全文获取类型
收费全文 | 1066篇 |
免费 | 2篇 |
专业分类
化学 | 514篇 |
晶体学 | 3篇 |
力学 | 22篇 |
数学 | 329篇 |
物理学 | 200篇 |
出版年
2013年 | 40篇 |
2010年 | 7篇 |
2009年 | 6篇 |
2008年 | 9篇 |
2007年 | 7篇 |
2006年 | 10篇 |
2005年 | 7篇 |
2004年 | 17篇 |
2003年 | 17篇 |
2002年 | 16篇 |
2000年 | 6篇 |
1998年 | 7篇 |
1997年 | 11篇 |
1996年 | 14篇 |
1995年 | 16篇 |
1994年 | 19篇 |
1993年 | 33篇 |
1992年 | 19篇 |
1991年 | 13篇 |
1990年 | 12篇 |
1989年 | 6篇 |
1988年 | 8篇 |
1987年 | 17篇 |
1986年 | 39篇 |
1985年 | 40篇 |
1984年 | 36篇 |
1983年 | 29篇 |
1982年 | 42篇 |
1981年 | 43篇 |
1980年 | 38篇 |
1979年 | 41篇 |
1978年 | 43篇 |
1977年 | 35篇 |
1976年 | 28篇 |
1975年 | 25篇 |
1974年 | 28篇 |
1973年 | 24篇 |
1972年 | 16篇 |
1971年 | 15篇 |
1970年 | 9篇 |
1968年 | 13篇 |
1960年 | 16篇 |
1959年 | 25篇 |
1958年 | 12篇 |
1957年 | 14篇 |
1955年 | 11篇 |
1938年 | 7篇 |
1936年 | 7篇 |
1909年 | 12篇 |
1878年 | 5篇 |
排序方式: 共有1068条查询结果,搜索用时 31 毫秒
41.
The synthesis of dimetallic olefin complexes of the type L1M1C7H7M2L2 (M1 = Fe, Co, Rh; M2 = Rh, Ir, Pd; L1 = CO, C5H5; L2 = diene, allyl, P(OR)3) is described. The fluxional structures were investigated by 13C-, 57Fe- and 103Rh-NMR.-spectroscopy, and a cisoid dimetallic coordination, including a (metal, metal)-bond, can be deduced for the C7H7-ring. 57Fe- and 103Rh-chemical shifts give indications for the charge distribution in the 34e-complexes. The homodimetallic complex (Cp)Rh(tropone)Rh(Cp) ( 13 , Cp = cyclopentadienyl) and the corresponding 2-methoxytropone complex 14 were synthesized in addition to the above mentioned complexes. A fluxional bis(1-3-η-allyl)-coordination of the two Rh-atoms was derived from the temperature-dependent 13C-NMR.-spectra. A spin simulation of the (Cp)-multiplets of 12 and 13 yields information about (Rh, Rh)-spin-coupling which amounts to ≈5 Hz at 30°. 相似文献
42.
Paul Von Ragué Schleyer José Walkimar De M. Carneiro 《Journal of computational chemistry》1992,13(8):997-1003
The closely related Cs ( 1 ) and C2v ( 3 ) structures of CH have been reinvestigated at many ab initio levels using MP2/6-31G** and MP2/6-311 + + G(2df, 2pd) geometries. The largest basis sets employed were 6-311G(3df, 2p), 6-311 + + G(3df, 3pd), and the Dunning “correlation consistent” polarized triple-split valence basis set (cc-pVTZ). Electron correlation was probed at the MP4 level, but the QCISD method was also used with the largest basis sets. While electron correlation favors 3 over 1 by about 2 kcal/mol, the correlated relative energies with all basis sets employed range from 0.36–1.03 kcal/mol in favor of 1 . The best estimate of this difference, 0.86 kcal/mol, is essentially identical with the (scaled) zero-point energy difference, 0.84 kcal/mol, favoring 3 over 1 . These results indicate that 1 and 3 have almost exactly the same energy at 0 K. Our best value for the dissociation energy of CH is 42.0 kcal/mol [QCISD(T)/6-311 + + G(3df, 3pd)//MP2(fu)/6-311 + + G(2df, 2pd), corrected to 298 K], which agrees very well with the experimental value. © 1992 by John Wiley & Sons, Inc. 相似文献
43.
