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Analytical data and quantitative near infrared (NIR) spectroscopy models for various lignocellulosic components (including Klason lignin and the constituent sugars glucose, xylose, mannose, arabinose, galactose, and rhamnose), ash, and ethanol-soluble extractives were obtained for 53 samples of paper and cardboard. These samples were mostly the type of materials typically found in domestic wastes (e.g. newspapers, printing paper, glossy papers, food packaging). A number of the samples (48) were obtained by separating a sample, after milling, into two particle size fractions. It was found that the fractions containing the smaller particles typically had higher ash and Klason lignin contents and lower glucose and xylose contents than the larger particle size fractions. Nevertheless, all of the sample types had attractive total sugars contents (>50%), indicating that these could be suitable feedstocks for the production of biofuels and chemicals in hydrolysis-based biorefining technologies. NIR models of a high predictive accuracy (R 2 of >0.9 for the independent validation set) were obtained for total sugars, glucose, xylose, Klason lignin, and ash, with values for the Root Mean Square Error of Prediction (RMSEP) of 2.36%, 2.64%, 0.56%, 1.98%, and 4.87%, respectively. Good NIR models (R 2 of >0.8) were also obtained for mannose, arabinose, and galactose. These results suggest that NIR spectroscopy is a suitable method for the rapid, low-cost, analysis of the major lignocellulosic components of waste paper/cardboard samples.

The Faraday Discussion on rechargeable non-aqueous metal–oxygen batteries is summarised. The remarks paper highlights the specific science contributions made in the vital areas of oxygen reduction and evolution reaction mechanisms in non-aqueous electrolytes; material developments for stable metal–oxygen battery cathodes; achieving stable metal anodes and protected interfaces; and, finally, contributions concerning the progress towards practical metal–oxygen batteries. Key conclusions associated with these papers will be highlighted in an order such that readers can identify papers that they would like to explore in more detail. [ABSTRACT FROM AUTHOR]

These concluding remarks summarize the Faraday Discussion on New Directions in Molecular Scattering. The discussion brought together scientists from a wide range of disciplines, from astrochemistry to coherent quantum control, and the submitted papers highlighted the need for innovation in experimental methods and computational tools to tackle more complex systems, relevant to chemistry in the real world. As recorded in the previous pages of this discussion, the meeting saw lively debate on numerous topical issues. This summary outlines some of the highlighted key developments in the field, and points towards future directions of molecular scattering research. [ABSTRACT FROM AUTHOR]

A summary of the Faraday Discussion presented in this issue and a perspective on that discussion is presented. The work highlights the specific science contributions made and the key conclusions associated with those findings so that readers can identify papers that they would like to explore in more detail. [ABSTRACT FROM AUTHOR]

It is a formidable challenge, and a distinct privilege, to provide the concluding remarks for this Faraday Discussion on Dense Ionic Fluids (DIFs). What follows is an inherently subjective distillation of the insights that have shaped our understanding of these complex systems over the last few days, with the goal of capturing the essence of the Discussion and providing suggestions for future investigations in this rapidly evolving field. DIFs are a fascinating class of electrolyte systems characterized by high ion concentrations in correlated domains. The multiscale nature of DIFs, and the challenges in connecting nanoscale phenomena to bulk properties, are discussed in the context of contemporary experimental and computational methods. Next, emerging trends are explored, and then the paper concludes by identifying promising future research directions. [ABSTRACT FROM AUTHOR]

There is much interest in developing new energy storage systems to replace currently available ones that mainly work based on Li-ion intercalations. One attractive area is the Li–air battery for which most of the research has involved liquid electrolytes. There have been few studies on the use of a solid electrolyte in a Li–air battery. Recently, we reported the successful use of a solid-state electrolyte in a Li–air battery resulting in a Li2O product and potentially much higher energy density than in a Li–air battery based on either a Li2O2 or LiO2 product (Science, 2023, 379, 499). In this paper we discuss how the discharge mechanism involved in this solid-state Li–air battery differs from that of a Li–air battery with a liquid electrolyte. The solid-state mechanism is further explored with density functional studies of various interfaces involving the discharge product. We discuss the relevance of the results to the discharge mechanism in the solid-state Li–air battery. [ABSTRACT FROM AUTHOR]

Uncovering the role of reaction intermediates is crucial to developing an understanding of heterogeneous catalysis because catalytic reactions often involve complex networks of elementary steps. Identifying the reaction intermediates is often difficult because their short lifetimes and low concentrations make it difficult to observe them with surface sensitive spectroscopic techniques. In this paper we report a different approach to identify intermediates for the formic acid decomposition reaction on Pd(111) and Pd(332) based on accurate measurements of isotopologue specific thermal reaction rates. At low surface temperatures (∼400 K) CO2 formation is the major reaction pathway. The CO2 kinetic data show this occurs via two temporally resolved reaction processes. Thus, there must be two parallel pathways which we attribute to the participation of two intermediate species in the reaction. Isotopic substitution reveals large and isotopologue specific kinetic isotope effects that allow us to identify the two key intermediates as bidentate formate and carboxyl. The decomposition of the bidentate formate is substantially slower than that of carboxyl. On Pd(332), at high surface temperatures (643 K to 693 K) we observe both CO and CO2 production. The observation of CO formation reinforces the conclusion of calculations that suggest the carboxyl intermediate plays a major role in the water–gas shift reaction, where carboxyl exhibits temperature dependent branching between CO2 and CO. [ABSTRACT FROM AUTHOR]

