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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5

Porous Organic Cage Membranes for Molecular Gas Separations (Final Technical Report for DE-SC0021357)

This proposal aims at demonstrating the development of a novel family of membranes, composed of porous organic cages (POC) which offer the possibility of displaying high separation performance for challenging molecular gas separations relevant to natural gas purification, and olefin/paraffin separation. The proposed POCs synthesized in membrane form will display the most desirable properties of polymers (facile processability and flexibility) and inorganic materials (hierarchically ordered pores with molecular sieving properties) leading to highly selective and permeable membranes. POCs should display distinctive structural, compositional, adsorption and transport properties than those of conventional porous materials, opening the doors for a new research direction in membrane science, and gas separations. Our preliminary results demonstrate the feasibility of preparing POC crystals with controlled size, and continuous POC membranes with remarkable high permeances, and separation ability for CO 2 /CH 4 , N 2 /CH 4 and C 3 H 6 /C 3 H 8 separations serving as a solid foundation for our proposed work. Fundamentally, this proposal aims at elucidating separation mechanisms of different gas mixtures related to natural gas composition, and olefin/paraffin separation over porous organic cage membranes. The proposed research will result in fundamental understanding of adsorption and transport properties of industrially relevant gas molecules through novel microporous membranes, and may lead to the development of a cost effective membrane technology for natural gas purification, and olefin/paraffin separation surpassing the conventional benchmark technology distillation. Furthermore, we aim at demonstrating selective water transport through POC membranes, which can be positively impactful in numerous industrial applications in which water is present. The ability to fabricate thin, chemically and mechanically stable POC membranes for societal relevant gas separations constitute a new and distinctive direction in membrane science. Our proposed work aims at addressing some of the challenges recognized in the Research Agenda for Transforming Separation Science . Specifically: (a) advancing understanding of complex mixtures on separation performance; (b) exploring thermodynamic and kinetic mechanisms through the elucidation of separation mechanisms, and (c) study potential stability issues of the membranes to be assessed by evaluating the long term membrane stability and performance at various temperatures and pressures. The team is uniquely qualified to execute the proposed work. The PI has solid expertise in the rational molecular engineering design of porous crystalline membranes for molecular gas separations. The PNNL collaborator has extensive experience in the synthesis, characterization, and functional applications of microporous crystals, with particular emphasis on gas adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Data supporting the manuscript "Nanometer Scale Imaging to Develop Quantitative Descriptors of Bipolar Membrane Junction Structure"

This dataset contains atomic force microscopy images associated with the manuscript "Nanometer Scale Imaging to Develop Quantitative Descriptors of Bipolar Membrane Junction Structure" by Maria Kelly, Emily R. Dunn, Ellis A. Spickermann, Josephine N. Gruber, César A. Lasalde-Ramírez, P. N. Romero Zavala, Éowyn Lucas, Ankur Gupta, Harry A. Atwater, and Wilson A. Smith. The dataset contains both raw images as well as segmented images produced by the image processing workflow described in the manuscript. A readme file and meta data file are included to provide additional details regarding the sample identity, image acquisition parameters, and file naming scheme.

36 MATERIALS SCIENCE↗

Evaluation of IrO 2 catalysts doped with Ti and Nb at industrially relevant electrolyzer conditions: A comprehensive study

A series of commercial Oxygen Evolution Reaction (OER) IrO 2 -based materials doped with acid-stable titanium and niobium species were comprehensively characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS), and X-ray Scattering. Electrocatalysts were integrated into Membrane Electrode Assembly (MEA) using a fabrication method developed under the US DOE H2NEW consortium. An electrolysis performance in a commercial setup as well as a laboratory screening system was performed at conditions relevant to industrial application. According to the comprehensive characterizations, the studied materials are closer to doped iridium oxides rather than core–shell structures. In an electrolysis cell, the IrO 2 /TiO x catalyst slightly outperforms the IrO 2 /NbO x based on the activity. It was demonstrated that the operation of electrolysis cells at elevated temperatures and the implementation of thinner Nafion-type membranes allows for substantially increased performance, which is consistent with the literature report. Finally, this work provides valuable baselines including characterization and performance for guiding future research in this direction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optimizing microfluidic flow cell geometry for in situ resonant soft X-ray characterization of molecular nanostructures

