Shared posts

21 Apr 07:20

Recent Developments in Sustainable Solubilization

by Eva Müller, Werner Kunz
Recent Developments in Sustainable Solubilization

We highlight several recent developments in sustainable solubilization. Particular attention is given to the use of bio-based solvents derived from renewable resources, the strategic use of water as a solvent, and alternative, sustainable solubilizers such as hydrotropes. These approaches offer promising strategies for achieving more environmentally responsible and sustainable formulations.


The large-scale use of toxic and environmentally hazardous solvents remains a major challenge in industrial manufacturing and consumer-goods production. Conventional solubilization processes often depend on harsh conditions, including elevated temperatures and pressures, resulting in high energy consumption, health risks, and environmental pollution. Developing sustainable alternatives is therefore an urgent scientific and societal priority. This article discusses recent advances in green solubilization and emerging strategies aiming to reconcile efficiency with environmental compatibility. We address the future role of classical and “green” solvents, including ionic liquids (ILs) and natural deep eutectic solvents (NADES), and critically assess their benefits and limitations from a sustainability perspective. Particular emphasis is placed on water as the potentially “greenest” solvent, highlighting how its intrinsic tendency to form structured, heterogeneous environments can be advantageous or detrimental for solubilization. In this context, we examine mesoscale structuring, surfactant-free microemulsions, and dynamic interfaces. Furthermore, naturally derived solubilizers such as hydrotropes, biosurfactants, and proteins are considered promising tools to enhance solubility while maintaining biocompatibility and low environmental impact. Selected examples from our own work illustrate how combining water-based structuring with bio-derived or benign additives can create new pathways toward energy-efficient and sustainable solubilization technologies.

08 Apr 11:47

Muconic acid: a renewable platform monomer for polymer materials

Green Chem., 2026, 28,5167-5192
DOI: 10.1039/D6GC00103C, Tutorial Review
Aocheng Wei, Qinyang Lei, Xiaomeng You, Xiaojun Shen, Lin Dai, Tong-Qi Yuan
Muconic acid occupies a pivotal position at the confluence of biology, chemistry, and industrial technology. Synthesis and polymerization of muconic acid hold promise advanced materials and applications.
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19 Mar 15:48

Heterogeneous Transfer Dehydrogenation for Catalytic Upcycling of Polyethylene

by Tim de la Croix, Nathalie Claes, Sara Bals, Dirk E. De Vos
Heterogeneous Transfer Dehydrogenation for Catalytic Upcycling of Polyethylene

Heterogeneous transfer dehydrogenation of polyethylene with ethylene was investigated to prepare partially unsaturated polymers, followed by olefin metathesis with functional alkenes and hydrogenation to yield telechelic polyethylenes. Using this method, various samples of high density polyethylene (HDPE) and low density polyethylene (LDPE) were degraded with ethyl acrylate to ester-terminated polyethylene macromonomers.


Polyethylene is the most widely produced plastic globally and a major component of plastic waste. In this work, a chemical recycling process is proposed, yielding telechelic macromonomers as useful building blocks for the polymer industry. Polyethylene was partially dehydrogenated using a reusable, heterogeneous platinum catalyst at moderate temperatures, employing ethylene as a convenient hydrogen acceptor. Various support materials and reaction conditions were investigated, with Pt/ZnO showing the best performance under a constant flow of ethylene. Dehydrogenated samples were subjected to olefin cross-metathesis with ethyl acrylate using a homogeneous Ru catalyst and then hydrogenated without additional catalyst. The final products, ester-terminated polyethylene macromonomers, have potential as building blocks for recyclable polyethylene-like materials and specialized block copolymers. The partially unsaturated polyethylene constitutes a versatile intermediate in the chemical recycling of polyethylene.