Abstract Geochemical and mineralogical investigations of plutonic rocks from the Meiβen massif indicate different magmatic evolution trends of the Freital sequence as well as for the central part of the complex Constant ε-NdT-345 values of ?1.5 of the Freital sequence and major/trace element data point to a fractional crystallization process. Based on ε-Nd values, 147Sm/144Nd ratios as well as on geochemical data affinities to alkali basalts cannot be excluded. Analogous conclusions have been drawn regarding mineral chemical data [10] and cathodoluminescence spectra of apatite [13]. Assimilation of old continental crust, reflected by relics of apatite and zircon, may be the reason that the ε-Nd values plot at the lower end of the “mantle array”. The pyroxene-monzodiorite from Gröba belongs to the same source environment as the Freital sequence (Nd-characteristics). The geological evolution of the central part of the studied plutonic complex is completely different to the Freital sequence: most of the intrusions show signatures of open system fractionation processes. The ε-NdT-345 value of ?1.46 of the Leuben monzonite indicates a narrow relation to the Freital sequence, whereas the ε-NdT-345 value of +2.27 of the Spitzgrund monzonite either reflects the derivation of another basic material then the Freital-type or the participation of other mixing component(s) from geologically young crust. Fabric and mineral chemical investigations of the porphyry-like granite GII point to a mixing process of basic xenocrysts, resembling the corresponding minerals of the Freital sequence, and granite melts [10]. Large amounts of old zircon cores [11] indicate the inheritance of continental crust components by the Hauptgranit. Isotopic investigations on various granitic samples (GII, Hauptgranit and Riesensteingranit) reflect an increasing trend towards the crustal source(s) of their parental melts. The ε-NdT-345 values are ?3.75, ?4.16 and ?6.13, respectively. Chemical parameters and the ε-NdT value of the Riesensteingranit agree with data of granites from the Saxonian Granulite Massif (see e.g. Wand et al. [8]; von Quadt, 1992). Thus, it may be possible that both granite types derived from similar sources. 相似文献
44.
Miša Biro Darja Kavšek Jakub Karasiński Piotr Szwarczewski Ewa Bulska Darinka Brodnjak Vončina 《Central European Journal of Chemistry》2014,12(6):687-699
The development and validation of a reliable analytical procedure for the determination of selected metals (Cd, Cr, Cu, Pb, Zn and Mn) in sediments accumulated in the Utrata River (Poland) is described. The aqua regia extraction followed by inductively coupled plasma optical emission spectrometry (ICP-OES) was used for this purpose. The optimized analytical procedure was validated, and adequate quality control actions were implemented in order to provide reliable data. The precision under’ within-laboratory’ reproducibility conditions was estimated from duplicate analysis. Certified reference material (CRM) was used in order to evaluate the accuracy of the results regarding the sewage sludge amended soil CRM 143R. The detection limits for all elements of interest were well-below their content in the investigated sediment samples. The obtained reliable data could be used for assessment of the relationship between human economic activity in the past and the geochemical features of the sediments. 相似文献
45.
Maja Vončina Robert Tisu Jožef Medved 《Journal of Thermal Analysis and Calorimetry》2017,129(1):117-122
Since titanium metal first became a commercial reality in 1950, corrosion resistance has been an important consideration in its selection as an engineering structural material. Titanium has gained acceptance in many media where its corrosion resistance and engineering properties have provided the corrosion and design engineer with a reliable and economic material. Titanium, like any other metal, is subject to corrosion in environments of air, oxygen, moisture, and so on. In this work, high-temperature stability of Ti and various Ti-alloys (by ASTM standard) was investigated. The best results showed that for Ti-Gr.5 alloy, the oxidation at 800 °C was 3.39% and at 900 °C 8.35%. For the comparison, commercial pure Ti-alloys Ti-Gr.2 and Ti-Gr.37 containing Al were used, whereas the oxidation resistance was much worse. 相似文献
46.
