On Homogeneous Nucleation of Dislocation Loops in Nanocrystalline Materials

In this article, we readdress the question of homogeneous nucleation of dislocation loops in the context of nanocrystalline materials. In this case, the commonly adopted assumption of an infinite medium is no longer valid, and image forces on dislocations must be accounted for in the analysis. An additional energy term associated with the presence of finite boundaries may act to promote homogeneous nucleation and growth of dislocation loops. Based on a simplified consideration of a circular dislocation loop in a spherical nanoparticle or nanosized grain in a polycrystal, energy calculations are carried out to estimate the activation energy for homogeneous nucleation of a dislocation loop in such a system. Two different cases are considered: (1) a single nanoparticle and (2) a grain in a polycrystalline nanomaterial. Based on simulations for aluminum, it is shown that this mechanism may be plausible in both cases, albeit only for small particles and grains in the nanometer range.     

Microstructural Properties of Combustion-Synthesized and Dynamically Consolidated Titanium Boride and Titanium Carbide

Full-density TiB₂ and TiC have been fabricated by combustion synthesis reactions followed by dynamic compaction of the still hot, porous ceramic body. The relationship between the morphologies and purities of the precursor powders used and the ceramic product structures is presented. Intergrain bonding and residual porosity of the dynamically consolidated products are found to depend strongly on the impurity levels of the precursor powders. Analysis of the TiC indicates that density and microhardness increase as a function of the C/Ti ratio, with maximum values at the ratio of 1.0.     

Automated effect-specific mammographic pattern measures

We investigate the possibility to develop methodologies for assessing effect specific structural changes of the breast tissue using a general statistical machine learning framework. We present an approach of obtaining objective mammographic pattern measures quantifying a specific biological effect, such as hormone replacement therapy (HRT). We compare results using this approach to using standard density measures. We show that the proposed method can quantify both age related effects and effects caused by HRT. Age effects are significantly detected by our method where standard methodologies fail. The separation of HRT subpopulations using our approach is comparable to the best methodology, which is interactive.      

Superswelling Microneedle Arrays for Dermal Interstitial Fluid (Prote)Omics

The noninvasive sampling of dermal interstitial fluid (ISF) for the monitoring of clinical biomarkers is a greatly appealing area of research. The identification of molecular biomarkers in biological fluids has been accelerated with -omics analyses but remains limited in ISF because of its time-consuming and complex extraction process. Here, the generation of microneedle (MN) patches made of superabsorbent acrylate-based hydrogels for the rapid sampling of dermal ISF is described to explore its proteome. In depth, iterative optimization allows the identification of novel acrylate-based compositions with the required chemical, mechanical, and biocompatibility properties allowing proteomic analysis of the extracted ISF for the first time after sampling with swelling MNs. The generated MN arrays show no cytotoxic effect, successfully cross the stratum corneum, and can collect up to 6 µL of dermal ISF in 10 min in vivo. Proteomics lead to the detection of 176 clinically relevant biomarkers in the collected samples validating the use of ISF as a relevant bodily fluid for disease monitoring and diagnostic. Importantly, it is discovered that extraction fingerprint is strongly dependent on the MNs chemistry, and thus specific biomarkers could be selectively extracted by tuning the composition of the patch, making the system versatile and specific.     

Molecular species of wax esters in jaw fat of atlantic bottlenose dolphin,Tursiops truncatus

The jaw fat of the Atlantic bottlenose dolphin (Tursiops truncatus) contains unusual wax esters which can be separated into short chain (<C₂₄) and long chain (>C₂₄) fractions by thin layer chromatography. The short chain wax esters (28 wt. %) have been characterized as a 72∶24∶4 mixture of isovaleroyl, isobutoryl, and 2-methylbutyrol, esters of C₁₄–C₁₈ n- and iso-alcohols. The intact <C₂₄ esters have been resolved into individual molecular species by gas liquid chromatography on open-tubular polyester columns. The long chain wax esters (12 wt. %) contain C₁₀–C₂₂ n- and iso-acids esterified to the same C₁₄–C₁₈ n- and iso-alcohols. Gas liquid chromatography of the intact, hydrogenated >C₂₄ esters on a short JXR column has characterized them according to carbon number and the number of methyl branches they contain.     