13 Mar 16:47

Chemical recycling of hydrofluorocarbons by transfer fluorination

by Niko A. Jenek

Nature Chemistry, Published online: 13 March 2026; doi:10.1038/s41557-026-02096-8

Fluorochemicals improve our quality of life, but there is an increasing concern over their production and the negative impact on health and the environment. Now chemical recycling of fluorochemicals via base-induced defluorination has been demonstrated, and the resulting potassium fluoride has been used to synthesize organic and inorganic compounds.
13 Feb 15:22

Fast, selective and scalable flow ammonolysis of oxiranes accessible from glycerol toward bio-based amines

Green Chem., 2026, 28,4982-4989
DOI: 10.1039/D5GC06027C, Paper
Florian Barbaz, Hubert Hellwig, Diana V. Silva-Brenes, Jean-Christophe M. Monbaliu
Fast and selective continuous-flow ammonolysis of glycidol and epichlorohydrin yields bio-based amines at pilot scale.
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04 Feb 08:33

Selective Carbocation Functionalization by Catalytic Transchalcogenation Reactions

by Jesse Dallenes, Sergio Posada‐Pérez, Jonas Wuyts, Igor Beckers, Frank De Proft, Dirk De Vos
Selective Carbocation Functionalization by Catalytic Transchalcogenation Reactions

Acid-generated carbocations are selectively trapped by sulfide and selenide donor molecules in the form of onium salts. Through manipulation of one of the donor's substituents, these onium salts undergo elimination towards the corresponding transchalcogenation products. This strategy enables the shuttling of toxic S and Se moieties, while providing a rational platform to improve reaction selectivity in carbocation functionalization.


ABSTRACT

Introducing functionalities via acid-mediated carbocation chemistry is conceptually straightforward, but typically lacks in selectivity and broad-scale applicability, which is further hampered by the need for toxic reaction partners. Here, we show that small S- and Se-based functionalities can be selectively and safely introduced into feedstock molecules via acid-catalyzed transchalcogenation reactions. A designable y-keto donor compound delivers the functionality through the formation of a trialkyl chalcogenonium intermediate that is prone to elimination in conjunction with the acid catalyst and its counteranion. We demonstrate how this strategy enables chemo-, regio-, and stereoselective construction of C(sp3)─S and ─Se bonds, offering clear advantages over classical acid-catalyzed carbocation functionalization.

24 Dec 11:27

Acetone Recycling: A Case Study in the Undergraduate Teaching Laboratory

by Elizabeth Sarah, Munday
Herein is described results from the first three months of piloting a solvent recycling scheme in the undergraduate teaching laboratory. Chemistry teaching laboratories use large volumes of acetone which are predominantly disposed of by incineration as non-halogenated waste. At UCL Chemistry we have begun recycling acetone wate generated by students and researchers. Not only does this have a large impact on reducing costs and emissions, it can also be embedded into teaching to educate students on the science behind, and impact of, sustainability initiatives. We have carried out a preliminary life cycle analysis based on our data for a three-month period of recycling acetone in the teaching laboratory, which demonstrates the carbon-saving and cost-saving benefits of the scheme.
24 Dec 11:25

From Waste to Value: Data-Driven Insights for Biomass Valorization

by Magesh, Ganesan
The conversion of biomass to value-added products represents a critical pathway toward sustainable chemical production and reduced fossil fuel dependence. This comprehensive review analyzes ~220,000 documents from the CAS Content Collection database between 2015-2025 to examine the technological evolution and research developments in biomass-conversion to chemicals and fuels, a critical pathway toward sustainable energy and chemical prod1uction. This review finds that moderate growth in journal publications with publication volume nearly doubled between 2015 and 2024, while patent publications show inconsistent growth, suggesting weak alignment between fundamental research and commercialization. Three dominant conversion technologies emerge: thermochemical (including carbonization, pyrolysis, and gasification), biochemical (fermentation and enzymatic hydrolysis), and chemical processes (hydrolysis and transesterification), with balanced distribution indicating no single dominant pathway. Plant-based residues and waste dominate as feedstocks due to their abundance and high lignocellulosic content, followed by oils and fats. Major products include fuels (carbon materials, aliphatic hydrocarbons, esters), platform chemicals and materials, fertilizers, and pharmaceuticals, with fuels and platform chemicals representing the largest research areas. China emerges as the dominant contributor, accounting for 73% of global patent filings, with Sinopec holding over 1,100 patents, four times higher than the second-largest assignee. Critical challenges include large-scale production limitations, high processing costs, and feedstock sustainability, while highlighting promising growth areas such as pyrolysis (36% year-over-year growth) and hydrothermal reactions. With biomass accounting for 1% of U.S. and 5% of EU total national grid energy generation, this review provides crucial insights for advancing sustainable biomass-based chemical systems while addressing the gap between academic research and industrial implementation. The analysis herein provides researchers with a deep understanding of current trends, emerging opportunities, and commercial insights in biomass valorization, serving as a foundational guide for both established scientists and non-specialists in this rapidly evolving field.
24 Dec 11:25

