全文获取类型
收费全文 | 11136篇 |
免费 | 307篇 |
国内免费 | 32篇 |
专业分类
化学 | 8292篇 |
晶体学 | 34篇 |
力学 | 182篇 |
数学 | 1821篇 |
物理学 | 1146篇 |
出版年
2020年 | 142篇 |
2019年 | 114篇 |
2018年 | 79篇 |
2017年 | 81篇 |
2016年 | 200篇 |
2015年 | 204篇 |
2014年 | 197篇 |
2013年 | 381篇 |
2012年 | 415篇 |
2011年 | 487篇 |
2010年 | 357篇 |
2009年 | 294篇 |
2008年 | 481篇 |
2007年 | 471篇 |
2006年 | 507篇 |
2005年 | 461篇 |
2004年 | 391篇 |
2003年 | 328篇 |
2002年 | 353篇 |
2001年 | 235篇 |
2000年 | 176篇 |
1999年 | 164篇 |
1998年 | 190篇 |
1997年 | 160篇 |
1996年 | 166篇 |
1995年 | 174篇 |
1994年 | 152篇 |
1993年 | 197篇 |
1992年 | 139篇 |
1991年 | 136篇 |
1990年 | 130篇 |
1989年 | 146篇 |
1988年 | 142篇 |
1987年 | 174篇 |
1986年 | 163篇 |
1985年 | 179篇 |
1984年 | 191篇 |
1983年 | 159篇 |
1982年 | 152篇 |
1981年 | 152篇 |
1980年 | 155篇 |
1979年 | 149篇 |
1978年 | 144篇 |
1977年 | 126篇 |
1976年 | 134篇 |
1975年 | 96篇 |
1974年 | 91篇 |
1973年 | 92篇 |
1971年 | 82篇 |
1970年 | 75篇 |
排序方式: 共有10000条查询结果,搜索用时 62 毫秒
131.
Zusammenfassung Für Elementbestimmungen in Abwasser wird ein Röntgenfluorescenzverfahren beschrieben. Zur Probenvorbereitung werden die Elemente durch Gefriertrocknung auf einem inerten Träger angereichert. Diese Anreicherung ist nicht selektiv und erfaßt praktisch alle in Abwasser gelösten und suspendierten Verunreinigungen. Für die Berechnung der Elementkonzentrationen aus den gemessenen Fluorescenzintensitäten wird ein Matrixkorrekturverfahren angegeben, welches dem unterschiedlichen Absorptionsverhalten der Probenmatrix Rechnung trägt. Die Massenabsorptionskoeffizienten werden durch Messung der diffus gestreuten Bremsstrahlung bzw. der Comptonstreustrahlung ermittelt. Die Selbstabsorption des zu bestimmenden Elementes wird rechnerisch berücksichtigt. Das Korrekturverfahren kann auf alle mit Röntgenfluorescenzanalyse bestimmbaren Elemente angewendet werden.
Determination of elements in waste water by x-ray fluorescence analysis: Sample preparation and matrix correction method
Summary For sample preparation the elements are enriched upon an inert carrier by freeze-drying. This enriching procedure is not selective and collects all dissolved and suspended contaminations from the waste water. In order to calculate the element concentrations from the measured fluorescence intensities a matrix correction method is given which considers the different absorption behaviour of the matrix. The mass absorption coefficients are obtained by measuring the scattered X-ray tube spectrum or a Compton scattered X-ray tube line, respectively. The self-absorption of the element to be determined is taken into account. The correction method is applicable to all elements detectable by X-ray fluorescence.
Herrn Dr. H. Wagner danken wir für das stete Interesse, die zahlreichen konstruktiven Diskussionen und die Hilfe beim Abfassen des Manuskripts. 相似文献
132.
