Article
Chemistry, Multidisciplinary
Tong Zhou, Xian-Bin Meng, Fu-Sheng Du, Zi-Chen Li
Summary: A renewable bicyclic lactone compound containing a cyclic ketal moiety, TOD, was synthesized from glycerol and levulinic acid. TOD could undergo ring-opening polymerization with benzyl alcohol as the initiator and TBD as the catalyst, yielding PTOD with a cis-2,4-disubstitued 2-methyl 1,3-dioxolane moiety. The copolymerization of L-lactide and TOD resulted in random copolymers with different TOD incorporation ratios and tunable T(g)s.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Physical
Alex J. Commisso, Gopal R. Sama, Timothy F. Scott
Summary: Conventional approaches to SLA use liquid resin formulations that can cross-link upon polymerization. However, using resins that yield semicrystalline thermoplastics allows for the attainment of high toughness and resistance to solvent swelling. In this study, semicrystalline thermoplastics were 3D printed using radical-mediated ring-opening photopolymerization. The printed copolymers showed strong interlayer adhesion and the potential for improved sustainability through recycling.
CHEMISTRY OF MATERIALS
(2023)
Article
Polymer Science
Lanfang Hu, Xun Zhang, Xiaohan Cao, Danjing Chen, Yue Sun, Chengjian Zhang, Xinghong Zhang
Summary: The study presents an easy and efficient method to synthesize semicrystalline polyesters via copolymerization of IBO and cyclic anhydrides, yielding polymers with high alternation degree, high molecular weights, and elevated melting temperatures. Besides, by manipulating the cis/trans isomerization of the C=C bond, unsaturated polyesters can exhibit a unique crystalline-amorphous-crystalline transformation.
Article
Polymer Science
Mahammad Anas, Tarun K. Mandal
Summary: The appropriate functionalization of synthetic polypeptides is crucial for generating self-assembled nanostructures, and this study presents a method to functionalize poly(L-glutamate)s with long chain alkyl groups. The resulting polypeptides possess weak crystallinity and display good thermoresponsive properties, forming vesicular nanoaggregates that can encapsulate organic dyes.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Polymer Science
Oleksandr Ivanchenko, Ugo Authesserre, Guilhem Coste, Stephane Mazieres, Mathias Destarac, Simon Harrisson
Summary: ε-Thionocaprolactone (TCL) can be easily copolymerized with vinyl esters to form degradable copolymers, with the molecular weight and dispersity controlled through xanthate-mediated RAFT polymerization. Analysis of the copolymer structure reveals a high level of TCL-TCL dyads, suggesting that the terminal copolymerization model is not accurate for describing TCL copolymerization.
Article
Polymer Science
Yi Wan, Yun Bai, Hai Xu, Jianghua He, Yuetao Zhang
Summary: The study successfully synthesized five chiral binuclear aluminum methyl complexes, which catalyze the ring-opening polymerization of rac-lactide in a controlled manner and produce polymers with high isoselectivity. The kinetic studies show a first-order dependence on monomer concentration, supporting an enantiomorphic site control mechanism for the catalysts. This strategy can also be applied to other lactones for ring-opening polymerization.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Polymer Science
Hongjuan Li, Xiangxiang Yan, Jie Huan, Sheng Wang, Xiaohong Li, Yatao Wang, Yingfeng Tu, Zhiping Li
Summary: We proposed a green cyclodepolymerization route for the efficient chemical recycling of poly(ethylene adipate) (PEA) to its cyclic oligomers, cyclic oligo(ethylene adipate)s (COEAs), using dibutyltin oxide as a catalyst and toluene as a solvent. Toluene was found to be a better solvent than chlorobenzene, providing higher yields and easier purification of COEAs from the reaction mixture. The yield of COEAs increased with reduced PEA concentration, prolonged reaction time, and increase of catalyst amount.
Article
Chemistry, Inorganic & Nuclear
Anand J. Gaston, Zoe Greindl, Carole A. Morrison, Jennifer A. Garden
Summary: This study describes four heterobimetallic (salen)Al catalysts and demonstrates that cooperative Al/Mg and Al/Zn combinations can significantly enhance catalyst activity, compared to mono-Al analogues. In contrast, Al/Li and Al/Ca combinations were found to inhibit the polymerization rate. Kinetic and computational studies suggest that chloride bridging in close intermetallic proximity enhances initiation and increases available monomer coordination sites in Al/Mg and Al/Zn complexes. Additionally, ab initio molecular dynamics calculations were utilized to investigate catalyst flexibility and reveal that ligand strain and molecular rigidity can enhance the performance of heterometallic catalysts.