C=C/N=O Metathesis Enables Oxidative Decarboxylation

by Bill, Morandi
Metathesis reactions proceeding through a (2+2) cycloaddition – (2+2) cycloreversion sequence are of great importance in synthetic chemistry. However, to date, this type of reactivity has only been demonstrated for a limited set of compatible sub-strate classes. We present herein the design and development of a novel reaction of this class, an iron (II)-catalyzed C=C/N=O metathesis, and its application to the mild oxidative decarboxylation of carboxylic acids. The reaction proceeds under air in a one-pot fashion, utilizing readily available, inexpensive reagents, and features an earth-abundant, environmentally benign iron catalyst. The reaction exhibits broad functional group tolerance, is efficiently scalable, and its late-stage applicability was showcased through the streamlined oxidative decarboxylation of 12 drug molecules. Divergent and convergent reactivity was demonstrated relying on the complementary C=C/O=N metathesis counterpart providing access to imines instead of ketones, and the method was extended to the synthesis of esters from α-aryloxy and α-alkoxy carboxylic acids. Results of preliminary mechanistic experiments, reaction profile analysis with ReactIR, and computational studies are presented to provide further insight into the transformation.
24 Dec 11:08

H2-driven biocatalytic O-demethylation of lignin derived aromatics in a closed-loop flow system powered by water electrolysis

Green Chem., 2026, 28,4006-4018
DOI: 10.1039/D5GC05054E, Paper
Open Access Open Access
Creative Commons Licence&nbsp This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Donato Calabrese, Guiyeoul Lim, Parsa Nayyara, Megan E. Wolf, Paul R. F. Cordero, Lindsay D. Eltis, Lars Lauterbach
We demonstrate an H2-driven, closed-loop biocatalytic system integrating water electrolysis with efficient O-demethylation of lignin aromatics for sustainable chemical production.
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24 Nov 13:34

Biodegradable Plastic Production from Waste C1 Carbon Sources: Current Trends and Future Directions

by Zeeshan Mustafa, Eun Yeol Lee
Biodegradable Plastic Production from Waste C1 Carbon Sources: Current Trends and Future Directions

This review summarizes the biotechnological conversion of C1 carbon sources (CO2, CO, formate, CH4, and CH3OH) into biodegradable plastics, specifically polyhydroxyalkanoates (PHAs). Microbial cell factories utilize these feedstocks in laboratory and industrial bioprocesses, enabling the sustainable production of PHAs homopolymer and heteropolymer as eco-friendly alternatives to petroleum-based plastics.


Abstract

Plastic pollution poses a growing environmental and health threat, prompting the search for sustainable alternatives. Polyhydroxyalkanoates (PHAs) are biodegradable bioplastics synthesized by various microorganisms as intracellular reserves of carbon and energy. Among the most promising strategies for sustainable PHA production is the use of C1 carbon sources such as methanol, methane, formate, carbon dioxide, and carbon monoxide which are inexpensive, abundant, and often derived from industrial waste. This review highlights the potential of methanotrophs, methylotrophs, formatotrophs, and autotrophs in converting C1 substrates into PHAs under nitrogen-limited and optimized fermentation conditions. It also explores recent advances in metabolic engineering and synthetic biology to enhance PHA yields and tailor polymer properties. Despite challenges such as low productivity, substrate toxicity, low metabolic capacity, low enzyme kinetics, high production cost and limited genetic tools, progress in microbial engineering, bioprocess development, and renewable energy integration is steadily advancing the commercial viability of C1-based PHA production. This approach offers a promising path toward circular bioeconomy solutions and environmentally friendly plastic alternatives.

