Catalytically Doped Semiconductors for Chemical Gas Sensing: Aerogel‐Like Aluminum‐Containing Zinc Oxide Materials Prepared in the Gas Phase

Atmospheric contamination with organic compounds is undesired in industry and in society because of odor nuisance or potential toxicity. Resistive gas sensors made of semiconducting metal oxides are effective in the detection of gases even at low concentration. Major drawbacks are low selectivity and missing sensitivity toward a targeted compound. Acetaldehyde is selected due to its high relevance in chemical industry and its toxic character. Considering the similarity between gas‐sensing and heterogeneous catalysis (surface reactions, activity, selectivity), it is tempting to transfer concepts. A question of importance is how doping and the resulting change in electronic properties of a metal‐oxide support with semiconducting properties alters reactivity of the surfaces and the functionality in gas‐sensing and in heterogeneous catalysis. A gas‐phase synthesis method is employed for aerogel‐like zinc oxide materials with a defined content of aluminum (n‐doping), which were then used for the assembly of gas sensors. It is shown that only Al‐doped ZnO represents an effective sensor material that is sensitive down to very low concentrations (<350 ppb). The advance in properties relates to a catalytic effect for the doped semiconductor nanomaterial.     

Fractional brownian motion: a maximum likelihood estimator and its application to image texture

Fractals have been shown to be useful in characterizing texture in a variety of contexts. Use of this methodology normally involves measurement of a parameter H, which is directly related to fractal dimension. In this work the basic theory of fractional Brownian motion is extended to the discrete case. It is shown that the power spectral density of such a discrete process is only approximately proportional to |f|a instead of in direct proportion as in the continuous case. An asymptotic Cramer-Rao bound is derived for the variance of an estimate of H. Subsequently, a maximum likelihood estimator (MLE) is developed to estimate H. It is shown that the variance of this estimator nearly achieves the minimum bound. A generation algorithm for discrete fractional motion is presented and used to demonstrate the capabilities of the MLE when the discrete fractional Brownian process is contaminated with additive Gaussian noise. The results show that even at signal-to-noise ratios of 30 dB, significant errors in estimation of H can result when noise is present. The MLE is then applied to X-ray images of the human calcaneus to demonstrate how the line-to-line formulation can be applied to the two-dimensional case. These results indicate that it has strong potential for quantifying texture.     

Photo-vulcanization using thiol-ene chemistry: Film formation,morphology and network characteristics of UV crosslinked rubber latices

The photo-vulcanization with versatile thiol-ene chemistry represents an innovative approach to crosslink diene-rubber materials both in latex and in solid film state. In this work, the structure of elastomer-based thiol-ene networks and the morphology after film formation are studied in detail using electron microscopic techniques, atomic force microscopy and multiple-quantum solid-state NMR spectroscopy. Additionally, film formation properties and corresponding macroscopic properties of photo-vulcanized natural rubber (NR) latex and its synthetic counterpart, isoprene rubber (IR) latex, are determined in dependence on the curing procedure (pre- and post-vulcanization). The results reveal that thiol-ene cured elastomers comprise homogenously distributed crosslinks with a low amount of short chain defects. Whilst photochemically pre-cured NR latex particles provide coherent films, the film formation and mechanical properties of IR are strongly governed by the crosslink density of the latex particles. In film state, photo-vulcanization promotes narrow crosslink distributions and excellent tensile properties of both NR and IR.     

Far-off and close-up dry matter intake modulate indicators of immunometabolic adaptations to lactation in subcutaneous adipose tissue of pasture-based transition dairy cows

