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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]

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]

The state-of-the-art in two new ambient ionization methods for mass spectrometry, desorption electrospray ionization (DESI) and paper spray (PS), is described and their utility is illustrated with new studies on tissue imaging and biofluid analysis. DESI is an ambient ionization method that can be performed on untreated histological sections of biological tissue in the open lab environment to image lipids, fatty acids, hormones and other compounds. Paper spray is performed in the open lab too; it involves electrospraying dry blood spots or biofluid deposits from a porous medium. PS is characterized by extreme simplicity and speed: a spot of whole blood or other biofluid is analyzed directly from paper, simply by applying a high voltage to the moist paper. Both methods are being developed for use in diagnostics as a means to inform therapy. DESI imaging is applied to create molecular maps of tissue sections without prior labeling or other sample preparation. Like other methods of mass spectrometry imaging (MSI), it combines the chemical speciation of multiple analytes with information on spatial distributions. DESI imaging provides valuable information which correlates with the disease state of tissue as determined by standard histochemical methods. Positive-ion data are presented which complement previously reported negative-ion data on paired human bladder cancerous and adjacent normal tissue sections from 20 patients. These data add to the evidence already in the literature demonstrating that differences in the distributions of particular lipids contain disease-diagnostic information. Multivariate statistical analysis using principal component analysis (PCA) is used to analyze the imaging MS data, and so confirm differences between the lipid profiles of diseased and healthy tissue types. As more such data is acquired, DESI imaging has the potential to be a diagnostic tool for future cancer detection in situ; this suggests a potential role in guiding therapy in parallel with standard histochemical and immunohistological methods. The PS methodology is aimed at high-throughput clinical measurement of quantitative levels of particular therapeutic agents in blood and other biofluids. The experiment allows individual drugs to be quantified at therapeutic levels and data is presented showing quantitative drug analysis from mixtures of therapeutic drugs in whole blood. Data on cholesterol sulfate, a new possible prostate biomarker seen at elevated levels in diseased prostate tissue, but not in healthy prostate tissue in serum are reported using paper spray ionization.

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]

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]

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]

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]

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]

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]

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]

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]

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]

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]

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 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]

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]

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]

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]

This paper aims to pull together the main points, messages and underlying themes to emerge from the Discussion. It sets these remarks in the context of where Carbon Capture and Storage (CCS) fits into the spectrum of carbon mitigation solutions required to meet the challenging greenhouse gas (GHG) emissions reduction targets set by the COP21 climate change conference. The Discussion focused almost entirely on carbon capture (21 out of 23 papers) and covered all the main technology contenders for this except biological processes. It included (chemical) scientists and engineers in equal measure and the Discussion was enriched by the broad content and perspectives this brought. The major underlying theme to emerge was the essential need for closer integration of materials and process design – the use of isolated materials performance criteria in the absence of holistic process modelling for design and optimisation can be misleading. Indeed, combining process and materials simulation for reverse materials molecular engineering to achieve the required process performance and cost constraints is now within reach and is beginning to make a significant impact on optimising CCS and CCU (CO2 utilisation) processes in particular, as it is on materials science and engineering generally. Examples from the Discussion papers are used to illustrate this potential. The take-home messages from a range of other underpinning research themes key to CCUS are also summarised: new capture materials, materials characterisation and screening, process innovation, membranes, industrial processes, net negative emissions processes, the effect of GHG impurities, data requirements, environment sustainability and resource management, and policy. Some key points to emerge concerning carbon transport, utilisation and storage are also included, together with some overarching conclusions on how to develop more energy- and cost-effective CCS processes through improved integration of approach across the science-engineering spectrum. The discussion was first-rate in the best traditions of Faraday Discussions and hopefully will foster and stimulate further cross-disciplinary interactions and holistic approaches. [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]

The paper presents a view on the achievements, challenges and prospects of mechanochemistry. The extensive reference list can serve as a good entry point to a plethora of mechanochemical literature. [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]

The electrochemical leaf enables the electrification and control of multi-enzyme cascades by exploiting two discoveries: (i) the ability to electrify the photosynthetic enzyme ferredoxin NADP+ reductase (FNR), driving it to catalyse the interconversion of NADP+/NADPH whilst it is entrapped in a highly porous, metal oxide electrode, and (ii) the evidence that additional enzymes can be co-entrapped in the electrode pores where, through one NADP(H)-dependent enzyme, extended cascades can be driven by electrical connection to FNR, via NADP(H) recycling. By changing a critical active-site tyrosine to serine, FNR's exclusivity for NADP(H) is swapped for unphosphorylated NAD(H). Here we present an electrochemical study of this variant FNR, and show that in addition to the intended inversion of cofactor preference, this change to the active site has altered FNR's tuning of the flavin reduction potential, making it less reductive. Exploiting the ability to monitor the variant's activity with NADP(H) as a function of potential has revealed a trapped intermediate state, relieved only by applying a negative overpotential, which allows catalysis to proceed. Inhibition by NADP+ (very tightly bound) with respect to NAD(H) turnover was also revealed and interestingly, this inhibition changes depending on the applied potential. These findings are of critical importance for future exploitation of the electrochemical leaf. [ABSTRACT FROM AUTHOR]

