全文获取类型
收费全文 | 325篇 |
免费 | 16篇 |
国内免费 | 1篇 |
专业分类
化学 | 258篇 |
晶体学 | 4篇 |
力学 | 3篇 |
数学 | 46篇 |
物理学 | 31篇 |
出版年
2024年 | 1篇 |
2023年 | 11篇 |
2022年 | 10篇 |
2021年 | 9篇 |
2020年 | 12篇 |
2019年 | 15篇 |
2018年 | 3篇 |
2017年 | 5篇 |
2016年 | 13篇 |
2015年 | 11篇 |
2014年 | 10篇 |
2013年 | 15篇 |
2012年 | 20篇 |
2011年 | 20篇 |
2010年 | 10篇 |
2009年 | 14篇 |
2008年 | 13篇 |
2007年 | 10篇 |
2006年 | 27篇 |
2005年 | 11篇 |
2004年 | 11篇 |
2003年 | 15篇 |
2002年 | 12篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 1篇 |
1998年 | 4篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 1篇 |
1991年 | 1篇 |
1990年 | 4篇 |
1989年 | 1篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1948年 | 1篇 |
1933年 | 2篇 |
排序方式: 共有342条查询结果,搜索用时 31 毫秒
251.
New 3-acylamino-2-oxazolidinone derivatives 3 were obtained in good yields by reaction of 5-aryl (or benzyl)3-(2-hydroxyethyl)1,3,4-oxadiazol-2(3H)ones 1 with sodium ethylate. Treatment of ethyl 5-aryl-2-oxo-1,3,4-oxadiazole-3(2H)-acetates 7 with aromatic aldehydes in the presence of sodium ethylate or sodium hydride afforded 3-acylamino-5-aryl-4-ethoxycarbonyl-2-oxazolidinone derivatives as two trans- 5 and cis- 6 racemics. Only RS,SR-racemates were obtained with acetophenone under the same conditions. 相似文献
252.
Onida B Camarota B Ugliengo P Goto Y Inagaki S Garrone E 《The journal of physical chemistry. B》2005,109(46):21732-21736
Recent joint IR and computational work (Onida et al. J. Phys. Chem B 2005) has allowed a detailed characterization of the isolated silanols at the surface of highly ordered benzene-silica hybrid material. In the present paper, a similar characterization is provided for a less ordered sample. The comparison permits the assignment of IR features to the interaction of silanols either with one another or with benzene rings of the structure. The extent of structural imperfections appears to be limited, for example, no more than pairs of interacting silanols are found, readily healed by thermal treatment. Evidence is also provided that probe molecules with simultaneous H-acceptor and H-donor properties (benzene, methylacetylene) may interact with both the acidic proton in silanols and the electronic cloud in the framework aromatic rings. 相似文献
253.
Romolo M. Dorizzi Beatrice Caruso Sandra Meneghelli Paolo Rizzotti 《Accreditation and quality assurance》2006,11(6):303-307
Most of the immunoassays workload is processed in clinical laboratories within a time span comparable to the clinical chemistry and the haematology assays and the analytical work is usually completed between 1:00 and 2:00 p.m. In order to accelerate the auto-verification of the results of tumour markers (Total and free PSA, CEA, CA 125, CA 15-3, CA 19-9, TPA, AFP, NSE, S 100 protein), and hormones (TSH, FT4, FT3, Prolactin, total testosterone) and Procalcitonin (PCT) we used DNSevTM expert system implementing 13 rules based on decision levels/reference intervals and reference change values. The auto-verification procedure has been implemented after a 6-month trial in June 2004 and in 2005 the immunoassays section supervisor was able to verify about 500 results in about 30 min 5 days/week. We conclude that the auto-verification of immunoassays implemented in our laboratory is fast and consistent among different supervisors and leaves more time for an effective and timely interaction with clinicians and general practitioners.Presented at the 10th Conference Quality in the Spotlight, March 2005, Antwerp, Belgium 相似文献
254.
Michael Strasser Philip Cooper Beatrice Dewald Trevor Payne 《Helvetica chimica acta》1988,71(5):1156-1176
Based on the substrate specificity for 5-lipoxygenase and the known stereochemical course of the reaction, a hypothetical model of the enzyme active site was developed and used to design 2 types of selective inhibitors of 5-lipoxygenase. Both inhibitor types used aromatic rings in place of ( Z )-olefins of the substrate and were designed to mimic the nonpolar end of arachidonic acid. One inhibitor type used a carboxylic-acid interaction with the O-binding centre of the enzyme in analogy with known cyclooxygenase inhibitors, whereas a second type employed a hydroxylamine function to interact with a presumed tyrosine or cysteinyl radical predicted to be in the enzyme active site. Selective 5-lipoxygenase inhibitors were 7-(hexyloxy) naphthalene-2-acetic acid ( 1 ) and N -methyl;- N (7-propoxynaphthalene-2-ethyl)hydroxylamine ( 2 ). Structure-activity relationships for both types of inhibitors are discussed. 相似文献
255.
