Thermal Stability of Polymer Additives: Comparison of Decomposition Models Including Oxidative Pyrolysis

The thermo‐oxidative stability of widely used polymer additives has been investigated. A comparative analytical approach with classic and innovative decomposition models for polymer additives was conducted and the results supported using quantum‐chemical calculations. Unique pyrolysis products of the analytes were compiled utilizing pyrolysis online coupled to gas chromatography followed by mass spectrometric detection (Pyr‐GC–MS). The pyrolysis was either performed under inert conditions or in an oxygen‐containing atmosphere. Squalane was applied as polymer‐mimicking liquid next to low density polyethylene (LDPE) and polyamide 6 (PA 6) as matrices for 10 selected additives. The additives included in this study range from antioxidants and plasticizers to processing aids. These were selected to address a range of application in consumer products and to cover different chemical classes. The toxicological relevance of additives and potential breakdown products was considered. Consequently, degradation of sterically hindered antioxidants, diarylamines, and a trimellitic acid derivative was investigated. The findings were used to predict the behavior of consumer products made of polymeric materials entailing additives. The level of Antioxidant 2246 [2‐tert‐butyl‐6‐[(3‐tert‐butyl‐2‐hydroxy‐5‐methylphenyl)methyl]‐4‐methylphenol] and one of its predicted decomposition products was determined in baby bottle nipples made of natural rubber [2‐tert‐butyl‐4‐methylphenol] utilizing the complementary technique of gas chromatography coupled to tandem mass spectrometry (GC–MS/MS). This study provides a comprehensive characterization of important polymer additives and enables the prioritization of degradation products for further risk assessment. J. VINYL ADDIT. TECHNOL., 25:E12–E27, 2019. © 2018 The Authors. Journal of Vinyl and Additive Technology published by Wiley Periodicals, Inc. on behalf of Society of Plastics Engineers     

HoxA is a transcriptional regulator for expression of the hup structural genes in free-living Bradyrhizobium japonicum

A chromosomally integrated Bradyrhizobium japonicum hoxA mutant is unable to oxidize hydrogen in free-living conditions. Derepressing conditions that induce hydrogenase activity in free-living, wild-type B. japonicum cells cannot induce expression of the hydrogenase structural genes in the hoxA mutant. The DNA-binding capacity of HoxA at the hup promoter region was studied by means of gel retardation. Both heterotrophically growing cells and cells induced to express hydrogenase activity contain a protein that specifically binds to the hup promoter region. Crude protein extracts isolated from a B. japonicum hoxA mutant do not contain this binding compound. The HoxA protein was overexpressed in E. coli and isolated in the form of a maltose-binding protein (MBP)-HoxA fusion. The MBP-HoxA hybrid protein specifically bound to a 50 bp region of the hupSL promoter known to be important for regulation of hupSL expression.     

ACAT inhibitors derived from hetero-Diels-Alder cycloadducts of thioaldehydes

Acyl-CoA:cholesterol acyltransferase (ACAT) is the enzyme largely responsible for intracellular cholesterol esterification. A systemic inhibitor of ACAT is believed to be able to slow or even reverse the atherosclerotic process. Towards that goal, a series of cyclic sulfides, derived from the hetero-Diels-Alder reaction of thioaldehydes with 1,3-dienes, and bearing carboxamide substituents, were prepared and evaluated for in vitro (in several tissues and species) and ex vivo ACAT inhibition. Minor changes in subsequent structure were found to have a significant effect in optimization of the biological activity of this series of compounds.     

Multifunctional hydrogels that promote osteogenic hMSC differentiation through stimulation and sequestering of BMP2

The extracellular environment controls many cellular activities thereby linking external material cues to internal cell function. By better understanding these processes, synthetic extracellular material niches can be tailored to present cells with highly regulated physical and/or chemical cues that promote or suppress selected cell functions. Here, poly(ethylene glycol) (PEG) hydrogels were functionalized with fluvastatin-releasing grafts and growth factor binding heparin domains to enable the dynamic exchange of information between the material and cells from the outside-in and inside-out (i.e., bidirectional signaling). By incorporating a fluvastatin-releasing graft and carefully controlling the dose and temporal release, materials were designed to promote bone morphogenic protein (BMP2) and alkaline phosphatase (ALP) production by human mesenchymal stem cells (hMSCs). When the release of fluvastatin was controlled to occur over 2 weeks, BMP2 and ALP production was increased 2.2-fold and 1.7-fold, respectively, at day 28 compared to hMSCs cultured in the absence of fluvastatin. By introducing a heparin functionality into the gel to sequester and localize the hMSC-produced BMP2, the osteogenic differentiation of hMSCs was further augmented over fluvastatin delivery alone. Osteopontin and core binding factor α1 gene expression was 6-fold and 4-fold greater for hMSCs exposed to fluvastatin in the presence of the heparin functionalities, respectively. These results demonstrate how multifunctional gels that interact with cells in a bidirectional manner can efficiently promote selected cell functions, such as the osteogenic differentiation of hMSCs.     