Liquid-phase resonant soft X-ray scattering (LP-RSoXS) is an emerging label-free technique to probe chemically resolved nanostructures of molecular or hybrid materials in liquid environments. Still, quantitative analysis is hindered by the pressure-induced deformation of thin silicon nitride (SiN) membranes used as windows in microfluidic flow cells, which attenuates the signal in nonlinear ways, making experimental optimization difficult. Here, in this work, we directly characterize this deformation under experimental conditions for a variety of cell configurations. We use this to develop a predictive model that combines transmission effects of SiN bowing, incident X-ray beam profiles, and material-dependent resonant scattering cross sections to simulate the effective scattering intensity at the detector across the carbon K-edge. Maps of the total signal across the flow cell window reveal that increasing the window width and polymer concentration shifts the anisotropic intensity distributions from the center toward the edges of the window. It was determined that an optimal SiN thickness of 50 nm, with a window aperture of 104 μm, maximizes the total signal for typical solute concentrations and energies across the carbon K-edge. Our results overturn the assumption that corner regions dominate the scattering signal, offering explicit design guidelines for maximizing LP-RSoXS signals and significantly advancing the quantitative application of this technique to the characterization of molecular and hybrid nanostructured materials in liquids.

Grabner, Devin [Washington State Univ., Pullman, W↗

Nanometer Scale Imaging to Develop Quantitative Descriptors of Bipolar Membrane Junction Structure

Swings in pH can be achieved by electrically polarizing a bipolar membrane (BPM) to drive water dissociation at the BPM junction for electrochemical conversion and separation processes. BPM junction design is critical to tailor performance for specific applications; however, characterization techniques capable of resolving the nanometer scale physical structure of the junction are limited. We present sample preparation, imaging, and analysis workflows that are adaptable to a variety of BPM junction architectures. Atomic force microscopy produces BPM junction images with nanometer scale lateral resolution for samples with and without a graphene oxide water dissociation catalyst in the junction. Subsequent image segmentation and analysis quantify line edge roughness and catalyst layer thickness as descriptors of junction structure. Comparison of pre- and post-electrodialysis junctions suggests electric field-induced alignment of catalyst particles during electrodialysis. This characterization workflow can inform manufacturing protocols, computational modeling, and failure mode analysis for next-generation BPMs.

97 MATHEMATICS AND COMPUTING↗

X-ray Photoelectron Spectroscopy Analysis of Nafion-Containing Samples: Pitfalls, Protocols, and Perceptions of Physicochemical Properties

X-ray photoelectron spectroscopy (XPS) is one of the most common techniques used to analyze the surface composition of catalysts and support materials used in polymer electrolyte membrane (PEM) fuel cells and electrolyzers, providing important insights for further improvement of their properties. Characterization of catalyst layers (CLs) is more challenging, which can be at least partially attributed to the instability of ionomer materials such as Nafion during measurements. This work explores the stability of Nafion during XPS measurements, illuminating and addressing Nafion degradation concerns. The extent of Nafion damage as a function of XPS instrumentation, measurement conditions, and sample properties was evaluated across multiple instruments. Results revealed that significant Nafion damage to the ion-conducting sulfonic acid species (>50% loss in sulfur signal) may occur in a relatively short time frame (tens of minutes) depending on the exact nature of the sample and XPS instrument. This motivated the development and validation of a multipoint XPS data acquisition protocol that minimizes Nafion damage, resulting in reliable data acquisition by avoiding significant artifacts from Nafion instability. The developed protocol was then used to analyze both thin film ionomer samples and Pt/C-based CLs. Comparison of PEM fuel cell CLs to Nafion thin films revealed several changes in Nafion spectral features attributed to charge transfer due to interaction with conductive catalyst and support species. This study provides a method to reliably characterize ionomer-containing samples, facilitating fundamental studies of the catalyst-ionomer interface and more applied investigations of structure-processing-performance correlations in PEM fuel cell and electrolyzer CLs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anodized Aluminum Oxide Membrane Ionic Memristors

