Alder ene functionalization of polyisobutene oligomer and styrene-butadiene-styrene triblock copolymer

The Alder ene functionalization reaction of double bonds containing macromolecules such as polyisobutene oligomer (PIB) and a styrene-butadiene-styrene triblock copolymer (SBS) samples with maleic anhydride (MAH) or diethyl maleate (DEM) as enophiles is described. The analysis of the products by means of different techniques assesses the addition of the polar molecules to the reactive vinylidene units of the polymer with functional degrees (FD) depending on the type of enophile and polymer reactivity. The role of the reaction conditions and the use as Lewis acids as catalysts are discussed in terms of their influence on the addition reaction extent and on the polymer molecular weight.     

A Synthetic Dynamic Polyvinyl Alcohol Photoresin for Fast Volumetric Bioprinting of Functional Ultrasoft Hydrogel Constructs

Tomographic volumetric bioprinting (VBP) enables fast photofabrication of cell-laden hydrogel constructs in one step, addressing the limitations of conventional layer-by-layer additive manufacturing. However, existing biomaterials that fulfill the physicochemical requirements of VBP are limited to gelatin-based photoresins of high polymer concentrations. The printed microenvironments are predominantly static and stiff, lacking sufficient capacity to support 3D cell growth. Here a dynamic resin based on thiol–ene photo-clickable polyvinyl alcohol (PVA) and thermo-sensitive sacrificial gelatin for fast VBP of functional ultrasoft cell-laden hydrogel constructs within 7–15 s is reported. Using gelatin allows VBP of permissive hydrogels with low PVA contents of 1.5%, providing a stress-relaxing environment for fast cell spreading, 3D osteogenic differentiation of embedded human mesenchymal stem cells and matrix mineralization. Additionally, site-specific immobilization of molecules-of-interest inside a PVA hydrogel is achieved by 3D tomographic thiol–ene photopatterning. This technique may enable spatiotemporal control of cell-material interactions and guides in vitro tissue formation using programmed cell-friendly light. Altogether, this study introduces a synthetic dynamic photoresin enabling fast VBP of functional ultrasoft hydrogel constructs with well-defined physicochemical properties and high efficiency.     

烯基琥珀酸酐(ASA)双键异构体结构的解析研究

针对目前通过ene反应制备烯基琥珀酸酐(ASA)所遇到的双键迁移后位置不确定的问题,利用油酸作原料合成并分离了烯基琥珀酸酐(ASA)-甲酯中含量最多的两个异构体化合物,之后采用臭氧化的方法对其中一个异构体的双键进行切断,并使用了核磁共振、质谱对产物结构进行了表征,从而逆推出了烯基琥珀酸酐(ASA)-甲酯中一个主要异构体的结构,为ASA的深度研究提供了结构上的有力支持。     

质子酸处理二维碳化钛/碳纳米管复合材料的电磁屏蔽性能与机械性能

通过质子酸胶体处理,实现了碳化钛Ti₃C₂T_x的制备。此外,使用单壁碳纳米管(SWCNT)作为增强成分,提升了质子酸处理碳化钛(H-MXene)的机械性能——不仅保持了电磁屏蔽性能,而且将拉伸性能提升了近400%。结果表明,H-MXene和碳纳米管具有作为高机械性能电磁(EMI)屏蔽复合材料的潜力。     

Thermal polymerization of thiol–ene network‐forming systems

The thermal polymerization of a tetrafunctional thiol (PETMP) and divinyl ether (TEGDVE) was monitored by temperature‐ramping differential scanning calorimetry (DSC) and the effects of inhibitor type and concentration, oxygen inhibition and initiator type were studied. The incorporation of inhibitors was required to produce a stable system at room temperature. Butylated hydroxytoluene (BHT) inhibited polymerization at low temperatures, but was inefficient at high temperatures and polymerization rates, and hence BHT is an ideal stabilizer. In contrast, a nitroxide inhibitor (NO‐67) was a very effective inhibitor and no polymerization occurred until all of the nitroxide was depleted. The presence of oxygen retarded the onset of polymerization but did not change the final conversion significantly. Polymerization with initiators having higher half‐life temperatures shifted the DSC peak to higher temperature because the rate of initiator decomposition and thus initiation was slower. Rheological investigations of the cure at different temperatures revealed that the gel time decreased significantly with increasing cure temperature, and the calculated apparent activation energy for PETMP/TEGDVE was 54 kJ mol^?1. Dynamical mechanical thermal analysis of the cured material was undertaken and frequency‐superposed results revealed that the glass transition region of PETMP/TEGDVE/azobisisobutyronitrile was much narrower than that of free‐radically cured dimethacrylate, but was similar to that of an epoxy resin cured with an aromatic diamine. This behaviour could be attributed to PETMP/TEGDVE network homogeneity, or to the less constrained crosslinks in the PETMP/TEGDVE network. Copyright © 2007 Society of Chemical Industry     

Metal‐Free Click Chemistry Reactions on Surfaces

In the last decade, interest in the functionalization of surfaces and materials has increased dramatically. In this regard, click chemistry deserves a central focus because of its mild reaction conditions, high efficiency, and easy post‐treatment. Among such novel click reactions, those that do not require any metal catalyst are of special interest, as metals may have undesirable effects in many fields. In this Review, the backgrounds and application of such metal‐free click reactions for the modification of surfaces are highlighted.     

Sunlight‐Induced Cross‐Linked Luminescent Films Based on Polysiloxanes and d‐Limonene via Thiol–ene “Click” Chemistry

The increasing pursuit of biocontained elastic materials led the investigation of the potential use of the monoterpene limonene in film synthesis via thiol–ene reaction. Poly[(mercaptopropyl)methylsiloxane] (PMMS) is first synthesized. By controlling the molar ratio of PMMS and functional monomers, such as polyethylene glycol allyl methyl ether or rhodamine‐B, PMMS is partially functionalized while leaving spare mercapto groups that could be further used as cross‐linking sites. On the basis of the functionalized PMMS, novel transparent silicone luminescent films with hydrophilic tunable properties are prepared by natural‐sunlight‐triggered thiol–ene “click” chemistry by using d ‐limonene as a cross‐linker. Their structures and properties are thoroughly characterized. Transparent luminescent films are coated on commercially available UV‐light emitting diode (LED) cell from solution medium followed by an in situ cross‐linking step; a colorful LED cell is obtained through this facile and efficient method. The UV‐LED coated by films show very intense photoluminescence under normal visible light or the light is on, and has very high coloric purity.