Exfoliated and reassembled graphite (ERG) forms macroscopic, high aspect ratio (1 : >106) and highly conductive coating layers that are strongly adherent to paper, wood, cloth, ceramic and other substrates. The coating precursor is an aqueous dispersion of graphite that exfoliates spontaneously in alkaline cellulose solutions, forming stable dispersions. These can be applied to the substrates by using different painting, coating and lithography techniques. The coating morphology changes from highly smooth to porous and rough, depending on the finishing procedure used. Coated paper sheets are flexible and they perform as leads in electrical circuitry and as electrodes in electrodeposition, supercapacitors, hygroelectricity cells and other electrochemical devices suitable for flexible and wearable electronics. These unique properties of ERG are explained as a consequence of the amphiphilic character of cellulose, which allows it to play the roles of exfoliant, dispersant, stabilizer, adhesive and plasticizer, while graphite powder is transformed into a cohesive laminated nanocomposite. [ABSTRACT FROM AUTHOR]

Electron microscopy (EM) introduced a fast and lasting change to structural and cellular biology. However, the sample preparation is still the bottleneck in the cryogenic electron microscopy (cryo-EM) workflow. Classical specimen preparation methods employ a harsh paper-blotting step, and the protein particles are exposed to a damaging air–water interface. Therefore, improved preparation strategies are urgently needed. Here, we present an amended microfluidic sample preparation method, which entirely avoids paper blotting and allows the passivation of the air–water interface during the preparation process. First, a climate jet excludes oxygen from the sample environment and controls the preparation temperature by varying the relative humidity of the grid environment. Second, the integrated "coverslip injector" allows the modulation of the air–water interface of the thin sample layer with effector molecules. We will briefly discuss the climate jet's effect on the stability and dynamics of the sample thin films. Furthermore, we will address the coverslip injector and demonstrate significant improvement in the sample quality. [ABSTRACT FROM AUTHOR]

This paper overviews the final remarks lecture delivered (by K. D. K.) at the end of this bioinorganic chemistry Faraday Discussion, held online for a worldwide audience from January 31 – February 3, 2022. This paper provides discussion in six sections: (1) the Introductory lecture, from Ed Solomon, emphasized past and present uses of advanced spectroscopic methods and theoretical approaches to elucidate metalloenzyme active site structure, physical properties and function. (2) The discussion topics are divided into groups having similar research themes, as seen from this author's perspective. Emphasis is given to the non-heme iron group of articles with dioxygen activation research. (3) Small molecule activation (e.g., N2, CO2 and O2 reduction; CH4 or H2O oxidation) is widely covered in this discussion; this authors' view of the important reactions in bioinorganic chemistry is discussed. (4) We discuss current practice and vision for employing materials chemistry to widely apply to electrocatalytic methods to effect small molecule activation (as above) to fulfill societal energy demands. (5) A discussion is given on the topic of synthetic models and the approach utilized therein. (6) New research on the authors' synthetic modeling is presented; preliminary results are given in the area of copper mediated peroxide activation. [ABSTRACT FROM AUTHOR]

Water-in-salt (WiS) electrolytes are promising systems for a variety of energy storage devices. Indeed, they represent a great alternative to conventional organic electrolytes thanks to their environmental friendliness, non-flammability, and good electrochemical stability. Understanding the behaviour of such systems and their local organisation is a key direction for their rational design and successful implementation at the industrial scale. In the present paper, we focus our investigation on the 21 m bis(trifluoromethanesulfonyl)imide (LiTFSI) WiS electrolyte, recently reported to have acidic pH values. We explore the speciation of an excess proton in this system and its dependence on the initial local environment using ab initio molecular dynamics simulations. In particular, we observe the formation of HTFSI acid in the WiS system, known to act as a superacid in water. This acid is stabilised in the WiS solution for several picoseconds thanks to the formation of a complex with water molecules and a neighboring TFSI− anion. We further investigate how the excess proton affects the microstructure of WiS, in particular, the recently observed oligomerisation of lithium cations, and we report possible notable perturbations of the lithium nanochain organisation. These two phenomena are particularly important when considering WiS as electrolytes in batteries and supercapacitors, and our results contribute to the comprehension of these systems at the molecular level. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Faraday Discussions" with the theme of biocatalysis. It provides information about the editorial staff, subscription prices, and contact details for ordering. The contents list includes papers and discussions on various topics related to biocatalysis, such as indigo production, enzyme evolution, and the degradation of microplastic particles. The document also includes information about exhibitors, sponsors, and poster titles. The journal aims to connect the world with the chemical sciences and invest profits back into the chemistry community. [Extracted from the article]

