Preparation of metal chelating active packaging materials by laminated photografting

Active packaging materials with surface immobilized metal chelating ligands were prepared by laminated photografting technique. The resulting materials presented transition metal scavenging properties with potential application in non-migratory antioxidant active packaging materials. Photografting of functional polymer ligands is typically performed in an oxygen-free environment, requiring a nitrogen inerting step, which limits potential industrial scale-up. Laminated photografting eliminates the need for nitrogen inerting by sandwiching the monomer solution between base material and an oxygen barrier layer. In this study, we demonstrated the ability to synthesize metal chelating active packaging materials, previously prepared by standard batch photografting, using a laminated photografting technique. The polypropylene-graft-poly(acrylic acid) and polypropylene-graft-poly(hydroxamic acid) chelating films prepared by laminated photografting presented similar surface chemistry as those reported previously, as characterized by infrared spectroscopy, and presented ferric ion chelating capacity of 182 ± 29 and 89 ± 10 nmol/cm², respectively, at pH 5.0. The reported laminated photografting represents a coating technology with potential for adaptation to roll-to-roll manufacture of metal chelating films on an industrial scale.     

氧化石墨烯和过渡金属碳/氮化合物固定化酶

二维纳米材料具有高机械强度和比表面积、大量表面官能团、良好的亲水性及生物相容性,是固定化酶的良好载体。本文选取经典的氧化石墨烯（GO）以及新型的过渡金属碳/氮化合物（MXenes）,分别介绍了它们的制备方法和结构、物理和化学性质,综述了它们在固定化酶领域的应用研究,并进行了比较。文中指出：GO由石墨烯经化学氧化再剥离制得,MXenes由其前体经刻蚀制得,不同的氧化或刻蚀方法制得的材料在组成、结构、性能等方面存在差异。GO表面的可反应官能团更多,包括羟基、羧基和环氧基,故在固定化酶领域应用广泛。MXenes固定化酶则主要利用表面的羟基反应或负电荷吸附,目前主要用于制备生物传感器。最后指出这两种材料还存在制备效率低、纳米片易聚集、循环利用性差等问题。今后的发展方向是要开发更为简单和安全的材料制备方法,探索更为有效的插层和剥离手段以及改善固定化酶的回收策略,进一步推进二维纳米材料在固定化酶领域的应用。     

喹唑啉分子印迹聚合物微球的吸附特性

以2,4-二氯-6,7-二甲氧基喹唑啉(DCQAL)为模板分子,采用单步溶胀聚合法制备了粒径均匀的分子印迹聚合物微球(M IPM s),并用静态吸附法研究了功能单体、三乙胺及水对M IPM s吸附性能的影响,考察了微球的识别性能。制得的M IPM s主要靠氢键作用吸附与识别模板分子,甲基丙烯酸(MAA)与模板分子间能产生较强的氢键作用,以其为功能单体制得的M IPM s具有较好的吸附与识别性能,其高亲和力与低亲和力结合点的最大表观吸附量分别为17.53μmol/g和117.02μmol/g,以4-氯-6,7-二甲氧基喹唑啉(CQAL)为竞争底物,其分离因子α达1.78。往吸附液中添加三乙胺或少量水会减弱M IPM s的吸附能力。     

A comparative study of the preparation and physical properties of polystyrene–silica mesocomposite and nanocomposite materials

In this paper, a comparative study with regard to the preparation and physical properties of as‐prepared polystyrene–silica mesocomposite (PSM) and polystyrene‐silica nanocomposite (PSN) materials is presented. Vinyl‐modified mesoporous silica particles with a wormhole structure were first prepared by doping a sol‐gel metal oxide with an optically active non‐surfactant (dibenzoyl‐L ‐tartaric acid) as a template, followed by template removal through Soxhlet extraction. The as‐prepared silica particles with/without mesopores were subsequently characterized using the Brunauer–Emmett–Teller method and transmission electron microscopy (TEM) and Fourier transform infrared, ¹³C NMR and ²⁹Si NMR solid‐state spectroscopy. A specific feed amount of silica particles was subsequently reacted with styrene monomer by free radical polymerization to yield a series of PSM and corresponding PSN materials. Both as‐prepared composite systems were further characterized using TEM and scanning electron microscopy/energy‐dispersive X‐ray mapping studies. A systematic comparative study of the physical properties of both as‐prepared composite materials clearly illustrated that PSM had effectively enhanced thermal stability, optical clarity and dielectric properties compared to the corresponding PSN counterpart. Evaluation was carried out using thermogravimetric analysis, differential scanning calorimetry, UV‐visible transmission spectroscopy and dielectric constant measurements. Copyright © 2011 Society of Chemical Industry     

