Insight into shear‐induced modification for improving processability of polymers: Effect of shear rate on the evolution of entanglement state

Many experimental results have revealed that the re‐entanglement kinetics of disentangled polymers is much slower than that predicted by tube theory. This retarded recovery of fully entangled state is of practical significance that shear‐induced modification may offer a way to improve processability for a polymer by reducing viscosity. This work tried to figure out the shear‐rate dependence variation of viscosity in the view of evolution of entanglement state through disentanglement and re‐entanglement, aiming to provide fundamental insights into application prospect of shear‐induced modification in preparing “in‐pellet” disentangled polymers prior to final processing. High‐density polyethylene was sheared on a parallel‐plate rotational rheometer with a linearly increased shear rate. Results showed that higher shear rate could induce further disentanglement, resulting in a lower viscosity with a reduction rate up to 93.7%, larger molecular weight between entanglements M_e , and longer re‐entanglement time. Additionally, less entanglement would give a larger lamellar thickness of sheared samples after nonisothermal crystallization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 598–606     

Solvent‐free ring‐opening polymerization of lactones with hydrogen‐bonding bisurea catalyst

Development of effective organocatalysts for the living ring‐opening polymerization (ROP) of lactones is highly desired for the preparation of biocompatible and biodegradable polyesters with controlled microstructures and physical properties. Herein, a new class of hydrogen‐bond donating bisurea catalysts is reported for the ROP of lactones under solvent‐free conditions. ROP of lactones mediated by the bisurea/7‐methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (MTBD) catalyst exhibits a living/controlled manner, affording the polymers and copolymers with the well‐defined structure, predictable molecular weight, narrow molecular weight distribution, and high selectivity for monomer at low catalyst loadings at ambient temperature. The possible mechanism of bisurea/MTBD‐catalyzed ROP of lactones is proposed, in which the bisurea activates the carbonyl group of lactones while MTBD facilitates the nucleophilic attack of the initiating/propagating alcohol by hydrogen bonding. Moreover, the poly(ε‐caprolactone‐co‐δ‐valerolactone) [P(CL‐co‐VL)] random copolymers with various compositions were synthesized using the bisurea/MTBD catalyst. The measurements of thermal properties and crystalline structure demonstrate that the CL and VL units are cocrystallized in the crystalline phase of P(CL‐co‐VL) copolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 90–100     

A query on the Mg 2p binding energy of MgO

Research on Chemical Intermediates - The low Mg 2p value (47.0 eV) of MgO reported in Res Chem Intermed 44(2018)829 is carefully analyzed and discussed based on a series of X-ray...     

Room temperature suzuki cross‐coupling polymerizations of aryl dihalides and aryldiboronic acid/acid esters with t‐Bu3P‐coordinated 2‐phenylaniline‐based palladacycle complex as the precatalyst

Room temperature Suzuki cross‐coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters with t‐Bu₃P‐coordinated 2‐phenylaniline‐based palladacycle complex, [2′‐(amino‐kN)[1,1′‐biphenyl]‐2‐yl‐kC]chloro(tri‐t‐butylphosphine)palladium, as a general precatalyst is described. Such room temperature Suzuki cross‐coupling polymerization is achieved by employing six equivalents or more of the base and affords polymers within an hour, with the yields and the molecular weights in general comparable to or higher than reported results that required higher reaction temperature and/or longer polymerization time. Our study provides a general catalyst system for the room temperature Suzuki cross‐coupling polymerization of aryl dibromides/diiodides with aryldiboronic acids/acid esters and paves the road for the investigation of employing other monodentate ligand‐coordinated palladacycle complexes including other electron‐rich monophosphine‐coordinated ones for room temperature cross‐coupling polymerizations. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1606–1611     

