Flame retarding effect of graphite in rotationally molded polyethylene/graphite composites

Linear low‐density polyethylene (LLDPE) compounds containing 10 wt % graphite fillers were rotationally molded into flat sheets. Flame retardancy was studied using cone calorimeter tests conducted at a radiative heat flux of 35 kW/m². Only the expandable graphite, an established flame retardant for polyethylene, significantly reduced the peak heat release rate. Compared with the neat polyethylene, it was easier to ignite the LLDPE composites containing carbon black, expandable graphite, and exfoliated graphite. However, rather unexpectedly, the inclusion of flake graphite increased the time to ignition by up to 80%. Simulations conducted with the ThermaKin numerical pyrolysis software suggest that increased reflectivity was mainly responsible for this effect. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41472.     

Proteomic profile of dry-cured ham relative to PRKAG3 or CAST genotype, level of salt and pastiness

Two-dimensional electrophoresis was used to compare dry-cured biceps femoris insoluble protein fraction according to genotype (PRKAG3Ile199Val and CASTLys249Arg/Ser638Arg) as well as salt and pastiness level. The PRKAG3 affected mainly muscle metabolic enzymes, indicating its possible influence on muscle metabolism with heterozygotes Ile/Val appearing different from both homozygous genotypes. The effect of CAST was smaller, affecting the quantity of one actin fragment. Dry-cured ham salt and pastiness level affected a wide variety of protein spots including metabolic enzymes, plasma proteins, chaperones and myofibrillar proteins, including protein fragments, indicating the connection with proteolysis. Pastiness was associated with salt content, reflected also by the fact that many spots were affected by both factors. Despite the absence of extreme pastiness (or low salt samples), some protein spots (actin, MHC fragment, desmin fragment) exhibited important differences in intensity according to pastiness (and salt level) suggesting they could be used as potential quality markers.     

HPLC determination of stevioside in plant material and food samples

 An HPLC method for the determination of sweet-tasting stevioside (STS) in the leaves of the plant Stevia rebaudiana and in some beverages (e.g. tea, orange juice) was developed. The pre-separation procedure consisted of extraction of STS from the plant material using boiling water and a solid-phase extraction (SPE). Recovery rates of the SPE for the analysed matrices ranged from 92.8% to 97.8% (for concentrations of STS of 105, 210 and 300 μg/ml; Relative Standard Deviation (RSD)≤3.3%). The chromatographic separations were realized using a C₁₈ column, the mobile phase consisting of methanol and water, and with UV detection at 210 nm. The limits of determination of STS were 5 μg/ml for the leaf extracts and the tea sample and 8 μg/ml for the juice sample. Received: 7 April 1998     

Change in the Electronic Structure of the Cobalt(II) Ion in a One-Dimensional Polymer with Flexible Linkers Induced by a Structural Phase Transition

A new 1D-coordination polymer [Co(Piv)₂(NH₂(CH₂)₆NH₂)]_n (1, Piv is Me₃CCO₂⁻ anion) was obtained, the mononuclear fragments {Co(O₂CR)₂} within which are linked by μ-bridged molecules of hexamethylenediamine (NH₂(CH₂)₆NH₂). For this compound, two different monoclinic C2/c (α-1) and P2/n (β-1) phases were found at room temperature by single-crystal X-ray diffraction analysis, with a similar structure of chains and their packages in unit cells. The low-temperature phase (γ-1) of crystal 1 at 150 K corresponds to the triclinic space group P-1. As the temperature decreases, the structural phase transition (SPT) in the α-1 and β-1 crystals is accompanied by an increase in the crystal packing density caused by the rearrangements of both H-bonds and the nearest ligand environment of the cobalt atom (“octahedral CoN₂O₄ around the metal center at room temperature” → “pseudo-tetrahedral CoN₂O₂ at 150 K”). The SPT was confirmed by DSC in the temperature range 210–150 K; when heated above 220 K, anomalies in the behavior of the heat flow are observed, which may be associated with the reversibility of SPT; endo effects are observed up to 300 K. The SPT starts below 200 K. At 100 K, a mixture of phases was found in sample 1: 27% α-1 phase, 61% γ-1 phase. In addition, at 100 K, 12% of the new δ-1 phase was detected, which was identified from the diffraction pattern at 260 K upon subsequent heating: the a,b,c-parameters and unit cell volume are close to the structure parameters of γ-1, and the values of the α,β,γ-angles are significantly different. Further heating leads to a phase transition from δ-1 to α-1, which both coexist at room temperature. According to the DC magnetometry data, during cooling and heating, the χ_MT(T) curves for 1 form a hysteresis loop with ~110 K, in which the difference in the χ_MT values reaches 9%. Ab initio calculations of the electronic structure of cobalt(II) in α-1 and γ-1 have been performed. Based on the EPR data at 10 K and the ab initio calculations, the behavior of the χ_MT(T) curve for 1 was simulated in the temperature range of 2–150 K. It was found that 1 exhibits slow magnetic relaxation in a field of 1000 Oe.     

