HEAT TRANSFER IN PARTIALLY MISCIBLE TERNARY SYSTEMS

In the study of mass transfer between partially miscible liquids, temperature perturbations have been found to have an important effect in the generation of interfacial activity. Micro- and macro-generated interfacial convection usually occurs in combination with one another even in fairly simple heat or mass transfer events. These combinations are responsible for the enhancement of mass transfer rates. In an effort to acquire a better understanding of the heat transfer effects in ternary liquid-liquid systems, temperature difference profiles were measured when contacting two partially miscible phases. A vertical and a rotational transfer cell were designed to contact the partially miscible phases without inducing external disturbances. Five thermocouples were immersed in the bottom liquid phase at predetermined positions below the interface. In order to understand the influence of the convection generated, the vertical cell was designed to hinder convection in one phase, while the rotational cell permits convection in both phases. The experimental results showed larger temperature differences in the rotational cell after the contact of the phases. Also, systems which were initially unsaturated presented larger heat effects than those in which the partially miscible solvents were initially saturated. Several parameters indicating the importance of heat effects in the ternary systems studied are reported.     

Profile of TREM2-Derived circRNA and mRNA Variants in the Entorhinal Cortex of Alzheimer’s Disease Patients

Genetic variants in TREM2, a microglia-related gene, are well-known risk factors for Alzheimer’s disease (AD). Here, we report that TREM2 originates from circular RNAs (circRNAs), a novel class of non-coding RNAs characterized by a covalent and stable closed-loop structure. First, divergent primers were designed to amplify circRNAs by RT-PCR, which were further assessed by Sanger sequencing. Then, additional primer sets were used to confirm back-splicing junctions. In addition, HMC3 cells were used to assess the microglial expression of circTREM2s. Three candidate circTREM2s were identified in control and AD human entorhinal samples. One of the circRNAs, circTREM2_1, was consistently amplified by all divergent primer sets in control and AD entorhinal cortex samples as well as in HMC3 cells. In AD cases, a moderate negative correlation (r = −0.434) was found between the global average area of Aβ deposits in the entorhinal cortex and circTREM2_1 expression level. In addition, by bioinformatics tools, a total of 16 miRNAs were predicted to join with circTREM2s. Finally, TREM2 mRNA corresponding to four isoforms was profiled by RT-qPCR. TREM2 mRNA levels were found elevated in entorhinal samples of AD patients with low or intermediate ABC scores compared to controls. To sum up, a novel circRNA derived from the TREM2 gene, circTREM2_1, has been identified in the human entorhinal cortex and TREM2 mRNA expression has been detected to increase in AD compared to controls. Unraveling the molecular genetics of the TREM2 gene may help to better know the innate immune response in AD.     

Understanding Local and Macroscopic Electron Mobilities in the Fullerene Network of Conjugated Polymer‐based Solar Cells: Time‐Resolved Microwave Conductivity and Theory

The efficiency of bulk heterojunction (BHJ) organic photovoltaics is sensitive to the morphology of the fullerene network that transports electrons through the device. This sensitivity makes it difficult to distinguish the contrasting roles of local electron mobility (how easily electrons can transfer between neighboring fullerene molecules) and macroscopic electron mobility (how well‐connected is the fullerene network on device length scales) in solar cell performance. In this work, a combination of density functional theory (DFT) calculations, flash‐photolysis time‐resolved microwave conductivity (TRMC) experiments, and space‐charge‐limit current (SCLC) mobility estimates are used to examine the roles of local and macroscopic electron mobility in conjugated polymer/fullerene BHJ photovoltaics. The local mobility of different pentaaryl fullerene derivatives (so‐called ‘shuttlecock’ molecules) is similar, so that differences in solar cell efficiency and SCLC mobilities result directly from the different propensities of these molecules to self‐assemble on macroscopic length scales. These experiments and calculations also demonstrate that the local mobility of phenyl‐C₆₀ butyl methyl ester (PCBM) is an order of magnitude higher than that of other fullerene derivatives, explaining why PCBM has been the acceptor of choice for conjugated polymer BHJ devices even though it does not form an optimal macroscopic network. The DFT calculations indicate that PCBM's superior local mobility comes from the near‐spherical nature of its molecular orbitals, which allow strong electronic coupling between adjacent molecules. In combination, DFT and TRMC techniques provide a tool for screening new fullerene derivatives for good local mobility when designing new molecules that can improve on the macroscopic electron mobility offered by PCBM.     

Extraction and characterization of soluble protein fractions from Phaseolus lunatus L seeds

Legume proteins as a potential source of valuable nutrients, are the object of several studies in order to obtain the best use. A basic knowledge becomes more important for those proteins from species not wholly utilized, before using them as food ingredients. The objective of this work was to determine several structural and nutritional characteristics of the protein fractions from Phaseolus lunatus, separated in different solvents. The relative amount of extraction for the albumins (ALB), globulins (GLB), prolamines (PRL), and glutelins (GLT) was 62.3, 34.8, 1.4 and 1.5%, respectively. The SDS-PAGE electrophoretic profile of both ALB and GLB, showed seven common bands in intervals from 10 to 95 kDa, and 14 to 99 kDa, respectively; the amino acids profile showed that PRL was the rich fraction in sulfurated amino acids (11.5 g/100 g protein); the content of lysine in the fraction of ALB was smaller than expected but the requirement of the FAO in the fractions of GLB and GLT was covered. In general, the fraction of GLB had the best balance of amino acids and digestibility (80%); however, it had a relationship of calculated protein efficiency ratio (C-PER) of 0.11, smaller than the ratio in ALB (0.97). The calorimetric analysis showed denatured temperatures around 90 degrees C for the ALB, GLB, and GLU fractions. The PRL fraction probably did not present a thermal transition because the proteins were denaturalized by the extraction conditions.     

