Reduction of Sulfoxides to Sulfides in the Presence of Copper Catalysts

Abstract  

Copper complexes catalyze the reduction of aliphatic and aromatic sulfoxides in the presence of silanes as reducing reagent. The influence of different reaction parameters on the catalytic activity is investigated in detail. The scope and limitations of the described catalyst is demonstrated in the reduction of various sulfoxides. In most cases, high conversion and excellent chemoselectivity are obtained.     

P3HT/PCBM Bulk Heterojunction Solar Cells: Impact of Blend Composition and 3D Morphology on Device Performance

The performance of polymer solar cells (PSC) strongly depends on the 3D morphological organization of the donor and acceptor compounds within the bulk heterojunction active layer. The technique of electron tomography is a powerful tool for studying 3D morphology of the layers composed of poly(3‐hexylthiophene) (P3HT) and a fullerene derivative ([6,6]‐phenyl‐C61‐butyric acid methyl ester; PCBM), especially to quantify the amount and distribution of fibrillar P3HT nanocrystals throughout the volume of the active layer. In this study, electron tomography is used to characterize P3HT/PCBM layers with different blend compositions, both before and after thermal annealing. The power conversion efficiency of the corresponding PSCs is strongly dependent on the overall crystallinity of P3HT and the way P3HT crystals are distributed throughout the thickness of the active layer.     

Optical reconstruction of high-speed surface dynamics in an uncontrollable environment

The ability to communicate with our voice can be regarded as the concatenation of the two processes "phonation" and "modulation." These take place in the larynx and palatal and oral region, respectively. During phonation the audible primary voice signal is created by mutual reaction of vocal folds with the exhaled air stream of the lungs. The underlying interactions of masses, fluids and acoustics have yet to be identified and understood. One part of the primary signal's acoustical source are vortex induced vibrations, as e.g., created by the Coand?effect in the air stream. The development of these vorteces is determined by the shape and 3-D movements of the vocal folds in the larynx. Current clinical in vivo research methods for vocal folds do not deliver data of satisfactory quality for fundamental research, e.g., an endoscope is limited to 2-D image information. Based hereupon, a few improved methods have been presented, however delivering only selective 3-D information, either for a single point or a line. This stands in contrast to the 3-D motions of the entire vocal fold surface. More complex imaging methods, such as MRI, do not deliver information in real-time. Thus, it is necessary to develop an easily applicable, more improved examination method, which allows for 3-D data of the vocal folds surfaces to be obtained. We present a method to calibrate a 3-D reconstruction setup including a laser projection system and a high-speed camera. The setup is designed with miniaturization and an in vivo application in mind. The laser projection system generates a divergent grid of 196 laser dots by diffraction gratings. It is calibrated with a planar calibration target through planar homography. In general, the setup allows to reconstruct the topology of a surface at high frame rates (up to 4000 frames per second) and in uncontrollable environments, as e.g., given by the lighting situation (little to no ambient light) and varying texture (e.g., varying grade of reflection) in the human larynx. In particular, this system measures the 3-D vocal fold surface dynamics during phonation. Applied to synthetic data, the calibration is shown to be robust (error approximately 0.5 μm) regarding noise and systematic errors. Experimental data gained with a linear z -stage proved that the system reconstructs the 3-D coordinates of points with an error at approximately 15 μm. The method was applied exemplarily to reconstruct porcine and artificial vocal folds' surfaces during phonation. Local differences such as asymmetry between left and right fold dynamics, as well as global parameters, such as opening and closing speed and maximum displacements, were identified and quantified.     

Compound-specific chlorine isotope analysis: a comparison of gas chromatography/isotope ratio mass spectrometry and gas chromatography/quadrupole mass spectrometry methods in an interlaboratory study

