Spinodal decomposition of two homopolymers with their block copolymer: A comparison of models

The dynamics of phase separation in the presence of a diblock copolymer have been studied using ternary and quaternary models of spinodal decomposition. The ternary model treats the block copolymer as a third component that is compatible with each of the mutually incompatible homopolymers. The quaternary model treats the block copolymer as a pair of specially constrained homopolymers. Both models predict core-shell morphologies with the copolymer concentrated at the interface. Both models predict larger domain sizes and less sharp phase boundaries in the early stages of spinodal decomposition. In the late stages, domain sizes are largest for the system of homopolymers without copolymer and smallest when a system containing copolymer is modeled as a quaternary blend. The scaling exponent observed for the quaternary model was s = 0.25 ± 0.02 compared to s ≅ 0.3 for the homopolymers without copolymer and for the ternary model. The quaternary model predicts internal phase separation within a pure diblock copolymer, whenever the corresponding homopolymers are sufficiently incompatible. © 1996 John Wiley & Sons, Inc.     

新型软质抗静电聚氯乙烯材料的研究

合成了一种长链季铵盐类化合物, 将其用作抗静电剂添加到软质聚氯乙烯(PVC)材料中, 测试了材料的表面电阻、力学性能, 并采用扫描电子显微镜测试研究了其结构. 结果表明: 随合成长链季铵盐的添加量增大, PVC材料的表面电阻率降低, 较小的添加量(4.5%)即可使材料的表面电阻率降低至3.0×10⁸ Ω以下, 达到了煤矿行业对高分子材料抗静电性能的要求. 在上述抗静电PVC材料中添加一定量的聚氧化乙烯(PEO), 可以降低抗静电材料对环境湿度的依赖性, 并提高PVC材料的力学性能和抗静电性能.     

Analysis of Fragmentation Pathways of Peptide Modified with Quaternary Ammonium and Phosphonium Group as Ionization Enhancers

Peptide modification by a quaternary ammonium group containing a permanent positive charge is a promising method of increasing the ionization efficiency of the analyzed compounds, making ultra-sensitive detection even at the attomolar level possible. Charge-derivatized peptides may undergo both charge remote (ChR) and charge-directed (ChD) fragmentation. A series of model peptide conjugates derivatized with N,N,N-triethyloammonium (TEA), 1-azoniabicyclo[2.2.2]octane (ABCO), 2,4,6-triphenylopyridinium (TPP) and tris(2,4,6-trimetoxyphenylo)phosphonium (TMPP) groups were analyzed by their fragmentation pathways both in collision-induced dissociation (CID) and electron-capture dissociation (ECD) mode. The effect of the fixed-charge tag type and peptide sequence on the fragmentation pathways was investigated. We found that the aspartic acid effect plays a crucial role in the CID fragmentation of TPP and TEA peptide conjugates whereas it was not resolved for the peptides derivatized with the phosphonium group. ECD spectra are mostly dominated by c_n ions. ECD fragmentation of TMPP-modified peptides results in the formation of intense fragments derived from this fixed-charge tag, which may serve as reporter ion.     

Quaternary ammonium ion dendrimers from methylation of poly(propylene imine)s

The poly(propylene imine) dendrimers DAB‐dendr‐(NH₂)₈, DAB‐dendr‐(NH₂)₃₂, and DAB‐dendr‐(NH₂)₆₄ were fully converted with iodomethane to quaternary ammonium ions at both chain ends and branch points and, with less iodomethane, were partially converted to quaternary ammonium ions mainly at end groups. Amidation of the primary amine ends followed by treatment with iodomethane gave the first dendrimers with quaternary ammonium ions only at branch points. After an exchange of iodide counterions for chloride, all of the quaternary ammonium ion dendrimers slightly increased the rate of decarboxylation of 6‐nitrobenzisoxazole‐3‐carboxylate ion in an aqueous solution. Similar quaternary ammonium ion dendrimers with more hydrophobic interiors or more hydrophobic chains on the ends were much more active catalysts for the decarboxylation. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 821–832, 2001     

A novel synthesis of polyethers with pendant hydroxyl groups by polyaddition of bis(oxetane)s with bis(phenol)s

