The calculation of the heat release rate by oxygen consumption in a controlled‐atmosphere cone calorimeter

The standard cone calorimeter according to ASTM E 1354 and ISO 5660 enables reaction‐to‐fire tests to be performed in ambient atmospheric conditions. A controlled‐atmosphere chamber modifies the standard apparatus in a way that allows tests to be performed in nonambient conditions as well. The enclosed chamber is placed underneath the standard exhaust hood and does not have a closed connection to the hood. With this open arrangement, the exhaust gases are diluted by excess air drawn in from the laboratory surroundings. Heat‐induced changes in the consequential dilution ratio affect the calculation of fire quantities and, when neglected, lead to deviations of up to 30% in heat release rate. The paper introduces a test protocol and equations to calculate the heat release rate taking dilution effects into account. A mathematical correction is shown that compensates for the dilution effects while avoiding extensive mechanical changes in the equipment. Copyright © 2013 John Wiley & Sons, Ltd.     

An Oral Mixed Fat Load Is Followed by a Modest Anti-inflammatory Adipocytokine Response in Overweight Patients with Metabolic Syndrome

We investigated the postprandial changes in plasma levels of adipocytokines in overweight patients with metabolic syndrome after an oral fat load. After an oral fat load and during a prolonged fast, blood was drawn at 0, 2, 3, 4 and 8 h for measurement of adiponectin, adipsin, cathepsin S, chemerin, hepatic growth factor, interferon‐γ‐inducible protein‐10, leptin, macrophage chemoattractant protein‐1, macrophage migration inhibitory factor, nerve growth factor, retinol binding protein‐4, resistin, serum amyloid A1, tissue inhibitor of metalloproteinase‐1 and thrombopoietin using a microbead‐based Luminex assay. Area under the curves (AUC) were calculated and compared. Plasma adiponectin levels were higher after an oral fat load compared to fasting at t = 2 h (950 ± 513 vs. ?1,881 ± 713 ng/ml) while the plasma levels for adipsin (?9 ± 5 vs. 16 ± 5 ng/ml), chemerin (?122 ± 35 vs. 13 ± 21 ng/ml), SAA‐1 (?391 ± 213 vs. 522 ± 173 ng/ml) and TPO (?335 ± 144 vs. 622 ± 216 ng/ml) were lower after an oral fat load compared to fasting. The baseline corrected AUC for IP‐10 was higher after fat load compared to fasting (median ?116 pg h/ml; IQR ?270 to 10 vs. ?21 pg h/ml; IQR ?136 to 418 (p = 0.047). In conclusion, in overweight male subjects with the metabolic syndrome, an oral fat load is accompanied with a modest anti‐inflammatory response of adipose tissue‐derived adipocytokines.     

Carboxylmethyl chitosan-graft-poly(γ-benzyl-l-glutamate) glycopeptides: Synthesis and particle formation as encapsulants

Amphiphilic glycopeptides, carboxylmethyl chitosan-graft-poly(γ-benzyl-l-glutamate) (m-Chi-g-PBLG), were synthesized through ring-opening polymerization of γ-benzyl-l-glutamate N-carboxyanhydride (NCA) using short chained m-Chi as the macroinitiator and employed to form vesicles in aqueous solution. The elemental and NMR analyses revealed that the polymerization degree (DP) of grafted PBLG could be tuned by varying the feed ratio of NCA to m-Chi. The conformation of the grafted PBLG chains transformed from β-sheet to α-helix was correlated with the PBLG chain length. The m-Chi-g-PBLG vesicles can be prepared using double emulsion method and their sizes can be adjusted between 140 and 250 nm. The encapsulation of a model compound, FITC-dextran, in the vesicles revealed their potential applications as encapsulants or carriers. The in vitro release data revealed that a sustained release of FITC-dextran for a time period over two weeks can be achieved.     

Computational study of thermal and mechanical properties of nylons and bio-based furan polyamides

We have investigated thermal and mechanical properties of bio-based furan polyamides and petroleum-based nylons with atomistic simulations. Glass transition temperatures estimated from a series of simulations at different temperatures were in good agreement with experimental measurements. Stress–strain relationships under uniaxial deformation conditions were also obtained and analyzed. Overall, polymers with smaller repeat units exhibited slightly higher glass transition temperatures and elastic moduli, which were attributed to higher cohesive energy densities. Furan polyamides displayed higher van der Waals cohesive energy densities and maintained more rigid planar structures near furan rings compared to nylons. As a result, bio-based furan polyamides showed higher glass transition temperatures and comparable mechanical properties despite having overall weaker hydrogen bonding than nylons.     