A review of the effects of water transfers in the La Grande Hydroelectric Complex (Québec,Canada)

Construction of the La Grande Complex in Eastern Canada called for complete or partial diversion of six rivers, the mean annual discharge of which varied from 60 to 1600 m³ s^?1, and the transfer of water from two adjoining watersheds (1586m³ s^?1) into La Grande Rivière. Three of these rivers with reduced flow, Eastmain (from 700 to 95m³ s^?1), Opinaca (from 260 to 35m³ s^?1), and Caniapiscau (from 1708 to 960m³ s^?1) and the waterways with increased flows, Boyd-Sakami (from 1 to 811m³ s^?1) and La Grande Rivière (from 1760 to 3400m³ s^?1) were intensively monitored from 1978 to 1988, while the others were surveyed sporadically. Very few modifications were observed, compared to previous conditions, in banks stability, water quality, and aquatic fauna of the affected rivers: those which appeared can be explained by the water level fluctuations, the water quality of the tributaries of the residual drainage basin, and/or by the direct influence of the reservoirs. In James Bay, the areal extent of the Eastmain River and La Grand Rivière plumes varied with discharge in an exponential relation, mostly under ice cover; resources from the coastal environment had not yet undergone any major changes. Because of the very small population dwelling in the area, less than 3000 inhabitants, modifications in the hydrological regime of these rivers did cause relatively few impacts, the main being greater banks instability in specific locations, reduction of the thickness and ice cover on La Grande Rivière, enhancement of navigation constraints on Eastmain River, and higher mercury levels in fish related to operation of the reservoirs.     

The quantum dynamic capacity formula of a quantum channel

The dynamic capacity theorem characterizes the reliable communication rates of a quantum channel when combined with the noiseless resources of classical communication, quantum communication, and entanglement. In prior work, we proved the converse part of this theorem by making contact with many previous results in the quantum Shannon theory literature. In this work, we prove the theorem with an ??ab initio?? approach, using only the most basic tools in the quantum information theorist??s toolkit: the Alicki-Fannes?? inequality, the chain rule for quantum mutual information, elementary properties of quantum entropy, and the quantum data processing inequality. The result is a simplified proof of the theorem that should be more accessible to those unfamiliar with the quantum Shannon theory literature. We also demonstrate that the ??quantum dynamic capacity formula?? characterizes the Pareto optimal trade-off surface for the full dynamic capacity region. Additivity of this formula reduces the computation of the trade-off surface to a tractable, textbook problem in Pareto trade-off analysis, and we prove that its additivity holds for the quantum Hadamard channels and the quantum erasure channel. We then determine exact expressions for and plot the dynamic capacity region of the quantum dephasing channel, an example from the Hadamard class, and the quantum erasure channel.     

Synthesis and structure-activity study of quaternary ammonium functionalized beta-cyclodextrin-carboxymethylcellulose polymers

Carboxymethylcellulose (CMC) and beta-cyclodextrin (beta-CD)-based polymers functionalized with two types of quaternary ammonium compounds (QACs), the alkaquat DMB-451 (N-alkyl (50% C14, 40% C12, 10% C10) dimethylbenzylammonium chloride) (DMD-451) named polymer DMB-451, and FMB 1210-8 (a blend of 32 w% N-alkyl (50% C14, 40% C12, 10% C10) dimethylbenzylammonium chloride and 48 w% of didecyldimethylammonium chloride) named polymer FMB 1210-8, were synthethized and characterized by Fourier transform infrared spectroscopy. The antimicrobial activities of these polymers against Eschericia coli were also evaluated at 25 degrees C in wastewater. The results have indicated that the polymer FMB 1210-8 possesses a high-affinity binding with bacterial cells that induces a rapid disinfection process. Moreover, in the same experimental conditions of disinfection (mixture of 1.0 g of polymer and 100 mL of wastewater), the polymer FMB 1210-8 has a higher antimicrobial efficiency (99.90%) than polymer DMB-451 (92.8%). This phenomenon might be associated to a stronger interaction with bacterial cells due to stronger binding affinity for E. coli cells and greater killing efficiency of the C10 alkyl chains QAC of polymer FMB 1210-8 to disrupt the bacterial cell membrane as compared to N-alkyl (50% C14, 40% C12, 10% C10) dimethylbenzylammonium chloride. Together, these results suggest that the polymer FMB 1210-8 could constitute a good disinfectant against Escherichia coli, which could be advantageously used in wastewater treatments due to the low toxicity of beta-CD and CMC, and moderated toxicity of FMB 1210-8 to human and environment.     

An investigation of the option space in conceptual building design for advanced building simulation

This article describes research conducted to gather empirical evidence on size, character and content of the option space in building design projects. This option space is the key starting point for the work of any climate engineer using building performance simulation who is supporting the design process. The underlying goal is to strengthen the role of advanced computing in building design, especially in the early conceptual stage, through a better integration of building performance simulation tools augmented with uncertainty analysis and sensitivity analysis. Better integration will need to assist design rather than automate design, allowing a spontaneous, creative and flexible process that acknowledges the expertise of the design team members. This research investigates and contrasts emergent option spaces and their inherent uncertainties in an artificial setting (student design studios) and in real-life scenarios (commercial design project case studies). The findings provide empirical evidence of the high variability of the option space that can be subjected to uncertainty analysis and sensitivity analysis.     

Evidence for Glass–glass Interfaces in a Columnar Cu–Zr Nanoglass

Comprehensive analyses of the atomic structure using advanced analytical transmission electron microscopy-based methods combined with atom probe tomography confirm the presence of distinct glass–glass interfaces in a columnar Cu-Zr nanoglass synthesized by magnetron sputtering. These analyses provide first-time in-depth characterization of sputtered film nanoglasses and indicate that glass–glass interfaces indeed present an amorphous phase with reduced mass density as compared to the neighboring amorphous regions. Moreover, dedicated analyses of the diffusion kinetics by time-of-flight secondary ion mass spectroscopy (ToF SIMS) prove significantly enhanced diffusivity, suggesting fast transport along the low density glass–glass interfaces. The present results further indicate that sputter deposition is a feasible technique for reliable production of nanoglasses and that some of the concepts proposed for this new class of glassy materials are applicable.