21 Nov 10:09

Towards greener-by-design fine chemicals. Part 2: technological frontiers

Chem. Soc. Rev., 2025, Advance Article
DOI: 10.1039/D5CS00930H, Review Article
Open Access Open Access
Creative Commons Licence&nbsp This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Theodore A. Gazis, Rodolfo I. Teixeira, Giulio Volpin, Ashish Yewale, Mert Can Ince, Mark J. Ford, Jan Harmsen, Marco Uboldi, Alice Melocchi, Mattia Sponchioni, Andrea Aramini, Renzo Luisi, Brahim Benyahia, Gianvito Vilé
This review highlights systemic innovations, such as digital retrosynthesis, AI-guided design, smart manufacture, modular plants and 3D printing, as levers for scalable, low-impact fine chemical production.
To cite this article before page numbers are assigned, use the DOI form of citation above.
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21 Nov 10:06

Lignin-based non-isocyanate polyurethanes: towards sustainable polyurethanes

Green Chem., 2025, Advance Article
DOI: 10.1039/D5GC04066C, Critical Review
Peter K. Karoki, Christian O. Kemefa, Xianzhi Meng, Yunqiao Pu, Mairui Zhang, Soyeon Jeong, Chang Geun Yoo, Arthur J. Ragauskas
This review highlights recent advances in lignin valorization for the sustainable synthesis of non-isocyanate polyurethanes (NIPUs), emphasizing on green routes, structural modifications, and emerging applications in bio-based materials.
To cite this article before page numbers are assigned, use the DOI form of citation above.
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20 Nov 12:36

Avoiding tomorrow's chemical mistakes today

Green Chem., 2025, Advance Article
DOI: 10.1039/D5GC05283A, Perspective
Open Access Open Access
Creative Commons Licence&nbsp This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Jeroen B. Guinée, Martina G. Vijver
Advancing SSbD requires an effective and efficient regulatory-based data strategy to improve data availability and quality for safety assessments and LCA; without it, new methods may merely become empty promises that avoid the real issue.
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19 Nov 09:39

Towards greener-by-design fine chemicals. Part 1: synthetic frontiers

Chem. Soc. Rev., 2025, Advance Article
DOI: 10.1039/D5CS00929D, Review Article
Open Access Open Access
Creative Commons Licence&nbsp This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Theodore A. Gazis, Jonas Wuyts, Areti Moutsiou, Giulio Volpin, Mark J. Ford, Rodolfo I. Teixeira, Katherine M. P. Wheelhouse, Philipp Natho, Polona Žnidaršič-Plazl, Sonja Jost, Renzo Luisi, Brahim Benyahia, Bert U. W. Maes, Gianvito Vilé
This review explores sustainable synthetic methodologies, highlighting advances in solvent use, catalysis, raw materials, and flow chemistry for pharmaceutical and agrochemical production.
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14 Nov 08:55

C(sp3)-H Halogenation by First-Row Transition Metal Catalysts in Homogeneous Conditions

Org. Biomol. Chem., 2025, Accepted Manuscript
DOI: 10.1039/D5OB01584G, Review Article
Open Access Open Access
Monika Loohach, Jaipriya Khatri, Kritika Dogra, Rachana Choudhary, Sarban Kumar Yadav, Basab Bijayi Dhar
The direct functionalization of unactivated C–H bonds has emerged as a promising strategy to achieve step-economical, atom-efficient, and environmentally benign chemical processes. In this context, ongoing research is focused on...
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13 Nov 09:29

How much protein do you really need? What the science says

by Mariana Lenharo

Nature, Published online: 12 November 2025; doi:10.1038/d41586-025-03632-1

Fitness influencers promote super-high-protein diets, but studies show there’s only so much the body can use.
13 Nov 09:28

Deoxyfluorination of Hydroxy-Substituted Boronates

by Oleksandr, Grygorenko
A practical and scalable protocol for the deoxyfluorination of hydroxyalkyl-substituted aryl- and alkenylboronates was developed. The optimized conditions (combining Deoxo-Fluor with TEA·3HF as the reagents and substrate pre-conversion to trifluoroborate salts) enabled efficient transformation across a wide range of (homo)benzylic and allylic alcohols, while tolerating protected carboxyl and amino groups. The resulting fluorinated boronates performed well as versatile building blocks in oxidation and Suzuki cross-coupling reactions. Furthermore, a telescoped one-pot strategy allowed direct utiliza-tion of crude fluorinated intermediates, enabling access to complex molecular frameworks containing alcohol, carbonyl, and ester functionalities, typically intolerant to the late-stage fluorination conditions. This methodology offers a general and efficient route for the incorporation of monofluorinated aliphatic fragments into structures of relevance for medicinal chem-istry and material science.
13 Nov 09:25

