全文获取类型
收费全文 | 213篇 |
免费 | 4篇 |
专业分类
化学 | 138篇 |
晶体学 | 3篇 |
力学 | 4篇 |
数学 | 10篇 |
物理学 | 62篇 |
出版年
2023年 | 2篇 |
2021年 | 2篇 |
2020年 | 3篇 |
2015年 | 5篇 |
2013年 | 3篇 |
2012年 | 10篇 |
2011年 | 12篇 |
2010年 | 2篇 |
2009年 | 7篇 |
2008年 | 3篇 |
2007年 | 6篇 |
2006年 | 8篇 |
2005年 | 5篇 |
2004年 | 4篇 |
2003年 | 3篇 |
2002年 | 5篇 |
2001年 | 8篇 |
2000年 | 6篇 |
1999年 | 9篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 9篇 |
1989年 | 3篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1979年 | 5篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1975年 | 6篇 |
1974年 | 3篇 |
1973年 | 5篇 |
1972年 | 2篇 |
1971年 | 6篇 |
1970年 | 3篇 |
1969年 | 3篇 |
1967年 | 4篇 |
1959年 | 4篇 |
1940年 | 2篇 |
1933年 | 2篇 |
1932年 | 1篇 |
1931年 | 1篇 |
1929年 | 1篇 |
1922年 | 1篇 |
1903年 | 1篇 |
1902年 | 1篇 |
排序方式: 共有217条查询结果,搜索用时 15 毫秒
61.
R. Keil 《Fresenius' Journal of Analytical Chemistry》1977,288(4):288
Ohne Zusammenfassung 相似文献
62.
R. Keil 《Fresenius' Journal of Analytical Chemistry》1981,305(5):374-378
Zusammenfassung Thorium wird durch Extraktion mit Triphenylarsinoxid in CHCl3 und Rückextraktion mit 4 M HCl auf ein kleines Volumen konzentriert. Die Endbestimmung erfolgt spektralphotometrisch als Arsenazo-III-Komplex bei 660 nm in Mikroküvetten. Auf diese Weise konnte vor allem die Bestimmung von Spurenmengen Th wesentlich verbessert werden. 7 ng Th sind in bis zu 200 ml Ausgangslösung noch bestimmbar. Untersuchungen mit über 60 Kationen und etwa 20 Anionen zeigten, daß diese in weiten Grenzen nicht stören. U6+ wird zwar auch mitextrahiert, gibt aber in der salzsauren Rückextraktionslösung mit Arsenazo III einen etwa 15mal weniger lichtabsorbierenden Farbkomplex. Da aber Uran von den getesteten Kationen trotzdem am meisten stört und in Analysenproben das Th oft begleitet, werden weitere einfache Maßnahmen gezeigt, die einen bis zu 5000fachen Überschuß an Uran erlauben. Es wurde gefunden, daß auch die Seltenen Erden nicht stören und die zum Test verwendeten Seltenen Erd-Chemikalien Th enthalten. Bestimmungen in Standardgesteinen und Zementproben bestätigen die Anwendbarkeit der Methode.
Selective spectrophotometric trace determination of thorium by arsenazo III following pre-concentration by extraction
Summary Thorium is concentrated to a small volume by extraction with triphenylarsine oxide in chloroform and back extraction with 4M HCl. The spectrophotometric determination is then carried out in a micro cuvette using the absorption of the arsenazo III complex at 660 nm. By this procedure a sensitivity of 7 ng of Th in 200 ml solution can be achieved. About 60 cations and 20 anions were found not to cause interferences in a wide concentration range. The most disturbing element is U6+ which is coextracted, but leads to an arsenazo complex, which absorbs light at 660 nm about 15 times less than the Th complex. By simple measures, up to 5000 times higher U contents, as to Th, can be tolerated. Also the rare earths do not disturb the Th determination and it was found, that most rare earths chemicals, which were used for the tests, contained Th. The reliability of the method was confirmed by the analysis of standard rocks and by comparing the Th analyses of concrete samples with those obtained by neutron activation analysis.
Für die Überprüfung des Manuskriptes möchte ich Herrn Dr. P. Baertschi herzlich danken. 相似文献
63.
64.
