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At least 307 records · Page 17

Bridging the Gap between Analytical and Microbial Sciences in Microbiome Research

Metabolites from the microbiome influence human, animal, and environmental health, but the diversity and functional roles of these compounds have only begun to be elucidated. Comprehensively characterizing these molecules are significant challenges, as it requires expertise in analytical methods, such as mass spectrometry and nuclear magnetic resonance spectroscopy, skills that not many traditional microbiologists or microbial ecologists possess. This creates a gap between microbiome scientists that want to understand the role of microbial metabolites in microbiome systems and the skills required to generate and interpret complex metabolomics data sets. To bridge this gap, microbiome scientists should engage analytical chemists to best understand the underlying chemical principles of the data. Conversely, analytical scientists are encouraged to engage with microbiome scientists to better understand the biological questions being asked with metabolomics and to best communicate its intricacies. Better communication across the chemistry/biology disciplines will further reveal the “dark matter” within microbiomes that maintain healthy humans and environments.

59 BASIC BIOLOGICAL SCIENCES↗

Transition from Vogel-Fulcher-Tammann to Arrhenius Ion-Conducting Behavior in Poly(Ethyl Acrylate)-Based Solid Polymer Electrolytes via Succinonitrile Plasticizer Addition

Solid polymer electrolytes (SPEs) offer potential advantages over liquid electrolytes, including flexibility, safety, and processability. However, they suffer from low room-temperature ionic conductivity. Recently, it has been reported a poly(ethyl acrylate) based (polyEA) SPE, by incorporating 50 wt% of succinonitrile (SN) solid plasticizer, 30 wt% of lithium salt and 5 wt% of fluoroethylene carbonate additive, which achieves a high room-temperature ionic conductivity of 1.01 × 10 −3 S cm −1 (Nat. Nanotechnol, 2022, 17, 768-776). This novel SPE exhibits stability against Li 0 and anodic stability up to 4.9 V vs Li + /Li. However, the specific mechanism responsible for its high ionic conductivity remains elusive. In this work, by adjusting the weight ratio of SN in the SPE, a transition from Vogel-Fulcher-Tammann to Arrhenius ion-conducting behavior is observed. It is demonstrated that the addition of SN leads to the gradual decoupling of Li-ion from the polymer backbone and its coordination with SN, as revealed by 6 Li solid-state nuclear magnetic resonance spectroscopy. As a result, Li-ion migration primarily occurs through SN rather than the segmental motion of the polymer backbone. Performances of the SPE in Cu||Li, Li||Li and a LiFePO 4 ||Li pouch cells are shown to demonstrate the commercial viability of this SPE in Li 0 -anode solid-state batteries.

Electrochemistry↗

Peak Map

Peak Map is a software tool that allows users to generate nuclide library files for gamma spectroscopy from a nuclear data reference. SAND2019-15220 M Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Leonard, Elliott↗

Protocols for isolating and characterizing polysaccharides from plant cell walls: a case study using rhamnogalacturonan-II

Abstract Background In plants, a large diversity of polysaccharides comprise the cell wall. Each major type of plant cell wall polysaccharide, including cellulose, hemicellulose, and pectin, has distinct structures and functions that contribute to wall mechanics and influence plant morphogenesis. In recent years, pectin valorization has attracted much attention due to its expanding roles in biomass deconstruction, food and material science, and environmental remediation. However, pectin utilization has been limited by our incomplete knowledge of its structure. Herein, we present a workflow of principles relevant for the characterization of polysaccharide primary structure using nature’s most complex polysaccharide, rhamnogalacturonan-II (RG-II), as a model. Results We outline how to isolate RG-II from celery and duckweed cell walls and from red wine using chemical or enzymatic treatments coupled with size-exclusion chromatography. From there, we applied mass spectrometry (MS)-based techniques to determine the glycosyl residue and linkage compositions of the intact RG-II and derived oligosaccharides including special considerations for labile monosaccharides. In doing so, we demonstrated that in the duckweed Wolffiella repanda the arabinopyranosyl (Ara p ) residue of side chain B is substituted at O- 2 with rhamnose. We used electrospray-MS techniques to identify non-glycosyl modifications including methyl-ethers, methyl-esters, and acetyl-esters on RG-II-derived oligosaccharides. We then showed the utility of proton nuclear magnetic resonance spectroscopy ( 1 H-NMR) to investigate the structure of intact RG-II and to complement the RG-II dimerization studies performed using size-exclusion chromatography. Conclusions The complexity of pectic polysaccharide structures has hampered efforts aimed at their valorization. In this work, we used RG-II as a model to demonstrate the steps necessary to isolate and characterize polysaccharides using chromatographic, MS, and NMR techniques. The principles can be applied to the characterization of other saccharide structures and will help inform researchers on how saccharide structure relates to functional properties in the future.