Preparation and Characterization of Imprinted Porous Materials with High Selectivity for Luteolin

In order to selectively separate luteolin from its crude solution, we synthesized imprinted porous materials with high recognition specificity for luteolin, using an imprinting technique. Modified luteolin was used as template, vinyltriethoxysilane as the functional monomer, and tetraethyl orthosilicate (TEOS) as the cross‐linking agent. The results showed the following optimum reaction conditions: The reaction ratio between luteolin and acryloyl chloride was 1 : 2 (0.10 g/0.20 g), adding 1.0 g precursor; the feasible elution time was 12 h; when the molar quantity of modified template molecule was 0.01 mol and ethenyltriethyloxy‐silane (VTEO) was 0.04 mol, the maximum yield reached 91.6 %. All samples were tested by Brunauer‐Emmett‐Teller method, Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy, equilibrium adsorption experiments and selective adsorption experiments. It was found that the imprinted porous materials showed excellent selectivity for luteolin in aqueous solution. Characterization by FTIR suggested that an addition reaction had occurred between the modified template molecule and VTEO while forming ester bonds in the functional precursor. Results from pore structure analysis indicated that the imprinted porous materials had good channels, and the average pore size of the prepared porous materials was between 35.85 and 95.82 Å. Adsorption dynamics analysis suggested that, when the adsorption time reached 3 h, the adsorption process had reached balance and the adsorption capacity was at steady state. These porous materials had highly selective recognition properties and high equilibrium adsorption capacity for the template molecule. The equilibrium adsorption capacity of the imprinted porous materials to the template molecule was 11.4 times that of the blank porous materials.     

表面离子印迹聚合物金属离子吸附材料研究进展

离子印迹聚合物吸附材料对模板离子具有强识别能力,对其可实现高选择吸附,因而离子印迹技术常用于制备高选择性吸附材料。但传统方法制备的离子印迹吸附材料,因识别位点容易被包埋导致其吸附容量小、吸附-脱附速率低,而表面离子印迹技术则是采用模板离子和聚合单体直接在载体表面或附近区域构筑选择性识别位点,所有活性位点均暴露,从而有效地解决了上述问题。本文从技术原理与合成原料、制备工艺方法以及载体材料类型等方面对表面印迹聚合物吸附材料近期研究进展情况进行了概述。针对相关研究现状,从载体材料、功能单体、目标离子等角度分析和讨论了表面离子印迹聚合物吸附材料当前发展中的不足及其所面临的挑战,并对表面离子印迹技术发展趋势和前景进行了展望。     

Preparation and Properties of Uniform-Sized Polymer Beads Imprinted with N-CBZ-L-Phenylalanine

ABSTRACT

A series of uniform-sized polymer beads molecularly imprinted for N-carbobenzoxy-L-phenylalanine (N-Cbz-L-Phe) were prepared by a two-step swelling and suspension polymerization method using polystyrene latex particles as precursors, 2-vinypyridine and α-methylacrylamide as host functional monomers and diethylene glycol diacrylate as crosslinker. The uniformly sized polystyrene precursors were synthesized by emulsifier-free emulsion polymerization. The obtained materials had an obvious imprinting effect to the template N-Cbz-L-phenylalanine. The imprinted polymer also had some adsorption to the molecules, which were similar to the template molecule configuration. The adsorbing dynamics of the polymer to the template molecule, and the effects of crosslinking degree of the polymer and the environmental temperature on the absorbing properties were also discussed.     

Synthesis and Electric Modulus Formalism of Novel Metal-Phthalocyanine Bridged Polymers

Novel nickel and copper phthalocyanine polymers, with uniformly carboxylic end groups and carbonyl groups as bridges linking the phthalocyanine units, were successfully prepared. Structural modelling and atomic absorption spectroscopy confirmed the network polymeric structure and suggested at least nine phthalocyanine units in each polymeric network. The dielectric properties of the prepared polymers were investigated over a wide range of frequencies at room temperature. The electric modulus formalism was used to study the conductivity relaxation in the prepared polymers. The collapsing of the real part of the conductivity function, σ’, at higher frequencies for both materials was observed indicating that the local molecular dynamics is due to the polymer conjugated backbone (functional and/or terminal groups) with no clear effect of the central metal.     

Development of bioactive materials based on surface chemistry

All bioactive materials developed up to 1990 were based on calcium phosphate. It was later revealed that materials that form bonelike apatite on their surfaces in the living body bond to living bone through the apatite layer, and that apatite formation on a material is induced by various functional groups on its surface. Based on these findings, bioactive titanium was prepared by forming sodium titanates on its surface via NaOH and heat treatments, and applied to an artificial total hip joint. Porous titanium metal able to exhibit osteoconductivity as well as osteoinductivity was prepared by forming anatase on its surface via NaOH, HCl and heat treatments. Various bioactive materials with different physical properties are expected to be derived from ceramics, metals and organic polymers by modifying their surfaces with functional groups effective for apatite nucleation.     

