Article
Polymer Science
Albert Prause, Michelle Hechenbichler, Robert F. Schmidt, Miriam Simon, Sylvain Prevost, Leide P. Cavalcanti, Yeshayahu Talmon, Andre Laschewsky, Michael Gradzielski
Summary: Temperature control of rheological properties of aqueous solutions can be achieved by the addition of temperature-responsive amphiphilic polymers. In this study, three sets of acrylamide-based block copolymers with different architectures were explored, and their viscosities showed a substantial increase with increasing temperature. The changes in rheological properties were correlated with the mesoscopic organization of the systems.
Article
Chemistry, Physical
Jessica Bassi da Silva, Peter Haddow, Marcos Luciano Bruschi, Michael Thomas Cook
Summary: This article investigates graft copolymers with brush-like architectures containing thermoresponsive monomers. The study explores the chemical structure of the thermoresponsive polymer and its impact on phase behavior and rheological properties. The materials show potential for temperature-responsive applications in the field of medical materials.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Chemistry, Multidisciplinary
Koji Okuno, Takuya Arisawa, Yuri Kamon, Akihito Hashidzume, Francoise M. Winnik
Summary: Thermoresponsive water-soluble polymers with different amide side chains were synthesized and found to have varying solubility, with secondary amide side chains leading to insoluble polymers and tertiary amide side chains resulting in soluble polymers.
Article
Polymer Science
Hang Xiao, Quan-Xi Shi, Min Su, Xiao-Li Sun, Hongli Bao, Wen-Ming Wan
Summary: This study demonstrates a one-pot strategy for the molecular design of stimuli-responsive opposite emission/absorption polymer material with unique properties. The nontraditional intrinsic luminescence in the visible region is achieved through reversible addition-fragmentation chain transfer polymerization-induced emission (PIE) of a specific moiety. The opposite emission/absorption properties are derived from the carbocation-quinoid mechanism, enabling fluorescence encryption capability. This work provides a proof of concept for a novel polymer material that might inspire different fields.
Article
Polymer Science
Maximilian Felix Toni Meier, Franck Thetiot, Narsimhulu Pittala, Ingo Lieberwirth, Cleiton Kunzler, Smail Triki, Ulrich Jonas
Summary: Novel macromolecular coordination ligands (MCLs) were designed by conjugating thermoresponsive polymers with 1,2,4-triazole coordination sites, leading to reversible aggregate formation. The thermal response, aggregate dimensions, and morphology were studied for potential applications in coordination chemistry.
Article
Biochemistry & Molecular Biology
Alvaro Leonel Robles Grana, Hortensia Maldonado-Textle, Jose Roman Torres-Lubian, Claude St Thomas, Ramon Diaz de Leon, Jose Luis Olivares-Romero, Luis Valencia, Francisco Javier Enriquez-Medrano
Summary: This study demonstrates the efficient control of polymerization of methacrylic monomers using a symmetrical trithiocarbonate chain transfer agent in the RAFT process. However, an atypical behavior is observed in the polymerization of MMA, where high initiator/CTA molar ratios are required to achieve predictable molecular weights without affecting dispersity.
Article
Polymer Science
Marija Kavaliauskaite, Medeina Steponaviciute, Justina Kievisaite, Arturas Katelnikovas, Vaidas Klimkevicius
Summary: The synthesis and study of well-defined thermoresponsive amphiphilic copolymers with various compositions have been reported. The kinetics of the reversible addition-fragmentation chain transfer (RAFT) (co)polymerization and the thermoresponsive properties of the copolymers in aqueous solutions were investigated.
Review
Polymer Science
Matilde Concilio, Valentin P. Beyer, C. Remzi Becer
Summary: Thermoresponsive polymers are attracting increasing interest in various fields, particularly in biomedical and nanotechnology applications. While the thermoresponsive behavior of polymers in pure water or water/organic solvent systems has been extensively studied, investigations on temperature-induced phase transitions in other organic solvents are relatively scarce. This review article focuses on the thermoresponsive behavior of polymers in different classes of organic solvents and mixtures, highlighting their versatility and potential.