09 BIOMASS FUELS↗

Contrast Matching Biopolymers: A SANS-Based Approach to Structural Characterization of Chitosan

Immobilizing enzymes in polysaccharide-based matrices has been shown to improve both their stability and their catalytic efficiency. Among available materials, chitosan was selected for its abundance, biocompatibility, and versatility in a range of applications. While the broader aim of this work is to study chitosan as a matrix for immobilizing carbonic anhydrase (CA) for CO₂ capture, this study focused on determining the contrast match point (CMP) of hydrogenated and deuterated chitosan in D₂O:H₂O mixtures to enable future structural investigations using small-angle neutron scattering (SANS). Previous work successfully synthesized deuterated chitosan from Rhizopus oryzae mycelia and assessed the degree of deuteration using Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). Building on this foundation, the current study determined the CMPs of both H-chitosan and D-chitosan by performing SANS measurements across a range of D₂O:H₂O solvent contrasts. The extracted CMPs for both forms correlated well with their respective calculated scattering length densities (SLDs), validating the experimental approach. These results establish a critical reference for selective contrast matching in future SANS studies of carbonic anhydrase immobilized in chitosan matrices, enabling detailed structural analysis of enzyme–matrix interactions.

Kosgallana, Chathurika J [ORNL] (ORCID:00000002851↗

SEDONA: SpEctroscopic Detection of Nerve Agents

Los Alamos National Laboratory developed the only portable screener to accurately detect the chemical nerve agents, providing results in seconds. Current airport detection system cannot scan for the threat of organophosphorus nerve agents and insecticides. Small quantities of these toxic chemicals can very quickly cause widespread exposure and severe symptoms. SEDONA screens through an unopened bottle using the principles of nuclear magnetic resonance spectroscopy. The system could be deployed and operated with minimal training. SEDONA dramatically reduces the likelihood of a successful nerve agent attack at airports, government buildings, embassies, sporting events, concerts, and political rallies.

47 OTHER INSTRUMENTATION↗

Probing photochemical kinetics and mechanisms using photoNMR

Nuclear magnetic resonance spectroscopy (NMR) is a form of spectroscopy that yields detailed mechanistic information about chemical structures, reactions, and processes. Photochemistry has widespread use across many industries and holds excellent utility for additive manufacturing (AM) processes. Here, we use photoNMR to investigate three photochemical processes spanning AM relevant timescales. We first investigate the photodecomposition of a photobase generator on the slow timescale, then the photoactivation of a ruthenium catalyst on the intermediate timescale, and finally the radical polymerization of an acrylate system on the fast timescale. In doing so, we gain fundamental insights to mission relevant photochemistries and develop a new spectroscopic capability at SNL.

