全文获取类型
收费全文 | 1800篇 |
免费 | 66篇 |
国内免费 | 4篇 |
专业分类
化学 | 1576篇 |
晶体学 | 4篇 |
力学 | 9篇 |
数学 | 106篇 |
物理学 | 175篇 |
出版年
2023年 | 20篇 |
2022年 | 13篇 |
2021年 | 40篇 |
2020年 | 39篇 |
2019年 | 26篇 |
2018年 | 30篇 |
2017年 | 27篇 |
2016年 | 51篇 |
2015年 | 60篇 |
2014年 | 73篇 |
2013年 | 90篇 |
2012年 | 105篇 |
2011年 | 107篇 |
2010年 | 62篇 |
2009年 | 59篇 |
2008年 | 95篇 |
2007年 | 103篇 |
2006年 | 97篇 |
2005年 | 80篇 |
2004年 | 62篇 |
2003年 | 44篇 |
2002年 | 58篇 |
2001年 | 25篇 |
2000年 | 28篇 |
1999年 | 18篇 |
1998年 | 15篇 |
1997年 | 10篇 |
1995年 | 17篇 |
1993年 | 9篇 |
1992年 | 10篇 |
1991年 | 15篇 |
1990年 | 13篇 |
1989年 | 13篇 |
1987年 | 9篇 |
1986年 | 10篇 |
1985年 | 11篇 |
1984年 | 12篇 |
1983年 | 12篇 |
1971年 | 9篇 |
1970年 | 11篇 |
1968年 | 13篇 |
1967年 | 15篇 |
1966年 | 18篇 |
1965年 | 19篇 |
1964年 | 27篇 |
1963年 | 24篇 |
1962年 | 10篇 |
1961年 | 19篇 |
1960年 | 11篇 |
1958年 | 10篇 |
排序方式: 共有1870条查询结果,搜索用时 46 毫秒
31.
H. Nowotny Helga Auer-Welsbach J. Bruss A. Kohl 《Monatshefte für Chemie / Chemical Monthly》1959,90(1):15-23
Zusammenfassung Die Parameter des D 88-Struktur werden mit Hilfe gut ausgebildeter Einkristalle von Ti5Si3 neu bestimmt. Die dazu isotype Kristallart Zr5Al3 wird im System: Zr–Al nachgewiesen. Im Schnitt: Ti5Sn3–Zr5Sn3 bzw. Zr5Pb3–Ti (5) Pb (3) tritt ein lückenloser bzw. sehr ausgedehnter Bereich von Mischkristallen mit D88-Typ auf.Mit 1 Abbildung 相似文献
32.
33.
Zusammenfassung Es wird eine neue polarographische Methode zur direkten Bestimmung des Pyridoxols in Injektionspräparaten und Tabletten beschrieben. Die ausgearbeitete Methode beruht auf der polarographischen Reduktion des Pyridoxolmoleküls im Milieu von Ammoniak-Ammoniumchlorid-Puffern und weiter auf der Bildung einer katalytischen Stufe des Pyridoxols in Veronalpuffern. Die polarographische Methode ist rascher und in manchen Fällen genauer und empfindlicher als die bisher in Gebrauch stehenden Methoden. Die Anwesenheit der in den Präparaten laufend vorkommenden Begleitstoffe des Pyridoxols stört nicht die polarographische Bestimmung. Die Methode kann auch zur Bestimmung des 3-Hydroxy-4-methoxymethyl-5-oxymethyl-2-methylpyridins benutzt werden, das ein Zwischenprodukt bei der Pyridoxolerzeugung ist.
Herrn Dr.P. Zuman danken wit für Ratsehläge bei der Abfassung dieser Arbeit. 相似文献
Summary A new polarographic method is described for the direct determination of pyridoxol in injection preparations and tablets. This method is based on the polarographic reduction of the pyridoxol in ammonia-ammonium chloride buffer medium and also on the formation of a catalytic stage of the pyridoxol in veronal buffers. The polarographic method is faster and in many cases more accurate and more sensitive than the methods now in use. The presence of the materials which always accompany the pyridoxol in the preparations does not interfere with the polarographic determination. The method can likewise be used for determining 3-hydroxy-4-methoxymethyl-5-oxymethyl-2-methylpyridine, which is an intermediate product in the manufacture of pyridoxol.
