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41.
Torsten Küppers Martin Köckerling Prof. Dr. Helge Willner Prof. Dr. 《无机化学与普通化学杂志》2007,633(2):280-284
The new tetracyanoborate K[B(CN)4]·CH3CN was synthesized by dissolution of the solvent‐free K[B(CN)4] in acetonitrile and subsequent careful crystallization. The crystal structure has been determined by single‐crystal X‐ray diffraction. It crystallizes in the orthorhombic space group P212121 with Z = 4. Some comparisons with related structures are made, and the vibrational spectrum is discussed. 相似文献
42.
Takanori Suzuki Prof. Shoko Tanaka Hidetoshi Kawai Dr. Kenshu Fujiwara Prof. 《化学:亚洲杂志》2007,2(1):171-177
The title heterocyclic donors undergo reversible C? C bond formation/cleavage upon electron transfer (dynamic redox behavior). The helical sense in both neutral and cationic states is interconvertible by facile ring flipping. The π‐type asymmetric center on the azepine nitrogen atom induces a significant degree of diasteromeric preference, thus endowing strong CD activity based on exciton coupling. Chiroptical properties could be modified not only by redox reactions but also by heat and protonation. The present redox pairs can serve as unprecedented three‐way‐input (e, H+, Δ) and two‐way‐output (UV/Vis, CD) response systems. 相似文献
43.
Yoshihiko Nishimori Katsuhiko Kanaizuka Dr. Masaki Murata Dr. Hiroshi Nishihara Prof. 《化学:亚洲杂志》2007,2(3):367-376
Films of linear and branched oligomer wires of Fe(tpy)2 (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C6H4N?NC6H4? S)2 ( 1 ), two bridging ligands, 1,4‐(tpy)2C6H4 ( 3 ) and 1,3,5‐(C?C? tpy)3C6H3 ( 4 ), and metal ions were used. The quantitative complexation of the ligands and FeII ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k1 (s?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k2 (cm2 mol?1 s?1). The strong effect of the electrolyte concentration on both k1 and k2 indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k1 and k2 on the potential gave intrinsic kinetic parameters without overpotential effects: k10=110 s?1, k20=2.6×1012 cm2 mol?1 s?1 for [n Fe 3 ], and k10=100 s?1, k20=4.1×1011 cm2 mol?1 s?1 for [n Fe 4 ] (n=number of complexation cycles). 相似文献
44.
Zusammenfassung Um der oft gehörten Meinung entgegenzutreten, die energetischen Wirkungsgrade lebender Organismen seien wesentlich höher als die technischer Verfahren, werden entsprechende Werte miteinander verglichen. Der sehr niedrige Wirkungsgrad der Photosynthese zusammen mit der kleinen Energiedichte der Sonnenstrahlung erzwang ab einer kritischen Größe die Aufspaltung in Energiesammler, die Pflanzen, und Verbraucher chemischer Energie, den Tieren. Dank den 10 mal höheren Wirkungsgraden in der Technik, lassen sich Solarmobile bauen, die von der auf sie fallenden Sonnenstrahlung angetrieben werden. Wegen des Multiplikationsgesetzes der Teilwirkungsgrade ergeben sich sowohl für die Speicherung der Sonnenenergie in den fossilen Brennstoffen wie in der Nahrungskette extrem niedrige Wirkungsgrade.
Herrn Prof. Dr.-Ing. U. Grigull zum 75. Geburtstag gewidmet 相似文献
Efficiencies in the world of life and in engineering
One often hears the opinion, that the efficiencies in the world of life are higher than in engineering. To disprove this, many values of efficiency of corresponding processes are compared. The very low efficiency of photosynthesis in living plants together with the low density of solar radiation has led the world of life to split into collectors of energy, the plants, and consumers of chemical energy, the animals. Thanks to the ten times higher efficiencies of solar cells, it is possible, to produce solar mobiles, vehicles that move driven by solar radiation.
Herrn Prof. Dr.-Ing. U. Grigull zum 75. Geburtstag gewidmet 相似文献
45.
Starting from Wheeler's composite theory, which takes both the multilayer adsorption and the capillary condensation into consideration, and assuming the equivalent cylindrical model, we have deduced a strict and relatively simpler formula for the calculation of pore size distribution by solving the integral equation directly. The formula is more convenient for application because of its recursion form. Following the same line of reasoning and using the mean value theorem of definite integrals under different conditions, we have unified the equations of Barrett-Joyner-Halenda, Dubinin, Cranston-Inkley, Dollimore-Heal and Roberts. A table of parameters which is required in the calculation is given. Besides the adsorption of nitrogen, the adsorption with water vapor as the adsorbate is investigated and the corresponding empirical equation of adsorption thickness is given. 相似文献
46.
Dr. H. Demel Dipl.-Ing H. J. Grießer Prof. Dr. K. Hummel 《Colloid and polymer science》1977,255(11):1131-1132
Ohne ZusammenfassungMit 1 Abbildung und 1 Tabelle 相似文献
47.
Yellowish crystals of K2[(UO2)As2O7] ( 1 ) have been synthesized by solid‐state reactions method. The structure of 1 [orthorhombic, Pmmn, a = 12.601(2), b = 13.242(2), c = 5.621(1) Å, V = 937.9(3) Å3, Z = 4] has been solved by direct methods and refined to R1 = 0.049, wR2 = 0.1060 for 1059 observed reflections. The structure of 1 is based upon [(UO2)As2O7]2? sheets formed by corner sharing between [UO6]6? distorted octahedra and [As2O7]4? polyarsenate groups. The K+ cations are either in eightfold or tenfold coordination and are located between the sheets. The topology of the uranyl arsenate sheet is related to silicate minerals of the melilite group and related synthetic silicate, aluminate and germanate compounds. 相似文献
48.
