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Aromatic carboxylic acids are prone to decarboxylate in high-temperature water (HTW). While the decarboxylation kinetics of several aromatic carboxylic acids have been explored, studies on their compatibility with organic syntheses in HTW are scarce. Herein, we report the hydrothermal synthesis (HTS) of 2,3-diarylquinoxaline carboxylic acids from 1,2-diarylketones and 3,4-diaminobenzoic acid. A detailed study of the reaction parameters was performed to identify reaction conditions towards minimal decarboxylation. Thirteen 2,3-diarylquinoxaline-6-carboxylic acids are obtained at temperatures between 150–230 °C within 5–30 minutes. The reported conditions feature comparable performance to those of classic syntheses, avoiding volatile organic solvents, strong acids and toxic catalysts. Decarboxylated quinoxalines arise as side products in variable amounts via direct decarboxylation of the 3,4-diaminobenzoic acid. To completely inhibit the decarboxylation, we show that suitable structural analogues of 3,4-diaminobenzoic acid can act as starting compounds. Thus, ester hydrolysis of methyl 3,4-diaminobenzoate and deprotection of di-Boc-protected 3,4-diminobenzoic can be coupled with the HTS of quinoxaline towards quinoxaline carboxylic acids, while fully avoiding decarboxylated side products.

Energy storage will be a primordial actor of the ecological transition initiated in the energy and transport sectors. As such, innovative approaches to design high-performance electrode materials are crucial for the development of the next generation of batteries. Herein, a novel dual redox-active and porous polyimide network (MTA-MPT), based on mellitic trianhydride (MTA) and 3,7-diamino-N-methylphenothiazine (MPT) monomers, is proposed for applications in both high energy density lithium batteries and symmetric all-organic batteries. The MTA-MPT porous polyimide was synthesized using a novel environmentally-friendly hydrothermal polymerization method. Rooted in its dual redox proprieties, the MTA-MPT porous polyimide exhibits a high theoretical capacity making it a very attractive cathode material for high energy density battery applications. The cycling performance of this novel electrode material was assessed in both high energy density lithium batteries and light-weight symmetric all-organic batteries, displaying excellent rate capability and long-term cycling stability. N. Goujon acknowledges the funding from the European Union's Horizon 2020 framework programme under the Marie Sklodowska-Curie agreement No. 101028682. M. Lahnsteiner, H. M. Moura, D. A. Cerron-Infantes and M. M. Unterlass acknowledge funding through the Austrian Science Fund's (FWF) START programme under grant no. Y1037-N28. We thank Dr Jerpme Roeser and Prof. Arne Thomas (TU Berlin) for gas sorption measurements.

Herein, we synthesized a series of siloxane-based poly(ionic liquid)s (PILs) with imidazolium-type species in the main chain via the multicomponent Debus–Radziszewski reaction. We employed oligodimethylsiloxane diamine precursors to integrate flexible spacers in the polymer backbone and ultimately succeeded in obtaining main-chain PILs with low glass transition temperatures (Tgs) in the range of −40 to −18 °C. Such PILs were combined with conventional hydrophobic vinylimidazolium-based PILs for the fabrication of porous membranes via interpolyelectrolyte complexation with poly(acrylic acid), which leads to enhanced mechanical performance in the tensile testing measurements. This study will enrich the structure library of main-chain PILs and open up more opportunities for potential industrial applications of porous imidazolium-based membranes. published

Noble metal nanoparticles anchored on flexible polyurethane foams were synthesized by hydrothermal synthesis. Through employing a robotic arm, these ‘catalytic sponges’ were used for organic reductions towards automated lab-scale organic synthesis.