36 MATERIALS SCIENCE↗

Design of CO 2 Selective Type 3 Porous Liquids Through Porous Host Morphology

Direct air capture (DAC) of CO 2 is a negative emission technology under development to limit the impacts of climate change. The dilute concentration of CO 2 in the atmosphere (~400 ppm) requires new materials for carbon capture with increased CO 2 selectivity that is not met with current carbon capture materials. Porous liquids (PLs) are an emerging candidate for carbon capture and consists of a combination of solvents and porous hosts that creates a liquid with permanent porosity. The fundamental mechanisms of carbon capture in a PL are relatively unknown. To uncover these mechanisms, PLs were synthesized consisting of three different zeolitic-imidazolate framework (ZIF-8, ZIF-67, or ZIF-69) porous host in a water/glycol/2-methylimidazole solvent. The most stable composition was based on ZIF-8 and exhibited carbon capture following exposure to CO 2 . Density functional theory identified a three-step carbon capture mechanism based on (i) reaction of OH- with ethylene glycol in the solution followed by (ii) formation of 2-hydroxyethyl carbonate, which (iii) further react with OH- to form a carbonate species. This mechanism was validated with experimental nuclear magnetic resonance spectroscopy (NMR) to identify the dissolved carbonate phases and the decrease in the pH during CO 2 exposure. Deuterated samples of the ZIF-8 PLs were synthesized and analyzed via neutron diffraction at the Spallation Neutron Sources at Oak Ridge National Laboratory. Results identified differences in diffraction for PLs pre- and post-CO 2 exposure that will be combined with ab initio molecular dynamics data of the same PL composition to identify how the presence of a solvent-porous host interfaces results in carbon capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dateset for Zeolite-confined organolanthanide catalysts for C-H borylation of hydrocarbons

This dataset supports a publication, "Trimethylaluminum Activates Zeolite-Confined Lanthanum Borohydrides to Enhance Catalytic C–H Borylation", in the Journal of the American Chemical Society which describes the lanthanum borohydride catalyzed reaction of pinacolborane and aromatic, heteroaromatic and aliphatic hydrocarbons. The chemical affects of AlMe3 treatment on the precatalyst are explored in detail. The dataset includes characterization of the precatalyst using solid-state nuclear magnetic resonance spectroscopy, X-ray adsorption spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and density functional theory.

F-block chemistry↗

A bicarbonate-rich liquid condensed phase in non-saturated solutions in the absence of divalent cations

Bicarbonate (HCO 3 - ) and sodium (Na + )-containing solutions contain droplets of a separate, bicarbonate-rich liquid condensed phase (LCP) that have higher concentrations of HCO 3 - relative to the bulk solution in which they reside. The existence and composition of the LCP droplets has been investigated by nanoparticle tracking analysis, nuclear magnetic resonance spectroscopy, refractive index measurements and X-ray pair distribution function analysis. The bicarbonate-rich LCP species is a previously unaccounted-for, ionic phenomenon which occurs even in solutions with solely monovalent cations. Its existence requires re-evaluation of models used to describe and model aqueous solution physicochemistry, especially those used to describe and model carbonate mineral formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Covalent integration of polymers and porous organic frameworks

Covalent integration of polymers and porous organic frameworks (POFs), including metal-organic frameworks (MOFs), covalent organic frameworks (COFs) and hydrogen-bonded organic frameworks (HOFs), represent a promising strategy for overcoming the existing limitations of traditional porous materials. This integration allows for the combination of the advantages of polymers, i.e., flexibility, processability and chemical versatility etc., and the superiority of POFs, like the structural integrity, tunable porosity and the high surface area, creating a type of hybrid materials. These resulting polymer-POF hybrid materials exhibit enhanced mechanical strength, chemical stability and functional diversity, thus opening up new opportunities for applications across a large variety of fields, such as gas separation, catalysis, biomedical applications, environmental remediation and energy storage. In this review, an overview of synthetic routes and strategies on how to covalently integrate different polymers with various POFs is discussed, especially with a particular focus on methods like polymerization within, on and among POF structures. To investigate the unique properties and functions of these resultant hybrid materials, the characterization techniques, including nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM) and scanning electron microscopy (SEM), gas adsorption analysis (BET) and computational modeling and machine learning, are also presented. The ability of polymer-POFs to manipulate the pore environments at the molecular level affords these materials a wide range of applications, providing a versatile platform for future advancements in material science. Looking forward, to fully realize the potential of these hybrid materials, the authors highlight the scalability, green synthesis methods, and potential for stimuli-responsive polymer-POF materials as critical areas for future research.