Hydrothermal Carbonization of Biomass: Major Organic Components of the Aqueous Phase

Process waters obtained from hydrothermal carbonization (HTC) of wheat straw, a biogas digestate derived thereof, and four woody biomass feedstocks were quantified regarding the total organic carbon (TOC) and selected organic compounds. HTC runs revealed that TOC loads were largely unaffected by process severity or type of feedstock whereas the C₂–C₆ fatty acids, determined by GC, displayed clear effects of temperature and feedstock. HPLC demonstrated simultaneously the initial increase and subsequent consumption of cellulose‐derived furfural and 5‐hydroxymethylfurfural as well as the increase of the lignin‐derived 2‐methoxyphenol. 2‐Methylbenzofuran, an example for a substance potentially harmful to aquatic biota, was observed in high concentration in the HTC liquor from wheat straw‐based feedstocks.     

A GPU‐Adapted Structure for Unstructured Grids

A key advantage of working with structured grids (e.g., images) is the ability to directly tap into the powerful machinery of linear algebra. This is not much so for unstructured grids where intermediate bookkeeping data structures stand in the way. On modern high performance computing hardware, the conventional wisdom behind these intermediate structures is further challenged by costly memory access, and more importantly by prohibitive memory resources on environments such as graphics hardware. In this paper, we bypass this problem by introducing a sparse matrix representation for unstructured grids which not only reduces the memory storage requirements but also cuts down on the bulk of data movement from global storage to the compute units. In order to take full advantage of the proposed representation, we augment ordinary matrix multiplication by means of action maps, local maps which encode the desired interaction between grid vertices. In this way, geometric computations and topological modifications translate into concise linear algebra operations. In our algorithmic formulation, we capitalize on the nature of sparse matrix‐vector multiplication which allows avoiding explicit transpose computation and storage. Furthermore, we develop an efficient vectorization to the demanding assembly process of standard graph and finite element matrices.     

Microbial Production of Natural and Unnatural Monolignols with Escherichia coli

Phenylpropanoids and phenylpropanoid-derived plant polyphenols find numerous applications in the food and pharmaceutical industries. In recent years, several microbial platform organisms have been engineered towards producing such compounds. However, for the most part, microbial (poly)phenol production is inspired by nature, so naturally occurring compounds have predominantly been produced to date. Here we have taken advantage of the promiscuity of the enzymes involved in phenylpropanoid synthesis and exploited the versatility of an engineered Escherichia coli strain harboring a synthetic monolignol pathway to convert supplemented natural and unnatural phenylpropenoic acids into their corresponding monolignols. The performed biotransformations showed that this strain is able to catalyze the stepwise reduction of chemically interesting unnatural phenylpropenoic acids such as 3,4,5-trimethoxycinnamic acid, 5-bromoferulic acid, 2-nitroferulic acid, and a “bicyclic” p-coumaric acid derivative, in addition to six naturally occurring phenylpropenoic acids.     

Efficient Enzymatic Cyclization of Disulfide-Rich Peptides by Using Peptide Ligases

Disulfide-rich macrocyclic peptides—cyclotides, for example—represent a promising class of molecules with potential therapeutic use. Despite their potential their efficient synthesis at large scale still represents a major challenge. Here we report new chemoenzymatic strategies using peptide ligase variants—inter alia, omniligase-1—for the efficient and scalable one-pot cyclization and folding of the native cyclotides MCoTI-II, kalata B1 and variants thereof, as well as of the θ-defensin RTD-1. The synthesis of the kB1 variant T20K was successfully demonstrated at multi-gram scale. The existence of several ligation sites for each macrocycle makes this approach highly flexible and facilitates both the larger-scale manufacture and the engineering of bioactive, grafted cyclotide variants, therefore clearly offering a valuable and powerful extension of the existing toolbox of enzymes for peptide head-to-tail cyclization.     

Physicochemical Characterization of Polymer-Stabilized Coacervate Protocells

The bottom-up construction of cell mimics has produced a range of membrane-bound protocells that have been endowed with functionality and biochemical processes reminiscent of living systems. The contents of these compartments, however, experience semidilute conditions, whereas macromolecules in the cytosol exist in protein-rich, crowded environments that affect their physicochemical properties, such as diffusion and catalytic activity. Recently, complex coacervates have emerged as attractive protocellular models because their condensed interiors would be expected to mimic this crowding better. Here we explore some relevant physicochemical properties of a recently developed polymer-stabilized coacervate system, such as the diffusion of macromolecules in the condensed coacervate phase, relative to in dilute solutions, the buffering capacity of the core, the molecular organization of the polymer membrane, the permeability characteristics of this membrane towards a wide range of compounds, and the behavior of a simple enzymatic reaction. In addition, either the coacervate charge or the cargo charge is engineered to allow the selective loading of protein cargo into the coacervate protocells. Our in-depth characterization has revealed that these polymer-stabilized coacervate protocells have many desirable properties, thus making them attractive candidates for the investigation of biochemical processes in stable, controlled, tunable, and increasingly cell-like environments.