INORGANIC CHEMISTRY
(2021)
Article
Polymer Science
Chun-Juei Chang, Wei Lee, Yu-Chi Liou, Yu-Lun Chang, Yi-Chun Lai, Shangwu Ding, Hsuan-Ying Chen, Hsing-Yin Chen, Yung-Chi Chang
Summary: The study demonstrated that dinuclear aluminum complexes exhibited higher catalytic activity than mononuclear aluminum complexes, particularly those with 1,3-substituted phenyl ligands. One Al atom in the dinuclear Al system acted as an electron-withdrawing group, influencing the other Al atom through associated aromatic ligands, thereby enhancing catalytic activity for the ROP of CL.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Polymer Science
Jinlong Chen, Yilin Dong, Chunsheng Xiao, Youhua Tao, Xianhong Wang
Summary: The research team successfully synthesized a novel class of poly(epsilon-lysine) mimics through ring-opening polymerization, avoiding tedious deprotection procedures, and exhibited high antimicrobial activities and excellent biocompatibility.
Article
Polymer Science
Ye Chen, Pengfei Zhang, Shan Liu, David Pahovnik, Ema Zagar, Junpeng Zhao, Guangzhao Zhang
Summary: This study presents a noncovalent protection strategy for one-step synthesis of PEO amine, producing alpha-amino-omega-hydroxyl PEO with controlled molar mass, low dispersity, and complete end functionality. The study also reveals the effects of initiator structure and retention of Et3B on the storage (oxidative) stability of PEO amine.
Article
Materials Science, Multidisciplinary
Rahime Soylemez, Zafer Uyar, Mustafa Degirmenci, Ahmet Kilic
Summary: In this study, tri-coordinated boron-based biodegradable polymers and their tetra-coordinated forms were synthesized. The properties and functionalities of the boron polymers were modified by introducing different ligands. The newly synthesized boron compounds were characterized and their thermal, morphological, and fluorescence behaviors were studied.
MATERIALS TODAY COMMUNICATIONS
(2022)
Article
Polymer Science
Natalie E. Goeppert, Michael Dirauf, Phil Liebing, Christine Weber, Ulrich S. Schubert
Summary: A monomer of 3-benzylmorpholine-2,5-dione is synthesized from l-phenylalanine and characterized by various techniques. A well-defined poly(ester amide) homopolymer is then synthesized using a binary catalyst system, showing high controllability of dispersities and molar masses. The resulting polyesteramides have potential as drug delivery vehicles, especially for hydrophobic drugs.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Hui Li, Jerome Ollivier, Sophie M. Guillaume, Jean-Francois Carpentier
Summary: This study reports the first chemical synthesis of poly(3-thiobutyrolactone) (P3TB) through ring-opening polymerization. The reactions proceed rapidly in the presence of various metal-based catalysts, and high selectivity can be achieved by manipulating reaction conditions and catalyst systems. The topology and stereochemistry of the resulting polymer have been characterized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Hans R. Kricheldorf, Steffen M. Weidner
Summary: The research showed that 2,2'-dihydroxybiphenyl is the most successful cocatalyst for bismuth subsalicylate in ring-opening polymerization of l-lactide, and optimization of reaction time and temperature is crucial for achieving high weight average molecular weights. Additionally, some unusual transesterification reactions were discovered, and triphenylphosphine was found to be an effective catalyst poison.
JOURNAL OF APPLIED POLYMER SCIENCE
(2021)
Article
Chemistry, Applied
Antonietta Mancuso, Vincenzo Vaiano, Pasqualmorica Antico, Olga Sacco, Vincenzo Venditto
Summary: This work investigates the photocatalytic hydroxylation of benzene to phenol using a photoreactive polymer composite, N-doped TiO2 (N-TiO2) embedded into a syndiotactic polystyrene aerogel (N-TiO2/sPS). The composite exhibits enhanced phenol selectivity and yield compared to bare N-TiO2. The best results were achieved under visible light and acidic conditions, with a phenol selectivity of 98%, yield of 57%, and benzene conversion of 58%. The composite material can be recovered and reused without significant loss of photoreactivity and reduction in phenol yield.