Hossain, Md Amjad↗

NMR Investigations of Crystalline and Glassy Solid Electrolytes for Lithium Batteries: A Brief Review

The widespread use of energy storage for commercial products and services have led to great advancements in the field of lithium-based battery research. In particular, solid state lithium batteries show great promise for future commercial use, as solid electrolytes safely allow for the use of lithium-metal anodes, which can significantly increase the total energy density. Of the solid electrolytes, inorganic glass-ceramics and Li-based garnet electrolytes have received much attention in the past few years due to the high ionic conductivity achieved compared to polymer-based electrolytes. This review covers recent work on novel glassy and crystalline electrolyte materials, with a particular focus on the use of solid-state nuclear magnetic resonance spectroscopy for structural characterization and transport measurements.

Morales, Daniel J. (ORCID:0000000271845727)↗

Studying the Suitability of Nineteen Lignins as Partial Polyol Replacement in Rigid Polyurethane/Polyisocyanurate Foam

In this study, nineteen unmodified lignins from various sources (hardwood, softwood, wheat straw, and corn stover) and isolation processes (kraft, soda, organosolv, sulfite, and enzymatic hydrolysis) were used to replace 30 wt.% of petroleum-based polyol in rigid polyurethane/polyisocyanurate (PUR/PIR) foam formulations. Lignin samples were characterized by measuring their ash content, hydroxyl content (Phosphorus Nuclear Magnetic Resonance Spectroscopy), impurities (Inductively Coupled Plasma), and pH. After foam formulation, properties of lignin-based foams were evaluated and compared with a control foam (with no lignin) via cell morphology, closed-cell content, compression strength, apparent density, thermal conductivity, and color analysis. Lignin-based foams passed all measured standard specifications required by ASTM International C1029-15 for type 1 rigid insulation foams, except for three foams. These three foams had poor compressive strengths, significantly larger cell sizes, darker color, lower closed-cell contents, and slower foaming times. The foam made with corn stover enzymatic hydrolysis lignin showed no significant difference from the control foam in terms of compressive strength and outperformed all other lignin-based foams due to its higher aliphatic and p-hydroxyphenyl hydroxyl contents. Lignin-based foams that passed all required performance testing were made with lignins having higher pH, potassium, sodium, calcium, magnesium, and aliphatic/p-hydroxyphenyl hydroxyl group contents than those that failed.

59 BASIC BIOLOGICAL SCIENCES↗

From the top: surface-derived carbon fuels greenhouse gas production at depth in a peatland

Tropical peatlands play an important role in global carbon (C) cycling, but little is known about factors driving carbon dioxide (CO 2 ) and methane (CH 4 ) emissions from these ecosystems, especially production in deeper soils. This study aimed to identify source material and processes regulating C emissions originating deep in three sites in a peatland on the Caribbean coast of Panama. We hypothesized that (1) surface-derived organic matter transported down the soil profile is the primary C source for respiration products at depth and that (2) high lignin content results in hydrogenotrophic methanogenesis as the dominant CH 4 production pathway throughout the profile. We used radiocarbon isotopic values to determine whether CO 2 and CH 4 at depth are produced from modern substrates or ancient deep peat, and we used stable C isotopes to identify the dominant CH 4 production pathway. Peat organic chemistry was characterized using 13 C solid-state nuclear magnetic resonance spectroscopy ( 13 C-NMR). We found that deep peat respiration products had radiocarbon signatures that were more similar to surface dissolved organic C (DOC) than deep solid peat. These results indicate that surface-derived organic matter was the dominant source for gas production at depth in this peatland, likely because of vertical transport of DOC from the surface to depth. Lignin, which was the most abundant compound (55 %–70 % of C), increased with depth across these sites, whereas other C compounds like carbohydrates did not vary with depth. These results suggest that there is no preferential decomposition of carbohydrates but instead preferential retention of lignin. Stable isotope signatures of respiration products indicated that hydrogenotrophic rather than acetoclastic methanogenesis was the dominant production pathway of CH 4 throughout the peat profile. These results show that deep C in tropical peatlands does not contribute greatly to surface fluxes of carbon dioxide, with compounds like lignin preferentially retained. This protection of deep C helps explain how peatland C is retained over thousands of years and points to the vulnerability of this C should anaerobic conditions in these wet ecosystems change.

