多官能单体TMPTA在LDPE表面光接枝聚合研究

以二苯甲酮(BP)为光引发剂、丙酮和水的混合物为溶剂,研究了室温下多官能单体三羟甲基丙烷三丙烯酸酯(TMPTA)在低密度聚乙烯(LDPE)表面的光接枝聚合(λ>300nm).研究表明,多官能单体的接枝速率较快,接枝聚合易产生交联结构,聚合后仍残留双键;延长聚合反应时间、增加单体用量有利于单体接枝转化率的提高;随引发剂用量增加,单体接枝转化率出现一峰值;在研究范围内,混合溶剂中水含量增加可使单体接枝转化率明显提高.扫描电镜观察到接枝膜表面形成了许多小球,表面粗糙度增加,疏水性提高.     

Concurrent Covalent and Supramolecular Polymerization

Covalent and supramolecular polymerizations, both of which offer their own unique advantages, have emerged as popular strategies for making artificial materials. Herein, we describe a concurrent covalent and supramolecular polymerization strategy—namely, one which utilizes 1) a bis‐azide‐functionalized diazaperopyrenium dication that undergoes polymeriation covalently with a bis‐alkyne‐functionalized biphenyl derivative in one dimension as a result of a rapid and efficient β‐cyclodextrin(CD)‐accelerated, cucurbit[6]uril(CB)‐templated azide–alkyne cycloaddition, while 2) the aromatic core of the dication is able to dimerize in a criss‐cross fashion by dint of π–π interactions, enabling simultaneous supramolecular assembly, resulting in an extended polymer network in an orthogonal dimension.     

Advanced Polymer Designs for Direct-Ink-Write 3D Printing

The rapid development of additive manufacturing techniques, also known as three-dimensional (3D) printing, is driving innovations in polymer chemistry, materials science, and engineering. Among current 3D printing techniques, direct ink writing (DIW) employs viscoelastic materials as inks, which are capable of constructing sophisticated 3D architectures at ambient conditions. In this perspective, polymer designs that meet the rheological requirements for direct ink writing are outlined and successful examples are summarized, which include the development of polymer micelles, co-assembled hydrogels, supramolecularly cross-linked systems, polymer liquids with microcrystalline domains, and hydrogels with dynamic covalent cross-links. Furthermore, advanced polymer designs that reinforce the mechanical properties of these 3D printing materials, as well as the integration of functional moieties to these materials are discussed to inspire new polymer designs for direct ink writing and broadly 3D printing.     

金属离子对在饮用水氯化过程中形成消毒副产物的影响的研究进展

饮用水氯化消毒的安全性问题一直是水处理领域的研究热点之一.由于天然水体中矿物质的普遍存在以及微量重金属污染的经常发生,开展金属离子对消毒副产物形成的影响规律研究,对于实际饮用水消毒副产物的控制及其对人类健康的影响评价都具有重要意义.本文以目前研究较多的一些典型金属离子和金属氧化物（如铜离子、铁离子、二氧化锰和二氧化铅等...     

含POSS光刻胶材料研究进展

光致抗蚀剂又称光刻胶,是微电子加工过程中的关键材料。多面体低聚倍半硅氧烷（POSS）是一种具有规则的笼型结构的聚合物增强材料,由POSS改性的聚合物实现了有机-无机纳米杂化,POSS刚性结构的引入阻碍了聚合物分子的运动,可以显著提高聚合物的玻璃化转变温度（T_g）,降低聚合物的介电常数,提高聚合物的力学性能,也提高了含POSS光致抗蚀剂的耐蚀刻性。基于这些优点,含POSS的光刻胶材料得到广泛关注。本文对含POSS光刻胶的研究进展作了简要介绍。     

Fermentation Kinetics for Xylitol Production by a Pichia stipitis d-Xylulokinase Mutant Previously Grown in Spent Sulfite Liquor

Spent sulfite pulping liquor (SSL) contains lignin, which is present as lignosulfonate, and hemicelluloses that are present as hydrolyzed carbohydrates. To reduce the biological oxygen demand of SSL associated with dissolved sugars, we studied the capacity of Pichia stipitis FPL-YS30 (xyl3Δ) to convert these sugars into useful products. FPL-YS30 produces a negligible amount of ethanol while converting xylose into xylitol. This work describes the xylose fermentation kinetics of yeast strain P.stipitis FPL-YS30. Yeast was grown in rich medium supplemented with different carbon sources: glucose, xylose, or ammonia-base SSL. The SSL and glucose-acclimatized cells showed similar maximum specific growth rates (0.146 h⁻¹). The highest xylose consumption at the beginning of the fermentation process occurred using cells precultivated in xylose, which showed relatively high specific activity of glucose-6-phosphate dehydrogenase (EC 1.1.1.49). However, the maximum specific rates of xylose consumption (0.19 g_xylose/g_cel h) and xylitol production (0.059 g_xylitol/g_cel h) were obtained with cells acclimatized in glucose, in which the ratio between xylose reductase (EC 1.1.1.21) and xylitol dehydrogenase (EC 1.1.1.9) was kept at higher level (0.82). In this case, xylitol production (31.6 g/l) was 19 and 8% higher than in SSL and xylose-acclimatized cells, respectively. Maximum glycerol (6.26 g/l) and arabitol (0.206 g/l) production were obtained using SSL and xylose-acclimatized cells, respectively. The medium composition used for the yeast precultivation directly reflected their xylose fermentation performance. The SSL could be used as a carbon source for cell production. However, the inoculum condition to obtain a high cell concentration in SSL needs to be optimized. Prepared for 29th Symposium on Biotechnology for Fuels and Chemicals.     

Ortho-Alkoxy-benzamide Directed Formation of a Single Crystalline Hydrogen-bonded Crosslinked Organic Framework and Its Boron Trifluoride Uptake and Catalysis

Boron trifluoride (BF₃) is a highly corrosive gas widely used in industry. Confining BF₃ in porous materials ensures safe and convenient handling and prevents its degradation. Hence, it is highly desired to develop porous materials with high adsorption capacity, high stability, and resistance to BF₃ corrosion. Herein, we designed and synthesized a Lewis basic single-crystalline hydrogen-bond crosslinked organic framework (H_COF-50) for BF₃ storage and its application in catalysis. Specifically, we introduced self-complementary ortho-alkoxy-benzamide hydrogen-bonding moieties to direct the formation of highly organized hydrogen-bonded networks, which were subsequently photo-crosslinked to generate H_COFs. The H_COF-50 features Lewis basic thioether linkages and electron-rich pore surfaces for BF₃ uptake. As a result, H_COF-50 shows a record-high 14.2 mmol/g BF₃ uptake capacity. The BF₃ uptake in H_COF-50 is reversible, leading to the slow release of BF₃. We leveraged this property to reduce the undesirable chain transfer and termination in the cationic polymerization of vinyl ethers. Polymers with higher molecular weights and lower polydispersity were generated compared to those synthesized using BF₃ ⋅ Et₂O. The elucidation of the structure–property relationship, as provided by the single-crystal X-ray structures, combined with the high BF₃ uptake capacity and controlled sorption, highlights the molecular understanding of framework-guest interactions in addressing contemporary challenges.