Article
Multidisciplinary Sciences
A. Carrere, J. d'Alessandro, O. Cochet-Escartin, J. Hesnard, N. Ghazi, C. Riviere, C. Anjard, F. Detcheverry, J. -p. Rieu
Summary: This study discovers that living cells can spontaneously self-assemble into finite-sized domains, similar to the microphase separation in inert matter.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Gue Seon Lee, Hyo Won Lee, Hyun Sub Lee, Taeyang Do, Jean-Louis Do, Jeewoo Lim, Gregory Peterson, Tomislav Friscic, Jeung Gon Kim
Summary: Ruthenium-alkylidene initiated ring-opening metathesis polymerization has been successfully achieved under solid-state conditions using a mechanochemical ball milling method. This method offers a green approach and expands the range of mechano-exclusive products. The Grubbs 3(rd)-generation complex based on carbene and pyridine catalysts outperforms other catalysts and retains similar mechanistic features as solution-phase reactions. High-speed ball milling provides sufficient mixing and energy to minimize or eliminate the use of solvents. The addition of a small amount of liquid additive enables the synthesis of high-molecular-weight polymers by minimizing chain-degradation.
Article
Chemistry, Multidisciplinary
Panpan Li, Jesse L. Davis, Jimmy W. Mays, Xu Wang, S. Michael Kilbey
Summary: Chain exchange behaviors in self-assembled block copolymer nanoparticles at room temperature were investigated. Structural differences between parent and binary systems of the nanoparticles were observed, especially in a blend of triblock and star copolymer nanoparticles. Chemical crosslinking was found to suppress chain exchange between the nanoparticles and freeze the nanostructures at a specific copolymer crosslinking density.
FRONTIERS IN CHEMISTRY
(2022)
Article
Polymer Science
Ankita Mandal, Indradip Mandal, Andreas F. M. Kilbinger
Summary: Single chain transfer agents are used to synthesize narrowly distributed heterotelechelic ROMP polymers in one pot, exploiting a new mechanistic and synthetic approach. The strategy allows for excellent control over molecular weight and dispersity of the resulting polymers, showcasing a straightforward and efficient method for synthesizing heterotelechelic ROMP polymers.
Review
Polymer Science
Lin-Lin Xiao, Xu Zhou, Kan Yue, Zi-Hao Guo
Summary: Conjugated block copolymers (cBCPs) are promising materials with high conductivity and morphological versatility, making the study of their self-assembly behaviors crucial for enhancing device performance.
Article
Polymer Science
Kenneth P. Mineart, William W. Walker, Joaquin Mogollon-Santiana, Ian A. Coates, Cameron Hong, Byeongdu Lee
Summary: Loaded polymer gels, which include nanocarrier domains like micelles and vesicles, are important materials in controlled release science. By using block copolymer self-assembly, these gels can form a physically-crosslinked network, providing a rich nanoscale phase space for property tuning. The study focuses on nanocarrier-loaded block copolymer organogels formed by AOT reverse micelles, styrenic ABA triblock copolymers, and aliphatic mineral oil, presenting a detailed nanostructural analysis and demonstrating micelle release and tensile response.
Article
Polymer Science
Inna O. Lebedeva, Ekaterina B. Zhulina, Oleg V. Borisov
Summary: Research indicates that block copolymers with chemically different bottlebrush blocks can self-assemble into nanostructures resembling micelles in selective solvents. The self-consistent field theoretical approach is utilized to predict the relationship between structural parameters of bottlebrush blocks and properties of micelles, including critical micelle concentration. Theoretical predictions suggest that replacing linear blocks with bottlebrush ones of the same polymerization degrees leads to changes in micellar core size and corona extension, as well as an increase in critical micelle concentration, which are in agreement with computer simulation results.
Article
Chemistry, Multidisciplinary
Qiuya Zhang, Mengfan Lu, Hanyu Wu, Lu Zhang, Xunda Feng, Zhaoxi A. Jin
Summary: In this study, inverse micellar nanostructures with open channels were successfully generated using a modified solvent exchange method. The addition of D-tartaric acid induced the formation of mesoporous spheres with regularly packed perpendicular cylindrical channels and subsequently mesoporous spheres with gyri-like open pores. The findings provide a simple and economical pathway for fabricating hexasomes with open channels, which could be beneficial for their further applications.
