Nucleophilic cosubstitution of poly(dichlorophosphazene) with alkyl ether and amino acid ester

The nucleophilic substitution reaction of poly(dichlorophosphazene) with sodium 2‐methoxyethoxide and glycine ethyl ester has been studied in detail. Polymers prepared with different methods have been characterized by ¹H NMR, and the results reveal that the addition sequence of the two nucleophilic reagents is an important factor in determining the structure of the resultant polymer. If alkyl ether is added first, the subsequently introduced amino acid ester not only reacts with residual P? Cl but also attacks the alkyl ether side units present by replacing either the whole group or just ? OCH₃. As a result, a new kind of side group (? OCH₂CH₂NHCH₂COOC₂H₅) can be detected in the macromolecule. To obtain polymers with desired compositions {poly[(methoxyethoxy)_x(ethylglycino)_yphosphazene]}, the amino acid ester should be introduced initially to react with poly(dichlorophosphazene), and it should be followed by the alkyl ether. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2417–2425, 2005     

Consistent estimation of the intensity function of a cyclic Poisson process

We construct and investigate a consistent kernel-type nonparametric estimator of the intensity function of a cyclic Poisson process when the period is unknown. We do not assume any particular parametric form for the intensity function, nor do we even assume that it is continuous. Moreover, we consider the situation when only a single realization of the Poisson process is available, and only in a bounded window. We prove, in particular, that the proposed estimator is consistent when the size of the window indefinitely expands. We also obtain complete convergence of the estimator.     

A Remark on Leray's Problem on Stationary Navier–Stokes Flows with Large Fluxes in Infinite Cylindrical Domains

We consider Leray's problem on stationary Navier–Stokes flows with arbitrary large fluxes in an unbounded cylinder with several exits to infinity. For a stationary Navier–Stokes flow with large fluxes in the unbounded cylinder, we prove that, if the difference between the pressure of the main flow and the pressure of the Poiseuille flow with the same flux in a branch of the cylinder remains bounded at |x| →∞, then the flow behaves at infinity of the branch like the Poiseuille flow.     

Certain Fixed Point Theorems and Application to the Fractal Space

In this paper, we present some important generalizations of the Banach contraction principle, in which the Lipschitz constant k is replaced by some real-valued control function. For the applications to...     

Novel biobased photo‐crosslinked polymer networks prepared from vegetable oil and 2,5‐furan diacrylate

Novel biobased crosslinked polymer networks were prepared from vegetable oil with 2,5‐furan diacrylate as a difunctional stiffener through UV photopolymerization, and the mechanical properties of the resulting films were evaluated. The vegetable oil raw materials used were acrylated epoxidized soybean oil (AESO), acrylated castor oil (ACO), and acrylated 7,10‐dihydroxy‐8(E)‐octadecenoic acid (ADOD). 2,5‐Furan dicarboxylic acid (FDCA), which can be synthesized through the oxidative dehydration of C6 sugars, was identified by the US Department of Energy as one of 12 priority chemicals for establishing the green chemistry industry of the future. 2,5‐Furan dimethanol (bis‐hydroxymethylfuran), which can be derived from FDCA, was used as a starting material to synthesize 2,5‐furan diacrylate, which was used as a biobased comonomer along with AESO, ACO, or ADOD to form photo‐crosslinked polymer networks. The synthesis of acrylate derivatives was confirmed using FT‐IR and ¹H‐NMR spectroscopic techniques. The composition of the reaction mixture was changed to obtain crosslinked polymer networks with various mechanical properties. The addition of 2,5‐furan diacrylate increased the tensile strengths of the polymer films by up to 1.4–4.2 times relative to those obtained without the addition. These fully biobased polymers derived from vegetable oil and sugar can be used as environmentally friendly renewable materials for various applications to replace the existing petroleum‐based polymers currently used. Copyright © 2013 John Wiley & Sons, Ltd.     