Noncovalent interaction networks provide a powerful means to represent and analyze protein structure. Such networks can represent both static structures and dynamic conformational ensembles. We have recently developed two tools for analyzing such interaction networks and generating hypotheses for protein engineering. Here, we apply these tools to the conformational regulation of substrate specificity in class A β-lactamases, particularly the evolutionary development from generalist to specialist catalytic function and how that can be recapitulated or reversed by protein engineering. These tools, KIF and KIN, generate a set of prioritized residues and interactions as targets for experimental protein engineering. [ABSTRACT FROM AUTHOR]

Organic synthesis often requires multiple steps where a functional group (FG) is concealed from reaction by a protecting group (PG). Common PGs include N-carbobenzyloxy (Cbz or Z) of amines and tert-butyloxycarbonyl (OtBu) of acids. An essential step is the removal of the PG, but this often requires excess reagents, extensive time and can have low % yield. An overarching goal of biocatalysis is to use "green" or "enzymatic" methods to catalyse chemical transformations. One under-utilised approach is the use of "deprotectase" biocatalysts to selectively remove PGs from various organic substrates. The advantage of this methodology is the exquisite selectivity of the biocatalyst to only act on its target, leaving other FGs and PGs untouched. A number of deprotectase biocatalysts have been reported but they are not commonly used in mainstream synthetic routes. This study describes the construction of a cascade to deprotect doubly-protected amino acids. The well known Bacillus BS2 esterase was used to remove the OtBu PG from various amino acid substrates. The more obscure Sphingomonas Cbz-ase (amidohydrolase) was screened with a range of N-Cbz-modified amino acid substrates. We then combined both the BS2 and Cbz-ase together for a 1 pot, 2 step deprotection of the model substrate CBz- L -Phe OtBu to produce the free L -Phe. We also provide some insight into the residues involved in substrate recognition and catalysis using docked ligands in the crystal structure of BS2. Similarly, a structural model of the Cbz-ase identifies a potential di-metal binding site and reveals conserved active site residues. This new biocatalytic cascade should be further explored for its application in chemical synthesis. [ABSTRACT FROM AUTHOR]

The prenylated-flavin mononucleotide-dependent decarboxylases (also known as UbiD-like enzymes) are the most recently discovered family of decarboxylases. The modified flavin facilitates the decarboxylation of unsaturated carboxylic acids through a novel mechanism involving 1,3-dipolar cyclo-addition chemistry. UbiD-like enzymes have attracted considerable interest for biocatalysis applications due to their ability to catalyse (de)carboxylation reactions on a broad range of aromatic substrates at otherwise unreactive carbon centres. There are now ∼35 000 protein sequences annotated as hypothetical UbiD-like enzymes. Sequence similarity network analyses of the UbiD protein family suggests that there are likely dozens of distinct decarboxylase enzymes represented within this family. Furthermore, many of the enzymes so far characterized can decarboxylate a broad range of substrates. Here we describe a strategy to identify potential substrates of UbiD-like enzymes based on detecting enzyme-catalysed solvent deuterium exchange into potential substrates. Using ferulic acid decarboxylase (FDC) as a model system, we tested a diverse range of aromatic and heterocyclic molecules for their ability to undergo enzyme-catalysed H/D exchange in deuterated buffer. We found that FDC catalyses H/D exchange, albeit at generally very low levels, into a wide range of small, aromatic molecules that have little resemblance to its physiological substrate. In contrast, the sub-set of aromatic carboxylic acids that are substrates for FDC-catalysed decarboxylation is much smaller. We discuss the implications of these findings for screening uncharacterized UbiD-like enzymes for novel (de)carboxylase activity. [ABSTRACT FROM AUTHOR]

