Article
Chemistry, Multidisciplinary
Xiaofei Sun, Chengliang Wang, Xu Zhang, Yan Zhang, Qingfu Wang, Jingjiang Sun
Summary: With the increasing prominence of environmental issues, bio-based polymers have become essential in alleviating environmental degradation by replacing traditional polymers. In this study, a new family of functional isosorbide-based polyesters and polyamides with high glass transition temperature were prepared via Passerini-Three component polymerization (P-3CP). The conditions for P-3CP were optimized, and the influence of the polymerization solvent, temperature, and feed ratio on the molar mass of the final polymers was investigated. The obtained polymers exhibited excellent thermal stability and amorphy, with variable glass transition temperatures. Cytotoxicity tests confirmed their biological safety. This novel strategy provides an efficient approach for producing functional isosorbide-based polyesters and polyamides, which hold promising prospects for biodegradable materials.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Qiao Zhang, Chenyang Hu, Xuan Pang, Xuesi Chen
Summary: In this study, multi-functional organocatalysts based on fluorides were used for the production and degradation of polyesters. The organofluoride catalysts showed excellent reactivity due to the hydrogen bond interaction between fluoride (F-) and alcohol initiator. They were effective in producing high molecular weight polyesters and enabling various polymerization reactions. Additionally, the organofluoride catalysts facilitated the upcycling of polyester plastic wastes via alcoholysis. The hierarchical degradation of polyester blend was also investigated.
Article
Chemistry, Physical
Ya-Ning Li, Sheng-Ye Zhang, Yang Ma, Yi-Jie Ding, Zhi-Hao Chen, Qiao-Ling Che, Long Qin, Xiu-Li Sun, Xiaohua Liu, Xiaoming Feng, Zhi-Pan Liu, Xiao-Yan Wang, Yong Tang
Summary: A highly efficacious photoinduced reversible complexationmediated polymerization system has been developed using amino alcohol N-oxide as the catalyst, allowing access to controlled high-molecular weight polymers of different methacrylates. The research shows that strong hydrogen bond effects play important roles in both monomer conversion and molecular weight controllability.
Article
Polymer Science
Xueting Wan, Jian Jiang, Yanyan Tu, Siyuan Xu, Jing Li, Huanjun Lu, Zhikai Li, Lianhu Xiong, Xiaohong Li, Youliang Zhao, Yingfeng Tu
Summary: The study presents a method for direct preparation of green copolyesters via cascade polycondensation-coupling ring-opening polymerization (PROP), which enables the introduction of multiple functional groups during synthesis, leading to the synthesis of biodegradable polyesters with high molecular weights.
Article
Chemistry, Multidisciplinary
Amandine L. Flourat, Lorenzo Pezzana, Sabrina Belgacem, Abdouramane Dosso, Marco Sangermano, Sami Fadlallah, Florent Allais
Summary: This study focuses on the synthesis of tunable bis-allylated compounds from cellulose-derived levoglucosenone and their use in thiol-ene click chemistry for 3D-printing. The resulting materials exhibit excellent reactivity and are suitable for creating well-defined three-dimensional objects.
Article
Chemistry, Multidisciplinary
Amandine L. Flourat, Lorenzo Pezzana, Sabrina Belgacem, Abdouramane Dosso, Marco Sangermano, Sami Fadlallah, Florent Allais
Summary: In this study, tunable bis-allylated compounds were efficiently synthesized from cellulose-derived levoglucosenone via a chemo-enzymatic pathway, and then polymerized through photocuring, resulting in thermosets suitable for 3D printing.
Article
Polymer Science
Florine Nonque, Antoine Benlahoues, Jules Audourenc, Audrey Sahut, Rene Saint-Loup, Patrice Woisel, Jonathan Potier
Summary: The study thoroughly investigated the free radical polymerizability of IMMA and highlighted the key parameters for controlling the molecular weight of PIMMA, including monomer and solvent transfer reactions. By understanding these parameters, PIMMA with tailored molecular weight and Tg could be prepared, offering the opportunity to create materials with different potential applications.
