Polyamide hydrolysis accelerated by small weak organic acids

It is well known that acidity, pH, of a solution accelerates the hydrolysis of soluble amides. Here we describe the unexpected result that weak small organic acids at low concentrations hydrolyze a polyamide at rates approximately twice that of a water HCl solution of the same pH. The effect of three small organic acids in dilute solutions, acetic, propanoic, and butanoic was studied. It is observed that the effect on the hydrolysis rate increases as the organic acid gets weaker. Butanoic, the weakest acid, has the strongest effect on increasing the hydrolysis rate. Measurements on the concentration of these acids in the polyamide reveal that there is a selective desire for these weak organic acids to diffuse into the polyamide. The concentration of these acids in the polyamide is found to be several multiples of the concentration in the water environment. And the acid concentration is highest for butanoic. The hydrolysis rate is shown to be governed by solubility, not pH of the water environment. The longer hydrocarbon tail on the carboxylic group increases its compatibility with the polyamide's monomer structure. Results are reported on the hydrolysis of polyamide-11 polymerized from aminoundecanoic acid, both neat and a commercial plasticized composition, placed in water at 100 °C and 120 °C under anaerobic conditions in high pressure glass tubes.     

Easy,Green and Safe Carbonylation Reactions through Zeolite‐Catalyzed Carbon Monoxide Production from Formic Acid

Zeolites with the right shape and acid site density and strength, such as certain ZSM‐5 forms, were able to cleanly decompose formic acid to carbon monoxide (CO), and the latter could be directly used in palladium‐catalyzed carbonylation reactions. A simple two‐reactor system was designed to produce CO conveniently and then further react this gas in a safe way. The two‐reactor system is particularly cheap, easy to set up and use. In addition, the carbonylation conditions without pressure allowed for very efficient CO incorporation, with only 1% of palladium(II) chloride (PdCl₂) and Xantphos.

     

Vacuolar and extracellular maturation of Saccharomyces cerevisiae proteinase A

The vacuolar aspartyl protease proteinase A (PrA) of Saccharomyces cerevisiae is encoded as a preproenzyme by the PEP4 gene and transported to the vacuole via the secretory route. Upon arrival of the proenzyme proPrA to the vacuole, active mature 42 kDa PrA is generated by specific proteolysis involving the vacuolar endoprotease proteinase B (PrB). Vacuolar activation of proPrA can also take place in mutants lacking PrB activity (prb1). Here an active 43 kDa species termed pseudoPrA is formed, probably by an autocatalytic process. When the PEP4 gene is overexpressed in wild-type cells, mature PrA can be found in the growth medium. We have found that prb1 strains overexpressing PEP4 can form pseudoPrA extracellularly. N-terminal amino acid sequence determination of extracellular, as well as vacuolar pseudoPrA showed that it contains nine amino acids of the propeptide, indicating a cleavage between Phe67 and Ser68 of the preproenzyme. This cleavage site is in accordance with the known substrate preference for PrA, supporting the notion that pseudoPrA is formed by autoactivation. When a multicopy PEP4 transformant of a prb1 mutant was grown in the presence of the aspartyl protease inhibitor pepstatin A, a significant level of proPrA was found in the growth medium. Our analyses show that overexpression of PEP4 leads to the secretion of proPrA to the growth medium where the zymogen is converted to pseudoPrA or mature PrA in a manner similar to the vacuolar processing reactions. Amino acid sequencing of secreted proPrA confirmed the predicted cleavage by signal peptidase between Ala22 and Lys23 of the preproenzyme.     

