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Investigation of horseradish peroxide and hydrogen peroxide mediated synthesis of amino-functional oligomers: Characterization and fluorescence study
Synthetic Metals ( IF 4.4 ) Pub Date : 2021-08-16 , DOI: 10.1016/j.synthmet.2021.116879
Feyza Kolcu 1, 2 , İsmet Kaya 1
Affiliation  

The insightful mechanism of two oligomerization methods using either horseradish peroxide (HRP)/hydrogen peroxide (H2O2) (enzymatic approach), or H2O2 (35% aqueous) (chemical approach) on 4-phenoxy aniline (PA) and 4-(4-chlorophenoxy)aniline (PACl) as two amino-functional monomers was studied. Four oligomers synthesized were described by FT-IR, UV-Vis, 1H-NMR and 13C-NMR techniques for the molecular structure analysis. The oligomers substituted with chlorine had stronger electron acceptor ability, which enhanced the intramolecular charge transfer between the donating moiety and chlorine acceptor substituent, resulting in a 48 nm red shift of the λmax for the n→π* electronic transition. Oligomers prepared by horseradish peroxidase shows better fluorescence properties than the monomers. The use of oxidoreductase enzyme (HRP) as the catalyst, for the one-step oligomerization of the monomers demonstrated to yield fluorescent products. Photoluminescence (PL) measurements enlightened that emission quantum yields of PACl-E in DMF were found to be 18% and 4.2% at the maximum emission wavelength of 412 nm and 482 nm, respectively. it is considered as green oligomerization/polymerization method Since HRP catalysis provided a green oxidative oligomerization method of aniline and their derivatives, four oligomers were produced by peroxidase-catalyzed oxidation oligomerization in relation to their electronic properties. HOMO-LUMO energy levels were calculated to make comments about electrochemical (E′g) band gaps of the oligomers which were lower than those of their regarding monomers. SEM images were provided to study the morphology of the oligomers. Intermolecular dihydrophenazine formation in the course of enzymatic oligomerization would eventuate in highly ordered structures.



中文翻译:

辣根过氧化物和过氧化氢介导的氨基功能低聚物合成的研究:表征和荧光研究

在 4-苯氧基苯胺 (PA) 上使用辣根过氧化物 (HRP)/过氧化氢 (H 2 O 2 )(酶法)或 H 2 O 2(35% 水溶液)(化学法)的两种低聚方法的深刻机制和 4-(4-氯苯氧基)苯胺 (PACl) 作为两种氨基官能单体进行了研究。通过FT-IR、UV-Vis、1 H-NMR和13 C-NMR技术描述合成的四种低聚物用于分子结构分析。被氯取代的低聚物具有更强的电子受体能力,这增强了供体部分和氯受体取代基之间的分子内电荷转移,导致λmax红移48 nm对于 n→π* 电子跃迁。辣根过氧化物酶制备的低聚物显示出比单体更好的荧光特性。使用氧化还原酶 (HRP) 作为催化剂,用于单体的一步低聚反应以产生荧光产物。光致发光 (PL) 测量结果表明,在 412 nm 和 482 nm 的最大发射波长下,PACl-E 在 DMF 中的发射量子产率分别为 18% 和 4.2%。它被认为是绿色低聚/聚合方法 由于 HRP 催化提供了苯胺及其衍生物的绿色氧化低聚方法,因此过氧化物酶催化氧化低聚产生了四种低聚物,这与它们的电子特性有关。计算 HOMO-LUMO 能级以评论电化学(E' g ) 低聚物的带隙低于其单体的带隙。提供SEM图像以研究低聚物的形态。在酶促低聚过程中分子间二氢吩嗪的形成将最终形成高度有序的结构。

更新日期:2021-08-17
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