Women in developing countries still face enormous challenges when accessing reproductive health care. Access to voluntary family planning empowers women allowing them to complete their education and join the paid workforce. This effectively helps to end poverty, hunger and promotes good health for all. According to the United Nations (UN) organization, in 2022, an estimated 257 million women still lacked access to safe and effective family planning methods globally. One of the main barriers is the associated cost of modern contraceptive methods. Funded by the Bill & Melinda Gates Foundation, Almac Group worked on the development of a novel biocatalytic route to etonogestrel and levonorgestrel, two modern contraceptive APIs, with the goal of substantially decreasing the cost of production and so enabling their use in developing nations. This present work combines the selection and engineering of a carbonyl reductase (CRED) enzyme from Almac's selectAZyme™ panel, with process development, to enable efficient and economically viable bioreduction of ethyl secodione to (13R,17S)-secol, the key chirality introducing intermediate en route to etonogestrel and levonorgestrel API. CRED library screening returned a good hit with an Almac CRED from Bacillus weidmannii, which allowed for highly stereoselective bioreduction at low enzyme loading of less than 1% w/w under screening assay conditions. However, the only co-solvent tolerated was DMSO up to ∼30% v/v, and it was impossible to achieve reaction completion with any enzyme loading at substrate titres of 20 g L−1 and above, due to the insolubility of the secodione. This triggered a rapid enzyme engineering program fully based on computational mutant selection. A small panel of 93 CRED mutants was rationally designed to increase the catalytic activity as well as thermal and solvent stability. The best mutant, Mutant-75, enabled a reaction at 45 °C to go to completion at 90 g L−1 substrate titre in a buffer/DMSO/heptane reaction medium fed over 6 h with substrate DMSO stock solution, with a low enzyme loading of 3.5% w/w wrt substrate. In screening assay conditions, Mutant-75 also showed a 2.2-fold activity increase. Our paper shows which computations and rational decisions enabled this outcome. [ABSTRACT FROM AUTHOR]

The full electrification of transportation will require batteries with both 3–5× higher energy densities and a lower cost than what is available in the market today. Energy densities of >1000 W h kg−1 will enable electrification of air transport and are among the very few technologies capable of achieving this energy density. Limetal–O2 or Limetal–air are theoretically able to achieve this energy density and are also capable of reducing the cost of batteries by replacing expensive supply chain constrained cathode materials with "free" air. However, the utilization of liquid electrolytes in the Limetal–O2/Limetal–air battery has presented many obstacles to the optimum performance of this battery including oxidation of the liquid electrolyte and the Limetal anode. In this paper a path towards the development of a Limetal–air battery using a cubic garnet Li7La3Zr2O12 (LLZ) solid-state ceramic electrolyte in a 3D architecture is described including initial cycling results of a Limetal–O2 battery using a recently developed mixed ionic and electronic (MIEC) LLZ in that 3D architecture. This 3D architecture with porous MIEC structures for the O2/air cathode is essentially the same as a solid oxide fuel cell (SOFC) indicating the importance of leveraging SOFC technology in the development of solid-state Limetal–O2/air batteries. [ABSTRACT FROM AUTHOR]

Developing batteries with energy densities comparable to internal combustion technology is essential for a worldwide transition to electrified transportation. Li–O2 batteries are seen as the 'holy grail' of battery technologies since they have the highest theoretical energy density of all battery technologies. Current lithium–oxygen (Li–O2) batteries suffer from large charge overpotentials related to the electronic resistivity of the insulating lithium peroxide (Li2O2) discharge product. One potential solution is the formation and stabilization of a lithium superoxide (LiO2) discharge intermediate that exhibits good electronic conductivity. However, LiO2 is reported to be unstable at ambient temperature despite its favorable formation energy at −1.0 eV per atom. In this paper – based on our recent work on the development of cathode materials for aprotic lithium oxygen batteries including two intermetallic compounds, LiIr3 and LiIr, that are found to form good template interfaces with LiO2 – a simple goodness of fit R factor to gauge how well a template surface structure can support LiO2 growth, is developed. The R factor is a quantitative measurement to calculate the geometric difference in the unit cells of specific Miller Index 2D planes of the template surface and LiO2. Using this as a guide, the R factors for LiIr3, LiIr, and La2NiO4+δ, are found to be good. This guide is attested by simple extension to other noble metal intermetallics with electrochemical cycling data including LiRh3, LiRh, and Li2Pd. Finally, the template concept is extended to main group elements and the R factors for LiO2 (111) and Li2Ca suggest that Li2Ca is a possible candidate for the template assisted LiO2 growth strategy. [ABSTRACT FROM AUTHOR]

Lithium–air batteries promise exceptional energy density while avoiding the use of transition metals in their cathodes, however, their practical adoption is currently held back by their short lifetimes. These short lifetimes are largely caused by electrolyte breakdown, but despite extensive searching, an electrolyte resistant to breakdown has yet to be found. This paper considers the requirements placed on an electrolyte for it to be considered usable in a practical cell. We go on to examine ways, through judicious cell design, of relaxing these requirements to allow for a broader range of compounds to be considered. We conclude by suggesting types of molecules that could be explored for future cells. With this work, we aim to broaden the scope of future searches for electrolytes and inform new cell design. [ABSTRACT FROM AUTHOR]