Peptide asparaginyl ligases (PALs) hold significant potential in protein bioconjugation due to their excellent kinetic properties and broad substrate compatibility. However, realizing their full potential in biocatalytic applications requires precise control of their activity. Inspired by nature, we aimed to compartmentalize a representative PAL, OaAEP1-C247A, within protein containers to create artificial organelles with substrate sorting capability. Two encapsulation approaches were explored using engineered lumazine synthases (AaLS). The initial strategy involved tagging the PAL with a super-positively charged GFP(+36) for encapsulation into the super-negatively charged AaLS-13 variant, but it resulted in undesired truncation of the enzyme. The second approach involved genetic fusion of the OaAEP1-C247A with a circularly permutated AaLS variant (cpAaLS) and its co-production with AaLS-13, which successfully enabled compartmentalization of the PAL within a patch-work protein cage. Although the caged PAL retained its activity, it was significantly reduced compared to the free enzyme (∼30–40-fold), likely caused by issues related to OaAEP1-C247A stability and folding. Nevertheless, these findings demonstrated the feasibility of the AaLS encapsulation approach and encourage further optimization in the design of peptide-ligating artificial organelles in E. coli, aiming for a more effective and stable system for protein modifications. [ABSTRACT FROM AUTHOR]

The article focuses on a general discussion about the scattering of larger molecules, particularly examining the differences in potential energy surfaces (PES) between HDO, H2O, and D2O. Topics include the reason for stronger back scattering in HDO compared to H2O and D2O, the role of symmetry and potential terms in scattering phenomena, and specific insights into the n10 term affecting back-scattering.

The article focuses on a discussion about scattering in extreme environments, specifically addressing the impact of molecular orientation on nuclear spin coupling measurements. Topics include the effect of relative orientation on measurement outcomes, the role of angular momentum in molecular collisions, and the absence of significant orientation effects in the studied system.

The field of molecular scattering is reviewed as it pertains to gas-gas as well as gas-surface chemical reaction dynamics. We emphasize the importance of collaboration of experiment and theory, from which new directions of research are being pursued on increasingly complex problems. We review both experimental and theoretical advances that provide the modern toolbox available to molecular-scattering studies. We distinguish between two classes of work. The first involves simple systems and uses experiment to validate theory so that from the validated theory, one may learn far more than could ever be measured in the laboratory. The second class involves problems of great complexity that would be difficult or impossible to understand without a partnership of experiment and theory. Key topics covered in this review include crossed-beams reactive scattering and scattering at extremely low energies, where quantum effects dominate. They also include scattering from surfaces, reactive scattering and kinetics at surfaces, and scattering work done at liquid surfaces. The review closes with thoughts on future promising directions of research. [ABSTRACT FROM AUTHOR]

Sulfur atoms serve as key players in diverse chemical processes, from astrochemistry at very low temperature to combustion at high temperature. Building upon our prior findings, showing cyclization to thiophenes following the reaction of ground-state sulfur atoms with dienes, we here extend this investigation to include many additional reaction products, guided by detailed theoretical predictions. The outcomes highlight the complex formation of products during intersystem crossing (ISC) to the singlet surfaces. Here, we employed crossed-beam velocity map imaging and high-level ab initio methods to explore the reaction of S(³P) with 1,3-butadiene and isoprene under single-collision conditions and in low-temperature flows. For the butadiene reaction, our experimental results show the formation of thiophene via H2 loss, a 2H-thiophenyl radical through H loss, and thioketene through ethene loss at a slightly higher collision energy compared to previous observations. Complementary Chirped-Pulse Fourier-Transform mmWave spectroscopy (CP-FTmmW) measurements in a uniform flow confirmed the formation of thioketene in the reaction at 20 K. For the isoprene reaction, we observed analogous products along with the 2H-thiophenyl radical arising from methyl loss and C3H4S (loss of ethene or H2 + acetylene). CP-FTmmW detected the formation of thioformaldehyde via loss of 1,3-butadiene, again in the 20 K flow. Coupled-cluster calculations on the pathways found by the automated kinetic workflow code KinBot support these findings and indicate ISC to the singlet surface, leading to the generation of various long-lived intermediates, including 5-membered heterocycles. [ABSTRACT FROM AUTHOR]

While the rotational energy transfer of ammonia by rare gas atoms and hydrogen molecules has been the focus of many studies, little is known about its vibrational relaxation, even though transitions involving the umbrella bending mode have been observed in many astrophysical environments. Here we explore the vibrational relaxation of the umbrella mode of ammonia induced by collisions with helium atoms by means of the close-coupling method on an ab initio potential energy surface. We compute cross sections up to kinetic energies of 1500 cm−1 and rate coefficients up to a temperature of 300 K for vibrational, rotational, and inversion transitions involving the lowest two vibrational states. We show that vibrational relaxation is much less efficient than rotation–inversion relaxation, although the rate coefficients for vibrational relaxation strongly increase with the temperature. We also observe important differences for vibrationally-elastic transitions within the lowest two vibrational states, i.e., for rotation–inversion transitions. These are a direct consequence of the difference in the tunnelling splitting of the lowest inversion levels. [ABSTRACT FROM AUTHOR]