Article
Polymer Science
Atsushi Sawamoto, Shin-nosuke Nishimura, Nobuyuki Higashi, Tomoyuki Koga
Summary: Controlling the thermoresponsive behavior of bio-based synthetic polymers is crucial for the development of smart functional materials. The synthesis of amino acid-derived vinyl polymers with different hydropathies and their thermal responses in water are reported, providing important insights for the precise design of stimuli-responsive bio-based polymers.
Article
Polymer Science
James B. Young, Jared Bowman, Cabell B. Eades, Alexander J. Wong, Brent S. Sumerlin
Summary: Controlled radical polymerization techniques allow for the synthesis of polymers with specific molecular weights and architectures. In this study, the role of light in triggering thermal depolymerization of polymers synthesized through reversible-addition-fragmentation chain-transfer (RAFT) polymerization was investigated. By targeting specific electronic transitions, the depolymerization efficiency was enhanced.
Article
Polymer Science
Dongdong Liu, Shuaiqi Yang, Shaojie Peng, Ying Chen, Li Zhang, Jianbo Tan
Summary: This study reports the first simultaneous synthesis and self-assembly of bottlebrush block copolymers at room temperature using photoinitiated polymerization-induced self-assembly (photo-PISA) with multifunctional macromolecular chain transfer agents (macro-CTAs). The bottlebrush block copolymers promote the formation of higher-order morphologies and exhibit a higher polymerization rate compared to linear block copolymers. The obtained bottlebrush block copolymer vesicles are used as seeds for further chain extension and formation of multicompartment nanoparticles with a sponge internal structure. This study expands polymer architectures employed in PISA and provides a new strategy for synthesizing polymer nanoparticles with unique structures.
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Nanoscience & Nanotechnology
Yen Theng Cheng, Qingbo Xia, Hongwei Liu, Marcello B. Solomon, Emma R. L. Brisson, Lewis D. Blackman, Chris D. Ling, Markus Mullner
Summary: We successfully demonstrated the synthesis of mesoporous carbon-coated anatase nanostructures using a modular approach. Through the combination of polymerization-induced self-assembly (PISA) and reversible addition-fragmentation chain-transfer (RAFT) dispersion polymerization, we fabricated uniform core-shell polymeric nanoreactors with tunable morphologies. The resulting TiO2/C materials possessed a porous structure with large specific surface areas (>85 m2/g) and various carbon contents (20-30 wt %). As anode components in lithium-ion batteries, these TiO2/C nanomaterials showed improved cycling stability, facilitated high overall capacities, and minimized capacity loss compared to their sans carbon counterparts and commercial anatase analogues.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Matthew J. Rymaruk, Cate T. O'Brien, Csilla Gyorgy, Bastien Darmau, James Jennings, Oleksandr O. Mykhaylyk, Steven P. Armes
Summary: Polymerization-induced self-assembly (PISA) is used to prepare lyotropic phases with diblock copolymer nano-objects in non-polar media. Through NMR and X-ray scattering studies, the copolymer compositions and phase transitions during benzyl methacrylate polymerization are revealed. The hexagonal cylinder phase undergoes an order-disorder transition upon heating to 150 degrees C, forming a pure hexagonally close-packed (HCP) phase upon cooling to 20 degrees C.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Polymer Science
Egor Polozov, Alexandra Grigoreva, Artem Vlasov, Sergey Zaitsev
Summary: The article discusses the application of 1-cyano-1-methylethylmethyl(4-pyridinyl)dithiocarbamate in reversible addition-fragmentation chain transfer (RAFT) polymerization of various monomers, showing good control over some monomers but slightly worse control over others. Polymers with narrow molecular weight distributions were obtained with this RAFT agent.