A Statistical-Chemometric Analysis Quantifying Impact of Stirring on Organic Reaction Yields: New Insights from the Huang et al. 2024 Data

by Andrew, Lover
Mechanical agitation (stirring) is a cornerstone of organic synthesis, but has received little scientific attention due to its “obvious” role in facilitating reactions. A very recent study by Huang and coworkers compared the isolated yields in approximately 600 paired stirred and unstirred reactions, across a range of standard synthetic reactions, and reported “almost no” differences. However, their study does not provide any quantitative metrics to estimate these differences. To more fully understand the magnitude of potential differences and to identify any reactions where yields do differ, a full multivariable statistical analysis was performed. Across all reaction types, in multivariable mixed models adjusted for reaction conditions including reaction scale, time, and reaction type, stirred reactions are associated with a 2.0 % (95% CI: 1.1 to 2.9%; p < 0.001) increase in isolated yield relative to unstirred reactions. Four reaction types also show statistically significant differences in individual mixed models. Cross-couplings (including Heck, Sonogoshira, and Suzuki reactions) showed a 2.1 % (95% CI: 1.4 to 2.9%; p < 0.001) increase in yield with stirring; electrochemical reactions (allylic C–H oxidation, silyl-Minisci) show a 3.0% (95% CI: 0.7 to 5.3%; p = 0.0091) greater yield; polar reactions (including the Fisher indole synthesis; Friedel-Crafts alkylations/acylations; Mannich reactions; Willamson ether synthesis; the Wittig reaction) show a 2.8 % increase (0.9 to 4.7%; p = 0.004) in yield with in stirred versus unstirred reactions; and rearrangements (Claisen and Schmidt reactions), which overall show an 8.4% (95% CI: 6.5 to 10.4%; p < 0.001) increase in yield with stirring relative to unstirred paired reactions. Finally, to assess any interactions between overall yield and the impact of stirring, all reactions were classified using k-means cluster partitioning into three classes by paired yield; individual models for these classes show a clear gradient, where the lowest-yielding reaction group shows the largest overall increase in isolated yield (4.5%; 95% CI: 2.6 to 6.4%; p < 0.0001) with stirring. Stirring of moderate yield reactions is associated with a 1.6% (95% CI: 0.4 to 2.9%; p = 0.0082) increase in yield, while the highest yielding reactions show smaller effect sizes in stirred versus unstirred reactions (0.8% increase; 95% CI: 0.4 to 1.3%; p< 0.0001). These results suggest that while the overall change in yields with stirring in these data for many reactions are modest, there is extensive variation of impact, and stirring is associated with real and practically important increases in isolated yields across a wide range of substrates and reaction manifolds. Future studies should incorporate design of experiment frameworks, to elucidate which reaction parameters drive these observed heterogeneous effects.
12 Nov 15:49

BrickSDLab: A low-cost self-driving lab platform made from LEGO® bricks for rapid prototyping and education

by Alexander, Böser
Despite the promise of self-driving laboratories to accelerate discovery, their widespread implementation is hindered by prohibitive cost and technical complexity. We introduce BrickSDLab, a fully functional self-driving lab platform built entirely from LEGO® components, designed to bridge this accessibility gap. BrickSDLab combines modular hardware - including syringe pumps, temperature and color sensors, magnetic stirring, and safety features—with a programmable NXT 2.0 control unit, enabling closed-loop experimentation in an affordable and intuitive form. Example applications include autonomous titration and feedback-driven reagent addition. This work illustrates how off-the-shelf prototyping systems can empower students, educators, and early-stage researchers to engage with self-driving lab concepts, making laboratory automation more inclusive and scalable.
12 Nov 12:38

Production of bio-based lactones as monomers for a circular polymer economy

by Daniyal Kiani

Nature Reviews Chemistry, Published online: 22 October 2025; doi:10.1038/s41570-025-00765-9

Catalytic methods for converting bio-derived feedstocks into lactones are reviewed, emphasizing scalable, energy-efficient processes. Free energy analysis guides process design and pathway selection, whereas literature highlights accessible lactone precursors from various metabolic and chemo-catalytic pathways.
12 Nov 10:43

Can mixed plastics be recycled and upcycled without separation?