Electrical properties of poly(arylene ether nitrile)/graphene nanocomposites prepared by in situ thermal reduction route

A series of functional metallo-supramolecular materials based on polyhedral oligomeric silsesquioxane (POSS) and phenanthroline ligand were prepared using a two-step approach. Firstly, using a phenanthroline ligand, an amino-functionalized transition metal complex was prepared by tin(II) chloride. In the second step, this metal complex was subsequently reacted with the octakis(3-chloropropyl)octasilsesquioxane, resulting for the metallosupramolecular polymers bearing POSS structure. All the synthesized compounds were fully characterized by spectroscopic analysis, thermal and electron microscopy techniques. Stimuli responsible properties of metallo-supramolecular materials were also investigated the reversibility upon external factors, such as electrochemical or the addition of competitive complexing ligands by electroanalytic techniques and UV–Vis spectroscopy. The electro- and chemo-responsive properties of the metallo-supramolecular materials were also improved. As a result, prepared phenanthroline-functionalized polyhedral silsesquioxane are good candidates for electronic, opto-electronic, and photovoltaic applications as a smart stimuli-responsive material.     

助剂掺杂对Fe—MCM-41在环己烷氧化反应中催化性能的影响

z以硅酸钠为硅源，十六烷基三甲基溴化铵为模板剂，硝酸铁为金属源，水热法直接合成Fe—MCM-41，再辅以助剂co和cr形成双金属掺杂的介孔材料，采用XRD、N2吸脱附、TG—DTA、FTIR、ICP对材料的结构和物化性质进行表征。以乙腈为溶剂，H2O2为氧化剂，考察所制备的材料对环己烷氧化的催化活性和选择性的影响。结果表明，与Fe—MCM41的催化性能相比，FeCo—MCM41会使环己烷的转化率下降，但环己醇的选择性增加；而FeCr—MCM41会使环己烷的转化率和环己酮的收率增加。     

助剂掺杂对Fe-MCM-41在环己烷氧化反应中催化性能的影响

以硅酸钠为硅源,十六烷基三甲基溴化铵为模板剂,硝酸铁为金属源,水热法直接合成Fe-MCM-41,再辅以助剂Co和Cr形成双金属掺杂的介孔材料,采用XRD、N2吸脱附、TG-DTA、FTIR、ICP对材料的结构和物化性质进行表征。以乙腈为溶剂,H2O2为氧化剂,考察所制备的材料对环己烷氧化的催化活性和选择性的影响。结果表明,与Fe-MCM-41的催化性能相比,FeCo-MCM-41会使环己烷的转化率下降,但环己醇的选择性增加;而FeCr-MCM-41会使环己烷的转化率和环己酮的收率增加。     

Acidity and catalytic activity of mesoporous ZSM-5 in comparison with zeolite ZSM-5, Al-MCM-41 and silica–alumina

Acidity of mesoporous HZSM-5 prepared using amphiphilic organosilane template molecules was measured. Brønsted acid sites were observed in the prepared sample, and the number and the strength of Brønsted acid sites were determined quantitatively by a method of infrared-mass spectroscopy/temperature-programmed desorption (IRMS-TPD) of ammonia. ΔH for ammonia adsorption as an index of the strength was ca. 150 kJ mol⁻¹ that was almost the same as on usual HZSM-5, but the number was smaller than that of HZSM-5. From the measured acidity, it was concluded that the mesoporous materials contained a smaller concentration of Brønsted acid site notable on the structure of HZSM-5. Measurements of turnover frequency (TOF) in the catalytic cracking of octane supported the conclusion. Density functional calculations showed that the defect sites Al–OH and Si–OH attached to the Brønsted acid site changed the strength of the acid sites to show some possible structures of the weak and strong Brønsted acid sites included in the mesoporous HZSM-5. Acidities of Al-MCM-41 and silica–alumina were also measured, and the difference in the solid acidities of these materials was discussed.     

纳米纤维素复合相变储能气凝胶制备进展

超轻质材料气凝胶具有超低密度、高比表面积等性能,是高分子材料领域的研究热点之一.综述了纤维素气凝胶的制备、纤维素复合相变储能材料的制备等.纳米纤维素特殊的物性及其模板效应,以纳米纤维素为软模板,自组装制备纳米纤维素复合相变储能气凝胶.探讨了纳米纤维素复合相变储能气凝胶的应用趋势.     