Bart M. J. M. Suijkerbuijk Dr. Duncan M. Tooke Dr. Anthony L. Spek Prof. Dr. Gerard van Koten Prof. Dr. Robertus J. M. Klein Gebbink Prof. Dr. 《化学:亚洲杂志》2007,2(7):889-903
A series of meso‐tetrakis‐(ERE donor) zinc(II) porphyrins n Zn (ERE donor=4‐R‐3,5‐bis[(E)‐methyl]phenyl; 1 Zn: E=NMe2, R=Br; 2 Zn: E=NMe2, R=H; 3 Zn: E=OMe, R=Br; 4 Zn: E=OMe, R=H) have been synthesized in excellent yields. As a result of the combination of a Lewis acidic site and eight Lewis basic sites within one molecule, monomeric molecules of n Zn self‐assemble to form one‐dimensional porphyrin polymers [ n Zn]∞ in the solid state, as confirmed for 1 Zn and 3 Zn by X‐ray crystallography. The coordination environment around the zinc(II) ions in these polymers is octahedral. They are ligated by four equatorial nitrogen atoms of the porphyrin and two apical E atoms (E=N, O) provided by the EBrE donor groups of adjacent n Zn molecules. Complexes 2 Zn and 4 Zn did not form single crystals, but solid‐state UV/Vis analysis points to the formation of similar structures. Solution UV/Vis and 1H NMR spectroscopy indicated that interactions between 1 Zn and 2 Zn monomers in the polymers are stronger than between 3 Zn and 4 Zn monomers. Interestingly, they also revealed that the presence of a neighboring bromine atom in the EBrE donor groups has a considerable influence on the coordination properties of the benzylic N or O atoms. The zinc(II) ions of the porphyrins most likely adopt only hexacoordination in the solid state, owing to the unique predisposition of Lewis acidic and basic sites in the n Zn molecules. Several parameters of the aggregates, for example, the interplanar separation between porphyrins and the zinc–zinc distances, change as a function of the coordinating E groups. The high degree of modularity in their synthesis makes these zinc(II) porphyrins an interesting new entry in noncovalent multiporphyrin assemblies. 相似文献
49.
Herwig G. Winkler Hagen T. Spath Prof. Dr. Karl Torkar 《Monatshefte für Chemie / Chemical Monthly》1975,106(2):535-545
The phase diagrams of the systems CsN3/Zn(N3)2 and KN3/Zn(N3)2 have been obtained employing the microscopic technique ofL. Kofler andA. Kofler. Within the system CsN3/Zn(N3)2 three eutectics at 148°C, 142°C, and 210°C were found. Besides Cs2Zn(N3)4, melting incongruently in the interval 153°C to 170°C, there exist two further compounds of the most probable composition Cs3Zn2(N3)7 and CsZn2(N3)5, melting congruently at 170°C and 210°C, resp. In the system KN3/Zn(N3)2 there exist two eutectics at 203°C and 172°C and two compounds, one of them, i.e. K2Zn(N3)4, melting congruently at 206°C, the other one, with composition KZn3(N3)7 or KZn4(N3)9, melting incongruently at 210°C.
Mit 8 Abbildungen
Herrn Professor Dr.Heribert Grubitsch zum 70. Geburtstag gewidmet. 相似文献
Mit 8 Abbildungen
Herrn Professor Dr.Heribert Grubitsch zum 70. Geburtstag gewidmet. 相似文献
50.
Prof. Dr. K. -H. Hellwege U. Johnsen Dipl.-Phys. W. Seufert 《Colloid and polymer science》1963,188(1):11-14
Zusammenfassung PÄT-Folien wurden in Luft, Stickstoff und Vakuum bei 20 °C mit 1 MeV-Elektronen bestrahlt. Untersucht wurden Löslichkeit und Viskosität von Proben, die unmittelbar nach der Bestrahlung gelöst wurden.In allen untersuchten Fällen trat bei hohen Bestrahlungsdosen ein unlöslicher, d. h. vernetzter Anteil auf, dessen Ausbildung jedoch durch in den Proben enthaltene Feuchtigkeit verzögert werden kann. Bei niedrigen Bestrahlungsdosen bewirkt Feuchtigkeit einen Abbau des Polymeren, wie durch Viskositätsmessungen gezeigt wird.Aus den Gel-Messungen wurde derp
0/q
0-Wert für Bestrahlung in Luft, Stickstoff und Vakuum zu 1,05 bestimmt.Die Änderung des Gel-Anteils bei Lagerung der Proben zwischen Bestrahlung und Lösung wird diskutiert.
Herrn Diplom-PhysikerH. Fischer sei an dieser Stelle für wertvolle Anregungen und Diskussionen besonders gedankt. 相似文献
Summary Polyethyleneterephthalate samples were irradiated in air, nitrogen and vacuum at 20 °C with 1 MeV electrons. The solubility of the samples and the viscosity of the solutions were studied immediately after irradiation. At high doses an insoluble crosslinked part was always observed. Crosslinking was delayed by moisture in the samples. At low irradiation doses moisture causes chain scission as shown by viscosity measurements. The ratiop 0/q 0 of degradation to crosslinking in the case of irradiation in air, nitrogen and vacuum was found by gel measurements to be 1.05. The insoluble gel-part changes with increasing storage time of the samples between irradiation and solution.
Herrn Diplom-PhysikerH. Fischer sei an dieser Stelle für wertvolle Anregungen und Diskussionen besonders gedankt. 相似文献