Memory effect in ion transport (IT) at the solid–solution interface is uniquely attractive in that the conductance depends on or “memorizes” the previous states. Hysteretic and rectified transport properties offer exciting potential to developing advanced iontronics and neuromorphic functions, improving the efficiency of energy conversion and electrochemical processes, and overcoming the selectivity-throughput bottleneck in the enrichment of low abundant species for environment- and energy-friendly separations, among others. Herein, memory effects are discovered in the rectified electrokinetic IT through anodized aluminum oxide (AAO) membranes containing densely packed highly ordered nanochannels (10 10 per cm 2 ). Characteristic memristor responses of pinched current–potential loops are resolved in voltammetric experiments and successfully reproduced through finite element simulation. Excitatory and inhibitory conductance states are shown to arise from the enrichment and depletion of mobile charge carriers. Structurewise, the transport symmetry is broken by the barrier oxide layer (BOL) on the one end of the cylindrical nanochannels across the AAO membranes. Charge selectivity is attributed to the gradient(s) of the space charge density across the BOL characterized by depth profiling via X-ray photoelectron spectroscopy analysis. The space charge gradient(s) overcomes the fundamental limitation of widely exploited surface charge effects to enable intense rectification and hysteresis prevailing at very high ionic concentrations up to 1–2 M. A new strategy is developed for controlling the preferential IT direction and selectivity via counterion intercalation and extraction/exchange. Mechanistic understanding is further confirmed through parameter variations such as potential scan rate and ionic strength, which also demonstrates convenient controls of the related functions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of cell compression on the performance and the structure of proton exchange membrane water electrolyzer (PEMWE) assembly

Here, in the field of water electrolysis, the proton exchange membrane water electrolyzer (PEMWE) is currently the most advanced technology for producing hydrogen without emitting CO 2 . Although PEMWE plants are already in operation, further research is needed to improve cell efficiency and reduce the use of rare materials, such as iridium oxide catalysts for the oxygen evolution reaction (OER). One of the main causes of performance loss in PEMWE is the relatively low electric conductivity of the porous transport layer (PTL) and of the anode catalyst layer, which results in ohmic losses and low catalyst utilization during high current density operation. The objective of this study is to investigate how optimization of the PTL and electrode interface can increase the cell performance. To this end, we tested different cell assemblies using fibrous and sintered PTLs, decreasing membrane thickness, reducing iridium loading, and inserting a microporous layer to increase contact surface area. Electrochemical characterization of each cell configuration was systematically performed at various compression levels as the pressure is a crucial parameter influencing the electrode/PTL contact area. In parallel, X-ray microcomputed tomography (micro-CT) was employed to investigate the effects of cell hydration and compression on the structure of PEMWE components. This study combining electrochemistry and micro-CT imaging presents how optimizing the electrode/PTL contact surface area, minimizes ohmic losses, and enables PEMWE operation with low iridium loading at high current densities.

Catalyst - PTL interface↗

Heterogeneous Multilayer Nanopores via Chemically Tuned Dielectric Breakdown for Single‐Molecule Sensing

Solid-state nanopores are powerful platforms for single-molecule sensing, yet their performance is often constrained by fabrication complexity, noise, and limited control over surface properties. Here we report a direct method to fabricate heterogeneous multilayer nanopores using chemically tuned controlled dielectric breakdown (CT-CDB). We integrate hBN, MoS 2 , or graphene atop a silicon nitride membrane to form five distinct bilayer and tri-layer architectures, with bare SiN x nanopore as a control. CT-CDB achieves pore formation reproducibly through material-stacks with high efficiency, good pore size control, and strong yield, validated by various characterizations. Transferrin protein translocation experiments, supported by simulations, reveal that multilayer configurations modulate protein conformations, ionic current blockade and dwell time distributions, reflecting combined effects of membrane type, interfacial chemistry, and local electric field gradients. A supervised machine learning framework is implemented to assist identifying multilayer structure effects embedded in signal signatures, with over 96% accuracy. This work presents a modular and scalable framework for functional nanopore engineering with complex structural integration, thereby expanding the potential of 2D materials in single-molecule sensing applications.