Composite Microfiltration Membranes Imprinted with cAMP

Composite microfiltration membranes covered with a thin layer of molecularly imprinted polymer (MIP) selective to adenosine 3′:5′‐cyclic monophosphate (cAMP) were obtained and their separation properties were studied. MIP layers were prepared using photoinitiated copolymerization of dimethylaminoethyl methacrylate (DMAEM) as a functional monomer and trimethylopropane trimethacrylate (TRIM) as a crosslinker in the presence of cAMP as template in ethanol/water mixture. Blank membranes were prepared under the same conditions, but without cAMP. It was found out that pH of aqueous solution of the template has an effect on the binding of cAMP with MIP membranes. It was concluded that the ability of MIP membranes to bind cAMP is a result of both ionic interactions between charged dimethylamino groups of polymer matrix and the phosphorous residue of cAMP molecule and the specific shape of recognizing sites. These sites are complementary to cAMP in terms of three dimensional shape as well as correct position of functional groups involved in the template binding. This paper shows that the binding capability of MIP membranes can be adjusted by varying the values of degree of modification (DM). Atomic Force Microscopy (AFM) and Scanning Force Microscopy (SEM) were used to visualise surfaces and cross sections of membranes to gain better understanding in the analysis of MIP layer deposited on membranes.     

Surface immobilization of star‐shaped poly(ethylene oxide) on poly(dimethylsiloxane)

A thin layer of star‐shaped poly(ethylene oxide) (PEO) (starPEO), on the polydimethylsiloxane (PDMS) membrane was prepared by a simple immobilization procedure. Photoreactive molecules were introduced on the surface of the polymeric support to achieve the formation of thin starPEO film from the materials having no functional groups. This novel technique enabled us to immobilize any kind of chemical, especially one that had no functional groups, and readily to control the amount of immobilization. The gas permeation properties of the starPEO‐immobilized PDMS membranes were investigated for pure propane and propylene. The permeance of gases were found to decrease in the starPEO‐immobilized PDMS membranes, although the ideal separation factors for propylene/propane were increased with the loading amount of silver ions, because of the facilitation action of silver ions in the immobilized PEO unit on the PDMS membranes, as propylene carriers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2369–2373, 2002     

介孔结构金属氧化物的制备与应用

介孔结构金属氧化物材料拥有大的表面积,特殊的结构特征,具备更多的催化点或反应点而备受关注。鉴于此,介绍了介孔结构金属氧化物的三种主要方法：溶胶一凝胶法、模板合成法和纳米晶粒组装法;探讨了介孔结构金属氧化物在催化、传感和能源等领域的应用。     

氧化镍空心壳材料的合成及其气敏特性测定

通过化学合成方法得到分散均匀的氧化亚铜方块,在此基础上以其作为硬模板采用模板技术,以六水合二氯化镍为金属源,通过“协同刻蚀”的方法获得氢氧化镍空心壳材料,并进一步热处理得到氧化镍空心壳材料。经过透射电子显微镜（TEM）,并结合广角X射线衍射等手段,证实所得材料为空心氧化镍材料。通过在旁热式气敏元件表面简单涂抹的办法制得气敏器件,并对其正丁醇气敏性能进行了测定。研究结果表明,该种材料在250 ℃下对正丁醇具有较好的敏感性,这表明该种材料是一种非常有前途的功能材料,有望获得广泛应用。     

Wet-chemistry processing of powdery raw material for high-tech ceramics

The purpose of this study was to develop wet-chemistry approaches for the synthesis of ultradispersed and mesoporous metal oxide powders and powdery composites intended for usage in the production of ceramic materials with desired properties. The focus is on the development of template synthesis of mesoporous metal silicates as well as obtaining nano- and subnanopowders by a modified sol-gel technique and template methods. Families of mesoporous (2 to 300 nm) metal silicates and nano-oxides and subnanopowders (4 to 300 nm) were synthesized by the template method and modified sol-gel technique, respectively. Texture and morphology of the obtained objects have been studied by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller analysis, and N₂ adsorption-desorption. It was found that morphological parameters of the metal oxide obtained by the modified sol-gel technique depend nonlinearly on the initial molar ratio value of the sol stabilizer and metal in the reaction medium as well as the nature of the stabilizer. It has been shown that the nature of structure-directing components determines the morphology of the silicate obtained by the template method: dispersion and shape of its particles. The developed laboratory technology corresponds to the conception of soft chemistry and may be adapted to the manufacture of ultradispersed materials for catalysis, solar cells, fuel cells, semiconductors, sensors, low-sized electronic devices of new generation, etc.