Article
Polymer Science
Hao Zhang, Zhou Zhou, Xiaofan Chen, Bo Yu, Zhenyang Luo, Xiang Li, Md Anisur Rahman, Ye Sha
Summary: Sequence-controlled organometallic polymers with side-chain metal functions such as ferrocene and ruthenocene have been prepared through regioselective ring-opening metathesis polymerization (ROMP). The properties of these polymers can be finely tailored by the metallocene sequence along the polymer chain, providing fundamental understanding of the structure-property relationship. This highly efficient chain-growth polymerization is expected to incorporate a variety of metal moieties into a single organometallic polymer for potential applications in electrochemical sensing, information processing, and magnetic materials.
Article
Biochemistry & Molecular Biology
Sudhir Ravula, Kathryn E. O'Harra, Keith A. Watson, Jason E. Bara
Summary: This study investigates the incorporation of ionic liquids (ILs) into poly(norbornene) to create unique materials with synergistic properties. By synthesizing different types of norbornene-based imidazolium-based ILs and using polymerization reactions, high molecular weight block copolymers were obtained. The resulting membranes displayed good gas separation performance.
Article
Chemistry, Multidisciplinary
Indradip Mandal, Ankita Mandal, Md Atiur Rahman, Andreas F. M. Kilbinger
Summary: In this study, the metathesis activity of conjugated 1,3 diene derivatives in ring opening metathesis polymerization (ROMP) using Grubbs' 3rd generation catalyst (G3) was investigated. Monosubstituted 1,3 dienes showed similar reactivities towards G3-alkylidenes as norbornene derivatives, making them suitable for chain transfer agents in catalytic ROMP. This unprecedented reactivity allowed for the synthesis of mono-end-functional poly(norborneneimide)s on a large scale. Additionally, more complex architectures such as star-shaped polymers could be synthesized catalytically via ROMP. This method was also utilized for the synthesis of ROMP block copolymers and ROMP-PEG diblock copolymer.
Article
Polymer Science
Toshiki Sonoda, Shingo Kobayashi, Masaru Tanaka
Summary: The successful utilization of regioselective ring-opening metathesis polymerization to synthesize polymers modified with tertiary amino groups has demonstrated unique properties in hydration, crystallization, and coating stability under physiological aqueous environment.
Article
Polymer Science
Samantha J. Scannelli, Mohammed Alaboalirat, Diego Troya, John B. Matson
Summary: Ring-opening metathesis polymerization (ROMP) mediated by Grubbs' third-generation catalyst (G3) is widely used to make bottlebrush polymers. This study investigated the effect of anchor groups on the livingness of ROMP, finding a positive correlation between anchor group energy levels and reaction rate constants, suggesting different degrees of livingness among the anchor groups.
Article
Chemistry, Multidisciplinary
Jianan Yuan, Xuemin Lu, Qingxiang Li, Zhiguo Lu, Qinghua Lu
Summary: This study fabricated micrometer-scale spiral structures with reversible chirality based on the assembly of a liquid crystalline block copolymer film assisted by enantiopure tartaric acid. The chiral spiral structures with controllable handedness were easily erased under ultraviolet light irradiation and restored via thermal annealing. This research provides guidance for fabrication of chiral micrometer-scale spiral structures with adjustable chiral properties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jared I. Bowman, Cabell B. Eades, Maria A. Vratsanos, Nathan C. Gianneschi, Brent S. Sumerlin
Summary: Polymerization-induced self-assembly (PISA) is a powerful technique for producing block copolymer nanostructures, and ultrafast photoiniferter PISA can be used to quickly create various nanostructures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Yann K. Petit, Eleonore Mourad, Christian Prehal, Christian Leypold, Andreas Windischbacher, Daniel Mijailovic, Christian Slugovc, Sergey M. Borisov, Egbert Zojer, Sergio Brutti, Olivier Fontaine, Stefan A. Freunberger
Summary: This study elucidates the mechanism of mediated peroxide and superoxide oxidation, explaining how redox mediators affect the generation of O-1(2). Charging begins with peroxide oxidation to a superoxide intermediate, and oxidation potentials above 3.5 V drive O-1(2) evolution from superoxide oxidation, while disproportionation produces some O-1(2).