Herein, we report a simple and versatile synthetic approach towards siloxane-based poly(ionic liquid)s (PILs) with unusually low glass transition temperatures (Tg) down to −73°C, and thus “liquid-like” behavior at room temperature. We designed a polydimethylsiloxane-derived copolymer carrying dialkylimidazolium moieties, and by careful selection of the side-chain length and the type of anions we were able to manipulate its Tg over a wide range and reach high ionic conductivities (σDC) up to 4.8 × 10−5 S/cm at 300 K. The ionized species make up only a minor fraction (

A simple route for the in-situ orientation of carbon nanofillers applied during the curing process of a carbon fiber reinforced polymer (CRFP) in a hot press, is demonstrated. Neat MWCNT, amine-functionalized MWCNT (MWCNT-NH2) and CNF were dispersed in an epoxy resin using a three-roll-mill (TRM) to ensure good dispersion. The process leads to a hierarchically structured functional composite where MWCNT/CNF are aligned in the z-direction (out-of-plane) of the carbon fiber plies, giving rise to improved mechanical and electrical performance. Our results demonstrate that aligned carbon nanofillers yield significantly more pronounced improvements than non-oriented fillers. An applicable processing route towards advanced functional composite materials with major practical importance is presented in this study.

Here, the hydrothermal synthesis (HTS) of 2,3‐diarylquinoxalines from 1,2‐diketones and o‐phenylendiamines (o‐PDAs) was achieved. The synthesis is simple, fast, and generates high yields, without requiring any organic solvents, strong acids or toxic catalysts. Reaction times down to 90 % in all cases). Moreover, it was shown that HTS has high compatibility: (i) hydrochlorides, a standard commercial form of amines, could be used directly as combined amine source and acidic catalyst, and (ii) Boc‐diprotected o‐PDA could be directly employed as substrate that underwent HT deprotection. A systematic large‐scale computational comparison of all reported syntheses of the presented quinoxalines from the same starting compounds showed that this method is more environmentally friendly and less toxic than all existing methods and revealed generic synthetic routes for improving reaction yields. Finally, the application of the synthesized compounds as fluorescent dyes for cell staining was explored., In hot water: 2,3‐Diarylquinoxalines and biquinoxalines are synthesized in a rapid, efficient and green fashion in nothing but high‐temperature water. Through a large‐scale computational analysis, the herein reported reaction conditions are compared with all reported syntheses of the presented compounds.

In this work, a novel class of fully organic, lightweight composite materials was prepared by incorporating highly crystalline, hydrothermally synthesized poly(p-phenylene pyromellitimide) (PPPI) microparticles into a commercial epoxy matrix. Particle loadings of up to 15 vol% could be achieved. Microstructural, mechanical, and thermal properties of these composites were investigated by scanning electron microscopy, three-point bending and Vickers hardness testing, dynamic mechanical analysis, nanoindentation, and thermogravimetric analysis. The incorporation of the PPPI filler particles into the epoxy matrix was found to be homogeneous. Powder X-ray diffraction shows that PPPI's crystallinity is retained in the composites, and infrared spectroscopy indicates a covalent bonding of PPPI to the epoxy matrix. Flexural modulus and storage modulus were increased by the PPPI addition, while the flexural strain at break was reduced. In contrast to that, the flexural strength remained unaffected by the incorporation of PPPI filler particles. Raising the filler content also resulted in an improvement of hardness. Furthermore, a decrease in glass-transition temperature with increasing PPPI content was observed, as well as a pronounced increase in thermal stability of the composites in comparison to the unfilled cured epoxy resin. These results indicate the high potential of this new class of composites with prospective applicability e.g. in the fields of sports equipment, aerospace, and automotive technology. published

We report on the hydrothermal polymerization (HTP) of polyimide (PI) networks using the medium H2O and the comonomers 1,3,5-tris(4-aminophenyl)benzene (TAPB) and pyromellitic acid (PMA). Full condensation is obtained at minimal reaction times of only 2 h at 200 °C. The PI networks are obtained as monoliths and feature thermal stabilities of >500 °C, and in several cases even up to 595 °C. The monoliths are built up by networks of densely packed, near-monodisperse spherical particles and annealed microfibers, and show three types of porosity: (i) intrinsic inter-segment ultramicroporosity (48 h), also PI/SiO2 hybrids that form through reaction with the reaction vessel. Moreover, we have developed a computational image analysis pipeline that deciphers the complex morphologies of these SEM images automatically and also allows for formulating a hypothesis of morphology development in HTP that is in good agreement with the manual morphology analysis. Finally, we upscaled the HTP of PI(TAPB–PMA) and processed the resulting powder into dense cylindrical specimen by green solvent-free warm-pressing, showing that one can follow the full route from the synthesis of these PI networks to a final material without employing harmful solvents., We report on the hydrothermal polymerization (HTP) of porous polyimide (PI) networks using the medium H2O and the comonomers 1,3,5-tris(4-aminophenyl)benzene (TAPB) and pyromellitic acid (PMA).