Résumé On décrit une nouvelle méthode polarographique pour le dosage direct du pyridoxol dans les préparations pour injections et dans les comprimés. La méthode élaborée repose sur la réduction polarographique de la molécule de pyridoxol dans le milieu tampon ammoniaque-chlorure d'ammonium, et, en outre, sur la formation d'une phase catalytique du pyridoxol dans les tampons au véronal. La méthode polarographique est plus rapide et dans de nombreux cas plus exacte et plus sensible que les méthodes utilisées jusqu'ici. La présence d'impuretés existant couramment dans les préparations à côté du pyridoxol ne gêne pas le dosage polarographique. On peut aussi utiliser la méthode pour le dosage de l'hydroxy-3 méthoxyméthyl-4 oxyméthyl-5 méthyl-2 pyridine, substance intermédiaire dans la préparation du pyridoxol.
Herrn Dr.P. Zuman danken wit für Ratsehläge bei der Abfassung dieser Arbeit. 相似文献
34.
Ohne Zusammenfassung 相似文献
35.
Zusammenfassung V-Si-Ge-Legierungen werden aus den Komponenten hergestellt und röntgenographisch untersucht. V3Si und V3Ge bilden eine lückenlose Mischreihe. Ebenso gehen die T1-Phasen V5Si3 und V5Ge3 homogen über, was auch für die C-stabilisierten Phasen mit teilweise aufgefüllter Mn5Si3-Struktur gilt. V11Ge8 löst praktisch kein Silicid und steht mit V5(Si, Ge)3 und (Ge, Si)-Mischkristall im Gleichgewicht. Im Disilicid erfolgt ein Si/Ge-Austausch bis etwa 11 (1000°C Homogenisierungstemp.). Bei dieser Temp. tritt nach kurzen Glühzeiten das sogenannte Digermanid (V17Ge31) noch nicht in Erscheinung.
Mit 1 Abbildung 相似文献
V-Si-Ge-alloys have been prepared out of the components and examined. V3Si and V3Ge do form a contineous solid solution, the same is true for V5Si3 and V5Ge3 either for the W5Si3-structure or for the carbon stabilized Mn5Si3-type phases. V11Ge8 does not dissolve any silicide. There are equilibria between V11Ge8, V5(Si,Ge)3 and a (Ge, Si)-solid solution. Silicon can be substituted by germanium in VSi2 up to 11 (1000°C homogenizing temperature). At this temperature the so called digermanide (V17Ge31) does not occur after a short anneal.
Mit 1 Abbildung 相似文献
36.
Jagoda M Warzeska S Pritzkow H Wadepohl H Imhof P Smith JC Krämer R 《Journal of the American Chemical Society》2005,127(43):15061-15070
For a number of phosphoryltransfer enzymes, including the exonuclease subunit of DNA polymerase I, a mechanism involving two-metal ions and double Lewis-acid activation of the substrate, combined with leaving group stabilization, has been proposed. Inspired by the active site structure of this enzyme, we have designed as a synthetic phosphoryl transfer catalyst the dicopper(II) macrocyclic complex LCu(2). Crystal structures of complexes [(L)Cu(2)(mu-NO(3))(NO(3))](NO(3))(2) (1), [(L)Cu(2)(mu-CO(3))(CH(3)OH)](BF(4))(2) (2), and [(L)Cu(2)(mu-O(2)P(OCH(3))(2))(NO(3))](NO(3))(2) (3) illustrate various possibilities for the interaction of oxoanions with the dicopper(II) site. 1 efficiently promotes the transesterification of dimethyl phosphate (DMP) in CD(3)OD, k(cat) = 2 x 10(-)(4) s(-)(1) at 55 degrees C. 1 is the only available catalyst for the smooth transesterification of highly inert simple dialkyl phosphates. From photometric titrations and the pH dependence of reactivity, we conclude that a complex [(L)Cu(2)(DMP)(OCH(3))](2+) is the reactive species. Steric bulk at the -OR substituents of phosphodiester substrates O(2)P(OR)(2)(-) drastically reduces the reactivity of 1. This is explained with -OR leaving group stabilization by Cu coordination, an interaction which is sensitive to steric crowding at the alpha-C-atom of substituent R. A proposed reaction mechanism related to that of the exonuclease unit of DNA polymerase I is supported by DFT calculations on reaction intermediates. The complex [(L)Cu(3)(mu(3)-OH)(mu-CH(3)O)(2)(CH(3)CN)(2)](ClO(4))(3) (4) incorporates a [Cu(OH)(OCH(3))(2)(CH(3)CN)(2)](-) complex anion, which might be considered as an analogue of the [PO(2)(OCH(3))(2)(OCD(3))](2)(-) transition state (or intermediate) of DMP transesterification catalyzed by LCu(2). 相似文献
37.
