Formation of Chlorotriophenoxy Radicals from Complete Series Reactions of Chlorotriophenols with H and OH Radicals

The chlorothiophenoxy radicals (CTPRs) are key intermediate species in the formation of polychlorinated dibenzothiophenes/thianthrenes (PCDT/TAs). In this work, the formation of CTPRs from the complete series reactions of 19 chlorothiophenol (CTP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method. The profiles of the potential energy surface were constructed at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution at 600–1200 K. The present study indicates that the structural parameters, thermal data, and rate constants as well as the formation potential of CTPRs from CTPs are strongly dominated by the chlorine substitution at the ortho-position of CTPs. Comparison with the study of formation of chlorophenoxy radicals (CPRs) from chlorophenols (CPs) clearly shows that the thiophenoxyl-hydrogen abstraction from CTPs by H is more efficient than the phenoxyl-hydrogen abstraction from CPs by H, whereas the thiophenoxyl-hydrogen abstraction from CTPs by OH is less impactful than the phenoxyl-hydrogen abstraction from CPs by OH. Reactions of CTPs with H can occur more readily than that of CTPs with OH, which is opposite to the reactivity comparison of CPs with H and OH.     

Modeling and analysis of passive worm propagation in the P2P file-sharing network

A number of worms, named P2P (peer-to-peer) passive worms, have recently surfaced, which propagate in P2P file-sharing networks and have posed heavy threats to these networks. In contrast to the majority of Internet worms, it is by exploiting users’ legitimate activities instead of vulnerabilities of networks in which P2P passive worms propagate. This feature evidently slows down their propagation, which results in them not attracting an adequate amount of attention in literature. Meanwhile, this feature visibly increases the difficulty of detecting them, which makes it very possible for them to become epidemic. In this paper, we propose an analytical model for P2P passive worm propagation by adopting epidemiological approaches so as to identify their behaviors and predict the tendency of their propagation accurately. Compared with a few existing models, dynamic characteristics of P2P networks are taken into account. Based on this proposed model, the sufficient condition for the global stability of the worm free equilibrium is derived by applying epidemiological theories. Large scale simulation experiments have validated both the proposed model and the condition.     

Aqueous One-pot Synthesis of Glycopolymers by Glycosidase-catalyzed Glycomonomer Synthesis Using 4,6-Dimetoxy Triazinyl Glycoside Followed by Radical Polymerization

Glycopolymers have attracted increased attention as functional polymeric materials, and simple methods for synthesizing glycopolymers remain needed. This paper reports the aqueous one-pot and chemoenzymatic synthesis of four types of glycopolymers via two reactions: the β-galactosidase-catalyzed glycomonomer synthesis using 4,6-dimetoxy triazinyl β-D-galactopyranoside and hydroxy group-containing (meth)acrylamide and (meth)acrylate derivatives as the activated glycosyl donor substrate and as the glycomonomer precursors, respectively, followed by radical copolymerization of the resulting glycomonomer and excess glycomonomer precursor without isolating the glycomonomers. The resulting glycopolymers bearing galactose moieties exhibited specific and strong interactions with the lectin peanut agglutinin as glycoclusters.     

Microwave dielectric properties of SrLa[Ga1−x(Mg0.5Ti0.5)x]O4 and SrLa[Ga1−x(Zn0.5Ti0.5)x]O4 (x = 0.2-0.8) ceramics

SrLa[Ga_1−x(R_0.5Ti_0.5)_x]O₄ (R = Mg, Zn) ceramics were prepared by a standard solid state sintering method. The single-phase ceramics with K₂NiF₄-type layered perovskite structure and I4/mmm space group were obtained, indicating that SrLa(R_0.5Ti_0.5) and SrLaGaO₄ can form the unlimited solid solutions. With increasing x for R = Mg and Zn, ε_r increases monotonously, the Qf value first increases and then decreases, while τ_f increases from a negative to a positive value. The optimized microwave dielectric properties were obtained as following: ε_r = 23.3, Qf = 89 400 GHz, τ_f = −0.8 ppm/°C for SrLa[Ga_0.6(Mg_0.5Ti_0.5)_0.4]O₄ and ε_r = 23.3, Qf = 76 200 GHz, τ_f = 0.2 ppm/°C for SrLa[Ga_0.7(Zn_0.5Ti_0.5)_0.3]O₄, indicating that the present solid solution ceramics are the promising candidates as microwave resonator materials for the telecommunication applications.     

One-step scalable preparation of graphene nanosheets and high-thermal-conductivity flexible graphene films

It is well known that graphene nanosheets (GNSs) have many excellent properties. However, it has been a difficult thing to exfoliate graphite into GNSs in a controllable and scalable manner. In this research, a new strategy named xylitol-assisted ball milling exfoliation (XABME) was developed for the scalable preparation of GNSs. The experimental results characterized by a series of measurements showed that GNSs were successfully exfoliated by the XABME strategy. The structure of the prepared nanosheets was featured by large lateral size and ultra-small thickness. Furthermore, the prepared GNSs easily achieved high production yield (≈54%). Lastly, the as-obtained GNSs and cellulose nanofibers (CNF) were compounded to form some nanomaterial films. The prepared films exhibited excellent flexibility and higher thermal conductivity, with the in-plane thermal conductivity of 90 wt% GNS film (8.0 W/(m·K)) being 11.4 times higher than that of the film without GNSs. This shows that GNSs could effectively enhance the thermal conductivity of the CNF matrix and indicate that these prepared films have great potentials in the thermal management of portable mobile devices.     

Eu@C86 isomers: Calculated relative populations

Abstract

Relative populations of four energy-lowest IPR (isolated-pentagon-rule) isomers of Eu@C₈₆ are computed using the Gibbs energy based on characteristics from density functional theory calculations (M06-2X/3-21G?～?SDD entropy term, M06-2X/6-31G*～SDD or B2PLYP(D)/6-31G*～SDD energetics). The calculations confirm that the recently isolated Eu@C₁(7)-C₈₆ species is a major isomer in a relevant temperature region. Relationship to the empty C₈₆ cages is discussed, too.     

Electrocatalytic Reduction of CO2 to Ethylene by Molecular Cu‐Complex Immobilized on Graphitized Mesoporous Carbon

The electrochemical reduction of carbon dioxide (CO₂) to hydrocarbons is a challenging task because of the issues in controlling the efficiency and selectivity of the products. Among the various transition metals, copper has attracted attention as it yields more reduced and C2 products even while using mononuclear copper center as catalysts. In addition, it is found that reversible formation of copper nanoparticle acts as the real catalytically active site for the conversion of CO₂ to reduced products. Here, it is demonstrated that the dinuclear molecular copper complex immobilized over graphitized mesoporous carbon can act as catalysts for the conversion of CO₂ to hydrocarbons (methane and ethylene) up to 60%. Interestingly, high selectivity toward C2 product (40% faradaic efficiency) is achieved by a molecular complex based hybrid material from CO₂ in 0.1 m KCl. In addition, the role of local pH, porous structure, and carbon support in limiting the mass transport to achieve the highly reduced products is demonstrated. Although the spectroscopic analysis of the catalysts exhibits molecular nature of the complex after 2 h bulk electrolysis, morphological study reveals that the newly generated copper cluster is the real active site during the catalytic reactions.