Article
Chemistry, Organic
Susanne M. Fischer, Simon Renner, A. Daniel Boese, Christian Slugovc
Summary: Electron-rich triarylphosphines exhibit superior catalytic performance in oxa-Michael additions, especially for converting poor and intermediate Michael acceptors as well as less acidic alcohols. The affinity between the phosphines and Michael acceptors, as well as the acidity of alcohols, have significant impacts on reaction speed. Additionally, the oxidation stability of the phosphines plays a role in their performance.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Analytical
I Dalfen, T. Burger, C. Slugovc, S. M. Borisov, I Klimant
Summary: Optical oxygen sensors based on various immobilized oxygen indicators in microparticles were studied under high hydrostatic pressure, revealing that all porous materials remained stable under elevated pressure. While the actual oxygen concentration did not change with increasing pressure, the sensors showed a significant decrease in calculated oxygen concentration, which was reversible.
SENSORS AND ACTUATORS B-CHEMICAL
(2022)
Article
Chemistry, Multidisciplinary
Bettina Schafzahl, Astrid C. Knall, Christian Slugovc
Summary: This study demonstrates the synthesis of pyridazines bearing three different substituents using the iEDDA reaction, and presents the second order rate constants for reactions with different dienophiles.
MONATSHEFTE FUR CHEMIE
(2022)
Article
Chemistry, Physical
Sebastijan Kovac, Bettina Schafzahl, Nadejda B. Matsko, Katharina Gruber, Martin Schmuck, Stefan Koller, Stefan A. Freunberger, Christian Slugovc
Summary: This work demonstrates the potential of pDCPD-based foams and hierarchically porous carbons as lightweight, tough, and stable matrix materials. The carbon foams exhibit uniform shrinkage, high porosity, and conductivity, while preserving the porous structure and 3D interconnectivity during carbonization. These materials show outstanding performance in Li-O2 batteries.
ACS APPLIED ENERGY MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Katharina Gallas, Dominik Wohlmuth, Zhiquan Li, Aliasghar Ajami, Aleksandr Ovsianikov, Robert Liska, Christian Slugovc
Summary: This study reports the synthesis of two dye-labeled azides through de-symmetrization using a copper (I)-catalyzed alkyne-azide cycloaddition (CuAAC) method. Dansyl derivative and perylene diimide derivative with alkyne functional groups were employed as the fluorescent dyes. The photo-physical properties of these dye dyads were described, and their performance in multi-photon grafting onto polyethylene glycol-based hydrogels was investigated. It was found that the dansyl-conjugated BAC derivative was suitable for multi-photon grafting with lasers operating at 800 nm, while the perylene diimide-bearing dye did not yield the desired result.
MONATSHEFTE FUR CHEMIE
(2023)
Article
Polymer Science
Karin Ratzenboeck, Johanna M. Uher, Susanne M. Fischer, David Edinger, Viktor Schallert, Ema Zagar, David Pahovnik, Christian Slugovc
Summary: One way to obtain recyclable polymeric materials is by incorporating reversible bonds in the polymers. This study investigates the reversibility of the oxa-Michael reaction in simple model systems, linear polymers, and polymer networks, and explores its scope and limitations. The results demonstrate that the retro oxa-Michael reaction of sulfone, acrylate, or acrylonitrile based adducts is fast at elevated temperatures (>100 degrees C) when Bronsted bases, such as KOH, are used as catalysts. Under these conditions, alcohols can be easily exchanged in oxa-Michael adducts within minutes. Furthermore, poly(ether)s derived from oxa-Michael reactions can depolymerize into small fragments in the presence of alcohols and exhibit self-healing properties in networks.
Article
Chemistry, Multidisciplinary
Sebastijan Kovacic, Katharina Gruber, Bernd Fuchsbichler, Martin Schmuck, Christian Slugovc
Summary: In this article, the authors demonstrate the fabrication of thin and macroporous carbon coatings on metal substrates using a combination of emulsion-templating and the doctor-blade method. The resulting carbon coatings retain a highly porous architecture and flexibility. These coatings can be used to create cathodes with high sulfur loadings for use in lithium-sulfur cells, without the need for binders or conductive fillers.