Petra Spitzer Bruno Rossi Yves Gaignet Stéphane Mabic Uwe Sudmeier 《Accreditation and quality assurance》2005,10(3):78-81
There is currently a major issue with the calibration of conductivity meters used for high purity water: the lack of availability of a reference material or reference methods for low conductivity ranges (conductivity below 1 S cm–1 at 25.0 °C, resistivity >1 M cm at 25.0 °C). This paper describes the current status of conductivity measurements in high purity water. A new and improved approach, currently being investigated, should allow us to make the calibration of conductivity meters used for low conductivity ranges traceable to the SI.Milipore, Milli-Q and Elix are registered trademarks of Millipore Corporation. 相似文献
38.
Michael?Sch?ferlingEmail author Michael?Riepl Petra?Pavlickova Hubert?Paul Dev?Kambhampati Bo?Liedberg 《Mikrochimica acta》2003,142(4):193-203
Two different types of -substituted alkanethiol/disulfide compounds have been used to prepare monolayer architectures on gold serving as platforms for the immobilization of receptor probe molecules – antibodies. These are: (i) carboxylic acid alkanethiols post-reacted with amino biotin to generate streptavidin surfaces, and (ii) N-hydroxysuccinimide-terminated disulfide surfaces. The properties of the monolayers, with and without attached receptor probe molecules, were analysed using infrared spectroscopy, ellipsometry, fluorescence scanning and atomic force microscopy. Several experimental parameters, such as condensation reagents, additives, probe and target concentrations and immobilization time, were systematically varied to determine the dynamic range and to optimize the sensitivity and signal-to-noise ratio of the biochip platforms. Fluorescence screening using Cy5-labelled antigens finally demonstrated that both surfaces could be successfully employed to immobilize the antibodies. The pros and cons of the two approaches are also discussed.Received November 15, 2002; accepted March 25, 2003
Published online July 28, 2003 相似文献
39.
Crystalline title compound (1) prepared from aqueous solution of theophylline and 1,4-diaminobutane has been structurally and thermally characterized. Both the two-step TG decomposition curve and elemental analysis of the hexagonal crystals show that it consists of theophylline and 1,4-diaminobutane in 2:1 molar ratio. Actually, presence of one type of both theophyllinate anions and 1,4-diammoniumbutane dication have been indicated by FTIR spectroscopy. The molecular structure of lattice compound (1) has been determined by single crystal X-ray diffraction, where the hydrogen positions have been obtained from differential Fourier maps. It has confirmed that the crystal is really built up from these ionic constituents bound together with an extensive net of hydrogen bonds. The coupled TG-FTIR analysis of the evolved gases has revealed that the diamine is released as a whole molecule in the first decomposition step. Clathrate 1 and the proton migration in it might serve as a structural model of solid aminophylline whose crystal structure is still unknown. 相似文献
40.
Žaneta Mesíková Petra Šulcová M. Trojan 《Journal of Thermal Analysis and Calorimetry》2006,84(3):733-736
Synthesis of the green
spinel pigment Co0.46Zn0.55(Ti0.064Cr0.91)2O4 by a novel two-step method of preparation have
been investigated. Inorganic pigments are almost always prepared by a solid
state reaction. It is classical ceramic method which used oxides, hydroxides
or carbonates as precursors. The reaction is performed at temperature higher
than 1300°C and an agent of mineralization is usually present. The presented
novel method of preparation decreases the calcining temperature necessary
for reaching of bright and clear hue of the pigments prepared. Main attention
was focused on the influence of two types of titanium raw materials on the
temperature region of the spinel structure formation and on the colour properties
of the pigments. The mixture of precursors with TiO2
gives a one-phase system when calcining at 1100°C but the colour properties
are more interesting at 1150°C. Thermal stability of this pigment is limited
by temperature 1300°C. This temperature is connected with partial oxidation
of Cr(III) to Cr(VI). Thermal analysis provided the first information about
the temperature region of the pigment formation and determined the thermal
stability of pigment. 相似文献