悬浮聚合法合成马拉硫磷分子印迹聚合物的吸附性能研究

基于分子印迹技术,采用悬浮聚合的方法,合成了马拉硫磷分子印迹聚合物。通过优化,确定最佳合成条件为:模板分子(马拉硫磷)∶功能单体(α-甲基丙烯酸)为1∶8,模板分子(马拉硫磷)∶交联剂(乙二醇二甲基丙烯酸酯)为1∶40,温度60℃,引发剂用量为1.0%。吸附性能测试结果表明,印迹聚合物对马拉硫磷的最大吸附量为4.62μg/mg,而非印迹聚合物对马拉硫磷的最大吸附量为2.21μg/mg;通过选择性实验得到印迹聚合物对灭线磷、甲拌磷、特丁硫磷、乐果、马拉硫磷、克线磷的吸附量分别为3.87、3.75、3.57、4.00、4.44、3.61μg/mg,而非印迹聚合物的吸附量分别为1.42、1.37、1.30、1.43、1.12、1.23μg/mg。     

Combining Atom Transfer Radical Polymerization and Click Chemistry: A Versatile Method for the Preparation of End‐Functional Polymers

Summary: The bromine chain ends of well‐defined polystyrene ( = 2 700 g · mol⁻¹, = 1.11) prepared using ATRP were successfully transformed into various functional end groups (ω‐hydroxy, ω‐carboxyl and ω‐methyl‐vinyl) by a two‐step pathway: (1) substitution of the bromine terminal atom by an azide function and (2) 1,3‐dipolar cycloaddition of the terminal azide and functional alkynes (propargyl alcohol, propiolic acid and 2‐methyl‐1‐buten‐3‐yne). The “click” cycloaddition was catalyzed efficiently by the system copper bromide/4,4′‐di‐(5‐nonyl)‐2,2′‐bipyridine. In all cases, ¹H NMR spectra indicated quantitative transformation of the chain ends of polystyrene into the desired function.

Preparation of well‐defined functional polymers possessing diverse chain‐end functionalities by the combination of atom transfer radical polymerization and click chemistry.     

Click Chemistry: A Potential Platform for Development of Novel Dental Restorative Materials

The main aim of this study is to develop novel polymer modified glass-ionomer cement (GIC) glasses utilizing click chemistry and RAFT polymerization. These novel glasses can serve as a platform to improve the properties of GIC's by incorporating chemistries and formulations that are not normally compatible with GIC's. Aluminofluoro-silicate glasses utilized in glass-ionomer dental cements were coated with azide terminated silane groups. In addition, a copolymer of acrylic acid-itaconic acid containing alkyne groups was synthesized by RAFT polymerization and was coupled via ‘click’ chemistry with the azide-coated GIC glass particles. FT-IR spectroscopy was used to characterize the synthesized materials and to confirm completion of the ‘click’ coupling reaction. The experimental cements cured, demonstrating that these modified glasses could be utilized in GIC formulations. The long setting and working times compared to control groups indicate that further improvements are necessary to fully utilize this chemistry. Our initial results in this study demonstrated the successful application of click chemistry in developing novel dental restorative materials, specifically glass-ionomer cements.     

A New Approach for the Synthesis of Miktoarm Star Polymers Through a Combination of Thiol–Epoxy “Click” Chemistry and ATRP/Ring‐Opening Polymerization Techniques

A new approach was developed for synthesis of certain A₃B₃‐type of double hydrophilic or amphiphilic miktoarm star polymers using a combination of “grafting onto” and “grafting from” methods. To achieve the synthesis of desired miktoarm star polymers, acetyl protected poly(ethylene glycol) (PEG) thiols (M_n = 550 and 2000 g mol^?1) were utilized to generate A₃‐type of homoarm star polymers through an in situ protective group removal and a subsequent thiol–epoxy “click” reaction with a tris‐epoxide core viz. 1,1,1‐tris(4‐hydroxyphenyl)ethane triglycidyl ether. The secondary hydroxyl groups generated adjacent to the core upon the thiol–epoxy reaction were esterified with α‐bromoisobutyryl bromide to install atom transfer radical polymerization (ATRP) initiating sites. ATRP of N‐isopropylacrylamide (NIPAM) using the three‐arm star PEG polymer fitted with ATRP initiating sites adjacent to the core afforded A₃B₃‐type of double hydrophilic (PEG)₃[poly(N‐isopropylacrylamide)] (PNIPAM)₃ miktoarm star polymers. Furthermore, the generated hydroxyl groups were directly used as initiator for ring‐opening polymerization of ε‐caprolactone to prepare A₃B₃‐type of amphiphilic (PEG)₃[poly(ε‐caprolactone)]₃ miktoarm star polymers. The double hydrophilic (PEG)₃(PNIPAM)₃ miktoarm star polymers showed lower critical solution temperature around 34 °C. The preliminary transmission electron microscopy analysis indicated formation of self‐assembly of (PEG)₃(PNIPAM)₃ miktoarm star polymer in aqueous solution. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 146–156     