Gold Stabilized with Iridium on Ceria–Niobia Catalyst: Activity and Stability for CO Oxidation

Topics in Catalysis - Monometallic gold and iridium, and bimetallic gold–iridium on ceria–niobia (Nb2O5–CeO2) catalysts were synthesized by deposition–precipitation with...     

ATR-FTIR Study of the Decomposition of Acetic Anhydride on Fosfotungstic Wells–Dawson Heteropoly Acid Using Concentration-Modulation Excitation Spectroscopy

The decomposition of acetic anhydride in liquid phase on a fosfotungstic Wells–Dawson heteropoly acid (HPA) was investigated by in situ ATR-FTIR spectroscopy. Transient and concentration-modulation excitation spectroscopy (MES) experiments in combination with phase-sensitive detection (PSD) were used to monitor the solid–liquid interface. The MES method is based on the periodic variation of a parameter of the reaction media such as, the reactant concentration. That periodic alteration causes varying infrared signals of the surface adsorbed species that are subsequently demodulated with the PSD methodology. Thus, the separation of the static signals from the changing ones is achieved, and species with different response can be observed in the spectra. Using MES-PSD coupled with ATR-FTIR, acetic anhydride was observed to decompose to acetic acid, acetate and acyl [CH₃C(O)⁺] species, involving Brønsted acid sites of the HPA catalyst. The CH₃C(O)⁺ is a very unstable intermediate species and it is the key intermediate in the Friedel–Crafts acylation reactions. Moreover, the acetate groups are spectator species since remain strongly adsorbed on the catalyst surface and do not further react.     

Expression of DDX11 and DNM1L at the 12p11 Locus Modulates Systemic Lupus Erythematosus Susceptibility

Objectives: This study employed genetic and functional analyses using OASIS meta-analysis of multiple existing GWAS and gene-expression datasets to identify novel SLE genes. Methods: Four hundred and ten genes were mapped using SNIPPER to 30 SLE GWAS loci and investigated for expression in three SLE GEO-datasets and the Cordoba {"type":"entrez-geo","attrs":{"text":"GSE50395","term_id":"50395"}}GSE50395-dataset. Blood eQTL for significant SNPs in SLE loci and STRING for functional pathways of differentially expressed genes were used. Confirmatory qPCR on SLE monocytes was performed. The entire 12p11 locus was investigated for genetic association using two additional GWAS. Expression of 150 genes at this locus was assessed. Based on this significance, qPCRs for DNM1L and KRAS were performed. Results: Fifty genes were differentially expressed in at least two SLE GEO-datasets, with all probes directionally aligned. DDX11, an RNA helicase involved in genome stability, was downregulated in both GEO and Cordoba datasets. The most significant SNP, rs3741869 in OASIS locus 12p11.21, containing DDX11, was a cis-eQTL regulating DDX11 expression. DDX11 was found repressed. The entire 12p11 locus showed three association peaks. Gene expression in GEO datasets identified DNM1L and KRAS, besides DDX11. Confirmatory qPCR validated DNM1L as an SLE susceptibility gene. DDX11, DNM1L and KRAS interact with each other and multiple known SLE genes including STAT1/STAT4 and major components of IFN-dependent gene expression, and are responsible for signal transduction of cytokines, hormones, and growth-factors, deregulation of which is involved in SLE-development. Conclusion: A genomic convergence approach with OASIS analysis of multiple GWAS and expression datasets identified DDX11 and DNM1L as novel SLE-genes, the expression of which is altered in monocytes from SLE patients. This study lays the foundation for understanding the pathogenic involvement of DDX11 and DNM1L in SLE by identifying them using a systems-biology approach, while the 12p11 locus harboring these genes was previously missed by four independent GWAS.     

A New Smoothened Antagonist Bearing the Purine Scaffold Shows Antitumour Activity In Vitro and In Vivo

The Smoothened (SMO) receptor is the most druggable target in the Hedgehog (HH) pathway for anticancer compounds. However, SMO antagonists such as vismodegib rapidly develop drug resistance. In this study, new SMO antagonists having the versatile purine ring as a scaffold were designed, synthesised, and biologically tested to provide an insight to their mechanism of action. Compound 4s was the most active and the best inhibitor of cell growth and selectively cytotoxic to cancer cells. 4s induced cell cycle arrest, apoptosis, a reduction in colony formation and downregulation of PTCH and GLI1 expression. BODIPY-cyclopamine displacement assays confirmed 4s is a SMO antagonist. In vivo, 4s strongly inhibited tumour relapse and metastasis of melanoma cells in mice. In vitro, 4s was more efficient than vismodegib to induce apoptosis in human cancer cells and that might be attributed to its dual ability to function as a SMO antagonist and apoptosis inducer.