Lithium–oxygen batteries are promising but have many challenges. Unlike lithium-ion batteries, they are usually discharge–charge cycled with capacity cutoff instead of potential cutoff, which brings controversy. Additionally, which superoxide intermediate, the dissolved or the adsorbed superoxide, is more reactive and leads to cell premature death and unsatisfactory discharge capacity? These questions puzzle researchers and impede the development of lithium–oxygen batteries. Herein, on one hand, we tried to decouple the influence of discharging potential and discharging current density on the discharge products and side reactions. We found that the electrode potential has more impact on the side reactions than the current density. The low potential leads to a high ratio of Li2CO3 to Li2O2 in the discharge product and hence more surface passivation. On the other hand, to identify the more reactive and aggressive species that cause surface passivation, a flow cell setup was applied to suppress the solution route and maximize the products from the surface route. Results show that more Li2CO3 was identified under a large flow rate and thus the intermediates in surface route appear to be more reactive than that in solution route. [ABSTRACT FROM AUTHOR]

Organic electrosynthesis has a long history. However, this chemistry is still new. Recently, we have seen its second renaissance with organic electrosynthesis being considered a typical green chemistry process. Therefore, a number of novel electrosynthetic methodologies have recently been developed. However, there are still many problems to be solved from a green and sustainable viewpoint. After an explanation of the historical survey of organic electrosynthesis, this paper focuses on recent remarkable developments in new electrosynthetic methodologies, such as novel electrodes, recyclable nonvolatile electrolytic solvents and recyclable supporting electrolytes, as well as new types of electrolytic flow cells. Furthermore, novel types of organic electrosynthetic reactions will be mentioned. [ABSTRACT FROM AUTHOR]

In the midst of an ongoing energy crisis, the search for new methods of energy harvesting has never been more important. Here we explore, analyse and discuss principles of ionotronic reverse-actuator devices based on the effect of double-layer charging. The designs that we consider in this paper operate based on a common principle – using external mechanical work, which would otherwise be wasted, to produce changes in the contact area of electrode and electrolyte, translated into the time variation of the double-layer capacitance. Periodic variation of capacitance, when connected to a reference voltage source, produces alternating electric current through a load. This concept is not new and in some forms was realised in the early works of Boland, Krupenkin and several papers of our group. The goal of the present paper is to build a comprehensive analytical platform for a description of operation of such devices in terms of materials, generated power as a function of the frequency of variation of applied force, electrical load, and other factors; the understanding of which allows us to optimise these systems and navigate their construction. The first design, discussed in the paper, is based on flat electrodes. It is the simplest one and, as such, helps elucidate some key factors determining power generation. While being easy to realise experimentally, it generates relatively low power, even when optimised. The second design, based on microporous electrodes is more sophisticated and allows a much larger power harvest. The results are also compared to the recently proposed capacitive rotor device. The developed theory is set to capture the key factors that determine the functioning of the considered reverse actuators. The structures under study are matched to fit into the sole of a shoe and produce power from walking and running. However, they can also be scaled-up to larger operating systems and various external loads. [ABSTRACT FROM AUTHOR]

The Faraday Discussion on New memory paradigms: memristive phenomena and neuromorphic systems was held from October 15–17 on the campus of the Rheinisch-Westfälische Technische Hochschule Aachen University, or RWTH Aachen University, under the auspices of the Royal Society of Chemistry. The Discussion brought together over 100 experts and students from over 20 different countries to present, question, and debate the latest breakthroughs in a field that is exhibiting dramatic growth. There were a large number of excellent oral presentations and posters covering the topics of the Discussion, and the conversations among the participants were lively and informative. The first day and a half encompassed the experimental characterization and analysis of memristors for which the primary resistive switching mechanisms involved electrochemical metallization, chemical valence transformation, or thermodynamic phase change, which illustrated the diversity of the physical properties that can be harnessed for building memristive systems. The final half-day of the Discussion was devoted to synaptic and neuromorphic functions of memristors, which have been growing explosively in the past few years and demonstrate that resistive switching is important for much more than a non-volatile memory, but can also be utilized for learning and computation. The high quality of the presentations and discussions in this section demonstrated that this new research area has been solidly launched and we can expect significant advancements and real applications within a few years as new discoveries from biology are incorporated into neuromorphic hardware. I will not attempt to recapitulate the content of all of the sessions here, since the papers collected for this Faraday Discussions volume speak more eloquently for themselves than I can affect. What I hope to accomplish is to point out a few general concepts that arose when considering multiple papers together, especially during the discussions, and point out a particularly novel concept that deserves special attention. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Faraday Discussions" volume 250, published in 2024. It provides information about the editorial staff, subscription prices, and contact details for the Royal Society of Chemistry. The journal focuses on discussions and papers related to challenges and prospects in organic photonics and electronics. The document also includes a list of sponsors, poster titles, and a list of participants. [Extracted from the article]

The Faraday Discussion meeting on 'challenges and prospects in organic and photonics and electronics' was held in Osaka, Japan, after the COVID pandemic and during the subsequent global difficulties, in the traditional face-to-face and condensed style, with many discussions, both after the short presentations and in front of the poster presentations. I would like to take this opportunity to thank the organising members, particularly Youhei Takeda and local professors, for their efforts in organising this meeting. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Faraday Discussions" volume 249, published in 2024. The journal focuses on the physical chemistry of the Royal Society of Chemistry and covers topics at the interface of chemistry, physics, and biology. The contents list includes papers and discussions on various aspects of water at interfaces, such as ion interactions, spectroscopy, hydrophobic hydration, ice nucleation, and interfacial water dynamics. The document also provides information about the editorial staff, subscription prices, and contact details for the Royal Society of Chemistry. [Extracted from the article]