JOURNAL OF POLYMER RESEARCH
(2021)
Article
Polymer Science
Victor D. Lechuga-Islas, Melisa Trejo-Maldonado, Steffi Stumpf, Ramiro Guerrero-Santos, Luis Elizalde-Herrera, Ulrich S. Schubert, Carlos Guerrero-Sanchez
Summary: The 3P method is a cost-effective and versatile approach for purifying specialty polymers, demonstrating superior capability in separating volatile residues while maintaining polymer quality and suitability for automation. This method offers a promising solution for the purification of (co)polymer libraries derived from high-throughput experimentation by achieving high purification efficiency with minimal solvent usage.
EUROPEAN POLYMER JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Catia Correia, Jose Martinho, Ermelinda Macoas
Summary: Carbon dots doped with Eu3+ ions were synthesized and their interaction and luminescence properties were characterized by vibrational spectroscopy and UV-vis excitation spectroscopy. The Eu3+ ions are strongly coordinated with the carboxylate groups at the surface of the Cdots and incorporated within the nanographene network in the carbon core. The luminescence of the Cdots is strongly quenched by Hg2+ and Ag+, and a ratiometric sensor can be built using their luminescence intensities ratio.
Article
Biochemistry & Molecular Biology
Quinn A. Besford, Simon Schubotz, Soosang Chae, Ayse B. Ozdabak Sert, Alessia C. G. Weiss, Gunter K. Auernhammer, Petra Uhlmann, Jose Paulo S. Farinha, Andreas Fery
Summary: This article introduces a brush system for studying molecular transport from droplets to external polymer brushes. The study finds that molecular transport is influenced by relative humidity.
Article
Pharmacology & Pharmacy
Leonor Corte-Real, Ana Rita Bras, Adhan Pilon, Nuno Mendes, Ana Sofia Ribeiro, Tiago D. Martins, Jose Paulo S. Farinha, M. Conceicao Oliveira, Fatima Gartner, M. Helena Garcia, Ana Preto, Andreia Valente
Summary: The need for new therapeutic approaches for triple-negative breast cancer is clinically relevant. A new family of ruthenium(II) organometallic complexes was synthesized with the aim of enhancing cancer cell uptake through a multi-targeting approach. These compounds showed promising anti-cancer effects against triple-negative breast cancer cells in experimental conditions.
Article
Materials Science, Biomaterials
Carla I. M. Santos, Monica Cicuendez, Gil Goncalves, Laura Rodriguez-Perez, M. Teresa Portoles, M. Amparo F. Faustino, M. Angeles Herranz, M. Graca P. M. S. Neves, Jose M. G. Martinho, Ermelinda M. S. Macoas, Nazario Martin
Summary: In this study, the biocompatibility and safety of functionalized nanodiamonds (NDs) were investigated through the assessment of the pro-inflammatory response of RAW-264.7 macrophages exposed to new nanodiamonds@corrole hybrids. The results showed that the hybrids had no pro-inflammatory effects on the macrophage cell line, making them an ideal candidate for various biomedical applications.
JOURNAL OF MATERIALS CHEMISTRY B
(2023)
Article
Chemistry, Physical
Barbara Casteleiro, Jose Manuel Gaspar Martinho, Jose Paulo Sequeira Farinha
Summary: In this study, we encapsulated Au25(MHA)18 nanoclusters into methacrylate polymer nanoparticles (PNPs) with a diameter of approximately 50 nm. The time evolution of these structures in aqueous dispersion showed the formation of gold nanoparticles (AuNPs) with a diameter of approximately 4 nm, resulting in a 2-fold emission amplification of the AuNCs due to the plasmon's field enhancement effect. The optical properties of the PNPs were unchanged upon drying due to negligible diffusion of AuNCs inside the PNPs in the absence of solvent.