F. E. Hahn D. Le Van L. Wittenbecher M. C. Moyes T. Von Fehren R. Fröhlich 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1863-1867
The stable singlet carbenes N,N '-bis(2,2-dimethylpropyl)-benzimidazolin-2-ylidene 1 and 1,3,4,5-tetramethylimidazol-2-ylidene 2 react with phosphaalkynes P L C-- t Bu ( 3a ) or P L C--N i Pr 2 ( 3b ) regioselective to give the aromatic 1,2,4-triphosphole derivatives ( 1 or 2 + 3a M 6a or 6b , respectively) or 1,2,3-triphosphetene ( 1 + 3b M 7 ) or azaphospholene ( 2 + 3b M 9 ) in almost quantitative yields. The mechanisms of the surprising formation of compound 9 under C--H-activation was studied by quantum chemical DFT calculations. 相似文献
47.
Dieter Weber Günther Burget Karl-Heinz Zirzow Hans Georg Von Schnering Alfred Schmidpeter 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4)
Abstract Alkalimetal diphenylphosphinites degrade (Ph-P)5 and P4 to give anions containing a chain of 2, 3 or 4 four- and two-coordinated phosphorus atoms. Representatives of the chain with two four-coordinated and one two-coordinated P atoms became first available from the aminolysis of tris (phosphoryl)phosphides1. 相似文献
48.
Thomas Von Criegern Alfred Schmidpeter 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):305-308
Abstract 2,2′-Dipyridyl ketone 4a, 2-benzoyl pyridine 4b, and pyridine-2-aldehyde 4c coordinate by N and O to the chlorospiro-phosphorane 1, substitute the chloride and give tricycliccations 6 of hexacoordinate phosphorus. Nucleophilic attack of trimethyl phosphite at the carbonyl center and loss of methyl chloride converts them to the neutral sixcoordinate diastereomeric species 7. From the coalescence temperature of their 1H-NMR signals ΔG for the interconversion of the diastereomers is estimated to 18 kcal mol?1. 相似文献
49.
Antonio Doménech‐Carbó María Teresa Doménech‐Carbó Francisco López‐López Francisco Manuel Valle‐Algarra Laura Osete‐Cortina Estrella Arcos‐Von Haartman 《Electroanalysis》2013,25(12):2621-2630
The solid state voltammetric response of Egypt blue, Han blue and ploss blue pigments upon attachment to graphite electrodes in contact with aqueous phosphate buffer at pH 7.0 is studied by voltammetry of microparticles and scanning electrochemical microscopy. Such voltammetric responses, combined with those for synthetic specimens consisting of binary mixtures of the pigment and SiO2 or CaCO3 as well as ternary ones of CaCO3 and SiO2 mixtures allow for the identification of the pigment and the support in samples from wall paintings using different electrochemical parameters, in particular upon performing the Tafel and modified Tafel analysis of voltammetric peaks. Identification of Egypt blue in microsamples of murals from a Roman archaeological site in Castulo (Jaén, Spain) is discussed. 相似文献
50.
Gregory Von White II Roger L. Clough James M. Hochrein Robert Bernstein 《Polymer Degradation and Stability》2013
Nylon 6.6 containing 13C isotopic labels at specific positions along the macromolecular backbone has been subjected to extensive thermal-oxidative aging at 138 °C for time periods up to 243 days. In complementary experiments, unlabeled Nylon 6.6 was subjected to the same aging conditions under an atmosphere of 18O2. Volatile organic degradation products were analyzed by cryofocusing gas chromatography mass spectrometry (cryo-GC/MS) to identify the isotopic labeling. The labeling results, combined with basic considerations of free radical reaction chemistry, provided insights to the origin of degradation species, with respect to the macromolecular structure. A number of inferences on chemical mechanisms were drawn, based on 1) the presence (or absence) of the isotopic labels in the various products, 2) the location of the isotope within the product molecule, and 3) the relative abundance of products as indicated by large differences in peak intensities in the gas chromatogram. The overall degradation results can be understood in terms of free radical pathways originating from initial attacks on three different positions along the nylon chain which include hydrogen abstraction from: the (CH2) group adjacent to the nitrogen atom, at the (CH2) adjacent the carbonyl group, and direct radical attack on the carbonyl. Understanding the pathways which lead to Nylon 6.6 degradation ultimately provides new insight into changes that can be leveraged to detect and reduce early aging and minimize problems associated with material degradation. 相似文献