This document is a discussion from the journal Faraday Discussions on the topic of electrified/charged aqueous interfaces. The discussion covers various aspects of simulating non-planar electrode surfaces, the role of water and ions in shaping the interfacial potential, and the behavior of ions near the charged surface. The simulations presented in the paper suggest that water plays a dominant role in shaping the potential profile, while ions may have a lesser effect. The text also discusses the challenges in interpreting experimental observations and the need for further research to understand interfacial water structure. Additionally, the document explores the behavior of ions and water molecules near charged surfaces in simulations, the effect of electric fields on water dynamics, and the use of different simulation methods to study nanoporous carbons and electrolyte-filled pore spaces. The researchers emphasize the importance of combining different techniques to obtain a comprehensive understanding of the interface. [Extracted from the article]

This paper provides a summary of the Faraday Discussions meeting on "Mechanochemistry: fundamentals, applications, and future" in the context of broad themes whose exploration might contribute to a unified framework of mechanochemical phenomena. [ABSTRACT FROM AUTHOR]

Alessandro Molle responded: Al 2 O 3 encapsulation of Xenes was engineered to minimizeornullifytheeffectonthesiliceneandmoregenerallyontheXenes. Alessandro Molle answered: The DFT simulation is reported as a conceptual experiment to sustain the experimental picture resulting from the XPS and Raman spectroscopy evidence of silicene stabilization aer encapsulation. Claudia Backes, Szymon Bartus, Cinzia Casiraghi, Andrea Ferrari, Ali Reza Kamali, Miroslav Kol ' ibal, Vimal Kumar, Alessandro Molle, Andrea Oyarzun, Vincenzo Palermo, Amretashis Sengupta, Alessandro Silvestri and Hua Zhang DOI: 10.1039/D1FD90006D Alessandro Silvestri opened the discussion of the paper by Alessandro Molle: Can the encapsulation technique described in the paper affect the chemicalphysical properties of the 2D material encapsulated? Thisfact stems from the details of the Al 2 O 3 growth, namely Al 2 O 3 is sequentially grown aer silicene,developingrstthroughAlsinglelayergrowthfollowedbyAl-O 2 co-deposition at room temperature, eventually ending up with a nal Al 2 O 3 layer with controlled thickness. [Extracted from the article]

The aim of this paper is to describe the scientific journey taken to arrive at present-day nanoelectrochemistry and consider how the area might develop in the future, particularly in light of papers presented at this Faraday Discussion. By adopting a generational approach, this brief contribution traces the story of the nanoelectrochemistry family within the broader electrochemistry field, with a focus on scientific capability and themes that were important to each generation. I shall consider research questions and the impact of technology that was developed or available in each period. Nanoelectrochemistry is still somewhat niche, but is attracting increasing numbers of researchers. It is set to become a major part of electrochemistry and interfacial science. It is studied by people with a fairly unique skillset, and I shall speculate on the skills and expertise that will be needed by nanoelectrochemists to address the challenges and opportunities that lie ahead. I conclude by asking: who will be the nanoelectrochemists of the future and what will they do? [ABSTRACT FROM AUTHOR]

Nanoelectrochemistry, where electrochemical processes are controlled and investigated with nanoscale resolution, is gaining more and more attention because of the many potential applications in energy and sensing and the fact that there is much to learn about fundamental electrochemical processes when we explore them at the nanoscale. The development of instrumental methods that can explore the heterogeneity of electrochemistry occurring across an electrode surface, monitoring single molecules or many single nanoparticles on a surface simultaneously, have been pivotal in giving us new insights into nanoscale electrochemistry. Equally important has been the ability to synthesise or fabricate nanoscale entities with a high degree of control that allows us to develop nanoscale devices. Central to the latter has been the incredible advances in nanomaterial synthesis where electrode materials with atomic control over electrochemically active sites can be achieved. After introducing nanoelectrochemistry, this paper focuses on recent developments in two major application areas of nanoelectrochemistry; electrocatalysis and using single entities in sensing. Discussion of the developments in these two application fields highlights some of the advances in the fundamental understanding of nanoelectrochemical systems really driving these applications forward. Looking into our nanocrystal ball, this paper then highlights: the need to understand the impact of nanoconfinement on electrochemical processes, the need to measure many single entities, the need to develop more sophisticated ways of treating the potentially large data sets from measuring such many single entities, the need for more new methods for characterising nanoelectrochemical systems as they operate and the need for material synthesis to become more reproducible as well as possess more nanoscale control. [ABSTRACT FROM AUTHOR]

Dihydrolevoglucosenone (DLG or Cyrene™) solvent is a green dipolar solvent produced from cellulose waste. Different studies have demonstrated that it can successfully replace dipolar solvents, such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA) and N-methylpyrrolidinone (NMP), in a variety of chemical reactions. In this paper, the first application of DLG in organic electrosynthesis is described, with results of its use in the electrochemical reduction of benzophenone derivatives (ca. E = −1.75 V vs. Ag/AgCl), as a greener alternative to other dipolar solvents with environmental concerns. Conductivity measurements show that the solvent presents conductivity and viscosity limitations that can be overcome by using EtOH as a cosolvent. The DLG/EtOH mixture resulted in a convenient solvent to carry out galvanostatic electroreductions of starting materials that exhibit high potential value. Furthermore, the reaction pathway (1e− or 2e−) was found to be dependent on the supporting electrolyte used; TBABF4 favored 2e− reduction to the corresponding alcohol (52–85%), whereas LiClO4 promoted C–C pinacolic coupling (47–70%). [ABSTRACT FROM AUTHOR]

