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81.
Dr. Philipp Holtkamp Dario Poier Beate Neumann Dr. Hans-Georg Stammler Prof. Dr. Norbert W. Mitzel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(11):3793-3798
The reactivity of the geminal frustrated Lewis pair (FLP) (F5C2)3SnCH2P(tBu)2 ( 1 ) was explored by reacting it with a variety of small molecules (PhOCN, PhNCS, PhCCH, tBuCCH, H3CC(O)CH=CH2, Ph[C(O)]2Ph, PhN=NPh and Me3SiCHN2), featuring polar or non-polar multiple bonds and/or represent α,β-unsaturated systems. While most adducts are formed readily, the binding of azobenzene requires UV-induced photoisomerization, which results in the highly selective complexation of cis-azobenzene. In the case of benzil, the reaction does not lead to the expected 1,2- or 1,4-addition products, but to the non-stereoselective (tBu)2PCH2-transfer to a prochiral keto function of benzil. All adducts of 1 were characterised by means of multinuclear NMR spectroscopy, elemental analyses and X-ray diffraction experiments. 相似文献
82.
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
83.
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
84.
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
85.
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
86.
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
87.
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
88.
Von R. Eidenschink 《Liquid crystals》2013,40(5):1517-1521
In einem mit trans, trans,-4-Methoxy-4′-pentyl-bicyclohexyl (1) geschmierten Gleitlager wurde im Temperaturbereich des Überganges zwischen der nematischen und der SB-Phase ein steiler Anstieg des Reibungsmomentes gemessen. Die Ergebnisse lassen erwarten, daß die schnelle und reversible Änderungen tribologischer Eigenschaften bei Phasenumwandlungen flüssiger Kristalle im Maschinenbau vorteilhaft anwendbar sind. Kleinere Reibungsmoment in der SB-Phase ergaben sich nach Dotieren von 1 mit 4-Pentyl-benzoesäure. Entsprechende Messungen mit 2,3,7,8,12,13-Hexakis[decanoyloxy]truxen im Temperaturbereich des Übergangs zwischen der Reentrant-ND-phase und der columnaren phase zeigten bei Temperaturerhöhung eine geringe Erhöhung des Reibungsmoments. 相似文献
89.
Falk Ebeler Dr. Yury V. Vishnevskiy Beate Neumann Dr. Hans-Georg Stammler Priv.-Doz. Dr. Rajendra S. Ghadwal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(31):e202200739
Mesoionic dithiolates [(MIDtAr)Li(LiBr)2(THF)3] (MIDtAr={SC(NDipp)}2CAr; Dipp=2,6-iPr2C6H3; Ar=Ph 3 a , 3-MeC6H4 (3-Tol) 3 b , 4-Me2NC6H4 (DMP) 3 c ) and [(MIDtPh)Li(THF)2] ( 4 ) are readily accessible (in≥90 % yields) as crystalline solids on treatments of anionic dicarbenes Li(ADCAr) ( 2 a - c ) (ADCAr={C(NDipp)2}2CAr) with elemental sulfur. 3 a - c and 4 are monoanionic ditopic ligands with both the sulfur atoms formally negatively charged, while the 1,3-imidazole unit bears a formal positive charge. Treatment of 4 with (L)GeCl2 (L=1,4-dioxane) affords the germylene (MIDtPh)GeCl ( 5 ) featuring a three-coordinated Ge atom. 5 reacts with (L)GeCl2 to give the Ge−Ge catenation product (MIDtPh)GeGeCl3 ( 6 ). KC8 reduction of 5 yields the homoleptic germylene (MIDtPh)2Ge ( 7 ). Compounds 3 a - c and 4 – 7 have been characterized by spectroscopic studies and single-crystal X-ray diffraction. The electronic structures of 4 – 7 have been analyzed by DFT calculations. 相似文献
90.
Jens Rudlof Niklas Aders Dr. Jan-Hendrik Lamm Beate Neumann Dr. Hans-Georg Stammler Prof. Dr. Norbert W. Mitzel 《ChemistryOpen》2021,10(10):1020-1027
Starting from 1,2-diethynylbenzene, a series of bidentate Lewis acids was prepared by means of hydrometalations, in particular hydrosilylation, hydroboration, hydroalumination and terminal metalation based on group 13 and 14 elements. In the case of terminal alkyne metalation, the Lewis-acidic gallium function was introduced using triethylgallium under alkane elimination. A total of six different Lewis acids based on a semiflexible organic scaffold were prepared, bearing −SiClMe2, −SiCl2Me, −SiCl3, −B(C6F5)2, −AlBis2 (Bis=bis(trimethylsilyl)methyl) and −GaEt2 as the corresponding functional units. In all cases, the Lewis acid functionalisation was carried out twice and the products were obtained in good to excellent yields. In the case of the twofold gallium Lewis acid, a different structural motif in the form of a polymer-like chain was observed in the solid state. All new bidentate Lewis acids were characterised by multinuclear NMR spectroscopy, CHN analysis and X-ray diffraction experiments. 相似文献