MONATSHEFTE FUR CHEMIE
(2023)
Review
Chemistry, Multidisciplinary
Karin Ratzenboeck, Susanne M. Fischer, Christian Slugovc
Summary: Poly(ethers) are an important class of polymers, which can be formed by ring-opening polymerization, Williamson ether synthesis, or self-condensation of alcohols. The oxa-Michael reaction provides another method to synthesize poly(ethers) with additional functional groups in the polymer backbone. However, research on oxa-Michael polymerization is still limited. In this article, we discuss the principles, synthesis, and preparation of various poly(ethers) and also highlight the challenges and future perspectives of oxa-Michael polymerization.
MONATSHEFTE FUR CHEMIE
(2023)
Article
Polymer Science
Susanne M. Fischer, Viktor Schallert, Johanna M. Uher, Christian Slugovc
Summary: In this study, we propose a method for preparing crosslinked polymers from off-stoichiometric oxa-Michael formulations, by a self-limiting base catalyzed reaction between difunctional Michael acceptors and substoichiometric amounts of diols, followed by anionic polymerization of the remaining vinyl groups. The properties of the resulting polymers can be easily tuned by varying the amount of diols.
Article
Chemistry, Physical
Susanne M. Fischer, Petra Kaschnitz, Christian Slugovc
Summary: The performance of the strong Lewis base TTMPP in catalyzing oxa-Michael reactions is assessed and compared with other arylphosphines and a Bronsted base. The study demonstrates that TTMPP shows superiority over other arylphosphine based Lewis bases and comparable activity to the benchmark catalyst. TTMPP is also capable of catalyzing oxa-Michael polymerization reactions of diacrylates and diols.
CATALYSIS SCIENCE & TECHNOLOGY
(2022)
Article
Materials Science, Multidisciplinary
Tobias Burger, Miriam de J. Velasquez-Hernandez, Robert Saf, Sergey M. Borisov, Christian Slugovc
Summary: Core-shell and multivariant metal-organic frameworks of the PCN-224 type, prepared using metal-free and metalated porphyrin building blocks, exhibit efficient gas transport and oxygen quenching. However, the contribution of the phosphorescent component is diminished in all mixed MOFs due to undesirable energy transfer, except for the physical mixture of individual crystals used as a reference.
JOURNAL OF MATERIALS CHEMISTRY C
(2022)
Article
Chemistry, Multidisciplinary
Karin Ratzenboeck, Mir Mehraj Ud Din, Susanne M. Fischer, Ema Zagar, David Pahovnik, A. Daniel Boese, Daniel Rettenwander, Christian Slugovc
Summary: Using water as a monomer in polymerization reactions is a sustainable strategy. The oxa-Michael polyaddition of water and divinyl sulfone demonstrates high yield polymerization in an interfacial reaction under nucleophilic or base catalysis at room temperature. The resulting polyethersulfone is then applied as a solid polymer electrolyte, showing excellent oxidative stability and conductivity.
Article
Materials Science, Multidisciplinary
Tobias Burger, Christian Winkler, Irene Dalfen, Christian Slugovc, Sergey M. Borisov
Summary: The optical oxygen sensing capabilities of porphyrin-based metal-organic frameworks were studied, revealing high oxygen permeability and bimolecular quenching constants. The frameworks showed exceptional gas transport, large pore sizes, and effective isolation of the sensing indicators. These materials have potential applications in detecting oxygen in trace and ultra-trace ranges.
JOURNAL OF MATERIALS CHEMISTRY C
(2021)
Article
Materials Science, Multidisciplinary
David Edinger, Hansjoerg Weber, Ema Zagar, David Pahovnik, Christian Slugovc
Summary: The melt polymerization of acrylamide initiated by nucleophiles allows for the preparation of polyamide 3 (PA 3) with a branching factor of about 1.5. The high share of branching units imparts a fully amorphous morphology featuring a low glass-transition temperature of 67 degrees C and renders the polymer water-soluble. The polymerization mechanism can be considered as an aza-Michael polymerization involving zwitterionic species as key intermediates, with the highest branching obtained at 83 degrees C.
ACS APPLIED POLYMER MATERIALS
(2021)
