Tracking Protein S‐Fatty Acylation with Proteomics

Recently, Hang and co‐workers developed “acyl‐PEG exchange” (APE), which allows the investigation of protein S‐fatty acylation with mass‐tag labelling and gel electrophoresis, methods that are accessible to any biochemistry laboratory.     

Anticoagulant, Antioxidant and Antitumor Activities of Heterofucans from the Seaweed Dictyopteris delicatula

In the present study, six families of sulfated polysaccharides were obtained from seaweed Dictyopteris delicatula by proteolytic digestion, followed by acetone fractionation and molecular sieving on Sephadex G-100. Chemical analyses demonstrated that all polysaccharides contain heterofucans composed mainly of fucose, xylose, glucose, galactose, uronic acid, and sulfate. The fucans F0.5v and F0.7v at 1.0 mg/mL showed high ferric chelating activity (～45%), whereas fucans F1.3v (0.5 mg/mL) showed considerable reducing power, about 53.2% of the activity of vitamin C. The fucan F1.5v presented the most prominent anticoagulant activity. The best antiproliferative activity was found with fucans F1.3v and F0.7v. However, F1.3v activity was much higher than F0.7v inhibiting almost 100% of HeLa cell proliferation. These fucans have been selected for further studies on structural characterization as well as in vivo experiments, which are already in progress.     

Myo-InositolTrisPyroPhosphate treatment leads to HIF-1α suppression and eradication of early hepatoma tumors in rats

Myo-inositol trispyrophosphate (ITPP), a synthetic allosteric effector of hemoglobin, increases the regulated oxygen-releasing capacity of red blood cells (RBCs), leading to suppression of hypoxia-inducible factor 1α (HIF-1α) and to down-regulation of hypoxia-inducible genes such as vascular endothelial growth factor (VEGF). As a consequence, tumor growth is markedly affected. The effect of weekly intravenous injection of ITPP on an orthotopic, syngenic rat hepatocellular carcinoma (HCC) model was compared to that for untreated animals and animals subjected to conventional Doxorubicin chemotherapy. The longitudinal examination of HCC was performed by microCT imaging, and the cellular and molecular changes were evaluated by histology and Western blotting analysis of HIF-1α, VEGF, and caspase-3 gene expression in the tumor and in the surrounding liver. Hematologic impact was evaluated by blood cell-count measurement and determination of P50 (oxygen partial pressure for a 50 % oxygen saturation of hemoglobin). The HCC evaluation by microCT revealed a high potency of ITPP for tumor growth inhibition, thus allowing long-term survival and even cure of almost all the treated animals. The P50 value of hemoglobin in RBCs underwent a shift of 30 % following ITPP injection. Under these conditions, HIF-1α activity was strongly decreased, VEGF expression was down-regulated, and apoptosis was induced in HCC and surrounding liver cells, as indicated by Caspase-3 expression. ITPP did not affect hematologic parameters during treatment. The observations of in vivo tumor eradication suggest a significant clinical potential for ITPP in cancer therapy.     

Hydrothermal degradation of adsorbed sulfur mustard on activated carbon

Thermal and hydrothermal degradations of adsorbed sulfur mustard (HD) on activated carbon particles from a chemical protective over-garment were studied. Carbon loaded with 5 wt.% HD was heated in a closed reactor at temperatures up to 160 °C for 0.5–6 h and analyzed by solid-state ¹³C MAS NMR. On dry carbon at room temperature, HD was stable for months. On a thoroughly pre-wetted carbon, adsorbed HD partially degraded to thiodiglycol (TDG) and TDG-sulfoxide (TDG-SO) within 2–3 months. Heating dry HD-loaded carbon to 160 °C caused partial degradation within 4 h to 1,4-thioxane, along with 1,4-dithiane and vinyl sulfides. Complete degradation within 2.5 h to the same products occurred upon hydrothermal treatment of the HD-loaded carbon, using a water/carbon ratio of 0.3:1. With higher water/carbon ratios of 0.6:1–5:1 at temperatures of 120 °C and above, adsorbed HD hydrolyzed rapidly within 0.5 h. The latter reaction led to the formation of TDG concurrent with either thioxane (at 160 °C) or TDG-SO and TDG-dimer (at 120 °C). The mechanisms of the observed degradation processes are discussed.     