Synthesis,Molecular Docking,In Vitro and In Vivo Studies of Novel Dimorpholinoquinazoline-Based Potential Inhibitors of PI3K/Akt/mTOR Pathway

A (series) range of potential dimorpholinoquinazoline-based inhibitors of the PI3K/Akt/mTOR cascade was synthesized. Several compounds exhibited cytotoxicity towards a panel of cancer cell lines in the low and sub-micromolar range. Compound 7c with the highest activity and moderate selectivity towards MCF7 cells which express the mutant type of PI3K was also tested for the ability to inhibit PI3K-(signaling pathway) downstream effectors and associated proteins. Compound 7c inhibited the phosphorylation of Akt, mTOR, and S6K at 125–250 nM. It also triggered PARP1 cleavage, ROS production, and cell death via several mechanisms. Inhibition of PI3Kα was observed at a concentration of 7b 50 µM and of 7c 500 µM and higher, that can indicate minority PI3Kα as a target among other kinases in the titled cascade for 7c. In vivo studies demonstrated an inhibition of tumor growth in the colorectal tumor model. According to the docking studies, the replacement of the triazine core in gedatolisib (8) by a quinazoline fragment, and incorporation of a (hetero)aromatic unit connected with the carbamide group via a flexible spacer, can result in more selective inhibition of the PI3Kα isoform.     

Synthesis of Radioiodinated Compounds. Classical Approaches and Achievements of Recent Years

This review demonstrates the progress in the synthesis of radioiodinated compounds over the past decade. The possibilities and limitations of radiopharmaceuticals with different iodine isotopes, as well as the synthesis of low and high molecular weight compounds containing radioiodine, are discussed. An analysis of synthesis strategies, substrate frameworks, isolation methods, and metabolic stability, and the possibility of industrial production of radioiodinated organic derivatives which can find applications in the synthesis of drugs and diagnostics are presented.     

超声辅助花生毛油水化脱胶工艺

为解决花生毛油水化脱胶率低的问题,该文采用超声辅助水化脱胶的方法对花生毛油进行脱胶处理。通过单因素试验考察加水量、水化温度、超声时间和超声功率对花生毛油脱胶效果的影响。在单因素试验的基础上进行响应面优化,并通过差示扫描量热、气相色谱-质谱联用、顶空-固相微萃取-气相色谱-质谱对花生毛油和脱胶油的热稳定性、脂肪酸组成和挥发性风味物质等进行差异性分析。结果表明,在加水量9%、水化温度75 ℃、超声时间15 min、超声功率65 W 的条件下,花生脱胶油的磷含量降至最低,为35.18 mg/kg,脱胶率达到最高,为89.78%。与水化脱胶相比,脱胶率提高27.43%,酸价、碘值以及过氧化值显著降低（P＜0.05）,获得的花生脱胶油颜色更加清澈透亮。超声辅助水化脱胶对花生毛油的热稳定影响较小;油脂中的饱和脂肪酸含量下降,油脂品质提升;醛类、吡嗪类和烃类等挥发性风味物质的含量降低,使得甜味和烘烤味等风味特征减弱。     

Double-Spirals Offer the Development of Preprogrammable Modular Metastructures

Metamaterials with adjustable, sometimes unusual properties offer advantages over conventional materials with predefined mechanical properties in many technological applications. A group of metamaterials, called modular metamaterials or metastructures, are developed through the arrangement of multiple, mostly similar building blocks. These modular structures can be assembled using prefabricated modules and reconfigured to promote efficiency and functionality. Herein, a novel modular metastructure is developed by taking advantage of the high compliance of preprogrammable double-spirals. First, the mechanical behavior of a four-module metastructure under tension, compression, rotation, and sliding is simulated using the finite-element method. Then, 3D printing and mechanical testing are used to illustrate the tunable anisotropic and asymmetric behavior of the spiral-based metastructures in practice. The results show the simple reconfiguration of the presented metastructure toward the desired functions. The mechanical behavior of single double-spirals and the characteristics that can be achieved through their combinations make our modular metastructure suitable for various applications in robotics, aerospace, and medical engineering.     

Understanding Humidity-Enhanced Adhesion of Geckos: Deep Neural Network-Assisted Multi-Scale Molecular Modeling

A higher relative humidity leads to an increased sticking power of gecko feet to surfaces. The molecular mechanism responsible for this increase, however, is not clear. Capillary forces, water mediating keratin-surface contacts and water-induced softening of the keratin are proposed as candidates. In previous work, strong evidence for water mediation is found but indirect effects via increased flexibility are not completely ruled out. This article studies the latter hypothesis by a bottom-up coarse-grained mesoscale model of an entire gecko spatula designed without explicit water particles, so that capillary action and water-mediation are excluded. The elasticity of this model is adjusted with a deep neural network to atomistic elastic constants, including water at different concentrations. Our results show clearly that on nanoscopic flat surfaces, the softening of keratin by water uptake cannot nearly account for the experimentally observed increase in gecko sticking power. Here, the dominant mechanism is the mediation of keratin-surface contacts by intervening water molecules. This mechanism remains important on nanostructured surfaces. Here, however, a water-induced increase of the keratin flexibility may enable the spatula to follow surface features smaller than itself and thereby increase the number of contacts with the surface. This leads to an appreciable but not dominant contribution to the humidity-increased adhesion. Recently, by atomistic grand-canonical molecular dynamics simulation, the room-temperature isotherm is obtained for the sorption of water into gecko keratin, to the authors’ knowledge, the first such relation for any beta-keratin. In this work, it relates the equilibrium water content of the keratin to the ambient relative humidity.