54 ENVIRONMENTAL SCIENCES↗

NMR spectroscopy of coin cell batteries with metal casings

Battery cells with metal casings are commonly considered incompatible with nuclear magnetic resonance (NMR) spectroscopy because the oscillating radio-frequency magnetic fields (“rf fields”) responsible for excitation and detection of NMR active nuclei do not penetrate metals. Here, we show that rf fields can still efficiently penetrate nonmetallic layers of coin cells with metal casings provided “B 1 damming” configurations are avoided. With this understanding, we demonstrate noninvasive high-field in situ 7 Li and 19 F NMR of coin cells with metal casings using a traditional external NMR coil. This includes the first NMR measurements of an unmodified commercial off-the-shelf rechargeable battery in operando, from which we detect, resolve, and separate 7 Li NMR signals from elemental Li, anodic β-LiAl, and cathodic Li x MnO 2 compounds. Real-time changes of β-LiAl lithium diffusion rates and variable β-LiAl 7 Li NMR Knight shifts are observed and tied to electrochemically driven changes of the β-LiAl defect structure.

25 ENERGY STORAGE↗

Nuclear-Electronic Orbital Ehrenfest Dynamics

The recently developed real-time nuclear-electronic orbital (RT-NEO) approach provides an elegant framework for treating electrons and selected nuclei, typically pro- tons, quantum mechanically in nonequilibrium dynamical processes. However, the RT-NEO approach neglects the motion of the other nuclei, preventing a complete de- scription of the coupled nuclear-electronic dynamics and spectroscopy. In this work, we describe the dynamical interaction between the other nuclei and the electron-proton subsystem with the mixed quantum-classical Ehrenfest dynamics method. The NEO- Ehrenfest approach propagates the electrons and quantum protons in a time-dependent variational framework, while the remaining nuclei move classically on the correspond- ing average electron-proton vibronic surface. This approach includes the non-Born- Oppenheimer eects between the electrons and quantum protons with RT-NEO and between the classical nuclei and the electron-proton subsystem with Ehrenfest dynam- ics. Spectral features for vibrational modes involving both quantum and classical nuclei are resolved from the time-dependent dipole moments. Moreover, nuclear quantum ef- fects are included directly in nonadiabatic dynamics simulations. The excited state intramolecular proton transfer in the o-hydroxybenzaldehyde molecule is shown to be faster and to exhibit a larger kinetic isotope eect with NEO-Ehrenfest compared to classical Ehrenfest dynamics. This work shows that the NEO-Ehrenfest method is a powerful tool to study dynamical processes with coupled electronic and nuclear degrees of freedom.

Zhao, Luning↗

A green degumming approach for lignocellulosic kenaf bast using ethanolamine deep eutectic solvent

Traditional chemical degumming methods for lignocellulosic bast fibers pose substantial challenges, especially when dealing with kenaf bast, which has a high lignin content. Here, these challenges include severe pollution and low efficiency, etc. Therefore, this study developed a novel, green, and efficient degumming approach for lignocellulosic kenaf bast, leveraging choline chloride-ethanolamine (ChCl-ETA) alkaline deep eutectic solvent (DES). The efficacy of the ChCl-ETA DES based degumming method was validated through comprehensive chemical composition analysis, scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TG), and two-dimensional (2D) nuclear magnetic resonance (NMR) spectroscopy. Subsequently, the optimal degumming conditions, with a choline chloride to ethanolamine ratio of 1:6 and a degumming temperature of 120 °C, were determined based on the results of the residual gum content. Significantly, the recycled ChCl-ETA DES mixtures could maintain a degumming capacity (revealed by the residual gum content of degummed fibers) comparable to that of the conventional double-boiling method for at least five degumming cycles without purification. Given its low-pollution process and high efficiency, this developed method holds great potential for industrial-scale applications of lignocellulosic bast fibers.

Choline chloride↗