COLLOID AND INTERFACE SCIENCE COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Goncalo Valente, Maria Esteve-Rochina, Sergio P. C. Alves, Jose M. G. Martinho, Enrique Orti, Joaquin Calbo, Filipe A. Almeida Paz, Joao Rocha, Manuel Souto
Summary: This study presents an innovative synthesis method for producing highly crystalline and stable perylene-based coordination polymers. The materials have tunable optical and electrochemical properties, and exhibit high stability in the solid state.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Wei-Jian Xu, Mao-Fan Li, Ana R. Garcia, Konstantin Romanyuk, Josee M. G. Martinho, Pavel Zelenovskii, Alexander Tselev, Luis Verissimo, Wei-Xiong Zhang, Xiao-Ming Chen, Andrei Kholkin, Joao Rocha
Summary: The design and synthesis of a new metal-nitrosyl ferroelectric crystal (DMA)(PIP)[Fe(CN)(5)(NO)] with potential phototunable polarization via a dual-organic-cation molecular design strategy is reported. The crystal exhibits a large polarization and a high Curie temperature, and the reversible photoisomerization of the nitrosyl ligand is accomplished by light irradiation. The optical accessibility and controllability of different ferroelectric states via photoinduced nitrosyl linkage isomerization present a new and attractive route to optically controllable macroscopic polarization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Pharmacology & Pharmacy
Giorgia Figari, Jose L. M. Goncalves, Herminio P. Diogo, Madalena Dionisio, Jose Paulo Farinha, Maria Teresa Viciosa
Summary: The impact of surface functionalization on mesoporous silica nanoparticle (MSN) carriers and the release of Fenofibrate (FNB) was investigated. The MSNs were modified with either (3-aminopropyl) triethoxysilane (APTES) or trimethoxy(phenyl)silane (TMPS), and the density of the functional groups was measured. The FNB loaded in the MSNs with ordered cylindrical pores showed amorphization, and the glass transition temperature slightly changed depending on the surface modification. Dielectric studies revealed multiple relaxations associated with different FNB populations and correlated their mobility with drug release profiles.
Article
Nanoscience & Nanotechnology
Barbara Casteleiro, Fernande Da Cruz-Boisson, Pierre Alcouffe, Sandra N. Pinto, Jose M. Gaspar Martinho, Marie-Therese Charreyre, Jose Paulo Sequeira Farinha, Arnaud Favier
Summary: This study reports the synthesis of biocompatible poly(N-acryloyl morpholine) (PNAM) surface-modified gold nanoclusters (AuNCs) with a diameter under 2 nm and near-infrared photoluminescence. Compared with AuNCs stabilized by small ligands, the PNAM-AuNCs exhibit better colloidal stability, increased photoluminescence lifetimes, and enhanced quantum yields. Furthermore, the properties of these PNAM-AuNCs can be successfully tuned using PNAM chains with different molecular weights. These PNAM-AuNCs provide an excellent platform for the development of bioimaging probes without organic dyes.
ACS APPLIED NANO MATERIALS
(2023)
Article
Chemistry, Applied
Carla I. M. Santos, Ana M. Santiago, Ana R. L. Araujo, Sandra Pinto, Rafaela R. Agostinho, Sonia Simao, Tomas P. Azevedo, Catarina Antunes, M. Amparo F. Faustino, Ines M. Araujo, M. Grada P. M. S. Neves, Jose M. G. Martinho, Ermelinda M. S. Macoas
Summary: In this study, three fluorescent probes were developed for the detection of hydrogen sulfide (H2S) using gallium (III) corrole complexes. The probes were designed with nitro groups at the beta-pyrrolic positions. The compounds CGa-NO2 and CGa-2NO2 showed response to H2S, while CGa-EtNO2 acted as a turn-off probe. Mechanistic studies revealed that H2S coordination with gallium(III) and reduction of nitro group to aminated corrole were involved in the interaction. The probes exhibited potential for ratiometric sensing of H2S in non-aqueous solutions and demonstrated response to H2S in HeLa cells.
