Electrophilic aromatic chlorination and haloperoxidation of chloride catalyzed by polyfluorinated alcohols: a new manifestation of template catalysis

We have demonstrated that a polyfluorinated alcohol, 2,2,2-trifluoroethanol, solvent enables haloperoxidase type activity and the oxychlorination of arenes (benzene and its alkylated derivatives) without a metal catalyst. The polyfluorinated alcohol has a dual function; it catalyzes electrophilic chlorination of less reactive arenes by several orders of magnitude and oxidation of chloride at lower H+ concentrations. DFT calculations show that a complementary charge template in the transition state explains the catalysis of the electrophilic chlorination.     

Effect of hot acid etching on the mechanical strength of ground YAG laser elements

High-power pumped Nd:YAG elements may exceed their tensile strength under high thermally induced stress. Providing extra strength to such rods is essential for their employment in high-power lasers. The tensile strength of YAG elements was increased by chemical etching in concentrated phosphoric acid. The highest tensile strength was achieved by etching of fine-ground YAG components: an average for slabs, and for rods, which are 3.6 times and 5 times higher than those of non-etched elements, respectively. The measurements were carried out by four-point flexure strength test. We have established a dependency among the micro-roughness of YAG elements, the surface morphology obtained by etching, and the tensile strength: the tensile strength of the etched element improves for finer after-etch surface texture, which is obtained for finer initial micro-roughness.

To assure the withstanding of Nd:YAG rods under high thermal gradients, a new approach was employed, namely, increasing the pump-power applied to the Nd:YAG rod till fracture. Our results show an increase by more than 2.7 times in tensile strength of etched Nd:YAG rods as compared to standard commercial rods, which corresponds to a thermal loading of excess of 434 W/cm.     

Modified whey protein coatings for improved gas barrier properties of biodegradable films

As a result of environmental concern, there is an increasing interest in the development of biodegradable polymers for packaging with suitable properties, as an alternative to the synthetic petroleum‐based polymers. However, such biodegradable polymers are prevented for use in wide industrial and commercial packaging because of their limited gas and vapor barrier properties. This obstacle urges innovative strategies to achieve enhanced gas barrier properties using “bio‐layering” technologies. Whey protein isolate (WPI), a by‐product of the cheese industry, has quite promising properties for packaging purposes. It possesses good oxygen, aroma, and oil barrier properties; however, its permeability to water vapor is high. In this study, several WPI coatings were obtained, adding polyvinyl alcohol and pectin to improve the coated film properties; in addition, nanoclays were used to improve water vapor barrier properties. Comparison of neat poly (lactic acid) film versus poly (lactic acid) coated with WPI presented advantage of the later: improvement of about 90% in the oxygen barrier properties and about 27% in the water vapor barrier properties. Copyright © 2016 John Wiley & Sons, Ltd.     

Surface instabilities in ultrathin, cross-linked poly(N-isopropylacrylamide) coatings

Near-the-surface instabilities with a cusplike morphology were observed in ultrathin photo-cross-linked poly(N-isopropylacrylamide) coatings upon swelling in water. The characteristic wavelength of the instability was approximately 25 times the dry thickness and scaled linearly with coating thickness between 30 and 1200 nm. Above 1200 nm, slippage of the coating along the confining substrate led to reticulated patterns with a much larger wavelength. To help interpret the origin of the instability, the coatings were also exposed to a solvent slightly worse than water (acetone) and a solvent slightly better than water (isopropanol). In all cases, the characteristic wavelength scaled linearly with respect to the swelling induced by each solvent. Both water and isopropanol produced well-defined cusps or folds in the gel surface, while acetone produced semiordered blisters that grew into one another. The features produced in acetone may be a consequence of swelling being close to the threshold value for the loss of planar stability. Through the use of a first-order linear perturbation of the Flory-Rehner model, it is shown that the emergence of a characteristic wavelength is consistent with an inhomogeneous distribution of solvent that results from diffusion of solvent into a dry coating.     

Renewal-anomalous-heterogeneous files

Renewal-anomalous-heterogeneous files are solved. A simple file is made of Brownian hard spheres that diffuse stochastically in an effective 1D channel. Generally, Brownian files are heterogeneous: the spheres' diffusion coefficients are distributed and the initial spheres' density is non-uniform. In renewal-anomalous files, the distribution of waiting times for individual jumps is not exponential as in Brownian files, yet obeys: ψα(t)∼t−1−α, 0<α<1. The file is renewal as all the particles attempt jumping at the same time. It is shown that the mean square displacement (MSD) in a renewal-anomalous-heterogeneous file, 〈r²〉, obeys, , where nrml〈r²〉 is the MSD in the corresponding Brownian file. This scaling is an outcome of an exact relation (derived here) connecting probability density functions of Brownian files and renewal-anomalous files. It is also shown that non-renewal-anomalous files are slower than the corresponding renewal ones.     

A probabilistic model of thermal explosion in polydisperse fuel spray

This work is concerned with an analysis of polydisperse spray droplets distribution on the thermal explosion processes. In many engineering applications it is usual to relate to the practical polydisperse spray as a monodisperse spray. The Sauter Mean Diameter (SMD) and its variations are frequently used for this purpose [13]. The SMD and its modifications depend only on “integral” characterization of polydisperse sprays and can be the same for very different types of polydisperse spray distributions.The current work presents a new, simplified model of the thermal explosion in a combustible gaseous mixture containing vaporizing fuel droplets of different radii (polydisperse). The polydispersity is modeled using a probability density function (PDF) that corresponds to the initial distribution of fuel droplets size. This approximation of polydisperse spray is more accurate than the traditional ‘parcel’ approximation and permits an analytical treatment of the simplified model. Since the system of the governing equations represents a multi-scale problem, the method of invariant (integral) manifolds is applied.An explicit expression of the critical condition for thermal explosion limit is derived analytically. Numerical simulations demonstrate an essential dependence of these thermal explosion conditions on the PDF type and represent a natural generalization of the thermal explosion conditions of the classical Semenov theory.     

Photoelectron energy distribution measurements from benzene in rare gas matrices

Photoelectronic energy distributions (PED's) are presented for benzene molecules embedded in solid Ar, Kr and Xe rare gas matrices obtained with monochromatized synchrotron radiation for selective excitation in the range hν = 8 eV to 15 eV. For photon energies in the transparent region of the matrices direct emission from the occupied benzene initial states in the band gap of the matrix is observed. Energy transfer from the matrix exciton states to the benzene guest molecules takes place when the host exciton states are excited. The PED's show that energy of unrelaxed excitons is transferred and that transfer to initial states just at the ionization threshold is favoured.     

Students' Understanding of the Particulate Nature of Matter

The particulate nature of matter is identified in science education standards as one of the fundamental concepts that students should understand at the middle school level. However, science education research in indicates that secondary school students have difficulties understanding the structure of matter. The purpose of the study is to describe how engaging in an extended project‐based unit developed urban middle school students' understanding of the particulate nature of matter. Multiple sources of data were collected, including pre‐ and posttests, interviews, students' drawings, and video recordings of classroom activities. One teacher and her five classes were chosen for an indepth study. Analyses of data show that after experiencing a series of learning activities the majority of students acquired substantial content knowledge. Additionally, the finding indicates that students' understanding of the particulate nature of matter improved over time and that they retained and even reinforced their understanding after applying the concept. Discussions of the design features of curriculum and the teacher's use of multiple representations might provide insights into the effectiveness of learning activities in the unit.