No abstract available. published

Various polyimides and polyamides have recently been prepared via hydrothermal synthesis in nothing but H2O under high‐pressure and high‐temperature conditions. However, none of the prepared polymers feature a truly conjugated polymer backbone. Here, we report on an expansion of the synthetic scope of this straightforward and inherently environmentally friendly polymerization technique to the generation of conjugated polymers. Selected representatives of two different polymer classes, pyrrone polymers and polybenzimidazoles, were generated hydrothermally. We present a mechanistic discussion of the polymer formation process as well as an electrochemical characterization of the most promising product., In hot water: The scope of hydrothermal polymerization has been expanded. Pyrrone polymers and polybenzimidazoles can now be generated in high‐temperature water by a straightforward one‐step synthesis.

Biogenic metal oxides (MxOy) feature structures as highly functional and unique as the organisms generating them. They have caught the attention of scientists for the development of novel materials by biomimicry. In order to understand how biogenic MxOy could inspire novel technologies, we have reviewed examples of all biogenic MxOy, as well as the current state of understanding of the interactions between the inorganic MxOy and the biological matter they originate from and are connected to. In this review, we first summarize the origins of the precursors that living nature converts into MxOy. From the point-of-view of our materials chemists, we present an overview of the biogenesis of silica, iron and manganese oxides, as the only reported biogenic MxOy to date. These MxOy are found across all five kingdoms (bacteria, protoctista, fungi, plants and animals). We discuss the key molecules involved in the biosynthesis of MxOy, the functionality of the MxOy structures, and the techniques by which the biogenic MxOy can be studied. We close by outlining the biomimetic approaches inspired by biogenic MxOy materials and their challenges, and we point at promising directions for future organic-inorganic materials and their synthesis. published

Hochkondensierte, vollständig konjugierte aromatische Verbindungen sind interessante Kandidaten zur Anwendung in organischer Elektronik. Mit steigender Kristallinität verbessern sich ihre elektronischen Eigenschaften. Hier wird gezeigt, dass die Kristallisation von drei Archetypen solcher Moleküle – Pentacentetron, Indigo und Perinon – hydrothermal erreicht werden kann. Dieser Befund ist angesichts der Strukturen dieser Verbindungen höchst erstaunlich. Darüber hinaus wird gezeigt, dass Perinon ausgehend von Naphthalinbisanhydrid und o-Phenylendiamin in ausschließlich hochtemperiertem Wasser und ohne Zusatz von Cosolventien oder Katalysatoren hergestellt werden kann. Weiterhin kann die Transformation durch den Einsatz von Mikrowellen-Strahlung drastisch beschleunigt werden. Dies ist der erste Bericht über die hydrothermale Herstellung von zwei kondensierten Heterocyclen. published

Miriam M. Unterlass introduces a Journal of Materials Chemistry/Materials Advances Editor's choice web collection on recent advances in hydrothermal materials synthesis (https://rsc.li/hydrothermal).

International audience; The year 2020 marks the 100th anniversary of the first article on poly merization, published by Hermann Staudinger. It is Staudinger who realized that polymers consist of long chains of covalently linked building blocks. Polymers have had a tremendous impact on the society ever since this initial publication. People live in a world that is almost impossible to imagine without synthetic polymers. But what does the future hold for polymer science? In this article, the editors and advisory board of Macromolecular Chemistry and Physics reflect on this question.

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Valuing diversity leads to scientific excellence, the progress of science and most importantly, it is simply the right thing to do. We can value diversity not only in words, but also in actions. From the structure of DNA,1 to computer science,2 and space-station batteries,3 several key scientific discoveries that enhance our lives today, were made by marginalized scientists. These three scientists, Rosalind E. Franklin, Alan M. Turing and Olga D. González-Sanabria, did not conform to the cultural expectations of how scientists should look and behave. Unfortunately, marginalized scientists are often viewed as just a resource rather than the lifeblood that constitutes science itself. We need to embrace scientists from all walks of life and corners of the globe; this will also mean that nobody is excluded from tackling the life-threatening societal challenges that lie ahead. An awareness of science policy is essential to safeguarding our future. Science policy deals with creating the framework and codes of conduct that determine how science can best serve society.4-6 Discussions around science policy are often accompanied by anecdotes of “good” and “bad” practices regarding the merits of diversity and inclusion. Excellence and truth, which flow inexorably from diversity and inclusion, are the bedrocks upon which science should influence political and economic outcomes. A vital area of science policy is to support the professional development of marginalized scientists, an objective that must be acted upon by scientific leaders and communicators...