The common practice of increasing dietary energy density during the close-up dry period (last ～3 wk prepartum) has been recently associated with a higher incidence of metabolic disorders after calving. Despite these reports, over-feeding of metabolizable energy (ME) during the far-off, nonlactating period is a common management policy aimed at achieving optimum calving body condition score (BCS) in pasture-based systems, as cows are generally thinner than total mixed ration cows at the end of lactation. Our hypothesis was that both far-off and close-up overfeeding influence the peripartum adipose tissue changes associated with energy balance and inflammatory state. Sixty mid-lactation, grazing dairy cows of mixed age and breed were randomly allocated to 1 of 2 groups that were managed through late lactation to achieve a low and high BCS (approximately 4.25 and 5.0 on a 10-point scale) at dry-off. The low BCS cows were then overfed ME to ensure that they achieved the same BCS as the higher BCS group by calving. Within each rate of BCS gain treatment, cows were offered 65, 90, or 120% of their pre-calving ME requirements for 3 wk pre-calving in a 2 × 3 factorial arrangement of treatments (i.e., 10 cows/treatment). Subcutaneous adipose tissue was collected via biopsy at ?1, 1, and 4 wk relative to parturition. Quantitative PCR was used to measure mRNA and microRNA expression of targets related to adipogenesis and inflammation. Cows overfed in the far-off period had increased expression of miR-143 and miR-378 prepartum (?1 wk) indicating greater adipogenesis, consistent with their rapid gain in BCS following dry-off. Furthermore, the lower postpartum expression of IL6, TNF, TLR4, TLR9, and miR-145, and a higher abundance of miR-99a indicated lower body fat mobilization in early lactation in the same group. In the close-up period, feeding either 65 or 120% of ME requirements caused changes in FASN, IL1B, IL6R, TLR9, and the microRNA miR-143, miR-155, and miR-378. Their respective expression patterns indicate a tentative negative-feedback mechanism in metabolically compromised, feed-restricted cows, and a possible immune-related stimulation of lipolysis in apparently static adipocytes in overfed cows. Data from cows fed 90% of ME requirements indicate the existence of a balance between lipolytic (inflammatory-related) and anti-lipolytic signals, to prime the mobilization machinery in light of imminent lactation. Overall, results indicate that far-off dry cow nutrition influences peripartum adipose tissue metabolism, with neither strategy negatively affecting the physiological adaptation to lactation. Furthermore, to ensure a favorable transition, cows should be subjected to a small feed restriction in the close-up period, irrespective of far-off nutritional management.     

Three‐dimensional modeling of porosity development during the gasification of a char particle

This work is devoted to the three‐dimensional, direct modeling of porosity and specific surface development during the gasification of a char particle. The model was developed for heterogeneous reactions occurring inside a char particle in a kinetically controlled regime. The main goal of this work is to analyze the impact of different pore size distributions on the particle carbon conversion rate. In particular, it is shown that under certain conditions the outer particle surface can influence the specific surface area. In this context the possible adaptation of the parameter ψ from the random pore model (RPM) developed by Bhatia and Perlmutter is explained. The results of simulations are compared against the RPM and discussed. Additionally, based on the results of simulations, the physics behind several input parameters used by the RPM are explored. Finally, the possible fragmentation of a chemically reacting char particle during its gasification in dependence of instantaneous porosity was investigated numerically. It was shown that the earliest fragmentation occurs at a carbon conversion of about 0.5–0.6 due to the disaggregation of the pore walls. The results are discussed and compared implicitly with data published in the literature. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1638–1647, 2017     

Problems with the mass spectrometric determination of tritium from cold fusion

Among the attempts to measure particles produced in the cold fusion of deuterium in palladium metal is the mass spectrometric observation of tritium. An experiment which has been reported in the popular press involves attaching a hollow Pd electrode to a vacuum chamber and measuring the tritium produced during electrolysis using a mass spectrometer. We present data demonstrating that mass 5 and 6, which could be mistaken for the ions DT⁺ and T₂ ⁺, can arise from ion-molecule reactions in the ionizer of the mass spectrometer giving the ions HD₂ ⁺ and D₃ ⁺. With H₂ and D₂ present in the vacuum chamber, there are at least eight reactions which lead to these triatomic species, and these may contribute to a complex time and pressure dependence of the signals.     

Lipidomic Approaches to Study HDL Metabolism in Patients with Central Obesity Diagnosed with Metabolic Syndrome

The metabolic syndrome (MetS) is a cluster of cardiovascular risk factors characterised by central obesity, atherogenic dyslipidaemia, and changes in the circulating lipidome; the underlying mechanisms that lead to this lipid remodelling have only been partially elucidated. This study used an integrated “omics” approach (untargeted whole serum lipidomics, targeted proteomics, and lipoprotein lipidomics) to study lipoprotein remodelling and HDL composition in subjects with central obesity diagnosed with MetS (vs. controls). Compared with healthy subjects, MetS patients showed higher free fatty acids, diglycerides, phosphatidylcholines, and triglycerides, particularly those enriched in products of de novo lipogenesis. On the other hand, the “lysophosphatidylcholines to phosphatidylcholines” and “cholesteryl ester to free cholesterol” ratios were reduced, pointing to a lower activity of lecithin cholesterol acyltransferase (LCAT) in MetS; LCAT activity (directly measured and predicted by lipidomic ratios) was positively correlated with high-density lipoprotein cholesterol (HDL-C) and negatively correlated with body mass index (BMI) and insulin resistance. Moreover, many phosphatidylcholines and sphingomyelins were significantly lower in the HDL of MetS patients and strongly correlated with BMI and clinical metabolic parameters. These results suggest that MetS is associated with an impairment of phospholipid metabolism in HDL, partially led by LCAT, and associated with obesity and underlying insulin resistance. This study proposes a candidate strategy to use integrated “omics” approaches to gain mechanistic insights into lipoprotein remodelling, thus deepening the knowledge regarding the molecular basis of the association between MetS and atherosclerosis.     