稀土／高分子复合材料的研究进展

详述了稀土／高分子复合材料的特异性能。着重说明了该复合材料的射线屏蔽性能和磁性能。指出稀土／高分子复合材料在X射线屏蔽应用中可有效弥补铅的弱吸收区;具有高稀土含量的复合高分子屏蔽材料具有强的热中子吸收能力;含稀土的共聚物具有强顺磁性,提出了制备磁性和磁智能稀土／高分子复合材料的可行性。此外,概述了稀土／高分子复合材料的3种主要制备方法：聚合法,简单掺混法和反应加工法。分析了稀土／高分子配位前体结构和配位数目对光性能的影响;指出了稀土／高分子复合材料可能具有的离聚物结构及其特征;提出原位生成稀土／高分子纳米复合结构的可行性,还对稀土／高分子复合材料的结构与性能的关系进行了详细的探讨,并对制备稀土／高分子复合材料所存在的问题进行了一定的说明。     

Mass Spectrometry Reveals High Levels of Hydrogen Peroxide in Pancreatic Cancer Cells

Reactive oxygen species (ROS) are critical for many cellular functions, and dysregulation of ROS involves the development of multiple types of tumors, including pancreatic cancer. However, ROS have been grouped into a single biochemical entity for a long time, and the specific roles of certain types of ROS in tumor cells (e.g., pancreatic ductal adenocarcinoma (PDAC)) have not been systematically investigated. In this work, a highly sensitive and accurate mass spectrometry-based method was applied to study PDAC cells of humans and of genetically modified animals. The results show that the oncogenic KRAS mutation promotes the accumulation of hydrogen peroxide (H₂O₂) rather than superoxide or hydroxyl radicals in pancreatic cancer cells. We further identified that the enriched H₂O₂ modifies cellular metabolites and promotes the survival of pancreatic cancer cells. These findings highlight the specific roles of H₂O₂ in pancreatic cancer development, which may provide new directions for pancreatic cancer therapy.     

Hyperchaotic behaviours and controlling hyperchaos in an array of RCL-shunted Josephson junctions

This paper deals with dynamical behaviours in an array composed of two resistive-capacitive-inductive-shunted (RCL-shunted) Josephson junctions (RCLSJJs) and a shunted resistor. Numerical simulations show that periodic, chaotic and hyperchaotic states can coexist in this array. Moreover, a scheme for controlling hyperchaos in this array is presented by adjusting the external bias current. Numerical results confirm that this scheme can be effectively used to control hyperchaotic states in this array into stable periodic states, and different stable periodic states with different period numbers can be obtained by appropriately choosing the intensity of the external bias current.     

平行磨削非轴对称非球面光学元件表面形貌

结合砂轮表面仿真及磨削过程的运动学仿真获得工件表面轮廓、形貌和粗糙度预计,可以作为磨削过程中的理论依据,是精密磨削加工技术中主要的研究内容之一。平行磨削技术是加工非轴对称非球面光学元件的重要手段,而相关的仿真过程报道还很少。提出一种基于平行磨削的精密磨削加工非球面表面生成的仿真方法,该方法主要包含使用高斯方法生成具有不同统计学特征的随机砂轮表面形貌,建立单磨粒运动轨迹方程和圆弧砂轮细分后与工件表面点接触的运动关系,据此给出平行磨削加工表面生成的数值算法,并对不同加工参数下的工件表面形貌进行仿真。仿真结果和测量结果的一致性验证了所给算法的正确性和有效性     

Synthesis of thermally responsive cylindrical molecular brushes via a combination of nitroxide-mediated radical polymerization and “grafting onto” strategy

Loosely grafted amphiphilic molecular brushes consisting of a hydrophobic polystyrene backbone and hydrophilic poly(ethylene glycol) monomethyl ether (MPEG) side chains, PS-MPEG, were synthesized by a novel two step method. In the first step, well-defined linear poly(p-chloromethylstyrene) PCMS with the degree of polymerization DP ≈ 200 and polydispersity index, M_w/M_n = 1.4 was prepared by bulk nitroxide (TEMPO)-mediated radical polymerization (NMP). In the second step, pendant p-chloromethyl units were coupled with activated chains of poly(ethylene glycol) monomethyl ether (MPEG) during the course of the Williamson etherification reaction. Using MPEG with M_n = 1100 g/mol over 50% repeating units on PCMS underwent nucleophilic substitution yielding a densely grafted brush with theoretical molecular weight M_n,th ≈ 123,000 g/mol. The molecular brush PS-MPEG assumed conformation of a stiff cylinder in both dilute toluene (non-selective good solvent for PS backbone and MPEG grafts) and water (selective for MPEG grafts) solutions as determined by small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS). The contour length L = 570 Å and L = 694 Å obtained by fitting the scattering data using model of Sharp-Bloomfield, Pedersen-Schurtenberger and Kholodenko worm revealed dimensions corresponding to theoretically estimated size of a single molecular brush. It was found that PS-MPEG molecular brush in dilute aqueous solutions exhibited lower critical solution temperature (LCST) in the physiological range.