Verschiedene Polyimide und Polyamide wurden in letzter Zeit durch hydrothermale Synthese in nichts als H2O unter Hochdruck- und Hochtemperaturbedingungen hergestellt. Keines dieser Polymere weist jedoch ein konjugiertes Polymerrückgrat auf. Hiermit berichten wir über eine Erweiterung des synthetischen Anwendungsbereichs dieser einfachen und von Natur aus umweltfreundlichen Polymerisationstechnik auf die Herstellung von konjugierten Polymeren. Ausgewählte Vertreter von zwei verschiedenen Polymerklassen, Pyrronpolymere und Polybenzimidazole, wurden hydrothermal synthetisiert. Neben einer mechanistischen Diskussion der Polymerbildung wird auch eine elektrochemische Charakterisierung des vielversprechendsten Produktes präsentiert. published

High-purity, symmetrically substituted perylene and naphthalene bisimides were obtained by hydrothermal condensation of monoamines with the corresponding bisanhydride. The hydrothermal imidization proceeds quantitatively, without the need for organic solvents, catalysts or excess of the amines. published

Poly(p-phenylene vinylene)s (PPVs) have been studied for decades, but research on this interesting class of conjugated polymers is far from being completed. New applications like in bioimaging keep emerging and even simple structural variations are still waiting to be explored. Surprisingly, not even dithioalkyl-substituted PPVs (S-PPVs) have been reported in the peer-reviewed literature, although the corresponding dialkoxy-substituted PPVs (O-PPVs) like MEH-PPV or MDMO-PPV are most frequently used and although thioalkyl substituents can improve the material properties significantly. We herein report the development of a highly efficient, scalable two-step synthesis of Gilch monomers for S-PPVs starting from low-cost 1,4-diiodobenzene. A low-temperature polymerization protocol has been developed for these monomers, affording high-molecular weight S-PPVs in excellent yields. The thermal, electrochemical, and photophysical properties of S-PPVs are reported to highlight the potential of these polymers. Furthermore, treatment with dimethyldioxirane is demonstrated to result in rapid conversion into sulfone-substituted PPVs (SO2-PPVs), introducing a route to high-molecular weight SO2-PPVs with exceptional stability and solid-state photoluminescence quantum yields of up to 0.46.

Carbon nanotubes (CNT) provide an outstanding property spectrum which can be used to improve a wide range of materials. However, the transfer of properties from the nanoscale to a macroscopic material is a limiting factor. Different approaches of functionalizing the surface of a CNT can improve the interaction with the surrounding matrix but is connected to difficult and expensive treatments, which are usually inconvenient for industrial applications. Here, a simple and eco-friendly method is presented for the oxidation of CNT, where hydrogen peroxide (H2O2) is the only chemical needed and no toxic emissions are released. Also, the extensive step of the incorporation of CNT to an epoxy matrix is simplified to an ultrasonic dispersion in the liquid hardener component. The effectiveness is proven by mechanical tests of produced CNT/CFRP and compared to a conventional processing route. The combination of those simple and cost efficient strategies can be utilized to produce multiscale composites with improved mechanical performance in an ecological and economical way.