Review
Polymer Science
Jose Paulo Sequeira Farinha
Summary: This review discusses strategies for preparing high-performance emissive polymer nanomaterials with high brightness and photostability, including designing polymer nanomaterials carrying multiple fluorescent dyes and increasing the brightness of each individual dye.
Article
Polymer Science
Barbara Casteleiro, Mariana Rocha, Ana R. Sousa, Andre M. Pereira, Jose M. G. Martinho, Clara Pereira, Jose P. S. Farinha
Summary: Gold nanoclusters (AuNCs) with fluorescence in the Near Infrared (NIR) were incorporated in mesoporous silica nanoparticles (MSNs) using a one-pot synthesis procedure, resulting in nanocomposite particles with simultaneous NIR fluorescence and superparamagnetic properties, which have high potential for application in multimodal bioimaging.
Article
Polymer Science
Yuanzhang Jiang, Xuyi Wang, Yanting Han, Dakai Gong, Yingchun Gu, Lin Tan
Summary: In this study, FeCl3 and poly(acrylic acid) (PAA) were doped into waterborne polyurethanes (WPUs) to create multifunctional materials with self-healing and antimicrobial properties. WPU/Fe/PAA-5.5, containing 5.5 wt % PAA, exhibited excellent mechanical properties, strong self-healing capabilities, and an impressive antimicrobial rate of over 90%. These supramolecular films were also highly recyclable through hot-pressing.
Article
Polymer Science
Longyu Tian, Min Wang, Guangming Liao, Baoliang Liu, Sujuan Zhang, Yucheng Sun, Zhen Meng, Jintao Zhang, Zaijun Lu
Summary: Two kinds of benzoxazine monomers were synthesized and used to prepare polybenzoxazine anion exchange membranes (AEMs) with quaternary ammonium functionalization. The LQPBZ AEM exhibited better ion conductivity and alkaline stability.
Article
Polymer Science
Claire A. Lemarchand
Summary: This study investigates the shock behavior of three different polymers through molecular dynamics simulations. The results reveal specificities in the shock behavior of polymers, including deviations from the linear relation between shock velocity and particle velocity, as well as differences in shear stress relaxation behind the shock front. It is found that the deviation of the Hugoniot locus is related to the change in the relative contribution of bonding and non-bonding potential energies, while polymers with higher glass transition temperatures exhibit slower shear stress relaxation.
Article
Polymer Science
Zengquan Liu, Xiaochun Yin, He Zhang, Shuo Gao, Qinglin Kuang, Yanhong Feng
Summary: A powder solid-state extension (PSSE) technology was proposed to address the high melt viscosity issue of UHMWPE. By uniaxial extension and sintering in the solid state, a highly self-reinforced material was prepared. X-ray diffraction and scattering techniques were used to study the structural evolution during the PSSE process, and a solid-phase induced transformation model was established.
Article
Polymer Science
Zhike Li, Anyu Luo, Rui Zhou, Xin Li, Haiyan Li
Summary: A novel high temperature resistance IL@SiO2 nanocapsules were successfully prepared and their friction and wear properties in PA6 composites were studied. The addition of IL@SiO2 nanocapsules reduced the friction coefficient and wear rate without affecting the mechanical properties of PA6. The synergy between the IL core and SiO2 wall in the nanocapsules improved the self-lubricating performance of the PA6 composites.
Article
Polymer Science
Xin Liu, Xuhong Guo, Qi Liao
Summary: In this study, an algorithm for accurately estimating viscosity is developed using molecular dynamics simulations and the Green-Kubo formula. This algorithm can be applied to complex systems with long correlations, such as macromolecular and biological simulation systems.
Article
Polymer Science
Hao Pu, Yun-Lei Hou, Jing -Zhou Chen, Dong -Lin Zhao
Summary: The use of modified graphene improves the interfacial adherence of carbon fibers to epoxy resin, resulting in enhanced interfacial and bending properties of CF and matrix in CF/EP composites, as well as increased interlaminar shear strength and flexural strength.