Transition metal catalysis hinges on the formation of metal–carbon bonds during catalytic cycles. The stability and reactivity of these bonds are what determine product chemo-, regio-, and enantioselectivity. The advent of electrosynthetic methodologies has placed the current understanding of these metal–alkyl bonds into a new environment of charged species and electrochemically induced reactivity. In this paper, we explore the often neglected impact of supporting electrolyte on homogeneous electrocatalytic mechanisms using the catalytic reduction of benzyl chlorides via Co and Fe tetraphenylporphyrins as a model reaction. The mechanism of this reaction is confirmed to proceed through the formation of the metal–alkyl intermediates. Critically, the stability of these intermediates, in both the Co and Fe systems, is found to be affected by the hydrodynamic radius of the supporting electrolyte, leading to differences in electrolyte–solvent shell. These studies provide important information for the design of electrosynthetic reactions, and provide a starting point for the rational design of functional supporting electrolytes. [ABSTRACT FROM AUTHOR]

In many practical applications, ions are the primary charge carrier and must move through either semipermeable membranes or through pores, which mimic ion channels in biological systems. In analogy to electronic devices, the "iontronic" ones use electric fields to induce the charge motion. However, unlike the electrons that move through a conductor, motion of ions is usually associated with simultaneous solvent flow. A study of electroosmotic flow through narrow pores is an outstanding challenge that lies at the interface of non-equilibrium statistical mechanics and fluid dynamics. In this paper, we will review recent works that use dissipative particle dynamics simulations to tackle this difficult problem. We will also present a classical density functional theory (DFT) based on the hypernetted-chain approximation (HNC), which allows us to calculate the velocity of electroosmotic flows inside nanopores containing 1 : 1 or 2 : 1 electrolyte solution. The theoretical results will be compared with simulations. In simulations, the electrostatic interactions are treated using the recently introduced pseudo-1D Ewald summation method. The zeta potentials calculated from the location of the shear plane of a pure solvent are found to agree reasonably well with the Smoluchowski equation. However, the quantitative structure of the fluid velocity profiles deviates significantly from the predictions of the Smoluchowski equation in the case of charged pores with 2 : 1 electrolyte. For low to moderate surface charge densities, the DFT allows us to accurately calculate the electrostatic potential profiles and the zeta potentials inside the nanopores. For pores with 1 : 1 electrolyte, the agreement between theory and simulation is particularly good for large ions, for which steric effects dominate over the ionic electrostatic correlations. The electroosmotic flow is found to depend very strongly on the ionic radii. In the case of pores containing 2 : 1 electrolyte, we observe a reentrant transition in which the electroosmotic flow first reverses and then returns to normal as the surface change density of the pore is increased. [ABSTRACT FROM AUTHOR]

Gradients of voltage, pressure, temperature, and salinity can transport objects in micro- and nanofluidic systems by well-known mechanisms. This paper explores the dynamics of particles in a viscosity gradient with numerical simulations. The different stochastic rules used to integrate the random motion of Brownian particles affect the steady-state distribution of particles in a diffusivity gradient. Importantly, the simulations illuminate the important role that the boundary conditions play, disallowing a steady-state flux when the boundary conditions mimic those of a closed container, but allowing flux when they mimic electrodes. These results provide an interpretation for measurements of a steady ionic current flowing between electrodes separated by a nanofluidic channel with a liquid viscosity gradient. [ABSTRACT FROM AUTHOR]

Multi-line molecular observations are an ideal tool for a systematic study of the physico-chemical processes in the Interstellar Medium (ISM), given the wide range of critical densities associated with different molecules and their transitions, and the dependencies of chemical reactions on the energy budget of the system. Recently high spatial resolution of typical shock tracers – SiO, HNCO, and CH3OH – have been studied in the potentially shocked regions in two nearby galaxies: NGC 1068 (an AGN-host galaxy) (Huang et al., Astron. Astrophys., 2022, 666, A102; Huang et al., in prep.) and NGC 253 (a starburst galaxy) (K.-Y. Huang et al., arXiv, 2023, preprint, arXiv:2303.12685, DOI: 10.48550/arXiv.2303.12685). This paper is dedicated to the comparative study of these two distinctively different galaxies, with the aim of determining the differences in their energetics and understanding large-scale shocks in different types of galaxies. [ABSTRACT FROM AUTHOR]

The document is a contents list for the journal "Faraday Discussions" for the year 2024. It provides information about the editorial staff, publishing details, and subscription prices. The journal focuses on rapidly developing areas of chemistry and its interfaces with other scientific disciplines. The specific issue covered in this document is a General Discussion on Rechargeable non-aqueous metal-oxygen batteries, which took place in York, UK in September 2023. The document also includes a list of papers and discussions featured in the journal. [Extracted from the article]