The polyaddition of 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene (BEOB) with 3,3′,5,5′-tetrachlorobisphenol A (TCBPA) was examined with or without catalysts. High molecular weight polymer (polymers 1) (M_n = 13,600) with pendant primary hydroxyl groups was obtained in a 99% yield without any gel products when the reaction was performed with 5 mol % of tetraphenylphosphonium bromide as a catalyst in NMP at 160°C for 96 h. However, when the reaction was carried out without a catalyst under the same conditions, a low molecular weight polymer (M_n = 3200) was obtained in a 51% yield. The structure of the resulting polymer was confirmed by IR, ¹H-NMR, and ¹³C-NMR spectra. In this reaction system, it was also found that tetraphenylphosphonium iodide and crown ether complexes such as 18-crown-6 (18-C-6)/KBr and 18-C-6/KI have high catalytic activity. Polyadditions of 1,4-bis[(3-methyl-3-oxetanyl)methoxymethyl]benzene with TCBPA and BEOB with 3,3′,5,5′-tetrabromobisphenol-S were also examined, and corresponding polymers (polymers 2 and 3) were obtained in good yields. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2781–2790, 1999     

Crystallographic Characterization of the Novel Inorganic-organic Hybrid Coordinated Polymer:[(C22H50N2)(Ag2I4)]n

1 INTRODUCTION Halometallates are the particularly suitable systems for designing the construction of unusual low-dimensional structural archetypes, from which peculiar electronic, thermal, catalytic and magnetic properties can arise. The syntheses of th…     

Synthesis and Crystallographic Characterization of Complex [(CH3)3NCH2CH2N(CH3)3][HgI4]·H2O Containing Novel Cation

The title compound has been synthesized by the reaction of HgI2 and [(CH3)3- NCH2CH2N(CH3)3]I2 with pH = 7.5 at room temperature, and its crystal structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in monoclinic system, space group P21/c with a = 8.3075(8), b =15.8084(19), c =15.390(2)(°A), β = 95.192(4)o, V = 2012.9(4)(°A)3, Z = 2, Dc = 2.824 g/cm3, F(000) = 1502, C14H39N4O2Hg2I8, Mr = 1711.87, μ(MoKα) = 13.768 mm-1, the final R = 0.0465 and wR = 0.1293 for 3046 observed reflections with I > 2(I). The title compound consists of cations ([C8H22N2]2+) and anion (HgI42-), which are combined by static attracting forces to form the so-called organic-inorganic hybrid material.     

Highly Stable Graphene Inks Based on Organic Binary Solvents

Formulating highly stable graphene-based conductive inks with consistency in electrical properties over the storage period has remained a significant challenge in the development of wearable electronics. Two highly stable graphene-based inks (Cyclohexanone:Ethylene glycol (CEG) ink and Cyclohexanone:Terpineol (CT) ink) are prepared by using two different organic binary solvents, for the first time, without using solvent exchange methods. Both the inks display remarkably high stability (stable even after two months) with negligible variability in electrical properties. Here, it is demonstrated how such inks can be utilized to coat flexible substrates to create wearable e-textiles. Both the inks coated e-textiles show significantly low sheet resistance (≈209.1 Ω □⁻¹ for CEG ink and ≈322.4 Ω □⁻¹ CT ink) that show less than a 15% increase in electrical resistance over two months. Therefore, these inks offer high productivity and reproducibility and can be one of the most effective methods for formulating graphene-based inks.     

(Thio)urea Containing Chiral Ammonium Salt Catalysts

(Thio)-urea-containing bifunctional quaternary ammonium salts emerged as powerful non-covalently interacting organocatalysts over the course of the last decade. The most commonly employed catalysts in this field are either based on Cinchona alkaloids, α-amino acids, or trans-cyclohexane-1,2-diamine. Our group has been heavily engaged in the design and use of such catalysts, i. e. trans-cyclohexane-1,2-diamine-based ones for around 10 years now, and it is therefore the intention of this short personal account to provide an overview of the, at least in our opinion, most significant and pioneering achievements in this field by looking on catalyst design and asymmetric method development, with a special focus on our own contributions.