The excitation energy in the multiphoton ionization spectrum of the trans-1-naphthol/N(2) cluster shows only a small red shift with respect to isolated naphthol, indicating a van der Waals pi-bound structure rather than a hydrogen-bonded one. To confirm this interpretation, high-level electronic structure calculations were performed for several pi- and hydrogen-bonded isomers of this cluster. The calculations were carried out at the second order M?ller-Plesset (MP2) level of perturbation theory with the family of correlation consistent basis sets up to quintuple-zeta quality including corrections for the basis set superposition error and extrapolation to the MP2 complete basis set (CBS) limit. We report the optimal geometries, vibrational frequencies, and binding energies (D(e)), also corrected for harmonic zero-point energies (D(0)), for three energetically low-lying isomers. In all calculations the lowest energy structure was found to be an isomer with the N(2) molecule bound to the pi-system of the naphthol ring carrying the OH group. In the CBS limit its dissociation energy was computed to be D(0) = 2.67 kcal/mol (934 cm(-1)) as compared to D(0) = 1.28 kcal/mol (448 cm(-1)) for the H-bound structure. The electronic structure calculations therefore confirm the assignment of the experimental electronic spectrum corresponding to a van der Waals pi-bound structure. The energetic stabilization of the pi-bound isomer with respect to the hydrogen-bonded one is rather unexpected when compared with previous findings in related systems, in particular phenol/N(2). 相似文献
133.
Cédric Kalinski Michael Umkehrer Nadine Jäger Wolfgang Hiller 《Tetrahedron letters》2006,47(12):2041-2044
A combinatorial synthetic route yielding fused tetrazolo[1,5-a]quinoxalines is described. The use of 2-fluorophenylisocyanide in the Ugi-tetrazole reaction (tetrazole-U-4CR) followed by a nucleophilic aromatic substitution (SNAr) affords the tricylic tetrazolo[1,5-a]quinoxaline moiety in good yields and with high diversity. 相似文献
134.
Fry BG Wüster W Ryan Ramjan SF Jackson T Martelli P Kini RM 《Rapid communications in mass spectrometry : RCM》2003,17(18):2047-2062
The evolution of the venomous function of snakes and the diversification of the toxins has been of tremendous research interest and considerable debate. It has become recently evident that the evolution of the toxins in the advanced snakes (Colubroidea) predated the evolution of the advanced, front-fanged delivery mechanisms. Historically, the venoms of snakes lacking front-fanged venom-delivery systems (conventionally grouped into the paraphyletic family Colubridae) have been largely neglected. In this study we used liquid chromatography with mass spectrometry (LC/MS) to analyze a large number of venoms from a wide array of species representing the major advanced snake clades Atractaspididae, Colubrinae, Elapidae, Homalopsinae, Natricinae, Psammophiinae, Pseudoxyrhophiinae, Xenodontinae, and Viperidae. We also present the first sequences of toxins from Azemiops feae as well as additional toxin sequences from the Colubrinae. The large body of data on molecular masses and retention times thus assembled demonstrates a hitherto unsuspected diversity of toxins in all lineages, having implications ranging from clinical management of envenomings to venom evolution to the use of isolated toxins as leads for drug design and development. Although definitive assignment of a toxin to a protein family can only be done through demonstrated structural studies such as N-terminal sequencing, the molecular mass data complemented by LC retention information, presented here, do permit formulation of reasonable hypotheses concerning snake venom evolution and potential clinical effects to a degree not possible till now, and some hypotheses of this kind are proposed here. The data will also be useful in biodiscovery. 相似文献
135.
Wolfgang Frenzel 《Fresenius' Journal of Analytical Chemistry》1998,361(8):774-779
A method for the semi-quantitative colorimetric determination of chromium(VI) at sub μg/L levels after sorptive preconcentration
is presented. The method is based on the retention of the reaction product (preformed in liquid phase) between Cr(VI) and
diphenylcarbazide on membrane embedded cation exchange material. The color intensity of the membrane can be correlated to
Cr(VI) concentrations in the range 0.05–50 μg/L (i.e. almost three orders of magnitude lower than the conventional spectrophotometric
procedure) with a detection limit of about 10 ng/L (using 50 mL of sample volume). Due to the visual inspection mode and comparative
color detection the precision is only 30–80% rsd which, however, is regarded as sufficient for screening purposes. Analysis
of real samples including different kinds of waters and extracts of soil and filter collected airborne particulate matter
demonstrated the applicability of the method for fast and species selective screening. Recovery experiments generally gave
reasonably good results, yet also revealed the risk of the conversion of chromium species during sample pretreatment procedures
due to redox reactions.
Received: 1 December 1997 / Revised: 23 February 1998 / Accepted: 10 March 1998 相似文献
136.