Article
Chemistry, Inorganic & Nuclear
Maria Strianese, Gerard Joseph D'Auria, Marina Lamberti, Alessandro Landi, Andrea Peluso, Antonio Varriale, Sabato D'Auria, Claudio Pellecchia
Summary: In this study, we used various spectroscopic techniques to investigate the interaction pathway between a newly synthesized family of zinc complexes and HS-. Computational analysis on the TD-DFT level revealed the fluorescence properties of these complexes and their different responses to HS-. Time-resolved fluorescence experiments demonstrated the potential of these systems to be used as HS- fluorescent sensors.
DALTON TRANSACTIONS
(2023)
Article
Polymer Science
Wanda Navarra, Olga Sacco, Vincenzo Venditto, Vincenzo Vaiano
Summary: In recent years, the focus of environmental pollution-related concern has shifted to aromatic substances due to their high stability and mutagenicity. Photocatalytic processes using TiO2 and sPS/P25 aerogel have been investigated for the conversion of nitroaromatic compounds into aniline. Under optimized conditions, an AN yield of over 99% was achieved, indicating the potential for scaling up the photocatalytic process for effective AN production from NB.
Article
Chemistry, Physical
Federica Santulli, Filippo Bruno, Mina Mazzeo, Marina Lamberti
Summary: We synthesized new hexadentate ligands with imine and pyridine nitrogen neutral donors, which have two coordinative pockets to promote the formation of bimetallic complexes. The bimetallic complexes S-1 and rac-1 were obtained by reacting the enantiomerically pure and racemic ligands with two equivalents of zinc amide precursor. Both complexes showed high activity in the polymerization of lactides under various reaction conditions and remained active even in technical grade melted lactide, demonstrating the robustness of the catalysts. Complex S-1 allows the production of linear or purely macrocyclic PLAs by back-biting reactions, depending on the reaction conditions. Mechanistic studies in NMR-scale solution were conducted to understand the active species in the polymerization process.
Article
Biochemistry & Molecular Biology
Federica Santulli, Ilaria Grimaldi, Daniela Pappalardo, Marina Lamberti, Mina Mazzeo
Summary: Chromium and aluminum complexes with salalen ligands were studied as catalysts for the ring-opening copolymerization (ROCOP) of succinic (SA), maleic (MA), and phthalic (PA) anhydrides with various epoxides. Their performance was compared to traditional salen chromium complexes. When used with 4-(dimethylamino)pyridine (DMAP) as the cocatalyst, all catalysts achieved a completely alternating enchainment of monomers to obtain pure polyesters. Switch catalysis allowed the same catalyst to combine the ROCOP of propylene oxide and maleic anhydride with the ring-opening polymerization (ROP) of glycolide (GA) in a one-pot procedure, resulting in a diblock polyester with precise composition.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Analytical
Maria Strianese, Giovanni Ferrara, Viktoriia Vykhovanets, Naym Blal, Daniela Guarnieri, Alessandro Landi, Marina Lamberti, Andrea Peluso, Claudio Pellecchia
Summary: In this study, a new family of fluorescent zinc complexes with extended pi-conjugated systems was synthesized and characterized. The complexes were investigated for their potential use in high-performance H2S sensing devices. The immobilization of the complexes into a polymeric matrix for solid-state portable devices was also explored. The results demonstrated that the complexes could be successfully applied in fast, simple, and cost-effective H2S sensing devices.
Article
Engineering, Chemical
Federica Tufano, Fabia Grisi, Chiara Costabile, Mina Mazzeo, Vincenzo Venditto, Antonella Caterina Boccia, Rosalba Fittipaldi, Lorella Izzo, Stefania Pragliola
Summary: The consumption and improper disposal of plastics have caused serious environmental concerns. New methods based on fluorescent tagging have been developed to facilitate the identification and sorting of different materials in plastic recycling. In this study, new fluorescent copolymers of polyethylene (PE) and polystyrene (PS) were synthesized and characterized for use as markers. These copolymers were found to have distinguishable fluorescent emissions even with a low concentration of only 1% in the PE/PS blends.