2D materials↗

Atomistic characterization of hydration-dependent fuel cell ionomer nanostructure: validation by vibrational spectroscopy

The development of Nafion alternatives for fuel cells and electrolyzers requires a fundamental understanding of hydration-dependent ion-exchange site acid/base chemistry. We present here reactive force field (ReaxFF) molecular dynamics (MD) simulations of Nafion at varying molar water/ion-exchange-site ratios (λ), which we correlate to our experimental and density functional theory-based vibrational spectra. ReaxFF describes the formation and breaking of covalent bonds, enabling simulations of proton exchange between sulfonic acid/sulfonate groups and water/hydronium. Our MD simulations determine the λ-dependent equilibrium proportions of protonated and deprotonated sites. We find that protonated sites persist across all λ from 0 to 20, challenging the widely accepted notion that all sites are ionized above a threshold λ value (e.g., 3 or 4). Our simulations generate hundreds of realistic exchange site environments, the characterization of which are based on 6 Å radii sulfur-centered ‘inner-spheres’. These inner- and outer-sphere regions elucidate an interplay of stereoelectronic factors that influence protonation states, including the number of inner-sphere waters (Λ). Our simulations produce broad λ-dependent distributions of Λ values, representing non-uniform exchange site hydration. Moreover, we demonstrate that these distributions are specific to both protonated and deprotonated sites, with significant overlap between the two distributions for all non-zero λ. These distributions underpin the IR spectra of hydrated membranes, with each exchange site contributing an IR spectrum characteristic of its protonation state and Λ. We expect that these nanostructural characterizations of Nafion exchange sites will contribute to the development of new ionomers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High protonic resistance of hydrocarbon-based cathodes in PEM fuel cells under low humidity conditions: Origin, implication, and mitigation

Hydrocarbon-based electrodes for proton-exchange membrane fuel cells face challenges in closing the performance gap with electrodes based on perfluorosulfonic acid ionomers, particularly under low humidity conditions. Alongside increased oxygen transport resistance and higher kinetic-induced overpotentials, the protonic resistance of these fluorine-free electrodes is the primary hurdle to improved performance. This study systematically investigates the origin and impact of the cathode protonic resistance on fuel cell performance, utilizing sulfonated phenylated polyphenylenes as hydrocarbon ionomers. Electrochemical characterization at low relative humidity (≤50 %) reveal a high protonic resistance arising from both lower conductivity of the hydrocarbon thin film compared to the bulk membrane and increased cathode tortuosity at a gas transport-optimized ionomer to carbon (I/C) ratio of 0.2. The poor protonic resistance at low relative humidities leads to a non-homogeneous current distribution across the thickness of the cathode electrode, resulting in lower catalyst utilization. To address this issue, reducing the thickness of the cathode CL while maintaining a constant Pt loading (i.e., increasing the Pt on carbon ratio) significantly reduces protonic resistance. This improvement compensates for the kinetic disadvantages of highly loaded carbon particles and results in a considerable performance increase by 40 % at 0.75 V under low relative humidities.