Two important periods in the history of mechanochemistry

Some form of mechanochemical experience has existed from fine grinding of materials since prehistoric times, yet the first systematic investigations on the chemical effects of mechanical action were carried out only at the end of the nineteenth century. Walthére Spring studied the consolidation and reactions of powdered materials due to high pressure at the University of Liège, in order to understand the formation of minerals in the earth’s crust and M. Carey Lea carried out experiments on the decomposition of compounds by grinding in a mortar. In some of his experiments mechanical action produced distinctly different result from the effect of heat. The first part of this paper compares the circumstances and results of Spring and Lea. The other important period in the history of mechanochemistry was the 1960s, the time when the first dedicated conferences were organized and a broader community of mechanochemists formed. This happened in the Soviet Union and Eastern Europe where several groups were working on subjects related to mechanochemistry. In 1968, the first dedicated conference was organized as a special session of the yearly meeting of Soviet colloid chemists. An attempt is made to reconstruct the circumstances leading to that event and the roles played by Rebinder and Thiessen in bringing it together. The next conference on mechanochemistry was already a separate event and it started a yearly series. Extensions have led to the INCOME conferences, including this one in Ko?ice in 2017.     

Oxidative dehydrogenation and cracking of ethane and propane over LiDyMg mixed oxides

The oxidative dehydrogenation and cracking of ethane and propane over LiDyMg mixed oxides is reported. High yields of olefins and only moderate formation of carbon oxides was observed. Both are primary products that hardly interconvert under the reaction conditions used. Addition of chloride increases the rate of reaction, while slightly decreasing the selectivity to olefins. The addition of carbon dioxide strongly decreases the rate of reaction, the negative order of 0.5 indicating that two active Li⁺sites are blocked by the adsorption of one CO₂molecule. The reaction proceeds at low oxygen pressure primarily via elimination of dihydrogen, while at higher oxygen partial pressure the hydrogen elimination occurs via water formation. It is speculated that dehydrogenation and cracking involve Li⁺and a rather nucleophilic oxygen site.     

Absorption methods for the determination of mass transfer parameters of packing internals: A literature review

Methods for the determination of mass‐transfer coefficients and effective interfacial areas in packed absorption columns are reviewed. For each parameter, the methods are grouped into categories on the basis of their physical principle; the chemical systems used, experimental protocol, and the advantages and inconveniences are discussed. The treatment of end effects, the influence of packed bed height, and the recent efforts in standardization of measurement methods are also treated. The aim of the review is to give a broad overview of the methods used in literature in the last eight decades, some of which might be reconsidered in the light of modern measurement techniques and to evaluate them in relation to precision, practicality and hazardousness thereby to facilitate the search for reliable, precise, and convenient experimental practices. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3246–3275, 2017     

Addition of ferulic acid,ethyl ferulate,and feruloylated monoacyl- and diacylglycerols to salad oils and frying oils

To determine antioxidative effects of ferulic acid and esterified ferulic acids, these compounds were added to soybean oils (SBO), which were evaluated for oxidative stability and frying stability. Additives included feruloylated MAG and DAG (FMG/FDG), ferulic acid, ethyl ferulate, and TBHQ. After frying tests with potato chips, oils were analyzed for retention of additives and polar compounds. Chips were evaluated for hexanal and rancid odor. After 15 h frying, 71% of FMG/FDG was retained, whereas 55% of ethyl ferulate was retained. TBHQ and ferulic acid levels were 6% and <1%, respectively. Frying oils with ethyl ferulate or TBHQ produced significantly less polar compounds than SBO with no additives. Chips fried in SBO with TBHQ or ferulic acid had significantly lower amounts of hexanal and significantly less rancid odor after 8 d at 60°C than other samples. Oils were also aged at 60°C, and stability was analyzed by PV, hexanal, and rancid odor. Oils with TBHQ or FMG/FDG had significantly less peroxides and hexanal, and a lower rancid odor intensity than the control. FMG/FDG inhibited deterioration at 60°C, whereas ethyl ferulate inhibited the formation of polar compounds in frying oil. Ferulic acid acted as an antioxidant in aged fried food. TBHQ inhibited oil degradation at both temperatures. Presented at the 94th AOCS Meeting & Expo, Kansas City, MO, May 4–7, 2003.