水胁迫下典型盐生植被梭梭光谱特征分析

荒漠地区由于气候干燥，降水稀少，水分常成为制约植被生长的因素之一，水分胁迫对植物长势和产量的影响比任何其他胁迫都要大。随着高光谱技术的发展，国内外已有众多学者利用高光谱数据研究植被遭受胁迫作用，然而这些研究对象多集中于甜菜、棉花、玉米、水稻等作物，针对干旱区盐生植被遭受胁迫作用的研究较少。梭梭作为荒漠、半荒漠地区的典型盐生植被之一，具有极高的经济和生态效益。选择梭梭作为研究对象，培育一年生梭梭，并设置三个水分梯度，形成受不同水分量胁迫的梭梭。使用原始光谱、红边位置参数，结合植被指数及二维相关光谱研究其叶片光谱特征，为干旱区利用高光谱遥感监测盐生植被提供借鉴。结果表明：(1)分析梭梭叶片反射光谱曲线发现，在可见光至中红外各波段范围内，受不同水分量胁迫作用的梭梭叶片光谱反射率有显著差异。在可见光(350～610 nm)波段，各水分处理的梭梭叶片反射率依次为100 mL>500 mL>200 mL，这是由于100和200 mL水分促进梭梭内部叶绿素合成，使该波段反射率降低，而过多的水分(500 mL)对梭梭内部的叶绿素合成没有更大的促进作用。在红光区(611～738 nm)，随着水分量的增多，受不同水分量胁迫的梭梭叶片光谱反射率依次减小。在738～1 181和1 228～1 296 nm波段，受不同水分量胁迫作用的梭梭叶片光谱反射率为：200 mL>100 mL>500 mL；在1 182～1 227 nm波段，受不同水分量胁迫作用的梭梭叶片光谱反射率为：100 mL>200 mL>500 mL。这是由于植被细胞结构对近红外区域的反射率影响较大，因而受不同水分胁迫作用的梭梭叶片光谱反射率有显著差异。在1 300～1 365和1 392～1 800 nm波段，受各水分胁迫作用的梭梭叶片反射率为：100 mL>200 mL>500 mL。这表明在500 mL水分胁迫量范围内，水分越多，叶子的细胞液、细胞膜对水分的吸收能力越强，使得反射率下降。通过对原始光谱求取一阶导数并提取红边位置参数发现，各水分处理下的梭梭叶片一阶微分光谱曲线中红边位置未发生移动。这是由于梭梭在长期的干旱环境影响下，形成了特殊的适应机制，水分对其红边位置影响不敏感。(2)选取若干植被指数分析各水分处理下的梭梭光谱指数变化。当水分胁迫量由100 mL增至200 mL时，WI/NDWI，MSI和NDII指数值变化显著，可用于研究水分胁迫下梭梭的光谱特征。(3)使用二维相关光谱技术分析受各水分胁迫作用的梭梭光谱特征，得出在100 mL水分胁迫下，在536，643，1 219和1 653 nm波段处，吸收峰对水分的微扰敏感；在200 mL水分胁迫下，在846和1 083 nm波段处，吸收峰对水分的微扰敏感；在500 mL水分胁迫下，在835和1 067 nm波段处，吸收峰对水分的微扰敏感。总之，在近红外波段，与100 mL水分量相比，梭梭受200和500 mL水分量胁迫时，吸收峰对水分的微扰敏感度上升。由100 mL水分胁迫下梭梭的二维同步相关谱图可知，1 044和1 665 nm，1 072和903 nm，903和1 264 nm，1 230和1 061 nm波段处形成正交叉峰，表明这些波段处光谱强度随水分的干扰同时变化。     

The catalytic performance study of polymerized ionic liquid synthesized in different conditions on alkylation of o‐Xylene with styrene