EUROPEAN POLYMER JOURNAL
(2021)
Article
Engineering, Environmental
Yihao Li, Lu Jiang, Rui Wang, Pingxiao Wu, Juan Liu, Shanshan Yang, Jiahao Liang, Guining Lu, Nengwu Zhu
Summary: This study investigates the oxidation mechanism of phenolic compounds by ferrate (Fe(VI)), showing increased degradation rates at higher pH levels. It identifies 14 degradation products, proposes two possible pathways, and highlights the crucial role of hydroxyl radicals in the degradation process. Density functional theory calculations reveal preferences for chlorine atom substitution over hydrogen atom and ortho-position substitution over para-position for all four compounds, providing valuable insights for environmental remediation.
JOURNAL OF HAZARDOUS MATERIALS
(2021)
Article
Chemistry, Organic
Jianyu Zhai, Jolene P. Reid
Summary: Recent strategies for enantioinduction focus on utilizing a chiral catalyst to noncovalently interact with the substrate. Stereoselectivity can be achieved by limiting the number of low energy diastereomeric transition states that the reacting components can adopt. Modern computational methods have been designed to overcome the difficulties associated with accurately modeling these types of interactions.
Article
Chemistry, Multidisciplinary
Wei Zhao, Yanfeng Lv, Ji Li, Zihao Feng, Yonghao Ni, Nikos Hadjichristidis
Summary: Functionalized polypeptides have gained significant interest in various fields due to their tunable physicochemical characteristics, and developing strategies to produce them without metallic contaminants is crucial for applications in high-value and sensitive domains. A highly efficient strategy combining Michael reaction with hydrogen-bonding organocatalytic ROP has been developed to access site-specific functionalized polypeptides with predesigned molecular weights and low polydispersities. This metal-free synthetic process offers high activity and selectivity at room temperature for preparing a library of chain-end and chain-middle functionalized polypeptides.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Polymer Science
Lianqian Wu, Brayan Rondon, Shoshana Dym, Wenqi Wang, Kuiru Chen, Jia Niu
Summary: Cationic polymerization is a powerful strategy for the production of well-defined polymers and advanced materials. Recent developments, including the use of light and electricity for spatiotemporally controlled polymerization, stereoselective polymerization, and chemically recyclable/degradable polymers, have greatly advanced the field. These advancements have significant implications for polymer science and beyond.
PROGRESS IN POLYMER SCIENCE
(2023)
Article
Polymer Science
Ethan A. Gormong, Theresa M. Reineke, Thomas R. Hoye
Summary: Incorporating renewable feedstocks into polymer backbones is crucial in modern polymer science. This study demonstrates the synthesis of 1,3-diyne polymers from bispropargyl ethers of isosorbide, isomannide, and isoidide, with varying glass transition temperatures. The saturated analogues show similar trends in Tg values compared to the diyne polymers, based on the stereochemical features of the isohexide unit in the backbone.
Article
Chemistry, Organic
Marcel A. Strauss, Daniel Kohrs, Julia Ruhl, Hermann A. Wegner
Summary: By studying the domino bidentate Lewis acid catalyzed inverse electron-demand Diels-Alder (IEDDA) reaction computationally and synthetically, a quinodimethane intermediate was identified as the key structure, leading to insights for optimizing reaction conditions and advancing new reactions in the future.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Huyan Zhou, Lu Zhang, Peng Wen, Yang Zhou, Yucheng Zhao, Qiaoqiao Zhao, Yu Gu, Ruopeng Bai, Mao Chen
Summary: In this study, photoredox-mediated reversible-deactivation radical polymerization (RDRP) was developed by activating (hetero)aryl sulfonyl chloride (ArSO2Cl) initiators with pyridines and designing a novel bis(phenothiazine)arene catalyst. The in situ formed sulfonyl pyridinium intermediates effectively promote controlled chain-growth from ArSO2Cl, enabling access to various well-defined polymers with high initiation efficiencies and controlled dispersities under mild conditions. This versatile method allows ON/OFF temporal control, chain-extension, and facile synthesis of different polymer brushes via organocatalyzed grafting reactions from linear chains. Time-resolved fluorescence decay studies and calculations support the reaction mechanism. This work provides a transition-metal-free RDRP to tailor polymers with readily available aromatic initiators, and will promote the design of polymerization leveraged from photoredox catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Ivor Smajlagic, Brandon White, Oyindamola Azeez, Melanie Pilkington, Travis Dudding
Summary: This study presents a cationic squaramide-cyclopropenium organocatalyst with charge-enhanced acidity, enabling novel chemical transformations. The origin of this reactivity was determined through computational analysis and in-depth experimental mechanistic studies.