Ion/molecule reactions for detecting ammonia using miniature cylindrical ion trap mass spectrometers
Gaseous ammonia, a common toxic industrial compound, is not detected readily in ion trap mass spectrometers because its molecular ion falls below the low-mass cutoff (~m/z 40) normally used when examining organic compounds. Instead, reactions of ammonia with halobenzene radical cations were used with internal electron ionization in two cylindrical ion trap miniature mass spectrometers to create a characteristic product ion by which to identify and quantify ammonia. Ammonia showed a linear response over the concentration range studied (parts per million [ppm] to parts per billion [ppb]) with limits of detection of 17 ppm and 220 ppb for experiments involving direct introduction and thermal desorption after pre-concentration, respectively. These values are comparable to ammonia's permissible exposure limit (50 ppm) and odor threshold (5 ppm). Receiver operating characteristic (ROC) curves were used to describe the method sensitivity, the probability of true positives, and the false positive rate for ammonia. A customized reaction scan function was created to select the species available for the ion/molecule reaction and set the amount of time the product ion could be accumulated in the trap. Product ion identity was verified using tandem mass spectrometry. Similar reactions with methylamine, ethylamine and the two nitriles, acetonitrile and benzonitrile, were explored. 相似文献
65.
Pareek A Borodin S Bashir A Ankah GN Keil P Eckstein GA Rohwerder M Stratmann M Gründer Y Renner FU 《Journal of the American Chemical Society》2011,133(45):18264-18271
Dealloying is widely utilized but is a dangerous corrosion process as well. Here we report an atomistic picture of the initial stages of electrochemical dealloying of the model system Cu(3)Au (111). We illuminate the structural and chemical changes during the early stages of dissolution up to the critical potential, using a unique combination of advanced surface-analytical tools. Scanning tunneling microscopy images indicate an interlayer exchange of topmost surface atoms during initial dealloying, while scanning Auger-electron microscopy data clearly reveal that the surface is fully covered by a continuous Au-rich layer at an early stage. Initiating below this first layer a transformation from stacking-reversed toward substrate-oriented Au surface structures is observed close to the critical potential. We further use the observed structural transitions as a reference process to evaluate the mechanistic changes induced by a thiol-based model-inhibition layer applied to suppress surface diffusion. The initial ultrathin Au layer is stabilized with the intermediate island morphology completely suppressed, along an anodic shift of the breakdown potential. Thiol-modification induces a peculiar surface microstructure in the form of microcracks exhibiting a nanoporous core. On the basis of the presented atomic-scale observations, an interlayer exchange mechanism next to pure surface diffusion becomes obvious which may be controlling the layer thickness and its later change in orientation. 相似文献
66.
Yulian Pang Shuheng Fan Qunying Wang Dennis Oprych Alfred Feilen Knut Reiner Dietmar Keil Yuriy L. Slominsky Sergey Popov Yingquan Zou Bernd Strehmel 《Angewandte Chemie (International ed. in English)》2020,59(28):11440-11447
Cyanines comprising either a benzo[e]‐ or benzo[c,d]indolium core facilitate initiation of radical photopolymerization combined with high power NIR‐LED prototypes emitting at 805 nm, 860 nm, or 870 nm, while different oxime esters function as radical coinitiators. Radical photopolymerization followed an initiation mechanism based on the participation of excited states, requiring additional thermal energy to overcome an existing intrinsic activation barrier. Heat released by nonradiative deactivation of the sensitizer favored the system, even under conditions where a thermally activated photoinduced electron transfer controls the reaction protocol. The heat generated internally by the NIR sensitizer promotes generation of the initiating reactive radicals. Sensitizers with a barbiturate group at the meso‐position preferred to bleach directly, while sensitizers carrying a cyclopentene moiety unexpectedly initiated the photosensitized mechanism. 相似文献
67.
