This is an important factor and it has to be taken into account when performing multiresidue pesticide analysis. 相似文献
992.
del Puerto E Sánchez-Cortés S García-Ramos JV Domingo C 《Chemical communications (Cambridge, England)》2011,47(6):1854-1856
A possibility of getting SERS spectra of insoluble aromatic compounds in colloidal silver solutions is described. The method tested for the organic pigment quinacridone quinone consists of dispersing it in calix[n]arenes. The potentials of such cavitands, both as dispersing and as silver functionalization agents, is reported as a function of the substitution in their lower rim and their cavity size. 相似文献
993.
Rocha-Rinza T Sneskov K Christiansen O Ryde U Kongsted J 《Physical chemistry chemical physics : PCCP》2011,13(4):1585-1589
Using advanced QM/MM methods, the surprisingly negligible shift of the lowest-lying bright electronic excitation of the deprotonated p-coumaric acid (pCA(-)) within the photoactive yellow protein (PYP) is shown to stem from a subtle balance between hypsochromic and bathochromic effects. More specifically, it is found that the change in the excitation energy as a consequence of the disruption of the planarity of pCA(-) inside PYP is nearly canceled out by the shift induced by the intermolecular interactions of the chromophore and the protein as a whole. These results provide important insights about the primary absorption and the tuning of the chromophore by the protein environment in PYP. 相似文献
994.
Four novel benzamido-functionalized prolinamides have been prepared and tested as organocatalysts for enantioselective aldol reaction of aldehydes and cyclic ketones in water. In particular, prolinamide derived from achiral ethylene diamine was the best catalyst leading to anti aldols in excellent diastereomeric (up to 98/2) and enantiomeric (up to 99/1) ratios, thereby showing that lateral amide functionalities might be a key issue for facilitating "in water" chemistry. These catalysts are cheaper and easier to prepare than those previously described. 相似文献
995.
Francàs L Sala X Escudero-Adán E Benet-Buchholz J Escriche L Llobet A 《Inorganic chemistry》2011,50(7):2771-2781
The preparation of three new octadentate tetranucleating ligands made out of two Ru-Hbpp-based units [where Hbpp is 3,5(bispyridyl)pyrazole], linked by a xylyl group attached at the pyrazolate moiety, of general formula (Hbpp)(2)-u-xyl (u = p, m, or o) is reported, together with its dinucleating counterpart substituted at the same position with a benzyl group, Hbpp-bz. All of these ligands have been characterized with the usual analytical and spectroscopic techniques. The corresponding tetranuclear ruthenium complexes of general formula {[Ru(2)(trpy)(2)(L)](2)(μ-(bpp)(2)-u-xyl)}(n+) [L = Cl or OAc, n = 4; L = (H(2)O)(2), n = 6] and their dinuclear homologues {[Ru(2)(trpy)(2)(L)](μ-bpp-bz)}(n+) [L = Cl or OAc, n = 2; L = (H(2)O)(2), n = 3] have also been prepared and thoroughly characterized both in solution and in the solid state. In solution, all of the complexes have been characterized spectroscopically by UV-vis and NMR and their redox properties investigated by means of cyclic voltammetry techniques. In the solid state, monocrystal X-ray diffraction analysis has been carried out for two dinuclear complexes {[Ru(2)(trpy)(2)(L)](μ-bpp-bz)}(2+) (L = Cl and OAc) and for the tetranuclear complex {[Ru(2)(trpy)(2)(μ-OAc)](2)(μ-(bpp)(2)-m-xyl)}(4+). The capacity of the tetranuclear aqua complexes {[Ru(2)(trpy)(2)(H(2)O)(2)](2)(μ-(bpp)(2)-u-xyl)}(6+) and the dinuclear homologue {[Ru(2)(trpy)(2)(H(2)O)(2)](μ-bpp-bz)}(3+) to act as water-oxidation catalysts has been evaluated using cerium(IV) as the chemical oxidant in pH = 1.0 triflic acid solutions. It is found that these complexes, besides generating significant amounts of dioxygen, also generate carbon dioxide. The relative ratio of [O(2)]/[CO(2)] is dependent not only on para, meta, or ortho substitution of the xylylic group but also on the concentration of the starting materials. With regard to the tetranuclear complexes, the one that contains the more sterically constrained ortho-substituted ligand generates the highest [O(2)]/[CO(2)] ratio. 相似文献
996.
