全文获取类型
收费全文 | 373篇 |
免费 | 16篇 |
国内免费 | 1篇 |
专业分类
化学 | 287篇 |
晶体学 | 4篇 |
力学 | 3篇 |
数学 | 41篇 |
物理学 | 55篇 |
出版年
2023年 | 12篇 |
2022年 | 12篇 |
2021年 | 9篇 |
2020年 | 12篇 |
2019年 | 15篇 |
2018年 | 4篇 |
2017年 | 5篇 |
2016年 | 16篇 |
2015年 | 11篇 |
2014年 | 10篇 |
2013年 | 16篇 |
2012年 | 20篇 |
2011年 | 24篇 |
2010年 | 11篇 |
2009年 | 14篇 |
2008年 | 16篇 |
2007年 | 11篇 |
2006年 | 24篇 |
2005年 | 11篇 |
2004年 | 13篇 |
2003年 | 16篇 |
2002年 | 12篇 |
2001年 | 7篇 |
2000年 | 5篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 1篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 7篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1948年 | 1篇 |
1933年 | 2篇 |
排序方式: 共有390条查询结果,搜索用时 78 毫秒
381.
382.
Sascha Reith Serhiy Demeshko Beatrice Battistella Alexander Reckziegel Christian Schneider Andreas Stoy Crispin Lichtenberg Franc Meyer Dominik Munz C. Gunnar Werncke 《Chemical science》2022,13(26):7907
Imidyl and nitrene metal species play an important role in the N-functionalisation of unreactive C–H bonds as well as the aziridination of olefines. We report on the synthesis of the trigonal imido iron complexes [Fe(NMes)L2]0,− (L = –N{Dipp}SiMe3); Dipp = 2,6-diisopropyl-phenyl; Mes = (2,4,6-trimethylphenyl) via reaction of mesityl azide (MesN3) with the linear iron precursors [FeL2]0,−. UV-vis-, EPR-, 57Fe Mössbauer spectroscopy, magnetometry, and computational methods suggest for the reduced form an electronic structure as a ferromagnetically coupled iron(ii) imidyl radical, whereas oxidation leads to mixed iron(iii) imidyl and electrophilic iron(ii) nitrene character. Reactivity studies show that both complexes are capable of H atom abstraction from C–H bonds. Further, the reduced form [Fe(NMes)L2]− reacts nucleophilically with CS2 by inserting into the imido iron bond, as well as electrophilically with CO under nitrene transfer. The neutral [Fe(NMes)L2] complex shows enhanced electrophilic behavior as evidenced by nitrene transfer to a phosphine, yet in combination with an overall reduced reactivity.A pair of trigonal imido iron complexes ([Fe(NMes)L2]0,−) in two oxidation states is reported. The anionic complex K{crypt.222}[Fe(NMes)L2] is best described as an iron(ii) imide. 相似文献
383.
Luca Valentini Lorenzo Pacini Fosca Errante Cecilia Morchio Beatrice Sanna Paolo Rovero Antonino Morabito 《Molecules (Basel, Switzerland)》2022,27(14)
The combination of pharmacologic and endoscopic therapies is the gold standard for treating intestinal failures. The possibility of chemical solubility in water is mandatory for intelligent capsules. Functionalised silk fibroin with peptides and covalently linking different molecular entities to its structure make this protein a platform for preparing gels dissolving in the small and large intestine for drug delivery. In the present study, we linked a peptide containing the cell-adhesive motif Arginine–Glycine–Aspartic acid (RGD) to degummed silk fibres (DSF). Regenerated silk fibroin (RS) films obtained by dissolving functionalised DSF in formic acid were used to prepare composite gelatin. We show that such composite gelatin remains stable and elastic in the simulated gastric fluid (SGF) but can dissolve in the small and large intestines’ neutral-pH simulated intestine fluid (SIF). These findings open up the possibility of designing microfabricated and physically programmable scaffolds that locally promote tissue regeneration, thanks to bio-enabled materials based on functionalised regenerated silk. 相似文献
384.
Grace van Dervoort Beatrice Sertl Fletcher Mary Hertzog Perry und Katherine Brooks Arsem 《Fresenius' Journal of Analytical Chemistry》1948,128(4-5):517-522
Zusammenfassung o-Nitrososalicylsäure kann leicht und ohne große Kosten hergestellt werden. Das Reagens gibt mit Nickel-Ionen ein rotes, in Wasser lösliches innerkomplexes Salz. Auf Grund dieser Reaktion kann Nickel-Ion einfach und empfindlich bestimmt werden. Da die meisten anderen Metalle mit dem Reagens gefärbte Salze wechselnder Löslichkeit geben, ist es wünschenswert, die vorstehende experimentelle Arbeit fortzusetzen.Gewidmet aus Anlaß des 100jährigen Bestehens des Laboratoriums Fresenius.Diese Arbeit übersandte Dr. Oskar Baudisch, Research Director of the New York State Research Institute of the Saratoga Springs Commission, Saratoga Springs, New York. 相似文献
385.