R. Keil 《Fresenius' Journal of Analytical Chemistry》1981,309(3):181-185
Zusammenfassung Die beschriebene Methode für die Bestimmung von Tl in Zement und dessen Ausgangsmaterialien eignet sich auch für die Spurenbestimmung in Gesteinen, Lösungen, usw. Spuren von Tl können aus großen Gehalten von Ca oder Fe durch Maskieren der Fremdelemente in mineralsaurer Lösung mit großen Mengen Citronensäure, Ascorbinsäure, wenn nötig auch mit KCN, und Extrahieren bzw. Konzentrieren des Tl als Diethyldithiocarbaminat-Komplex mit kleinen Mengen Methylisobutylketon bei pH 10,5 abgetrennt werden. Tl+ und auch Tl3+ werden erfaßt. Der Methylisobutylketon-Extrakt kann direkt in die Flamme eingesprüht werden. Die Empfindlichkeit ist in Methylisobutylketon-Lösung etwa um 30% besser als in rein wäßriger Lösung. Ein Zusatz von Cd, welches unter den gegebenen Bedingungen ebenfalls mitextrahiert wird, verbessert die Empfindlichkeit durch Interferenzeffekt nochmals um weitere 30 %. Wird eine Proben-Einwaage von 1 g zur Extraktion verwendet, so kann noch 0,1 ppm Tl im Ausgangsmaterial nachgewiesen werden. 60 untersuchte Kationen und etwa 20 Anionen stören in weiten Grenzen nicht. Mit der flammenlosen Atomisierung im Graphitrohrofen können noch 20–100mal kleinere Mengen Tl bestimmt werden, wenn das Tl im Methylisobutyl-Extrakt mit HNO3 in die Nitratform gebracht und mit Alkohol verdünnt wird. Die Methoden wurden mit Standardgesteinen und Zementproben mit zugesetztem Tl überprüft.
Trace determination of thallium in rocks by flame or flameless atomic absorption spectrophotometry following pre-concentration by extraction
Summary A sensitive method for the trace analysis of Tl in cement raw materials, rocks and other samples by AAS is described. To the aqueous sample solutions, containing mainly Ca or Fe, large amounts of citric and ascorbic acid were added for masking interfering cations. Tl is extracted and concentrated as the diethyldithiocarbamate complex in methyl-isobutylketone at pH 10.5. This extract can directly be injected into the flame. The sensitivity was found to be 30% higher than for aqueous solutions and can be enhanced by another 30% by addition of some Cd. For a 1 g-sample the sensitivity is about 0.1 ppm Tl. Some 60 cations and 20 anions may be present in rather large amounts without disturbing the Tl-determination. A procedure for the flameless AAS is also described leading to a 20–100 times higher sensitivity. The methods were tested with standard rocks and with cement samples to which defined amounts of Tl had been added.
Für die Überprüfung des Manuskriptes möchte ich den Herren Dr. P. Baertschi und O. Antonsen herzlich danken. 相似文献
68.
69.
Wells JM Roth MJ Keil AD Grossenbacher JW Justes DR Patterson GE Barket DJ 《Journal of the American Society for Mass Spectrometry》2008,19(10):1419-1424
A recently developed prototype mobile laboratory mass spectrometer, incorporating an atmospheric pressure ionization (API) interface, is described. This system takes advantage of the small size, lower voltage requirements, and tandem MS abilities of the cylindrical ion trap mass analyzer. The prototype API MS uses small, low-power pumps to fit into a 0.1-m(3) self-contained package weighing <45 kg. This instrument has been adapted to allow rapid interfacing to electrospray ionization, desorption electrospray ionization, and direct analysis in real-time sources. Initial data indicate that these techniques provide rapid detection and identification of compounds for quality control, homeland security, and forensic applications. In addition, this instrument is self-contained and compact, making it ideally extensible to mobile laboratory and field analyses. Initial MS and MS/MS data for analyses of drugs, food, and explosives are presented herein. 相似文献
70.
Tobias Titze Alexander Lauerer Dr. Lars Heinke Dr. Christian Chmelik Dr. Nils E. R. Zimmermann Prof. Frerich J. Keil Prof. Douglas M. Ruthven Prof. Jörg Kärger 《Angewandte Chemie (International ed. in English)》2015,54(48):14580-14583
Diffusion in nanoporous host–guest systems is often considered to be too complicated to comply with such “simple” relationships as Fick’s first and second law of diffusion. However, it is shown herein that the microscopic techniques of diffusion measurement, notably the pulsed field gradient (PFG) technique of NMR spectroscopy and microimaging by interference microscopy (IFM) and IR microscopy (IRM), provide direct experimental evidence of the applicability of Fick’s laws to such systems. This remains true in many situations, even when the detailed mechanism is complex. The limitations of the diffusion model are also discussed with reference to the extensive literature on this subject. 相似文献