A proposed structural model for amyloid fibril elongation: domain swapping forms an interdigitating {beta}-structure polymer

We propose a model illustrating how proteins, which differ intheir overall sequences and structures, can form the propagating,twisted ß-sheet conformations, characteristic of amyloids.Some cases of amyloid formation can be explained through a `domainswapping' event, where the swapped segment is either a ß-hairpinor an unstable conformation which can partially unfold and assumea ß-hairpin structure. As in domain swapping, herethe swapped ß-hairpin is at the edge of the structure,has few (if any) salt bridges and hydrogen bonds connectingit to the remainder of the structure and variable extents ofburied non-polar surface areas. Additionally, in both casesthe swapped piece constitutes a transient `building block' ofthe structure, with a high population time. Whereas in domainswapping the swapped fragment has been shown to be an     

Developing conductive immiscible polystyrene/polypropylene blends with a percolated conducting polyaniline/polyamide filler by tuning its specific interactions with the styrene-based triblock compatibilizer grafted with maleic anhydride

An approach to induce conductivity in immiscible polystyrene/polypropylene (PS/PP) blends is described using a percolated conducting polyaniline/polyamide (PANI/PA) filler combined with a polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene-graft-maleic anhydride compatibilizer. The approach is based on the ability of the compatibilizer to concomitantly stabilize the cocontinuous morphology and to improve the state of dispersion of the PANI/PA filler. Selective localization of PANI/PA in the PS phase with improved filler dispersion is achieved with the optimal master batch (MB) preparation technique followed by its optimized sequence addition to the blend components. This results in an increase in the dc conductivity by six decades as compared with that of the neat compatibilized blend at an effective 4.8-wt % PANI concentration. An investigation of the effect of functionality and concentration of the filler and the compatibilizer on the filler connectivity in the blend is performed. The prevailing specific interactions are analyzed by Fourier transform infrared spectroscopy and thermogravimetric analysis of the MBs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48433.     

Nanostructured supported palladium catalysts—Non-oxidative methane coupling

The Pd on α-Al₂O₃ catalysts with Pd particles in the low nanometer range have been prepared by a sonochemical reduction and a colloidal method, respectively. The two catalysts differ in their particle size, the widths of their particle size distributions and the amount of carbon incorporation in the Pd lattice.The adsorptive properties of the Pd/Al₂O₃ samples are different as a result of the different preparation methods. The methane adsorption capacity of that sample with smaller particles is lower than that of the catalyst with larger particles and the energy of activation is nearly doubled. DRIFTS and TPD results of CO adsorption supported by transmission electron microscopy data indicate that the PdSON catalyst with smaller and more homogeneous particles than PdCOL is highly dispersed which influences the coupling-hydrogenolysis process.The catalytic activity evidenced the formation of different adspecies during methane coupling and chemisorption on both catalysts. During the hydrogenation the carbon adspecies formed mainly methane at low adsorption temperatures. The significant amount of adsorbed methane at 773 K is governed by the highly active coordination unsaturated sites at the surface.     

Using functional programming to recognize named structure in an optimization problem: Application to pooling

Branch‐and‐cut optimization solvers typically apply generic algorithms, e.g., cutting planes or primal heuristics, to expedite performance for many mathematical optimization problems. But solver software receives an input optimization problem as vectors of equations and constraints containing no structural information. This article proposes automatically detecting named special structure using the pattern matching features of functional programming. Specifically, we deduce the industrially‐relevant nonconvex nonlinear Pooling Problem within a mixed‐integer nonlinear optimization problem and show that we can uncover pooling structure in optimization problems which are not pooling problems. Previous work has shown that preprocessing heuristics can find network structures; we show that we can additionally detect nonlinear pooling patterns. Finding named structures allows us to apply, to generic optimization problems, cutting planes or primal heuristics developed for the named structure. To demonstrate the recognition algorithm, we use the recognized structure to apply primal heuristics to a test set of standard pooling problems. © 2016 The Authors AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers AIChE J, 62: 3085–3095, 2016     

Theory of asymmetric organocatalysis of Aldol and related reactions: rationalizations and predictions

Computational studies have led to models to understand some classic and contemporary asymmetric reactions involving organocatalysts. The Hajos-Parrish-Eder-Sauer-Wiechert reaction and intermolecular aldol reactions as well as Mannich reactions and oxyaminations catalyzed by proline and other amino acids, and Diels-Alder reactions catalyzed by MacMillan's chiral amine organocatalysts have been studied with density functional theory. Quantitative predictions for several new catalysts and reactions are provided.     

Effect of nanocellulose fibers and acetylated nanocellulose fibers on properties of poly(ethylene‐co‐vinyl acetate) foams

Cellulose nanofibers are promising materials in the development of polymeric foams, because they act as heterogeneous nucleation sites for the growth of cells during foaming. In this research, we studied the incorporation of cellulose nanoparticles in poly(ethylene‐co‐vinyl acetate)‐EVA foams. The foams were produced with different fiber contents. We observed the effect of a chemical treatment by acetylation on the cellulose fibber, that is, we evaluated the use of hydrophilic and hydrophobic cellulose nanofibers in EVA foams. The main results indicate that with the addition of only 1% of cellulose nanofibers, cell density significantly reduces when compared with the pure EVA foams. On the other hand, by increasing the cellulose content, the agglomeration of nanofibers also increases, which results in heterogeneous cell sizes. The same phenomenon was observed in the foams produced with acetylated cellulose nanofibers, regardless of the fiber content used. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44760.