Friedrich Müller C. Morton E. C. Gilbert Cobb H. M. Partridge M. R. Thompson H. Th. St. Britton W. S. Hughes Beatrice M. Wilson W. B. Pleass A. Roche J. Roche E. B. R. Prideaux F. T. Winfield K. Drewski Fr. L. Hahn A. Petit Erich Müller F. Ishikawa T. Murooka Sho-Chow Woo Don M. Yost M. Delépine O. Stelling R. Bennewitz W. Pugh B. Stehlik N. Allen N. H. Furman I. Tananaeff und L. Tronstad 《Fresenius' Journal of Analytical Chemistry》1933,95(1-3):48-57
Ohne Zusammenfassung 相似文献
386.
Rosa Sparaco Antonia Scognamiglio Angela Corvino Giuseppe Caliendo Ferdinando Fiorino Elisa Magli Elisa Perissutti Vincenzo Santagada Beatrice Severino Paolo Luciano Marcello Casertano Anna Aiello Gilberto De Nucci Francesco Frecentese 《Molecules (Basel, Switzerland)》2023,28(1)
We recently identified 6-nitrodopamine and other nitro-catecholamines (6-nitrodopa, 6-nitroadrenaline), indicating that the endothelium has the ability to nitrate the classical catecholamines (dopamine, noradrenaline, and adrenaline). In order to investigate whether drugs could be subject to the same nitration process, we synthesized 4-nitro- and 7-nitropropranolol as probes to evaluate the possible nitration of the propranolol by the endothelium. The separation of the enantiomers in very high yields and excellent enantiopurity was achieved by chiral HPLC. Finally, we used Riguera’s method to determine the absolute configuration of the enantiomers, through double derivatization with MPA and NMR studies. 相似文献
387.
Beatrice Lansbergen Srija Tewari Ireneusz Tomczyk Maik Seemann Henning Louis Buchholz Mike Rippegarten Daniel Chamier Cieminski Dr. Fabio Juliá Prof. Dr. Tobias Ritter 《Angewandte Chemie (International ed. in English)》2023,62(52):e202313659
We report the first reductive vinylation of alkyl iodides. The reaction uses a vinyl thianthrenium salt, a palladium catalyst, and an alkyl zinc intermediate formed in situ to trap the LnPdII(vinyl) complex formed after oxidative addition before it undergoes undesired homocoupling to form butadiene. 相似文献
388.
Vishal Budhija Phebe H. van Langevelde Konstantin B. Krause Dr. Beatrice Cula Dr. D. G. H. Hetterscheid Dr. Matthias Schwalbe 《欧洲无机化学杂志》2023,26(14):e202200743
Synthesis, characterization and reactivity studies of a hetero-dicopper complex, particularly towards oxygen reduction are presented. A bischlorido copper(II) trishistidine-type coordination unit is positioned directly above a copper porphyrin unit. The close distance between the two coordination fragments is secured by a rigid xanthene backbone. Surprisingly, the dinuclear complex is not active towards oxygen reduction unlike the earlier published mononuclear analogues with a bispyridylamine copper center. However, the compound architecture of this multinuclear metal complex is interesting and can play an important role in the development of new catalysts for ORR. 相似文献
389.
The C−F bond activation of pentafluoropyridine and 2,3,5,6-tetrafluoropyridine at [Ni(cod)2] (cod=1,5-cyclooctadiene) in the presence of the phosphine PPh2(Ind) (Ind=3-methyl-2-indolyl) led to the formation of the nickel(II) fluorido bis(phosphine) complexes trans-[Ni(F)(2-C5NF4){PPh2(Ind)}2] and trans-[Ni(F)(2-C5HNF3){PPh2(Ind)}2]. The complexes are characterized by the presence of intramolecular hydrogen bonds between the NH group of the phosphine ligands and the fluorido ligand. Stochiometric model reactions of nickel(II) fluorido complexes with PhB(OH)2 revealed that the former can be considered as intermediates in Suzuki–Miyaura cross coupling reactions. Catalytic experiments were attempted using 10 mol-% of trans-[Ni(F)(2-C5NF4){PPh2(Ind)}2] as catalyst and the activities of the PPh2(Ind) complex were compared to the ones of an analogous nickel(II) fluorido complex, bearing PPh3 instead of PPh2(Ind) as ligands. The latter exhibited a somewhat lower catalytic activity suggesting a slight influence of the H-bonds in the outer coordination sphere. 相似文献
390.
Aneta Slodczyk Philippe Colomban Stephanie Willemin Olivier Lacroix Beatrice Sala 《Journal of Raman spectroscopy : JRS》2009,40(5):513-521
OH− and H3O+ species in hydrates and simple oxides are rather well characterised from their IR, Raman and inelastic neutron points of view. For the H+ (H2O) species in solid state the variability is well established and assignment remains discussed. The question of the vibrational signature of isolated proton (e.g. the ionic proton, a proton sharing its interaction with more than two acceptors) and its dynamic nature (proton gas, polaron,…) is open. H+‐containing modified perovskites A(Ba,Sr,…) B(Zr,Ce,Ti,…) O3 are potential ceramic membranes for fuel cell and medium temperature water electrolysis (300–800 °C). Comparison studies of the protonated and non‐protonated lanthanide/rare earth‐modified perovskites of type Ba(Sr)Zr(Ti)O3 as well as Al‐modified BaTiO3 show that a broad component centred at 2500 cm−1 is observed after ‘proton insertion’. Its intensity is correlated to the protonic species content as well as to the conductivity of the materials. The mixed nature of this feature is discussed: fluorescence related to the dangling bonds, A, B, C bands or new phenomena related to the ionic protons and associated electronic defect. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献