The synthesis of N-methyl-benz[f]isoindole ( 2 ) and N-methyl-dibenz[e,g]isoindole ( 3 ) is reported. The NMR. spectra of N-methyl-isoindole ( 1 ) and of 2 have been analysed and the implications concerning the alternation of bond lengths are discussed. The photophysical properties of 1 to 3 have been investigated by the following methods: HeI photoelectron (PE.) spectroscopy, UV./VIS. absorption (polarization measurements by the stretched-foil technique) and emission spectroscopy (fluorescence spectra, lifetimes and quantum yields, phosphorescence spectra), and flash spectroscopy (triplet-triplet absorption spectra). The discussion of the results is based on HMO. and PPP SCF CI. calculations and points to the relationship between the heterocycles 1 to 3 and the corresponding benzenoid hydrocarbons obtained by replacement of the ? NMe? subunit by ? CH?CH? . Some comments concerning the ground state properties of isoindole and related compounds are derived from the analysis of their electronic structure. 相似文献
137.
The perturbed-chain statistical associating fluid theory (PC-SAFT) is studied for a wide range of temperature, T, pressure, p, and (effective) chain length, m, to establish the generic phase diagram of polymers according to this theory. In addition to the expected gas-liquid coexistence, two additional phase separations are found, termed "gas-gas" equilibrium (at very low densities) and "liquid-liquid" equilibrium (at densities where the system is expected to be solid already). These phase separations imply that in one-component polymer systems three critical points occur, as well as equilibria of three fluid phases at triple points. However, Monte Carlo simulations of the corresponding system yield no trace of the gas-gas and liquid-liquid equilibria, and we conclude that the latter are just artefacts of the PC-SAFT approach. Using PC-SAFT to correlate data for polybutadiene melts, we suggest that discrepancies in modelling the polymer density at ambient temperature and high pressure can be related to the presumably artificial liquid-liquid phase separation at lower temperatures. Thus, particular care is needed in engineering applications of the PC-SAFT theory that aims at predicting properties of macromolecular materials. 相似文献
138.
Chemical syntheses of 2′-amino-2′-deoxyarabinonucleosides of uracil, thymine, cytosine, adenine, and guanine and their conversion into suitably protected 3′-phosphoramidite building blocks 24–28 for oligonucleotide synthesis are described. The 2-(4-nitrophenyl)ethoxycarbonyl (npeoc) group was used for protection of the aglycon and the 2′-amino functions. 相似文献
139.
Wolfgang A. Herrmann 《Angewandte Chemie (International ed. in English)》1978,17(11):800-812
In recent years, aliphatic diazo compounds have proved to be more and more versatile as reagents in the preparative chemistry of organometallic complexes. As readily accessible compounds, they are not only suitable for the synthesis of known kinds of metal complexes but also open fresh routes to novel complex systems. The comparatively new field of diazoalkane complex chemistry exhibits numerous unexpected and novel reactions, and introduces interesting and promising aspects into the chemistry of carbonylmetal compounds. 相似文献
140.
A comparison of different nebulisers for direct hyphenation of capillary and nano liquid chromatography (Cap-LC, Nano-LC) and quadrupole-based collision cell inductively coupled plasma mass spectrometry (CC-ICP–MS) for phosphorylation profiling of tryptic protein digests is described. Helium was used as cell gas and specially tuned instrumental conditions were used to achieve background minimisation at the mass of phosphorus, because of kinetic energy discrimination of the interfering polyatomic ions. The proposed set-up is based on a modified capillary electrophoresis interface and a home-made 4 mL spray chamber. It enables the use of gradient conditions with a highly concentrated organic mobile phase as often used in protein phosphorylation analysis, without the need to apply membrane desolvation for removal of the organic phase or further background minimisation. No significant signal suppression or other negative effects caused by the organic mobile phase occur, because of the low flow rates used in Cap-LC and the robust plasma conditions of the CC-ICP–MS instrument. A tryptic digest of beta-casein was investigated as model compound to demonstrate the applicability of the proposed set-up for phosphorylation profiling in protein analysis using quadrupole based collision-cell ICP–MS as phosphorus-specific detector. Detection limits for phosphorylated peptides down to the sub picomole level were obtained. As a complementary technique, electrospray ionisation tandem mass spectrometry (ESI–MS–MS) with data base searching was used for further characterisation of the phosphorylated peptides detected. 相似文献