A New Versatile Water‐Soluble Iniferter Platform for the Preparation of Molecularly Imprinted Nanoparticles by Photopolymerisation in Aqueous Media

The multi‐step synthesis of a new water‐soluble dithiocarbamate iniferter platform for the preparation of nanoparticles and ‐gels in aqueous solvents by photoinduced living‐radical polymerisation is described herein. The water solubility of the dithiocarbamate iniferter was achieved by incorporating two unprotected glucose units into the iniferter structure by copper(I)‐catalysed azide–alkyne cycloaddition (“click chemistry”). Molecularly imprinted nanoparticles (MIPs) specific for 2,4‐dichlorophenoxyacetic acid and the corresponding non‐imprinted particles (NIPs) were prepared in pure water by using the prepared iniferter as photoinitiator. Radioligand binding tests confirmed a high imprinting factor, and the living character of the iniferter was demonstrated by re‐initiating a second photochemical polymerisation on the NIP nanoparticles in water by using ethylene glycol methacrylate phosphate. Our newly synthesised structure is a promising tool for iniferter‐mediated photopolymerisations in aqueous media for the preparation of biocompatible nanomaterials with high potential for biomedical applications in a bottom‐up fashion.     

The Electrochemical Behavior in Aqueous Media of Conducting Polymers: I: The Methanol Soluble Fraction Obtained on the Cu(II) Catalyzed Polymerization of 2,5-Dibromo-3-Methylthiphene

Abstract

The methanol soluble amorphous fraction obtained on the CuCl₂ induced polymerization of 2,5-dibromo-3-methylthiophene exhibits redox waves on cyclic voltammetric potential polarization for a copper redox couple (for the metal ion incorporated in the polymer matrix) and a redox couple associated with the polymer matrix itself. Furthermore, when used as an electrode for the ferri/ferrocyanide couple in the electrolyte phase it acts as a well behaved electrode surface. Electrodes made from this material show a remarkable stability in aqueous media.     

Infrared Spectroscopic Study on the Hofmann Td-Type Clathrates: Mn(NH3)2M(CN)4·2 C6H5NH2 (M = Zn, Cd or Hg)

Infrared spectra of Mn(NH₃)₂M(CN)₄·2C₆H₅NH₂ (M = Zn, Cd or Hg) are reported. The spectral data suggest that these compounds are similar in structure to Hofmann-T_d-type clathrates.     

A New Chemo‐Enzymatic Route to Side‐Chain Liquid‐Crystalline Polymers: The Synthesis and Polymerization of 6‐(4‐Methoxybiphenyl‐4′‐oxy)hexyl Vinyl Hexanedioate

A novel synthetic method combining chemo and enzymatic synthesis strategies was employed to prepare a vinyl acetate type monomer, 6‐(4‐methoxybiphenyl‐4′‐oxy)hexyl vinyl hexanedioate (VA‐LC). Homo‐ and copolymers of VA‐LC with maleic anhydride (MAn) were prepared by conventional free radical polymerization using 2,2′‐azobisisobutyronitrile (AIBN) and 1,1′‐azobis (cyclohexane carbonitrile) (AHCN) as an initiator at 95 and 60 °C, respectively. The thermal properties of the generated polymeric material were investigated by differential scanning calorimetry (DSC), and the optical texture was inspected by polarizing optical microscopy (POM). While the monomer VA‐LC does not exhibit liquid‐crystalline properties, poly(VA‐LC), and the alternating copolymer of VA‐LC with maleic anhydride both displayed such properties.

     

初中化学(科学)启蒙教材中“实验”“插图”“科普知识”的比较分析*

我国大陆和台湾的化学(科学)教材在化学启蒙方面的内容编写有着各自的特点和优势,因此以我国大陆人教版初中《化学》与我国台湾康轩文教版《自然与生活科技》为例,通过问卷调查法与对比分析法,研究化学启蒙阶段的学生对待化学的态度以及海峡两岸教材中“实验”“插图”“科普知识”等3部分内容的设置差异。结果表明:(1)化学实验是启蒙阶段学生对化学感兴趣的起始点,也是初接触时的难点,其中以我国台湾《自然与生活科技》教材中化学实验的探究性及层次性更深;(2)化学启蒙阶段教材中插图的科学性、清晰度以及精美程度对学生学习化学的兴趣和态度有较大影响;(3)化学教材中的模型图实物化有助于学生拨云见日,了解化学的真实模样。     