25 ENERGY STORAGE↗

Simultaneous occupancy of Cu C and Cu D in the ammonia monooxygenase active site

Ammonia monooxygenase (AMO), a copper-dependent membrane enzyme, catalyzes the first and rate-limiting step of nitrification: the oxidation of ammonia to hydroxylamine. Despite its central role in the global nitrogen cycle and its biotechnological relevance, structural characterization of AMO has lagged behind that of its homolog, particulate methane monooxygenase (pMMO), due to the slow growth rates of ammonia-oxidizing bacteria and the instability of AMO upon purification. Recent cryoEM studies of Nitrosomonas europaea AMO and Methylococcus capsulatus (Bath) pMMO in native membranes revealed new structural features, including two adjacent copper-binding sites in the transmembrane region, Cu C and Cu D , believed to constitute the active site. Although multiple structures were determined under various conditions, simultaneous occupancy of Cu C and Cu D was never observed, leaving their potential functional interplay unresolved. Here we report the 2.6 Å resolution cryoEM structure of AMO from Nitrosospira briensis C-128 in isolated native membranes. This structure reveals the first instance of simultaneous copper occupancy of the Cu C and Cu D sites, along with occupancy of the periplasmic Cu B site. Electron paramagnetic resonance (EPR) spectroscopic data indicate that the Cu B site is primarily occupied by Cu(II), while Cu C and Cu D are primarily occupied by diamagnetic ions, presumably Cu(I). Notably, a lipid molecule is bound between the Cu C and Cu D sites, separating them by ∼8.0 Å. The results underscore the importance of studying these enzymes in their native environments across species to resolve conserved and divergent molecular features.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Dynamics Investigation of Oil Wetting on Synthetic Polymer Substrates

Understanding the interaction of polymer surfaces with nonpolar, low surface tension liquids, or whether a substrate is oleophobic versus oleophilic, is critical for applications ranging from antifingerprint coatings to oil–water separation membranes and oil spill remediation. Despite its technological importance, the molecular mechanisms underpinning polymer–oil wetting are not well characterized. Here, we employ molecular dynamics simulations to investigate the behavior of n-hexadecane in contact with chemically distinct polymer surfaces, spanning eight constitutional unit chemistries as well as amorphous and crystalline morphologies. This permits a critical examination of both thermodynamic and dynamic descriptors of oleophobicity, including oil contact angle, dewetting free energy, interfacial diffusivity, and a proposed “ghost probe energy,” which does not require explicit simulation of oil–polymer interactions. We find that the oil contact angle does not reliably distinguish oleophobic behavior across polymer chemistries, whereas other metrics provide clearer and more consistent differentiation. Analysis of the results reveals that polymer–oil wetting behavior is primarily governed by interfacial van der Waals interactions and modulated by surface flexibility and morphology. Collectively, this work establishes a computational framework for characterizing oil wetting and provides additional insight into what molecular-level factors dictate trends in oleophobicity.

lipids↗

Anti-Ebola virus mAb 3A6 protects highly viremic animals from fatal outcome via binding GP(1,2) in a position elevated from the virion membrane

Abstract Monoclonal antibodies (mAbs) against Ebola virus (EBOV) glycoprotein (GP 1,2 ) are the standard of care for Ebola virus disease (EVD). Anti-GP 1,2 mAbs targeting the stalk and membrane proximal external region (MPER) potently neutralize EBOV in vitro and are protective in a mouse model of EVD. However, their neutralization mechanism is poorly understood because they target a GP 1,2 epitope that has evaded structural characterization. Using X-ray crystallography and cryo-electron tomography of mAb 3A6 complexed with its stalk–MPER epitope, we reveal a previously undescribed mechanism in which 3A6 binds to a conformation of GP 1,2 that is lifted from the virion membrane. We further show that in both domestic guinea pig and rhesus monkey EVD models, 3A6 provides therapeutic benefit at high-viremia advanced disease stages and at the lowest dose yet demonstrated for any anti-EBOV mAb-based monotherapy. The findings reported here can guide design of next-generation highly potent anti-EBOV therapeutics and vaccines.