Article
Polymer Science
Wei-Chung Ke, Jin-Wei Lin, Manohar Reddy Busireddy, Yueh-Hsing Lee, Jiun-Tai Chen, Chain-Shu Hsu
Summary: This study introduces a crosslinkable monomer, TAIC, to synthesize three crosslinked polyimide films, which exhibit improved thermal, mechanical, and dielectric properties. The introduction of TAIC enhances the tensile strength, reduces the dielectric constant and dielectric loss, and decreases the coefficient of thermal expansion of the polyimide films.
Article
Polymer Science
Alex Kwasi Kumi, Ruiling Fan, Ye Chen, Yumei Zhang
Summary: The difference in leaching of amylopectin from cellulose/amylopectin/1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) blends during regeneration in water and aqueous ethanol has been studied. Molecular dynamics simulations showed that the dissolution and regeneration mechanisms of amylopectin in [Bmim][Cl] are similar to cellulose in ionic liquids. Water regeneration leads to weak electrostatic interactions, resulting in high leaching of amylopectin. In contrast, ethanol-water interactions enhance electrostatic interactions among amylopectin chains, limiting amylopectin leaching in aqueous ethanol.
Article
Polymer Science
Xi Zeng, Junwei Zhou, Junbiao Peng, Chunsheng Zhang, Danling Wang, Yihu Song, Qiang Zheng
Summary: This study utilizes an oligomer deep eutectic solvent (DES) based on polyethylene glycol to regulate the vulcanization kinetics of rubber. The results show that the DES can accelerate vulcanization at low temperatures without affecting the crosslinking density and Mullins effect.
Article
Polymer Science
Qianqian Yue, Yongfei Peng, Xingjian Liu, Aihua He, Huarong Nie
Summary: The addition of metal deactivators can effectively suppress the aging of TBIR, prolong its lifespan, and have no negative effects on its physical and processing properties. These research findings are of great importance for improving the stability and aging resistance of polymers.
Article
Polymer Science
J. Gomez-Caturla, J. Ivorra-Martinez, R. Tejada-Oliveros, V Moreno, D. Garcia-Garcia, R. Balart
Summary: This work focuses on the development of environmentally friendly PLA formulations by using different esters derived from geraniol as plasticizers. The results show that these esters have good compatibility with PLA, and they can effectively enhance the elongation and plasticity of PLA, reduce its glass transition temperature, and slightly improve its water absorption capabilities.
Article
Polymer Science
Dandan Li, Zhaohui Lu, Zhao Ke, Ke Xu, Fengna Dai, Youhai Yu, Guangtao Qian, Chunhai Chen
Summary: In this study, cross-linked PI aerogel membranes with low dielectric constant and high moisture resistance were prepared by co-polymerization and scraping coating technology. The incorporation of fluorinated blocks and benzimidazole ring structures resulted in novel PI aerogel membranes with fascinating dielectric properties and outstanding moisture resistance.
Article
Polymer Science
Zhaoyang Chu, Qing Zhang, Haihua Luo, Han Zhou, Fapei Zhang, Wei Chen, Wenhua Zhang
Summary: Multi-physical fields solution processing strategy is a universal and facile method for preparing various conjugated polymer films and high-performance devices. In this study, we employed a combined microfluidic flow and ultrasonication strategy (FU) for processing CP solutions, and found a pronounced synergetic effect in promoting the pre-ordering of chains in solution. The conformation order and anisotropy of the solution were revealed through various characterizations. A non-classical nucleation model for polymer crystallization in non-equilibrium solution processing was confirmed. The roles of microfluidic flow and ultrasonication in chain aggregation and crystallization were addressed through multi-physical simulations. Compared to pristine solutions, the FU strategy showed improved solution anisotropy and crystallization kinetics, resulting in higher crystallinity in films and increased mobilities in OFET devices. The FU processing strategy provides a universal approach for regulating chain conformation and aggregation in conjugated polymer solutions.