Cellulose nanocrystals (CNCs) are topical in materials science but their full potential is yet to be fulfilled because of bottlenecks in the production: the process consumes huge amounts of water, recycling the strong acid catalyst is difficult, and purification steps are cumbersome, particularly with lengthy dialysis. Production of CNCs with HCl vapour overcomes many of these difficulties but the dispersion of CNCs from the already hydrolysed fibre matrix is a formidable challenge. This study is a fundamental effort to explore very basic means to facilitate CNC dispersion from cotton linter fibres (filter paper), hydrolysed to levelling off degree of polymerization by HCl vapour. The introduction of carboxylic groups on the cellulose crystal surface proved the most efficient method to alleviate dispersion with good yields (ca. 50%) and a provisional possibility to tune the CNC length. By contrast, attempts to directly disperse untreated hydrolysed fibres in various organic solvents and aqueous surfactant solutions were unsuccessful. The results showed that hydrolysis of native cellulose fibres by HCl vapour is indeed a viable method for producing CNCs but it has more potential as a pre-treatment step rather than a full-fledged process on its own. [ABSTRACT FROM AUTHOR]

With the increase in the greenhouse effect and reduction of fossil fuel resources, it is urgent to find a feasible solution to directly convert power to chemicals using renewable energy and achieving zero carbon emissions targets. It is necessary to convert renewable energy (i.e., solar, wind, water, etc.) into electrical power replacing fossil-fuel-fired power. Therefore, the power-to-chemicals approach is gaining more and more attention. In the past two decades, non-thermal plasma, electro-catalysis, photo-catalysis, and their hybrid approaches have shown great potential for the power-to-chemicals solution. This paper introduces the application of plasma technology in energy conversion, focusing on three main routes for plasma-enabled ammonia synthesis, and analyses the state-of-the-art. Research results of ammonia synthesis based on plasma technology are discussed. The application of advanced in situ diagnostics evidences the importance of specific intermediate species and reaction pathways. Electrons, vibrationally-excited species, free radicals, and surface-adsorbed species play important roles in plasma-catalytic ammonia synthesis. Combined with experiments and simulations, the mechanisms of plasma-catalytic ammonia synthesis are examined. Vibrationally-excited species can effectively reduce the catalytic surface energy barrier. The techno-economics of the plasma-enabled ammonia synthesis technology is discussed in view of its competitive advantages. It is emphasized that the power-to-chemicals approach can be adapted for most chemical manufacturers, and these methods would play crucial roles in reducing carbon emissions and environmental pollution. Finally, suggestions are provided for the sustainable development of the power-to-chemicals industry in the future. [ABSTRACT FROM AUTHOR]

The field of nanoalloys has been advancing at a rapid pace in the last two decades. Many new characterization methods and theoretical advances have produced a substantial knowledge of the nanoalloys' properties and structure. Most of the work has been limited to binary alloys. A path forward for the field will be the study of nanoalloys with three or more metals. Adding new components will produce new properties and possibly more fabrication controls. In this paper, we will discuss the challenges that will arise in multi-metallic nanoalloys. We will show that entropy and twin boundaries play a dominant role in multi-metallic alloys. [ABSTRACT FROM AUTHOR]

Sources identied include gas-phase reactions, heterogeneous processes (dark and photo-enhanced, on ground and aerosol surfaces), combustion emissions (road traffic, biomass burning, wildres),biogenic sources(soil bacteria,biocrusts), potential ocean surface sources, andcondensedphasephotolysis (e.g.ofnitrate aerosol). Adam Milsom returned to the discussion of the paper by Guo Li by communicating: The phase state of an aerosol can affect key aerosol multiphase processes such as chemical reaction and water uptake. Danah Alshammari, William Bloss, Ying Chen, Judith C. Chow, Shahzad Gani, Roy Harrison, Dawei Hu, Guo Li, Gordon McFiggans, Adam Milsom, Andrea M. Oyarz ' un Aravena, Christian Pfrang, Zongbo Shi, Deepchandra Srivastava, Peter Styring, Hang Su, John G. Watson and Jingsha Xu DOI: 10.1039/D1FD90015C Ying Chen opened the discussion of the paper by Guo Li: I have a question regardingyouroutdoorchamber. For the inorganic particles, the aerosol concentrations are estimated by the anion concentrations, in equilibrium with the measured NH 3 (g). [Extracted from the article]

As part of an ongoing study of the structure and properties of mixtures of ionic liquids in which one component has a hydrocarbon chain and the other a semiperfluorocarbon chain, we now report a study of the mixtures [C8MIM]1−x[C10MIM-F17]x[Tf2N], [C10MIM]1−x[C8MIM-F13]x[Tf2N] and [C10MIM]1−x[C10MIM-F17]x[Tf2N], where [C8MIM][Tf2N] is 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide, [C10MIM][Tf2N] is 1-decyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C8MIM-F13][Tf2N] is 1-(1H,1H,2H,2H-perfluorooctyl)-3-methylimidizolium bis(trifluoromethylsulfonyl)imide and [C10MIM-F17][Tf2N] is 1-(1H,1H,2H,2H-perfluorodecyl)-3-methylimidizolium bis(trifluoromethylsulfonyl)imide. The mixtures were investigated using small-angle X-ray (SAXS) and neutron (SANS) scattering complemented by molecular dynamics simulations (with viscosity and surface tension measurements also possible for the mixtures [C10MIM]1−x[C8MIM-F13]x[Tf2N]). Unlike previous studies of [C8MIM]1−x[C8MIM-F13]x[Tf2N], where no strong evidence of alkyl/fluoroalkyl chain segregation or triphilic behaviour was seen (Elstone et al., J. Phys. Chem. B, 2023, 127, 7394–7407), these new mixtures show the formation of small aggregates of varying sizes of each component, even though all were co-miscible across the full range of compositions. Thus, while a clear polar non-polar peak (PNPP) was observed at large or small values of x, at intermediate compositions the small-angle neutron scattering at low q was dominated by scattering from these small aggregates, while at other compositions, there was little or no evidence of the PNPP. The origins of this behaviour are discussed in terms of inter-chain interactions. [ABSTRACT FROM AUTHOR]

