Conjugated block copolymers via functionalized initiators and click chemistry

Conjugated block copolymers are potentially useful for organic electronic applications and the study of interfacial charge and energy transfer processes; yet few synthetic methods are available to prepare polymers with well‐defined conjugated blocks. Here, we report the synthesis and thin film morphology of a series of conjugated poly(3‐hexylthiophene)‐block‐poly(9,9‐dioctylfluorene) (P3HT‐b‐PF) and poly(3‐dodecylthiophene)‐block‐poly(9,9‐dioctylfluorene) (P3DDT‐b‐PF) block copolymers prepared by functional external initiators and click chemistry. Functional group control is quantified by proton nuclear magnetic resonance spectroscopy, size‐exclusion chromatography, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. The thin film morphology of the resulting all‐conjugated block copolymers is analyzed by a combination of grazing‐incidence X‐ray scattering, atomic force microscopy, and transmission electron microscopy. Crystallization of the P3HT or P3DDT blocks is present in thin films for all materials studied, and P3DDT‐b‐PF films exhibit significant PF/P3DDT co‐crystallization. Processing conditions are found to impact thin film crystallinity and orientation of the π–π stacking direction of polymer crystallites. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 154–163     

Assessment of laser-induced thermal load on silicon nanostructures based on ion desorption yields

Experimental assessment of the thermal load induced by fast laser pulses on micro- and nanostructures through IR imaging is currently too slow and lacks the spatial resolution to be useful. In this paper, we introduce a method based on measuring the laser-induced yields of ions to compare the thermal loads on nanofabricated silicon structures, when exposed to nanosecond laser pulses. The laser fluences at which the ion yields of, for example, sodiated and potassiated peptides ions are equal for two different structures correspond to equivalent thermal loads. Using alkalinated peptides is a convenient choice because the corresponding ion intensities are easily measured up to the melting point of silicon. As an example, we compare the nanosecond laser heating of silicon nanopost arrays with diverse post diameters and periodicities. Assessment of the thermal load through ion yield measurements can also be used to verify model assumptions for heat transport regimes in nanostructures.     

Experimental and Computational Studies of a Multi‐Electron Donor–Acceptor Ligand Containing the Thiazolo[5,4‐d]thiazole Core and its Incorporation into a Metal–Organic Framework

A ligand containing the thiazolo[5,4‐d]thiazole (TzTz) core (acceptor) with terminal triarylamine moieties (donors), N,N′‐(thiazolo[5,4‐d]thiazole‐2,5‐diylbis(4,1‐phenylene))bis(N‐(pyridine‐4‐yl)pyridin‐4‐amine ( 1 ), was designed as a donor–acceptor system for incorporation into electronically active metal–organic frameworks (MOFs). The capacity for the ligand to undergo multiple sequential oxidation and reduction processes was examined using UV/Vis‐near‐infrared spectroelectrochemistry (UV/Vis‐NIR SEC) in combination with DFT calculations. The delocalized nature of the highest occupied molecular orbital (HOMO) was found to inhibit charge‐transfer interactions between the terminal triarylamine moieties upon oxidation, whereas radical species localized on the TzTz core were formed upon reduction. Conversion of 1 to diamagnetic 2+ and 4+ species resulted in marked changes in the emission spectra. Incorporation of this highly delocalized multi‐electron donor–acceptor ligand into a new two‐dimensional MOF, [Zn(NO₃)₂( 1 )] ( 2 ), resulted in an inhibition of the oxidation processes, but retention of the reduction capability of 1 . Changes in the electrochemistry of 1 upon integration into 2 are broadly consistent with the geometric and electronic constraints enforced by ligation.     

Acceleration of randomized Kaczmarz method via the Johnson–Lindenstrauss Lemma

The Kaczmarz method is an algorithm for finding the solution to an overdetermined consistent system of linear equations Ax = b by iteratively projecting onto the solution spaces. The randomized version put forth by Strohmer and Vershynin yields provably exponential convergence in expectation, which for highly overdetermined systems even outperforms the conjugate gradient method. In this article we present a modified version of the randomized Kaczmarz method which at each iteration selects the optimal projection from a randomly chosen set, which in most cases significantly improves the convergence rate. We utilize a Johnson–Lindenstrauss dimension reduction technique to keep the runtime on the same order as the original randomized version, adding only extra preprocessing time. We present a series of empirical studies which demonstrate the remarkable acceleration in convergence to the solution using this modified approach.     

Effect of the plasma location on the deflagration-to-detonation transition of a hydrogen–air flame enhanced by nanosecond repetitively pulsed discharges

This work presents a method for using nanosecond repetitively pulsed (NRP) plasma discharges for accelerating a propagating flame such that the deflagration-to-detonation transition occurs. A strategy is developed for bringing the location of the plasma near the tube wall and, thus, reducing the presence of the electrodes in the combustion tube as well as presenting a configuration in which cooling of the electrodes is viable for practical applications. Time-of-flight measurements were used in combination with energy deposition measurements and high-speed OH*-chemiluminescence imagery to investigate the flame acceleration process. For stoichiometric hydrogen–air flames, successful transition to detonation was achieved by applying a burst of 110 pulses at 100 kHz, with energies as low as 10 mJ per pulse. This was also achieved when plasma discharges were applied in the vicinity of the wall. Two enhancement mechanisms for flame acceleration were identified. The essential role of shock–flame interaction was established as being the main mechanism for flame acceleration when the discharges are located near the wall. This work presents an effective alternative that allows for NRP discharges to be applied near the wall while successfully maintaining a promising success rate for detonation transition.     

The Reaction of D-Glucose With Substituted Anilines: Investigation by Carbon-13 NMR Spectroscopy

Carbon-13 NMR data are provided for a series of N-glycosyl amines and Amadori rearrangement products that were prepared by reaction of D-glucose with substituted anilines. These data demonstrate that ¹³C NMR is a useful method for characterizing the products isolated from reactions of D-glucose with amines.