Chlorine isotope analysis of chlorinated hydrocarbons like trichloroethylene (TCE) is of emerging demand because these species are important environmental pollutants. Continuous flow analysis of noncombusted TCE molecules, either by gas chromatography/isotope ratio mass spectrometry (GC/IRMS) or by GC/quadrupole mass spectrometry (GC/qMS), was recently brought forward as innovative analytical solution. Despite early implementations, a benchmark for routine applications has been missing. This study systematically compared the performance of GC/qMS versus GC/IRMS in six laboratories involving eight different instruments (GC/IRMS, Isoprime and Thermo MAT-253; GC/qMS, Agilent 5973N, two Agilent 5975C, two Thermo DSQII, and one Thermo DSQI). Calibrations of (37)Cl/(35)Cl instrument data against the international SMOC scale (Standard Mean Ocean Chloride) deviated between instruments and over time. Therefore, at least two calibration standards are required to obtain true differences between samples. Amount dependency of δ(37)Cl was pronounced for some instruments, but could be eliminated by corrections, or by adjusting amplitudes of standards and samples. Precision decreased in the order GC/IRMS (1σ ≈ 0.1‰), to GC/qMS (1σ ≈ 0.2-0.5‰ for Agilent GC/qMS and 1σ ≈ 0.2-0.9‰ for Thermo GC/qMS). Nonetheless, δ(37)Cl values between laboratories showed good agreement when the same external standards were used. These results lend confidence to the methods and may serve as a benchmark for future applications.     

Data Extraction from Terahertz Time Domain Spectroscopy Measurements

The potential of terahertz (THz) time domain spectroscopy to simultaneously determine the complex dielectric parameters of materials and their geometrical thickness is of high interest for scientific spectroscopy and for general metrology. This paper provides an overview of the background of the data extraction from THz measurements and discusses the accuracy and ambiguity of this extraction process. It is shown that the signal to noise ratio of the measurement as well as the bandwidth of the accessible THz spectrum define the limitation of the achievable accuracy in the data extraction.     

Gyroid‐Structured 3D ZnO Networks Made by Atomic Layer Deposition

3D continuous ZnO morphologies with characteristic feature sizes on the 10 nm length scale are attractive for electronic device manufacture. However, their synthesis remains a challenge because of the low crystallization temperature of ZnO. Here, we report a method for the robust and reliable synthesis of fully crystalline 3D mesoporous ZnO networks by means of atomic layer deposition (ALD) of ZnO into a self‐assembled block copolymer template. By carefully optimizing the processing conditions we are able to synthesize several‐micrometer‐thick layers of mesoporous ZnO networks with a strut width of 30 nm. Two 3D mesoporous morphologies are manufactured: a periodic gyroid structure and a random worm‐like morphology. Exploiting the ALD property to conformally coat complex surfaces of high aspect ratio, the channel network of a 3D continuous channel network of a self‐assembled block copolymer is replicated into ZnO. X‐ray photoemission spectroscopy and x‐ray diffraction measurements reveal that the chemical composition of the mesoporous structures is uniform and consists of wurtzite‐ZnO throughout the film. Scanning electron microscopy reveals an average pore dimension of 30 nm. The potential of this material for a hybrid photovoltaic application is demonstrated by the manufacture of a poly(3‐hexylthiophene)/ZnO solar cell.     

The use of AC potentials in electrospraying and electrospinning processes

The use of AC potentials in electrospraying and electrospinning processes was demonstrated. Carboxymethylcellulose (CMC) was electrosprayed onto semiconducting and insulating substrates using both DC and AC potentials. On the semiconducting substrate, both AC and DC methods were capable of producing significant CMC coverage. However, only the AC potential was capable of producing significant coverage on the insulating substrate, possibly due to a reduction in the amount of surface charging. In the electrospinning investigation, poly(ethylene oxide) (PEO) fibers were spun into mats using both DC and AC driving potentials. The AC potential resulted in a significant reduction in the amount of fiber ‘whipping’ and the resulting mats exhibited a higher degree of fiber alignment but were observed to contain more residual solvent. The average fiber diameter for both DC and AC-spun mats exhibited a strong dependence on solution concentration.     

Photosensitive 2,5-distyrylpyrazine particles produced from rapid expansion of supercritical solutions

Solvent-free, photoreactive particles of 2,5-distyrylpyrazine (DSP) monomer were developed by rapid precipitation from an expanding supercritical chlorodifluoromethane solution. DSP polymer particles were produced by solid-state photopolymerization. DSP particles below a critical diameter of about 0.5 μm were found to be mechanically stable and did not fragment upon photopolymerization. The rate of DSP photopolymerization was shown to be size-sensitive. Nano-scale particles demonstrated superior photoreactivity in the solid state in comparison to micro-scale crystals. UV spectra of DSP at different degrees of conversion were investigated and the extinction coefficients were calculated for the DSP monomer and polymer in sulfuric acid.