Vinyl Ester Oligomer Crosslinked Porous Polymers Prepared via Surfactant-Free High Internal Phase Emulsions

Using vinyl ester resin (VER) containing styrene (or methyl methacrylate) and vinyl ester oligomer (VEO) as external phase, Pickering high internal phase emulsions (Pickering HIPEs) having internal phase volume fraction of up to 95 vol% were prepared with copolymer particles as sole stabilizer. Polymerizing the external phase of these Pickering HIPEs led to porous polymers (poly-Pickering-HIPEs). Compared to the polystyrene- (PS-) based poly-Pickering-HIPEs which were prepared with mixture of styrene and divinylbenzene (DVB) as crosslinker, the poly-Pickering-HIPEs herein showed much higher elastic modulus and toughness. The elastic modulus of these poly-Pickering-HIPEs increased with increasing the VEO concentration in the external phase, while it decreased with increasing internal phase volume fraction. Increasing VEO concentration in the external phase also resulted in a decrease in the average void diameter as well as a narrow void diameter distribution of the resulting poly-Pickering-HIPEs. In addition, there were many small pores in the voids surface caused by the volume contraction of VER during the polymerization, which suggests a new method to fabricate porous polymers having a well-defined hierarchical pore structure

Motion of water monomers reveals a kinetic barrier to ice nucleation on graphene.

The interfacial behaviour of water remains a central question to fields as diverse as protein folding, friction and ice formation. While the properties of water at interfaces differ from those in the bulk, major gaps in our knowledge limit our understanding at the molecular level. Information concerning the microscopic motion of water comes mostly from computation and, on an atomic scale, is largely unexplored by experiment. Here, we provide a detailed insight into the behaviour of water monomers on a graphene surface. The motion displays remarkably strong signatures of cooperative behaviour due to repulsive forces between the monomers, enhancing the monomer lifetime ( ≈ 3 s at 125 K) in a free-gas phase that precedes the nucleation of ice islands and, in turn, provides the opportunity for our experiments to be performed. Our results give a molecular perspective on a kinetic barrier to ice nucleation, providing routes to understand and control the processes involved in ice formation

Author Correction: Motion of water monomers reveals a kinetic barrier to ice nucleation on graphene.

The interfacial behaviour of water remains a central question to fields as diverse as protein folding, friction and ice formation[1,2]. While the structural and dynamical properties of water at interfaces differ strongly from those in the bulk, major gaps in our knowledge at the molecular level still prevent us from understanding these ubiquitous chemical processes. Information concerning the microscopic motion of water comes mostly from computational simulation[3,4] but the dynamics of molecules, on the atomic scale, is largely unexplored by experiment. Here we present experimental results combined with ab initio calculations to provide a detailed insight into the behaviour of water monomers on a graphene surface. We show that motion occurs by activated hopping on the graphene lattice. The dynamics of water diffusion displays remarkably strong signatures of cooperative behaviour due to repulsive forces between the monomers. The repulsive forces enhance the monomer lifetime ($t_m \approx 3$ s at $T_S = 125$ K) in a $\textit{free-gas}$ phase that precedes the nucleation of ice islands and, in turn, provides the opportunity for our experiments to be performed. Our results give a unique molecular perspective of barriers to ice nucleation on material surfaces, providing new routes to understand and potentially control the more general process of ice formation

Loss of endothelial hypoxia inducible factor-prolyl hydroxylase 2 induces cardiac hypertrophy and fibrosis

BACKGROUND: Cardiac hypertrophy and fibrosis are common adaptive responses to injury and stress, eventually leading to heart failure. Hypoxia signaling is important to the (patho)physiological process of cardiac remodeling. However, the role of endothelial PHD2 (prolyl-4 hydroxylase 2)/hypoxia inducible factor (HIF) signaling in the pathogenesis of cardiac hypertrophy and heart failure remains elusive. METHODS AND RESULTS: Mice with Egln1Tie2Cre (Tie2-Cre-mediated deletion of Egln1 [encoding PHD2]) exhibited left ventricular hypertrophy evident by increased thickness of anterior and posterior wall and left ventricular mass, as well as cardiac fibrosis. Tamoxifen-induced endothelial Egln1 deletion in adult mice also induced left ventricular hypertrophy and fibrosis. Additionally, we observed a marked decrease of PHD2 expression in heart tissues and cardiovascular endothelial cells from patients with cardiomyopathy. Moreover, genetic ablation of Hif2a but not Hif1a in Egln1Tie2Cre mice normalized cardiac size and function. RNA sequencing analysis also demonstrated HIF-2α as a critical mediator of signaling related to cardiac hypertrophy and fibrosis. Pharmacological inhibition of HIF-2α attenuated cardiac hypertrophy and fibrosis in Egln1Tie2Cre mice. CONCLUSIONS: The present study defines for the first time an unexpected role of endothelial PHD2 deficiency in inducing cardiac hypertrophy and fibrosis in an HIF-2α– dependent manner. PHD2 was markedly decreased in cardiovascular endothelial cells in patients with cardiomyopathy. Thus, targeting PHD2/HIF-2α signaling may represent a novel therapeutic approach for the treatment of pathological cardiac hypertrophy and failure