Iva Movre Šapić Vesna Volovšek Krešimir Furić Lahorija Bistričić Vladimir Dananić 《Macromolecular Symposia》2011,305(1):122-125
In this work we investigated the solidification of aminopropylsilanetriol dissolved in water (∼25%) under different conditions by Raman spectroscopy. The solidification was carried out at three different temperatures 8 °C, 23 °C and 60 °C. The influence of electromagnetic radiation on the polymerization process was also studied. Samples were held to solidify in dark and at UV (254 nm and 356nm) spectral range. In order to investigate the influence of the substrate on the resulting polymer structure, teflon, PVC, glass, brass and silica were used. Best ordered polymerized structure was achieved for samples deposited on plastics and solidified in dark, at room temperature. 相似文献
997.
Michal Karady Ondřej Novák Aleš Horna Miroslav Strnad Karel Doležal 《Electroanalysis》2011,23(12):2898-2905
On‐line LC‐EC/ESI‐MS has been established as a fast and simple method to mimic some types of oxidation reaction of various drugs and to study the formation and structure of the resulting products. This technique has been applied to a 2,6,9‐trisubstituted purine, R‐roscovitine, which is known to be an inhibitor of some cyclin‐dependent kinases (CDKs) and a potential anticancer drug. Oxidation of R‐roscovitine in an electrochemical cell (EC), operated under various conditions, resulted in appearance of 6 major products. These were further analyzed by high‐resolution mass spectrometry, their structures were elucidated by accurate mass measurement and compared to previously identified R‐roscovitine in vitro/in vivo metabolites. Although none of the observed products was structurally identical to those identified previously in vitro/in vivo, all of them, except for the methoxylated products, resembled similarity due to appearing through the same reaction type. R‐roscovitine in the EC cell underwent N‐dealkylation of the isopropyl moiety, hydroxylation of the aromatic side‐chain, dihydroxylation, methoxylation and dimer formation. The hydroxylation product was identified as Olomoucine II, a R‐roscovitine derivative, which displays 10‐times higher CDK‐inhibiting activity than R‐roscovitine and the occurrence of which, as R‐roscovitine product, has not yet been observed in vitro/in vivo. 相似文献
998.
999.
Monika Müllerová Karol Holý Pavol Blahušiak Martin Bulko 《Journal of Radioanalytical and Nuclear Chemistry》2018,315(2):237-241
The influence of meteorological parameters on radon exhalation rate was analyzed. The analyses show a significant influence of precipitation on radon exhalation rate. The highest exhalation rate was found during dry periods and the lowest during the periods of strong precipitation. We also tested two different types of detectors for the measurement of radon exhalation rate—the ionization chamber (AlphaGUARD) and the scintillation chamber of Lucas type. The exhalation rates measured by these detectors were in a good agreement. Likewise, there was an agreement in radon exhalation rates determined from short term and long term increases in radon activity concentration. 相似文献
1000.
Eva Kuzielová Matúš Žemlička Jiří Másilko Martin T. Palou 《Journal of Thermal Analysis and Calorimetry》2018,133(1):63-76
Stability of Dyckerhoff cement Class G partially substituted (15 mass%) by metakaolin (MK), silica fume (SF) and ground granulated blast-furnace slag (BFS) was investigated after 7 days of curing under standard and two different autoclaving conditions. Mercury intrusion porosimetry, X-ray diffraction analysis and combined thermogravimetric–differential scanning calorimetry were used to evaluate pore structure development, compressive strength and their dependence on the type of additives in relation to the particular phase composition. Hydrothermal curing led to the formation of α-C2SH and jaffeite, mostly in the case of referential samples and compositions with addition of slowly reacting BFS. Whilst modest hydrothermal curing (0.6 MPa, 165 °C) favoured formation of α-C2SH, larger amounts of jaffeite were determined after curing at the highest used pressure and temperature (2.0 MPa, 220 °C). Undesired transformation of primary hydration products was prevented especially by addition of highly reactive and very fine SF. Particular composition attained the best pore structure characteristics and compressive strength after curing at 0.6 MPa and 165 °C. Formation of more stable phases with C/S ratio close to 1 was proved by wollastonite formation during DSC analyses. More severe conditions of curing, however, led to the significant deterioration of microstructure and strength of corresponding sample, probably due to the formation of trabzonite, killalaite and zoisite. Considering the values of hydraulic permeability coefficient and compressive strength, replacement of cement by MK improved significantly the properties of cement when compared with the referential as well as with other blended compositions under the mentioned curing conditions. 相似文献