Highly fused, fully conjugated aromatic compounds are interesting candidates for organic electronics. With higher crystallinity their electronic properties improve. It is shown here that the crystallization of three archetypes of such molecules-pentacenetetrone, indigo, and perinone-can be achieved hydrothermally. Given their molecular structure, this is a truly startling finding. In addition, it is demonstrated that perinone can also be synthesized in solely high-temperature water from the starting compounds naphthalene bisanhydride and o-phenylene diamine without the need for co-solvents or catalysts. The transformation can be drastically accelerated by the application of microwave irradiation. This is the first report on the hydrothermal generation of two fused heterocycles. published

Organic colorants are an important type of compounds mainly characterized by the presence of conjugated moieties and color-generating functions (chromophores), such as carbonyl, azo or nitroso functions. They find various applications in coloring all kinds of substances – from plastics to clothes – but are unfortunately often synthesized by toxic and environmentally harmful routes. This review first explains the physicochemical basis of colorants, then gives an introduction to their classifications and general syntheses and ends with a highlight of recent advances in the environmentally friendly hydrothermal synthesis of colorants. Los colorantes orgánicos son una clase de compuestos comerciales muy importantes que se caracterizan, principalmente, por la presencia de grupos conjugados y funciones que generan color (cromóforos) como los grupos carbonilo, azo o nitroso. Estos compuestos encuentran diversas aplicaciones en la coloración de todo tipo de sustancias, desde plásticos hasta textiles; sin embargo, las rutas sintéticas de dichos compuestos son a menudo muy tóxicas y nocivas para el medio ambiente. Esta revisión explica, en primer lugar, las bases fisicoquímicas de los colorantes y sigue con una introducción a las clasificaciones y síntesis generales. Finalmente, se destacan los nuevos avances en la síntesis hidrotermal de colorantes de alto rendimiento.

Hydrothermal polymerization (HTP) is a benign and inherently green synthetic approach to synthesize highly crystalline polyimides (PIs) in nothing but high-temperature water (HTW). In a typical HTP experiment, highly crystalline PI microparticles of sheet-like as well as flower-like morphology are obtained. Within this contribution, the effect of four additives (PEG400, PEG8000, P123, CTAB) on the crystallinity and morphology of the PI poly(p-phenylene pyromellitimide) is investigated. From the experiments performed, it becomes evident that the type as well as the concentration of additive heavily influences morphology. However, even the highest tested concentration of additive (67 g L−1 of PEG8000) does not lead to a change in average crystallinity, as determined from powder X-ray diffraction. Hence, this approach provides a straightforward method to intentionally tune PI particle morphology without losing the outstanding materials properties generated by the high crystallinity obtained via HTP. Additionally, a hypothesis regarding the poly(ethylene glycol)-induced morphology alteration is presented. published

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich. This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively. Inspired by geological ore formation processes, we apply one-step hydrothermal (HT) polymerization to the toughest existing high-performance polymer, poly(p-phenyl pyromellitimide) (PPPI). We obtain highly-ordered and fully imidized PPPI as crystalline flakes and flowers on the micrometer scale. In contrast to classical 2-step procedures that require long reaction times and toxic solvents and catalysts, HT polymerization allows for full conversion in only 1 h at 200 °C, in nothing but hot water. Investigation of the crystal growth mechanismviascanning electron microscopy (SEM) suggests that PPPI aggregates formviaa dissolution–polymerization–crystallization process, which is uniquely facilitated by the reaction conditions in the HT regime. A conventionally prefabricated polyimide did not recrystallize hydrothermally, indicating that the HT polymerization and crystallization occur simultaneously. The obtained material shows excellent crystallinity and remarkable thermal stability (600 °C under N2) that stem from a combination of a strong, covalent polymer backbone and interchain hydrogen bonding.

Inorganic–organic hybrid materials allow for combining features typical of the inorganic component with those of the organic component in one material. Generally, the preparation of organic and inorganic compounds requires considerably different synthesis conditions. Hence, the development of one-pot routes to inorganic–organic hybrid materials is challenging. We herein report a fully green one-pot synthesis of polyimide/silica (PI/SiO2) hybrids. Specifically, we co-condense both components hydrothermally, using nothing but the respective precursors and water. Furthermore, we show that the PI and the SiO2 component can be covalently connected under hydrothermal conditions, using the compatibilizer (3-aminopropyl)-triethoxysilane. We thoroughly investigate the effect of different reaction conditions, including temperature, pH, precursor concentration and reaction time on the morphology and crystallinity of the final materials. The polyimide component, poly(hexamethylene pyromellitimide) was chosen for its thermoplasticity, which allows for processing both the PI and the PI/SiO2via sintering. For being a solvent-free method, sintering qualifies as a green processing technique. This work is the first report of the simultaneous hydrothermal condensation of an inorganic and an organic material. published

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