In this work, a series of novel acidic polymerized ionic liquids were used as heterogeneous catalyst for alkylation of o‐Xylene with styrene. And the effect of the amount of initiator and the type of acid used for ion exchange on catalyst structure and the catalytic performance of catalysts for alkylation were studied thoroughly. The experiment results show: when the percentage of the amount of initiator in the total material is 3%, the polymerized ionic liquid catalyst MPM‐SO₃H‐[C₃V][SO₃CF₃] has the most uniform with a specific surface area of 97.30 m²/g and a pore volume of 0.35 cm³/g. Benefiting from the unique structure features, MPM‐SO₃H‐[C₃V][SO₃CF₃] manifested an excellent catalytic performance for alkylation of o‐Xylene with styrene, along with the conversion of styrene was 96.8% and the yield of 1‐Phenyl‐1‐ortho‐xylene ethane was 94.7%. Therefore, this work provides a novel reference to the synthesis of polymerized ionic liquids and clearly explains the advantage of novel acidic polymerized ionic liquids on alkylation.     

New Type of Columnar Liquid Crystal Superlattice in Double-Taper Ionic Minidendrons

Wedge-shaped molecules, such as dendrons, are among the most important building blocks for directed supramolecular self-assembly. Here we present a new approach aimed at widening the range and complexity of potential mesophases by introducing double-tapered mesogens. Two series of compounds are presented, both alkali metal salts (Li, Na, Cs) of 3,4,5-tris-alkoxybenzoic acid with a second tapered tris-alkoxyaryl group attached at the end of an alkoxy chain. The double-tapered compounds all display an unusual hexagonal columnar phase consisting of one ionic and three non-ionic columns per unit cell. The cation size has an unexpectedly drastic effect on unit cell size. Unlike most columnar phases, the current phases show unusually high dimensional stability on heating, and high stiffness in spite of being 80–85 % aliphatic, attributed to their molecular topology. The described approach may lead to co-assemblies of multifunctional materials, for example, parallel p- and n-semiconducting nanowires or parallel ionic and electronic conductors.     

[2]Pseudorotaxane-Based Supramolecular Optical Indicator for the Visual Detection of Cellular Cyanide Excretion

Cyanide is extremely hazardous to living organisms and the environment. Owing to its wide range of applications and high toxicity, the development of functional materials for cyanide detection and sensing is highly desirable. Host–guest complexation between bis(p-phenylene)-34-crown-10 H and N-methylacridinium salt G remarkably decreases the detection limit for cyanide anions compared with that of the guest itself. The [2]pseudorotaxane selectively recognizes the cyanide anion with high optical sensitivity as a result of the nucleophilic addition of the cyanide anion at the 9-position of G . The host–guest complexation is further incorporated into supramolecular materials for the visual detection of cyanide anions, especially the detection of cellular cyanide excretion with a detection limit of 0.6 μm . This supramolecular method provides an extremely distinct strategy for the visual detection of cyanide anions.     

Nukiangendines A and B,two novel 13,14-seco-abietanes from Abies nukiangensis

From Abies nukiangensis, two novel 13,14-seco-abietane diterpenes, nukiangendines A (1) and B (2) were isolated. Their relative structures were determined by extensive NMR and HRMS spectroscopic analysis. The absolute configuration of 1 was established by ECD calculations. Compound 1 showed significant anti-hepatitis C virus (HCV) effects.     

Nanomaterials in Cerebrovascular Disease Diagnose and Treatment

Cerebrovascular diseases (CVDs) are among the most serious diseases with high mortality and disability rates. The prevalent diagnosis and treatment methods of CVDs include imaging and interventional therapy. With the development of nanotechnology, large numbers of nanomaterials have been applied to the diagnosis and treatment of CVDs, mainly including carbon nanotubes, quantum dots, fullerenes, and dendrimers. In this review, the applications of nanomaterials in the field of diagnosis and treatment of CVDs, mainly including drug target delivery, imaging, therapy, endovascular treatment, and angiogenesis, are summarized. The applications of nanomaterials in the field of CVD are almost in the laboratory, and more effort is needed for clinical translation. The aim of this review is to provide useful information for future research and equipment development.