Green Chem., 2025, 27,14978-15001
DOI: 10.1039/D5GC03714J, Critical Review
Jaime J. M. Pang, Yan Hui Lee, Haonan Zhao, Albert Ong, Jason Y. C. Lim
In this review, we examine the possibility of using mixed and/or contaminated plastic feedstock for chemical recycling, upcycling and formation of physical polymer blends.
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31 Oct 14:32

A feasible methanol economy for a green future

Green Chem., 2025, Advance Article
DOI: 10.1039/D5GC04615G, Paper
Open Access Open Access
Creative Commons Licence&nbsp This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Hidde Kolmeijer, Abhinandan Nabera, Antonio J. Martín, Gonzalo Guillén-Gosálbez, Javier Pérez-Ramírez
This study models a future methanol economy where combining biomass, biogas, and air-captured CO2 achieves net-zero emissions at about 32 USD2025 per person per month, close to Paris Agreement-aligned costs while delivering deeper emission cuts.
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31 Oct 14:14

Cover Feature: Exploring Acrylic Acid as an Oxirane Nucleophile: Direct Access to Poly(β‐Hydroxy Acrylates) (ChemSusChem 18/2025)

by Céline Montanari, Lukas Marcos Celada, Wenhao Zhang, Peter Olsén
Cover Feature: Exploring Acrylic Acid as an Oxirane Nucleophile: Direct Access to Poly(β-Hydroxy Acrylates) (ChemSusChem 18/2025)

The Cover Feature shows ring-opening acrylation with acrylic acid, which enables a scalable, high-yield route to β-hydroxy acrylates via direct reaction with oxiranes (epoxides). This simple, atom-economic process yields monomers for transparent, thermally stable polymers with tunable mechanical properties, ranging from soft and stretchable to stiff and strong. The work highlights the potential of acrylic acid in next-generation sustainable materials. More information can be found in the Research Article by P. Olsen and co-workers (DOI: 10.1002/cssc.202500575).


30 Oct 13:04

Transfer Hydrogenation with Waste‐Derived Aqueous Solutions of Formic Acid Catalysed by the SulfoShvo Catalyst

by Justus Diekamp, Milan D. Kulaš, Jakob Albert, Thomas Seidensticker
Transfer Hydrogenation with Waste-Derived Aqueous Solutions of Formic Acid Catalysed by the SulfoShvo Catalyst

Transfer hydrogenation of carbonyl and olefinic compounds with the buffer-free combination of waste-derived, aqueous formic acid solution and the sulfoShvo catalyst at pH = 1 and elevated temperatures in pressure autoclaves.


The OxFA process provides aqueous formic acid (FA) solutions of around 53 wt% directly from biomass-derived byproducts such as glycerol. The direct utilisation of this diluted FA stream in transfer hydrogenation reactions without neutralisation or buffering is demonstrated, enabled by the highly hydrophilic, acid-stable sulfoShvo catalyst operating at pH 1. Using levulinic acid (LA) as a model substrate, optimisation in pressure autoclaves identified 130 °C and catalyst loadings as low as 0.2 mol% as effective reaction conditions. Even under these harsh acidic conditions, the catalyst displays remarkable performance: at 100 °C, long-term stability is achieved with a turnover number (TON) of 3680, while operation at 130 °C allows efficient hydrogenation but reveals gradual deactivation at very low loadings (0.025 mol%). Beyond LA, a range of water-soluble carbonyl and olefinic substrates is successfully hydrogenated, highlighting the broad applicability of this sustainable approach. Overall, this study establishes the OxFA/sulfoShvo system as a robust and atom-economical strategy for the direct use of biomass-derived FA solutions in catalytic hydrogenation.

03 Oct 12:15

A global analysis of the rise, reign, and retreat of topics in research toward sustainable platform chemicals

Green Chem., 2025, 27,12985-13003
DOI: 10.1039/D5GC02863A, Paper
Open Access Open Access
Creative Commons Licence&nbsp This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
Paul Tautorat, Benedetta Tremolada, Antonio J. Martín, Lucas F. Santos, Gonzalo Guillén-Gosálbez, Javier Pérez-Ramírez, Bjarne Steffen
We analyse global research trends in the sustainable production of ammonia, methanol, olefins, and aromatics by integrating topic modelling, generative AI, and expert judgment to analyse over 90 000 research articles spanning three decades.
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03 Oct 12:13

A mechanochemical Kolbe-Schmitt reaction: Carboxylation of catechol providing building blocks for renewable plasticizers

by Dries, De Vos
Jonas Wuyts

Go Dries!