Proceedings Paper
Polymer Science
Antonietta Mancuso, Olga Sacco, Vincenzo Venditto, Wanda Navarra, Pasqualmorica Antico, Christophe Daniel, Vincenzo Vaiano
Summary: Experimental measurement and mathematical modeling were used to investigate the selective absorption of aromatic molecules (benzene, phenol, and toluene) from aqueous solutions by syndiotactic polystyrene (sPS) monolithic aerogels. The results showed high absorption efficiency for non-polar compounds (approximately 94% for toluene and approximately 77% for benzene) but poor absorption efficiency for the polar compound phenol (approximately 12%). NaCl did not affect the absorption efficiency of toluene and benzene, but phenol could not be removed from the aqueous phase in the presence of NaCl. These findings suggest that sPS aerogels can be used to selectively recover non-polar compounds from seawater.
MACROMOLECULAR SYMPOSIA
(2023)
Article
Chemistry, Physical
Wanda Navarra, Olga Sacco, Raffaella Rescigno, Christophe Daniel, Vincenzo Vaiano, Domenico Pisano, Bruno Brancato, Francesco Casertano, Mario Raiola, Vincenzo Venditto
Summary: In this study, a photocatalytic system utilizing a highly porous polymer containing commercial zinc sulfide and zero-valent iron catalyst (Fe/ZnS) was investigated for the degradation of PCE-contaminated groundwater. Experimental studies conducted on a pilot-scale photoreactor operating in continuous mode showed that PCE degradation in natural groundwater can reach 85-95%. A kinetic model was also developed and found to accurately describe the experimental data, allowing for potential scaling up of the photocatalytic system for PCE degradation.
CATALYSIS COMMUNICATIONS
(2023)
Article
Biochemistry & Molecular Biology
Ilaria Grimaldi, Federica Santulli, Marina Lamberti, Mina Mazzeo
Summary: Salen, Salan, and Salalen chromium (III) chloride complexes have been studied as catalysts for the ring-opening copolymerization reactions. The salan and salalen complexes showed high activity in the production of polycarbonates, while the salen complex exhibited the best performance in the copolymerization of phthalic anhydride with the epoxides. Diblock polycarbonate-polyester copolymers were selectively obtained by one-pot procedures, and all chromium complexes showed high activity in the chemical depolymerization of polycyclohexene carbonate.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Biochemistry & Molecular Biology
Raffaella Rescigno, Olga Sacco, Vincenzo Venditto, Alessandra Fusco, Giovanna Donnarumma, Mariateresa Lettieri, Rosalba Fittipaldi, Vincenzo Vaiano
Summary: In this study, P-doped TiO2 photocatalysts with different molar percentages were prepared and their photocatalytic activity under visible light irradiation was tested. The doping of phosphorus significantly enhanced the photocatalytic activity, as evidenced by the decolorization of methylene blue dye. The most active photocatalyst also showed better performance than commercial TiO2 under simulated sunlight irradiation, and had a high inactivation efficiency against Escherichia coli.
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Antonietta Mancuso, Alessandro Gottuso, Francesco Parrino, Rosaria Anna Picca, Vincenzo Venditto, Olga Sacco, Vincenzo Vaiano
Summary: Cu, Fe, and V oxides supported on N-TiO2 were synthesized and their photocatalytic activities in phenol production were tested. Cu/N-TiO2 showed higher activity and yield compared to Fe/N-TiO2 and V/N-TiO2 due to its strong optical absorption and weak interaction with phenol molecules.
Article
Chemistry, Inorganic & Nuclear
Federica Tufano, Federica Tufano, Mariachiara Cozzolino, Ilaria D'Auria, Maria Strianese, Mina Mazzeo, Marina Lamberti
Summary: In this study, mono- and bimetallic complexes based on zinc were used for the synthesis of sustainable aliphatic and semi-aromatic polyesters. The bimetallic complexes showed higher activity and better control of polymerization processes compared to the monometallic complexes, highlighting the importance of cooperation between the two zinc centers in polyester synthesis.
DALTON TRANSACTIONS
(2023)
Article
Polymer Science
Paige A. Shaw, Maxime Klausen, Mark Bradley
Summary: A light-responsive polymer capable of controlled release of camptothecin and generation of reactive oxygen species (ROS) was developed, which exhibited high cancer cell killing activity through both camptothecin release and ROS generation.
Article
Polymer Science
Donghui Zhang, Shiqi Liu, Zhihao Cai, Weizhe Luo, Guojian Liu, Runhui Liu
Summary: A straightforward and efficient method for synthesizing NPC monomers has been developed in this study, which enhances the availability of NPC monomers and facilitates the synthesis of polypeptides.