Article
Chemistry, Physical
Joao P. Prates Ramalho, Ana Dordio, Alfredo J. Palace Carvalho
Summary: The study indicates that micro and nanoplastics have strong adsorption capabilities in aqueous environments, with different types of plastics exhibiting different behaviors under different shapes of aggregated nanoparticles. However, all types of plastics show a tendency to stay stably associated in clusters, resisting further fragmentation and degradation.
JOURNAL OF MOLECULAR STRUCTURE
(2022)
Article
Biochemistry & Molecular Biology
Nisa Magalhaes, Guilherme M. Simoes, Cristiana Ramos, Jaime Samelo, Alexandre C. Oliveira, Hugo A. L. Filipe, Joao P. Prates Ramalho, Maria Joao Moreno, Luis M. S. Loura
Summary: This study combines atomistic molecular dynamics (MD) simulations and fluorescence spectroscopy to characterize the interaction between rhodamines 123 and B (Rh123 and RhB, respectively) and POPC bilayers. The study provides detailed insights on the similarities and differences in the behavior of bilayer-inserted Rh123 and RhB, related to the structure of the probes. The higher affinity of RhB for the membranes increases the local concentration and explains its higher apparent affinity for P-glycoprotein reconstituted in model membranes.
Article
Biochemistry & Molecular Biology
Julie Meimoun, Yupin Phuphuak, Remi Miyamachi, Yong Miao, Marc Bria, Cyril Rousseau, Guilherme Nogueira, Andreia Valente, Audrey Favrelle-Huret, Philippe Zinck
Summary: Cyclodextrins (CDs) are cyclic oligosaccharides widely used in various fields. This study successfully achieved quantitative functionalization of various types of CDs using 4-dimethylaminopyridine (DMAP) as a catalyst. The inclusion complex formed between DMAP and β-CD was characterized for the first time, and its association constant was estimated.
Article
Materials Science, Multidisciplinary
Kifah Nasr, Audrey Favrelle-Huret, Rosica Mincheva, Gregory Stoclet, Marc Bria, Jean-Marie Raquez, Philippe Zinck
Summary: This study successfully synthesized several DEFDC biobased semiaromatic copolyesters with variable interesting properties and demonstrated their potential applications in food packaging and other fields.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Biochemistry & Molecular Biology
Raquel Eustaquio, Joao P. Prates Ramalho, Ana T. Caldeira, Antonio Pereira
Summary: In this study, a simple, low-cost and effective synthetic strategy was developed to produce new red-shifted 4-styrylcoumarin derivatives as inexpensive fluorescent labels for biomolecules. These derivatives demonstrated bathochromic shifts and large Stokes shifts, and their photophysical properties were rationalized using density functional theory and time-dependent density functional theory calculations.
Article
Energy & Fuels
Lucas G. Celia-Silva, Rafaela N. Martins, Alfredo J. Palace Carvalho, Joa P. Prates Ramalho, Pedro Morgado, Eduardo J. M. Filipe, Luis F. G. Martins
Summary: This study systematically investigates the pre-aggregation behavior of asphaltene in the absence and presence of ionic liquids (ILs) using molecular dynamics simulations. The effects of cation chain length and anion dimension on asphaltene aggregation are studied. The results show that ILs have a dispersing effect on asphaltene, and this effect is influenced by the alkyl side chain length of the cation and the radius of the anion. The findings are supported by DFT calculations. The study also demonstrates that CO2 acts as a precipitating agent, but does not affect the relative performance of the ILs.