基于加涅学习结果分类理论的化学新教材习题比较研究——以“物质结构基础及化学反应规律”为例

基于加涅的学习结果分类理论,将人教版、鲁科版和苏教版化学必修教材中涉及新课标主题3--“物质结构基础及化学反应规律”的习题从言语信息、智慧技能、认知策略、动作技能、态度维度进行对比分析,结果表明:3者在学习结果的5个维度总体分布趋势相同,智慧技能维度习题占比最大,言语信息维度次之,其余3个维度习题占比均较小;进一步将属于智慧技能维度的教材习题划分为辨别、具体概念、定义概念、规则和高级规则5个由低到高的水平,统计3个版本习题在5个水平中的分布,结果表明:人教版和苏教版具体概念水平的习题占比最大,鲁科版中规则水平习题占比最大,且总体上鲁科版习题智慧技能水平最高,苏教版略高于人教版。并由此获得对教材习题编写和使用的几点启示。     

Calix[4]Arene Cavitands: A Solid State Study on the Interactions of their Aromatic Cavity with Neutral Organic Guests Characterised by Acid CH3 or CH2 Groups

Abstract

To gain information on CH-π aromatic interactions involved in the formation of host-guest adducts, the geometrical parameters which define the solid state structures of the complexes of calix[4]arenes in the cone conformation with guests having acid CH₃ or CH₂ groups have been studied. Most of the data have been obtained from the CH₃CN and CH₂Cl₂ calix[4]arene complexes retrieved from the literature. To understand the effect of the acidity on these parameters, p-cyclohexylcalix[4]arene-biscrown-3 ? CH₃CN, p-tert-butylthiacalix[4]arene ? CH₃CN, p-tert-butylthiacalix[4]arene ? CH₃NO₂, 1,3-dipropoxy-p-tert-butylcalix[4]arene ? ClCH₂CN and 1,3-dipropoxy-p-tert-butylcalix[4]arene ? CH₂(CN)₂ complexes were prepared, crystallised and investigated in the solid state. CH₃X guests are bound preferentially by hosts having a C₄ symmetry. The interaction is directional, but it is independent from the basicity of the host and acidity of the guest, indicating that classic hydrogen bond do not play a major role. On the contrary CH₂XY guests find the best matching with hosts having a C_2v symmetry, interacting specifically with two diametrical aromatic rings. These interactions are directional and show a correlation between the acidity of the guest and the CH-π aromatic distance, thus supporting a stronger contribution of “classic” hydrogen bond in these latter complexes. These results are in agreement with the hypothesis that CH-π aromatic interactions derive from the superimposition of different types of intermolecular forces, whose contribution depends on several factors as the nature of the interacting partners.     

Part II: NiMoO4 Nanostructures Synthesized by the Solution Combustion Method: A Parametric Study on the Influence of Material Synthesis and Electrode-Fabrication Parameters on the Electrocatalytic Activity in the Hydrogen Evolution Reaction

Earth-abundant NiMo-oxide nanostructures were investigated as efficient electrocatalytic materials for the hydrogen evolution reaction (HER) in acidic media. Synthesis and non-synthesis parameters were thoroughly studied. For the non-synthesis parameters, the variation in Nafion loading resulted in a volcano-like trend, while the change in the electrocatalyst loading showed that the marginal benefit of high loadings attenuates due to mass-transfer limitations. The addition of carbon black to the electrocatalyst layer improved the HER performance at low loadings. Different carbon black grades showed a varying influence on the HER performance. Regarding the synthesis parameters, a calcination temperature of 500 °C, a calcination time between 20 and 720 min, a stoichiometric composition (Ni/Mo = 1), an acidic precursor solution, and a fuel-lean system were conditions that yielded the highest HER activity. The in-house NiMoO₄/CB/Nafion electrocatalyst layer was found to offer a better long-term performance than the commercial Pt/C.     

促进学生无机物认识方式的持续进阶——鲁科版高中化学必修新教材无机物主题编写思路及使用建议

分析了2017年版高中化学课程标准对必修课程无机物主题的要求,明确了该主题承载的学科观念和指向核心素养的表现性要求.阐述鲁科版高中化学必修新教材无机物主题编写思路,描述学生无机物认识方式持续进阶的路径,并据此提出新教材的使用建议.     

Substituent Effect on the Electronic Properties and Nature of the W≡C Bond in trans‐Cl(OC)(H3P)3W(≡C‐para‐C6H4X) (X = H,F, SiH3, CN,NO2, SiMe3, CMe3, NH2, NMe2) Complexes: A Computational Quantum Chemistry Study

In this investigation, we describe substituent effect on the dipole moment, ionization potential, electron affinity, structure, frontier orbitals energy, in the trans‐Cl(OC)(H₃P)₃W(≡C‐para‐C₆H₄X) (X = H, F, SiH₃, CN, NO₂, SiMe₃, CMe₃, NH₂, NMe₂) complexes using MPW1PW91 quantum chemical calculations. The nature of chemical bond between the [Cl(OC)(H₃P)₃W]⁻ and [C‐para‐C₆H₄X]⁺ fragments was illustrated with energy decomposition analysis (EDA). Percentage composition in terms of the defined groups of frontier orbitals for these complexes was inspected to investigate the character in metal–ligand bonds. Quantum theory of atoms in molecules (QTAIM) was used for illustration of metal–ligand bonds in these complexes.