Glial Modulation of Energy Balance: The Dorsal Vagal Complex Is No Exception

The avoidance of being overweight or obese is a daily challenge for a growing number of people. The growing proportion of people suffering from a nutritional imbalance in many parts of the world exemplifies this challenge and emphasizes the need for a better understanding of the mechanisms that regulate nutritional balance. Until recently, research on the central regulation of food intake primarily focused on neuronal signaling, with little attention paid to the role of glial cells. Over the last few decades, our understanding of glial cells has changed dramatically. These cells are increasingly regarded as important neuronal partners, contributing not just to cerebral homeostasis, but also to cerebral signaling. Our understanding of the central regulation of energy balance is part of this (r)evolution. Evidence is accumulating that glial cells play a dynamic role in the modulation of energy balance. In the present review, we summarize recent data indicating that the multifaceted glial compartment of the brainstem dorsal vagal complex (DVC) should be considered in research aimed at identifying feeding-related processes operating at this level.     

A New Strategy to Preserve and Assess Oxygen Consumption in Murine Tissues

Mitochondrial dysfunctions are implicated in several pathologies, such as metabolic, cardiovascular, respiratory, and neurological diseases, as well as in cancer and aging. These metabolic alterations are usually assessed in human or murine samples by mitochondrial respiratory chain enzymatic assays, by measuring the oxygen consumption of intact mitochondria isolated from tissues, or from cells obtained after physical or enzymatic disruption of the tissues. However, these methodologies do not maintain tissue multicellular organization and cell-cell interactions, known to influence mitochondrial metabolism. Here, we develop an optimal model to measure mitochondrial oxygen consumption in heart and lung tissue samples using the XF24 Extracellular Flux Analyzer (Seahorse) and discuss the advantages and limitations of this technological approach. Our results demonstrate that tissue organization, as well as mitochondrial ultrastructure and respiratory function, are preserved in heart and lung tissues freshly processed or after overnight conservation at 4 °C. Using this method, we confirmed the repeatedly reported obesity-associated mitochondrial dysfunction in the heart and extended it to the lungs. We set up and validated a new strategy to optimally assess mitochondrial function in murine tissues. As such, this method is of great potential interest for monitoring mitochondrial function in cohort samples.     

Pre-adolescent children exhibit lower aerosol particle volume emissions than adults for breathing,speaking, singing and shouting

Speaking and singing are activities linked to increased aerosol particle emissions from the respiratory system, dependent on the utilized vocal intensity. As a result, these activities have experienced considerable restrictions in enclosed spaces since the onset of the COVID-19 pandemic due to the risk of infection from the SARS-CoV-2 virus, transmitted by virus-carrying aerosols. These constraints have affected public education and extracurricular activities for children as well, from in-person music instruction to children’s choirs. However, existing risk assessments for children have been based on emission measurements of adults. To address this, we measured the particle emission rates of 15 pre-adolescent children, all eight to ten years old, with a laser particle counter for the test conditions: breathing at rest, speaking, singing and shouting. Compared with values taken from 15 adults, emission rates for breathing, speaking and singing were significantly lower for children. Particle emission rates were reduced by a factor of 4.3 across all conditions, whereas emitted particle volume rates were reduced by a factor of 4.8. These data can supplement SARS-CoV-2 risk management scenarios for various school and extracurricular settings.     

Electro-thermal and -mechanical model of thermal breakdown in multilayered dielectric elastomers

Multiple breakdown phenomena may take place when operating dielectric elastomers. Thermal breakdown, which occurs due to Joule heating, becomes of special importance when using multilayered stacks of dielectric elastomers, due to the large volume-to-surface-area-ratio. In this article, a 2D axisymmetric finite-element model of a multilayered stack of dielectric elastomers is set up in COMSOL Multiphysics®. Both the electro-thermal and electro-mechanical couplings are considered, allowing for determination of the onset of thermal breakdown. Simulation results show that an entrapped particle in the dielectric elastomer drastically reduces the possible number of layers in the stack. Furthermore, the possible number of layers is greatly affected by the ambient temperature and the applied voltage. The performance of three hyperelastic material models for modeling the elastomer deformation are compared, and it is established that the Gent model yields the most restrictive prediction of breakdown point, while the Ogden model yields the least restrictive estimation.