Catechol, an important aromatic platform molecule which can be derived from biomass, was carboxylated by mechanochemical Kolbe-Schmitt reaction of disodium catecholate with CO2, providing a mixture of mono- and dicarboxylated catechol derivatives. While classical protocols require harsh reaction conditions, involving a high temperature and/or CO2 pressure, a mild ball milling method was developed. This represents the first mechanochemical Kolbe-Schmitt reaction featuring a low CO2 pressure and reactivity at room temperature. From the individual catechol-based mono- and dicarboxylic acid reaction products, a library of novel renewable plasticizers was synthesized through esterification of the carboxylic acid functionalities and acetylation of the phenolic hydroxy groups. The resulting esters were evaluated in poly(vinylchloride) (PVC) and poly(lactic acid) (PLA), revealing plasticizing efficiencies competitive to benchmark commercial plasticizers. These efficiencies were maintained when the best performing ester substitution pattern was installed on the ball mill-derived mixture of mono- and dicarboxylated catechols, making resource intensive separation (e.g. chromatographic separation) of these ortho-dihydroxybenzene(di)carboxylic acids redundant.
22 Sep 11:40

Stirring the Debate: How Mixing Influences Reproducibility and Efficiency in Synthetic Organic Chemistry

by Timothy, Noel
Mixing is fundamental to chemical processes, ensuring the proximity and interaction of different reactants necessary for a reaction to proceed. A recent report has suggested that stirring may have little impact on reaction outcomes for some solution-phase organic reactions. While such findings may hold under specific, controlled conditions, they risk oversimplifying the complexity of mixing phenomena in chemical synthesis. Here, we discuss the underlying principles of mixing, its relevance to synthetic organic chemistry and materials science, and practical considerations for reproducible and safe experimental practices. We argue that while some reactions may appear insensitive to agitation, mixing remains critical for reproducibility, selectivity, and scalability, particularly in heterogeneous or industrially relevant systems.
17 Sep 13:41

Activation Energies Reveal Unusual Temperature Sensitivity in Mechanochemical Reactions

by Sven, Grätz
Mechanochemistry is gaining momentum as a solvent-efficient alternative to classical synthesis. Its widespread appeal rests not only on the avoidance of bulk solvents but also on the notion that it typically proceeds without external heating. This view has fostered a long-standing assumption—reflected even in the IUPAC definition—that temperature plays only a minor role in mechanochemical transformations. In this work, we challenge this assumption by systematically determining activation energies (Ea) of organic reactions under ball milling, resonant acoustic mixing (RAM), and solution conditions. Using the Diels–Alder reaction between anthracene and maleic anhydride as a benchmark, we found significantly higher Ea values in the solid state (~25–29 kcal·mol-1) than in solution (~15 kcal·mol-1). A similar trend was observed for the Knoevenagel condensation, indicating that elevated activation barriers are a general feature of mechanochemical systems. Progressive addition of solvent revealed a continuum from neat grinding to solution behavior, with Ea decreasing systematically as liquid-assisted grinding (LAG) content increased. These findings demonstrate, for the first time, that mechanochemical reactions are not less, but more strongly influenced by temperature than solution reactions. By linking this unusual temperature sensitivity to the decisive yet poorly understood role of LAG, our study provides a new conceptual framework for interpreting mechanochemical reactivity and clarifies how solid-state and solution chemistry are connected.
17 Sep 13:39

Shaking Up Photochemistry: The Future Frontiers of Mechanophotocatalysis

by Eli, Zysman-Colman
Solution-state photocatalysis is fundamentally reliant on the use of organic solvents, which are associated with significant safety, sustainability, and implementation challenges for conducting light-driven reactions. Mechanophotocatalysis tantalizingly addresses these issues by significantly reducing the use of solvent, using mechanical mixing to mediate light-driven transformations. In this perspective, we examine the motivations for combining photocatalysis with mechanochemistry, as-sess how this nascent methodology has evolved, and speculate on future research directions that should be explored in order for mechanophotocatalysis to emerge as a useful and complementary methodology for conducting photochemical reactions under solvent-minimized conditions.