Spectroscopic and photophysical studies of the hydroquinone family of photochromic Schiff bases analyzed over a 17-orders-of-magnitude time scale

The hydroquinone family of photochromic Schiff bases has been studied by means of stationary and time-resolved spectroscopic absorption and emission techniques in the UV-Vis spectral range in the temporal range from 100 fs to 1 h. The studies have revealed that besides the ultrafast excited state intramolecular proton transfer reaction there is also another deactivation channel from the initially excited state. For the symmetric molecule with two intramolecular hydrogen bonds, the efficiency of the proton transfer reaction has been found to be at least ten times reduced when compared to that of the asymmetric molecule with one intramolecular hydrogen bond. The long-lived transient species absorbing in the UV range and coexisting with the photochrome have been observed in differently interacting solvents. Evidence for different conformers of almost all of the tautomers involved in the photochromic cycle has been also found.     

Developing flexible procedural knowledge in undergraduate calculus

Mathematics experts often choose appropriate procedures to produce an efficient or elegant solution to a mathematical task. This flexible procedural knowledge distinguishes novice and expert procedural performances. This article reports on an intervention intended to aid the development of undergraduate calculus students’ flexible use of procedures. Two sections of the same course were randomly assigned to treatment and control conditions. Treatment students completed an assignment on which they resolved derivative-finding problems with alternative methods and compared the two resulting solutions. Control students were assigned a list of functions to differentiate. On the post-intervention test, treatment students were more likely to use a variety of solution methods without prompting than the control. Moreover, the set of treatment section solutions were closer to those of a group of mathematics experts. This study presents evidence that not only is flexible procedural knowledge a key skill in tertiary mathematics, it can be taught.     

Doping‐Induced Absorption Bands in P3HT: Polarons and Bipolarons

In this work, we focus on the formation of different kinds of charge carriers such as polarons and bipolarons upon p‐type doping (oxidation) of the organic semiconductor poly(3‐ hexylthiophene‐2,5‐diyl) (P3HT). We elucidate the cyclic voltammogram during oxidation of this polymer and present spectroscopic changes upon doping in the UV/Vis/near‐IR range as well as in the mid‐IR range. In the low‐oxidation regime, two absorption bands related to sub‐gap transitions appear, one in the UV/Vis range and another one in the mid‐IR range. The UV/Vis absorption gradually decreases upon further doping while the mid‐IR absorption shifts to lower energy. Additionally, electron paramagnetic resonance (EPR) measurements are performed, showing an increase of the EPR signal up to a certain doping level, which significantly decreases upon further doping. Furthermore, the absorption spectra in the UV/Vis range are analyzed in relation to the morphology (crystalline vs. amorphous) by using theoretical models. Finally, the calculated charge carriers from cyclic voltammogram are linked together with optical transitions as well as with the EPR signals upon p‐type doping. We stress that our results indicate the formation of polarons at low doping levels and the existence of bipolarons at high doping levels. The presented spectroscopic data are an experimental evidence of the formation of bipolarons in P3HT.     

Six mutually orthogonal Latin squares of order 48

A direct construction of six mutually orthogonal Latin squares of order 48 is given. © 1997 John Wiley & Sons, Inc. J Combin Designs 5:463–466, 1997     

Hydrogen bond effects in the ground and excited singlet states of 4H-1-benzopyrane-4-thione in water--theory and experiment

The hydrogen bond energies for 4H-1-benzopyrane-4-thione (BPT) in its ground and two lowest excited singlet electronic states have been determined using ab initio methods. It was shown that the BPT molecule can form, as an acceptor, four relatively strong hydrogen bonds with water molecules, leading to a stable complex in the ground electronic state S(0). The hydrogen bonds involving the sulfur atom from the thiocarbonyl group were found to be stronger than those involving the oxygen atom from the benzopyran moiety. The former hydrogen bonds were predicted to become significantly weaker upon excitation to the S(1) state and, in contrast, stronger upon excitation to the S(2) state. Calculated changes in the hydrogen bond energy due to the S(0)→ S(1) and S(0)→ S(2) excitation are in very good agreement with the experimental values obtained from the absorption solvatochromic study, according to a procedure proposed by us in [E. Krystkowiak, et al., J. Photochem. Photobiol. A: Chem., 2006, 184, 250]. The maxima of absorption spectra of the BPT-water hydrogen-bonded complex, calculated taking into consideration nonspecific solute-solvent interactions, are also in good agreement with the experimental results.     

Comments on “The use of MoO3 and NiO (pure or mixed) oxide catalysts in the decomposition of KMnO4” by S.A. Halawy and M.A. Mohamed

The recent paper by Halawy and Mohamed [S.A. Halawy, M.A. Mohamed, Thermochim. Acta 345 (2000) 157] has raised several problems which need to be resolved. Our comments are given under the headings of the sections of the original paper.     

Active control of working machines seat suspension aimed at health protection against vibration

The paper presents the model and simulation of passive and active earth-moving machines seat suspension. The object of the simulation is the visco-elastic passive seat suspension with an air-spring, hydraulic shock-absorber and scissors guidance mechanism. Passive seat suspension amplifies the vibration amplitude at low frequency range of excitation signal (the resonance effect). In order to help the working machines operators against vibration, the active system with different control strategies is elaborated. Active system improves significantly the behavior of the seat suspension at low frequency excitation, with the most effectiveness obtained for the resonance frequency. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Molecular Structure and Spectral Characteristics of the Complex [Ni(Bu3P)2(NCS)2], and Its Catalytic Properties in Hydrosilylation Reaction

According to X-ray diffraction data, the nickel complex [Ni(Bu₃P)₂(NCS)₂] has a square-planar structure with the two phosphine ligands trans to each other and the thiocyanate ligand coordinated by the nitrogen atom. The IR and ¹H, ^{1 3}C, and ^{3 1}P NMR data show that the same structure is preserved in solutions. The catalytic activity of the complex in hydrosilylation of 1-hexene with chlorohydrosilanes HSiMe_{3 - n} Cl _n varies in the series HSiCl₃ > HSiMeCl₂ > HSiMe₂Cl. The reactions of the complex with hydrosilanes involve substitution of the anionic ligand and formation of silyl complexes.