Article
Chemistry, Inorganic & Nuclear
Alexandre C. Oliveira, Hugo A. . L. Filipe, Joao P. Prates Ramalho, Armindo Salvador, Carlos F. G. C. Geraldes, Maria Joao Moreno, Luis M. S. Loura
Summary: The correct parametrization of lanthanide complexes is crucial for their characterization using computational tools, and this study establishes the best strategies for parametrization and demonstrates the successful capture of dynamic properties.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Michael Lalanne-Tisne, Audrey Favrelle-Huret, Wim Thielemans, Joao P. Prates Ramalho, Philippe Zinck
Summary: Organocatalysts are important in polymerization reactions. This study used Density Functional Theory to investigate the ring-opening polymerization of trimethylene carbonate, revealing a dual mechanism and confirming TBD as a more efficient catalyst.
Review
Chemistry, Multidisciplinary
Wajid Ali, Hazrat Ali, Sami Souissi, Philippe Zinck
Summary: More than 390 million tons of fossil fuel plastics have been produced in 2022, causing major health issues and environmental pollution. Bioplastics are considered as a promising alternative due to their carbon neutrality and biodegradability, but technical and cost limitations prevent them from fully substituting fossil fuel plastics.
ENVIRONMENTAL CHEMISTRY LETTERS
(2023)
Article
Thermodynamics
Felisberto S. Mendes, Carlos E. M. Cruz, Rafaela N. Martins, Joao P. Prates Ramalho, Luis F. G. Martins
Summary: This study investigated the solute-solvent interaction and mobility in aqueous solutions of two non-steroidal anti-inflammatory drugs (ketoprofen and ibuprofen) by measuring their mutual diffusion coefficients using the Taylor dispersion method. Molecular dynamics simulations were also conducted to calculate the intra-diffusion coefficients of the solutes. The results showed that ibuprofen had a higher mutual diffusion coefficient in water than ketoprofen, and the simulations were able to accurately predict the experimental values.
JOURNAL OF CHEMICAL THERMODYNAMICS
(2023)
Article
Polymer Science
Catarina Bravo, Nicolas Merle, Mathieu Sauthier, Marc Bria, Julien De Winter, Philippe Zinck
Summary: This work presents a simple and effective method for the polymerization of butadiene using nickel allyl complexes as catalysts, achieving chain transfer and the formation of branched polybutadiene. This method allows for the one-pot synthesis of polymers with specific structures.
Article
Biochemistry & Molecular Biology
Raquel Eustaquio, Joao P. Prates Ramalho, Ana Teresa Caldeira, Antonio Pereira
Summary: Fluorescent labels are crucial in various scientific applications, and this study introduces four promising and inexpensive coumarin derivatives as fluorescent labels for biomolecules.
Article
Biochemistry & Molecular Biology
Margarida M. Cordeiro, Hugo A. L. Filipe, Patricia dos Santos, Jaime Samelo, Joao P. Prates Ramalho, Luis M. S. Loura, Maria J. Moreno
Summary: In this study, the interaction between H33342 and lipid bilayers was investigated using both experimental and computational approaches. The results showed that the partition coefficient of H33342 did not vary significantly over a wide pH range. This highlights the importance of considering the association with lipid bilayers when predicting the affinity for biomembranes.
Article
Chemistry, Organic
Daniela P. Fonseca, Ana C. Amorim, Elisabete P. Carreiro, Joao P. Prates Ramalho, Gesine J. Hermann, Hans-Juergen Federsel, Ana Rita C. Duarte, Anthony J. Burke
Summary: The organocatalyst cinchonidine-squaramide was immobilized within three different deep eutectic solvents (DESs) and evaluated in an asymmetric Michael addition reaction. The results showed excellent yields (up to 99%) and enantioselectivities (up to 98%) using only 1 mol% of organocatalyst. The high recyclability of this system was demonstrated with 9 cycles using DES (betaine:D-sorbitol:water), and 5 cycles were achieved with only 0.5 mol% of organocatalyst, obtaining products with high yields (up to 95%) and excellent enantioselectivities (up to 94%).
Article
Chemistry, Multidisciplinary
Raquel Eustaquio, Joao P. Prates Ramalho, Ana T. Caldeira, Antonio Pereira
Summary: A series of novel 2-piperidinium-4-styrylcoumarin derivatives with large Stokes shifts and high fluorescence quantum yields were synthesized using an efficient and low-cost synthetic strategy as potential fluorescent labels for biomolecules. Density functional theory and time-dependent density functional theory calculations were performed to rationalize the observed photophysical properties.