In studying Γ jk;l i = 0,g ij;k = 0 field theory we require that the underlying structure (Γ βγ α ,g αβ ) be invariant underL (4), the four-dimensional Lorentz group. This can be accommodated into the theory by increasing the dimension to five. In our computer studies we still found a turnabout point forg 44 on running down thex-axis, suggesting that this group may be consistent with a bounded particle. However, with still longer runs down thex-axis, there was some indication that a singularity may be developing. 相似文献
256.
Fabrizio Machetti Beatrice Anichini Stefano Cicchi Alberto Brandi Wanda Wieczorek K. Michal Pietrusiewicz Jean-Claude Gehret 《Journal of heterocyclic chemistry》1996,33(4):1091-1098
Hexahydro-, 5b-1 and 6a,f,1 and tetrahydrophospholo[2,3-d]isoxazoles 8, 9 and 10 were synthesized by 1,3-dipolar cycloaddition of nitrones 3b-1 and benzonitrile oxide ( 4 ) to 2,3-dihydro-1-phenyl-1H-phosphole 1-oxide ( 1 ) and 2,3-dihydro-1-ethoxy-1H-phosphole 1-oxide ( 2 ). The structural assignment to the compounds was confirmed by an X-ray study of two compounds of the series 5a and 5m . The compounds show a good activity as fungicides against Plasmopara viticola on vines and against Botrytis cinerea on apples. Compounds 5a-d showed weak to moderate activity as herbicides. 相似文献
257.
Goti A Anichini B Brandi A Kozhushkov S Gratkowski C de Meijere A 《The Journal of organic chemistry》1996,61(5):1665-1672
Bicyclopropylidene smoothly undergoes 1,3-dipolar cycloadditions to nitrones or nitrile oxides under different reaction conditions. The strained bisspirocyclopropanated isoxazolidines obtained from nitrones easily rearrange upon heating with selective opening of one of the two spirofused cyclopropane rings. This process produces 4-pyridone, 7-indolizinone, and 2-quinolizinone derivatives containing a spirocyclopropane moiety in the alpha-position to the carbonyl group in good yields. The same sequence of cycloaddition and rearrangement can be achieved in a "one-pot" operation with considerable benefit for the reaction yield. Bisspirocyclopropaneisoxazolines obtained from nitrile oxides are more stable than their saturated counterparts and rearrange only at higher temperature less chemoselectively. Opening of both spiro-fused cyclopropyl rings followed by aromatization produces interesting 2-substituted dihydrofuro[2,3-c]pyridine derivatives. 相似文献
258.
[reaction: see text] A comparative study shows that the isopropylsulfinyl group for which an enantiodivergent and highly diastereoselective approach is reported behaves better than the tert-butylsulfinyl and p-tolylsulfinyl groups, both in terms of reactivity and stereoselectivity in the Corey-Chaykovsky reaction of chiral sulfinylimines and the organocatalytic allylation of acyl hydrazones. 相似文献
259.
Reaction of the N-tosylaziridines (p-CH(3)C(6)H(4)SO(2))NCH(2)CHR (1a, R = H; 1b, R = Me; 1c, R = n-Bu; 1d, R = i-Pr) with (bpy)Ni(cod) (2; bpy = 2,2'-bipyridine; cod = 1,5-cyclooctadiene) or (bpy)NiEt(2) (3) results in elimination of cod or butane from 2 and 3, respectively, and oxidative addition of an aziridine C-N bond to give the azametallacyclobutane complexes (bpy)Ni(NTosCHRCH(2)) (4a, R = H; 4b, R = Me; 4c, R = n-Bu; 4d, R = i-Pr) as maroon solids in 50-70% isolated yields. The structure of 4b exhibits a puckered four-membered azametallacycle containing a pyramidal nitrogen and with Ni-N(1) = 1.911(5) A; the tosyl group on N and the methyl substituent on the adjacent C are disposed in an anti conformation. The monodeuterated aziridine syn-(p-CH(3)C(6)H(4)SO(2))NCHDCH-n-Bu (1e) reacts with either 2 or 3 to give (bpy)Ni[NTosCH(n-Bu)CHD] (4e) in 60-65% yield, having an anti arrangement of the methine and methylene protons in the azametallacycle, and indicates that >95% inversion of stereochemistry has occurred at the methylene carbon during the oxidative-addition reaction. When the azametallacyclobutane complexes 4a-e are exposed to oxygen, oxidatively induced reductive elimination ensues, giving the free aziridines in 30-60% isolated yields. In the oxidation of 4e, the product aziridine is spectroscopically identical to its parent, 1e, indicating the elimination that forms the C-N bond also proceeds with inversion of stereochemistry (approximately 92% by (1)H NMR) at the methylene carbon. 相似文献
260.