Structure and energetics of hydrogen chemisorbed on a single graphene layer to produce graphane

Chemisorption of hydrogen on graphene is studied using atomistic simulations with the second generation of reactive empirical bond order Brenner inter-atomic potential. The lowest energy adsorption sites and the most important metastable sites are determined. The H concentration is varied from a single H atom, to clusters of H atoms up to full coverage. We found that when two or more H atoms are present, the most stable configurations of H chemisorption on a single graphene layer are ortho hydrogen pairs adsorbed on one side or on both sides of the graphene sheet. The latter has the highest hydrogen binding energy. The next stable configuration is the ortho–para pair combination, and then para hydrogen pairs. The structural changes of graphene caused by chemisorbed hydrogen are discussed and are compared with existing experimental data and other theoretical calculations. The obtained results will be useful for nanoengineering of graphene by hydrogenation and for hydrogen storage.     

Hot‐melt adhesives based on co‐polyamide and multiwalled carbon nanotubes

Composites of two hot melt adhesives based on co‐polyamides, one high viscosity (coPA_A), the other low viscosity (coPA_B), and multiwalled carbon nanotubes (MWCNTs) were prepared using twin‐screw extrusion via dilution of masterbatches. Examination of these composites across the length scales confirmed that the MWCNTs were uniformly dispersed and distributed in the polymer matrices, although some micron size agglomerations were also observed. A rheological percolation was determined from oscillatory rheology measurements at a mass fraction of MWCNTs below 0.01 for coPA_B and, between 0.01 and 0.02 for coPA_A. Significant increases in complex viscosity and storage modulus confirmed the “pseudo‐solid” like behavior of the composite materials. Electrical percolation, determined from dielectric spectroscopy was, found to be at 0.03 and 0.01 MWCNT mass fraction for coPA_A and coPA_B based composites, respectively. Addition of MWCNTs resulted in heterogeneous nucleation and altered the crystallization kinetics of both copolymers. Indirect evidence from contact angle measurements and surface energy calculations confirmed that MWCNT addition enhanced the adhesive properties of coPA_B to a level similar to coPA_A. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45999.     

Thermal and nonthermal physiochemical processes in nanoscale films of amorphous solid water

Amorphous solid water (ASW) is a disordered version of ice created by vapor deposition onto a cold substrate (typically less than 130 K). It has a higher free energy than the crystalline phase of ice, and when heated above its glass transition temperature, it transforms into a metastable supercooled liquid. This unusual form of water exists on earth only in laboratories, after preparation with highly specialized equipment. It is thus fair to ask why there is any interest in studying such an esoteric material. Much of the scientific interest results from the ability to use ASW as a model system for exploring the physical and reactive properties of liquid water and aqueous solutions. ASW is also thought to be the predominant form of water in the extremely cold temperatures of many interstellar and planetary environments. In addition, ASW is a convenient model system for studying the stability of amorphous and glassy materials as well as the properties of highly porous materials. A fundamental understanding of such properties is invaluable in a diverse range of applications, including cryobiology, food science, pharmaceuticals, astrophysics, and nuclear waste storage, among others. Over the past 15 years, we have used molecular beams and surface science techniques to probe the thermal and nonthermal properties of nanoscale films of ASW. In this Account, we present a survey of our research on the properties of ASW using this approach. We use molecular beams to precisely control the deposition conditions (flux, incident energy, and incident angle) and create compositionally tailored, nanoscale films of ASW at low temperatures. To study the transport properties (viscosity and diffusivity), we heat the amorphous films above their glass transition temperature, T(g), at which they transform into deeply supercooled liquids prior to crystallization. The advantage of this approach is that at temperatures near T(g), the viscosity is approximately 15 orders of magnitude larger than that of a normal liquid. As a result, the crystallization kinetics are dramatically slowed, increasing the time available for experiments. For example, near T(g), a water molecule moves less than the distance of a single molecule on a typical laboratory time scale (～1000 s). For this reason, nanoscale films help to probe the behavior and reactions of supercooled liquids at these low temperatures. ASW films can also be used for investigating the nonthermal reactions relevant to radiolysis.