Highly concentrated battery electrolytes exhibit a low flammability as well as a high thermal and electrochemical stability, and they typically form stable solid electrolyte interphases in contact with electrode materials. The transport properties of these electrolytes in batteries are strongly influenced by correlated movements of the ions. In the case of a binary electrolyte, the transport properties can be described by three Onsager coefficients and a thermodynamic factor. In order to determine these four target quantities, at least four experimental quantities are needed. Overdetermination by measuring five or more experimental quantities is uncommon. Here we have combined electrochemical impedance spectroscopy, electrophoretic NMR measurements and concentration cell measurements for characterizing two highly concentrated sulfolane/LiFSI electrolytes. Two sets of four experimental quantities and one set of five experimental quantities were compared with regard to the uncertainties of the resulting four target quantities. We show that the methods employing only four experimental quantities either lead to large uncertainties of the Onsager coefficients or to large uncertainties of the thermodynamic factor, while only the overdetermination by five experimental quantities leads to acceptable uncertainties of all four target quantities. The results for the Onsager coefficients are discussed with regard to dynamic ion correlations and to transport limitations in battery cells. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DESs) are a class of ionic liquid with emerging applications in ionometallurgy. The characteristic high viscosity of DESs, however, limit mass transport and result in slow dissolution kinetics. Through targeted application of high-power ultrasound, ionometallurgical processing time can be significantly accelerated. This acceleration is primarily mediated by the cavitation generated in the liquid surrounding the ultrasound source. In this work, we characterise the development of cavitation structure in three DESs of increasing viscosity, and water, via high-speed imaging and parallel acoustic detection. The intensity of the cavitation is characterised in each liquid as a function of input power of a commercially available ultrasonic horn across more than twenty input powers, by monitoring the bubble collapse shockwaves generated by intense, inertially collapsing bubbles. Through analysis of the acoustic emissions and bubble structure dynamics in each liquid, optimal driving powers are identified where cavitation is most effective. In each of the DESs, driving the ultrasonic horn at lower input powers (25%) was associated with greater cavitation performance than at double the driving power (50%). [ABSTRACT FROM AUTHOR]

Nanoparticles (NPs) of iron oxide are dispersed in mixtures of water and ionic liquid, here ethylammonium nitrate (EAN), and the NP/NP and NP/solvent interactions are studied. They are analysed via small-angle X-ray scattering and dynamic light scattering coupled to forced Rayleigh scattering, from 22 °C to 80 °C. The NPs are well-dispersed as individual objects in the whole range of compositions and temperatures thanks to sufficient repulsion due to the organization of the solvents at the interface. The surface changes from hydrophilic to hydrophobic around a proportion of 50 vol% water : 50 vol% EAN, following the evolution of the bulk mixtures, which remain heterogeneous in the whole range of compositions. [ABSTRACT FROM AUTHOR]

Room-temperature ionic liquids are an exciting group of materials with the potential to revolutionize energy storage. Due to their chemical structure and means of interaction, they are challenging to study computationally. Classical descriptions of their inter- and intra-molecular interactions require time intensive parametrization of force-fields which is prone to assumptions. While ab initio molecular dynamics approaches can capture all necessary interactions, they are too slow to achieve the time and length scales required. In this work, we take a step towards addressing these challenges by applying state-of-the-art machine-learned potentials to the simulation of 1-butyl-3-methylimidazolium tetrafluoroborate. We demonstrate a learning-on-the-fly procedure to train machine-learned potentials from single-point density functional theory calculations before performing production molecular dynamics simulations. Obtained structural and dynamical properties are in good agreement with computational and experimental references. Furthermore, our results show that hybrid machine-learned potentials can contribute to an improved prediction accuracy by mitigating the inherent shortsightedness of the models. Given that room-temperature ionic liquids necessitate long simulations to address their slow dynamics, achieving an optimal balance between accuracy and computational cost becomes imperative. To facilitate further investigation of these materials, we have made our IPSuite-based training and simulation workflow publicly accessible, enabling easy replication or adaptation to similar systems. [ABSTRACT FROM AUTHOR]

This document is a list of research papers and posters presented at a conference on biocatalysis and enzymatic reactions. The papers cover a range of topics, including the synthesis of chiral alcohols, protein dynamics in enzyme catalysis, hydrogen production, and enzyme catalyzed depolymerization. The posters that received prizes focused on expanding the biocatalytic toolbox and enzymatic enantioselective nucleophilic aromatic substitution. The research comes from universities and institutes in various countries, including the United Kingdom, Italy, Czech Republic, Germany, Spain, Turkey, Chinese Taipei, and Thailand. [Extracted from the article]