Porous Poly(Acrylic Acid) from High Internal Phase Emulsion: Effects of Emulsification Parameters on Porous Structure

Highly porous poly (acrylic acid) (P(AA)) with tunable pore structure was prepared through polymerizing of acrylic acid in the aqueous phase of an oil-in-water (O/W) high internal phase emulsion (HIPE). Compared with the conventional O/W HIPE normally using toluene or hexane as internal phase, the introducing paraffin, which have a much higher viscosity than toluene or hexane, caused the HIPEs herein could be stabilized by Tween 60 of low to 0.5 wt%. It was found the amount of liquid paraffin played a key role for the stability of the emulsion and the morphology of the resulting porous materials. Moreover, the average void size and the interconnectivity degree of the porous materials could also be tailored by altering the acrylic acid and surfactant concentration in aqueous phase

Medium Access Control in Vehicular Ad Hoc Networks

The distinguishing properties of Vehicular Ad hoc wireless Networks (VANETs) strongly challenge the design of Medium Access Control (MAC) protocols, which are responsible for the medium access coordination among active vehicles, as well as the accommodation of both driving safety applications and non-safety applications. In this paper, we focus on a comprehensive survey of VANET MAC schemes by integrating various related issues and challenges. Our analysis not only deepens the understanding of MAC techniques in VANETs but also presents the key ideas and potential directions for future research in this area. In order to significantly improve the communication performance of VANETs, more research efforts on MAC techniques must be made for optimizing multichannel coordination and allocation approaches, enhancing the Quality of Service (QoS) capability, and combating the hidden terminal problem, broadcast storm problem and even ACK (acknowledgment) explosion problem

Aligned Porous Beads Prepared by Frozen Polymerization of Emulsion-Templates Involving Tiny Emulsifier

High internal phase emulsion (HIPE) templated porous materials are attracting increasing interests due to its high porosity and tunable structure. However, large amounts (5-50 vol%) of suitable non-ionic surfactants are commonly required to stabilize conventional HIPE due to the high internal volume fraction of HIPE. In this work, applying frozen polymerization in HIPE, aligned porous beads were prepared with tiny surfactant (~0.1 wt%). These interconnected aligned porous beads were prepared through directional freezing, and frozen ultraviolet (UV) initiation of an oil-in-water (o/w) HIPE. The HIPEs are extruded by needle, and then directionally frozen in liquid nitrogen to form beads. The frozen beads were exposed under UV irradiation in a -20 °C ethanol bath to initiate the monomers in the aqueous phase. Moreover, the morphology of the resulting porous beads were tailored by vary the ratio of oil/water and the amount of emulsifier

Improved 2-round collision attack on IoT hash standard ASCON-HASH

Lightweight cryptography algorithms are a class of ciphers designed to protect data generated and transmitted by the Internet of Things. They typically have low requirements in terms of storage space and power consumption, and are well-suited for resource-limited application scenarios such as embedded systems, actuators, and sensors. The NIST-approved competition for lightweight cryptography aims to identify lightweight cryptographic algorithms that can serve as standards. Its objective is to enhance data security in various scenarios. Among the chosen standards for lightweight cryptography, ASCON has been selected. ASCON-HASH is a hash function within the ASCON family. This paper presents a detailed analysis of the differential characteristics of ASCON-HASH, utilizing the quadratic S-box. Additionally, we employ message modification techniques and ultimately demonstrate a non-practical collision attack on the 2-round ASCON-HASH, requiring a time complexity of 298 hash function calls

Stability of surfactant-free high internal phase emulsions and its tailoring morphology of porous polymers based on the emulsions

International audienceStable water-in-oil (w/o) high internal phase emulsions (HIPEs) having an internal phase of up to 95 vol% were prepared. The poly(styrene-methyl methacrylate-acrylic acid) (P(St-MMA-AA)) copolymer particles were used as stabilizer. The HIPEs prepared with addition of copolymer particles to the aqueous phase were stabilized by copolymer particles initially, followed by the mixture of copolymer particles and copolymer as the particles eventually dissolves in the organic phase, and finally by only copolymer. Stable w/o HIPEs having an internal phase of up to 92 vol% were also formed with P(St-MMA-AA) copolymer dissolved in the organic phase as the sole stabilizer. Porous polymers (polyHIPEs) were prepared based on these two types of surfactant-free HIPEs. The morphology of the polyHIPEs, such as the surface roughness of the voids and average void diameter, were tailored by tuning the internal phase volume fraction, NaCl, copolymer, and crosslinker concentrations

Macroporous Polymers with Aligned Microporous Walls from Pickering High Internal Phase Emulsions

A novel class of macroporous polymers, open macroporous polymers with aligned microporous void walls, were prepared by combining particle-stabilized high internal phase emulsion (Pickering HIPE) and unidirectional freezing technique. These Pickering HIPEs were prepared by utilizing poly­(urethane urea)/(vinyl ester resin) nanoparticles as the sole stabilizer, and this nanoparticles also acted as building blocks for the resulting macroporous polymers. Moreover, the morphology and compression modulus of the resulting porous materials could be tuned easily. This means now Pickering-HIPE templated open-cell foams can be prepared, and this route was normally achieved with surfactant and/or chemical reaction involved