Science & Technology - Other Topics↗

A distinct subpopulation of membrane vesicles in Pseudomonas putida is enriched in enzymes for lignin catabolism

Bacterial membrane vesicles (MVs) mediate diverse microbial processes and are emerging as powerful biomedical tools, but MV population heterogeneity remains an open question. Here, we separate, enumerate, and characterize two MV populations from the soil bacterium Pseudomonas putida during growth with or without lignin-derived carbon, a major carbon source from plant cells in the rhizosphere. Small MVs (MV-S, diameter ~100 nm) were produced from all cultures, whereas large MVs (MV-L, diameter ~300 nm) were observed during the late stationary phase of lignin cultivations. MV-S contained selectively packaged proteins with diverse physiological functions, whereas the MV-L proteome was smaller and largely enriched in outer membrane proteins. Interestingly, enzymes known to mediate the catabolism of lignin-derived aromatic compounds were enriched in MV-S. Overall, this study highlights the need for careful consideration of MV populations in microbial systems.

59 BASIC BIOLOGICAL SCIENCES↗

Multimodal In Situ Characterization Uncovers Unexpected Stability of a Cobalt Electrocatalyst for Acidic Sustainable Energy Technologies

An accelerated development of durable and affordable sustainable energy technologies is often hindered by a limited understanding of how non-precious materials within these systems degrade. In acidic proton exchange membrane fuel cells and water electrolyzers, metallic cobalt (Co) is considered an unstable component that is often combined with precious metals or other stabilizers. To understand the mechanisms behind Co instability, we employ an experimental platform that quantifies dissolution with on-line inductively coupled plasma mass spectrometry and product formation with electrochemical mass spectrometry during electrochemical testing, along with ex- situ characterization. Under varied conditions (electrocatalysis, time, gas-type saturation, and ion concentration), windows of Co stability are observed that are different than predicted with classical chemical thermodynamics, suggesting new stabilization and degradation mechanisms than previously understood. Notably, Co is active for the hydrogen evolution reaction (HER), with prolonged stability that is ~300 mV different than thermodynamically projected. Additionally, in an oxygenated environment, Co concurrently performs the HER and oxygen reduction reaction (ORR) yet undergoes different morphology changes and dissolution mechanisms. Interestingly, in the absence of electrocatalysis, there is a 22x decrease in dissolution in an oxygen-free environment, proposing a route to decrease Co losses during device shutdown protocols. Lastly, under more extreme operating conditions, Co becomes stable after a substantial amount of dissolution, suggesting that high concentrations of Co 2+ ions in the microenvironment induce the formation of a stable CoHO 2 surface. Altogether, these results can be leveraged to improve the design and development of more robust and cost-effective sustainable energy technologies, as well as promote strategic strategies for prolonged material utilization.

Dissolution↗

Design and Characterization of Hybrid Multilayer Structures: Layer-by-Layer Growth of Polymer and Graphene Oxide Assemblies and Their Utility in Fuel Cell Applications

We report the layer-by-layer growth of poly- (ethylenimine) (PEI) that has been modified with sulfamate functionalities (S-PEI) using Zr 4+ -complexation interlayer linking chemistry. We have also deposited adlayers of graphene oxide (GO) that have been modified to possess sulfate functionalities (SGO), onto the S-PEI layers. The multilayer assemblies are formed with sulfamate/sulfate and sulfate/sulfate (S-PEI + S-GO) interlayer linking chemistry. In all cases the adlayer thickness is consistent with predictions based on van der Waals volume and/or molecular mechanics calculations. X-ray photoelectron spectroscopy (XPS) is used to characterize the Zr/S stoichiometry in the multilayer assembly. The utility of these hybrid multilayer structures is demonstrated in a Proton Exchange Membrane (PEM) fuel cell, where they are shown to reduce H 2 gas crossover by 15% with only a 12 nm thick layer.

fuel cell↗

Multi-modal characterization of nitrate reduction nano-catalysts with periodic strain distribution

Strain engineering serves as a pivotal strategy to optimize catalytic activity in electrocatalysis. However, the catalyst sizes under industrial conditions are usually large and even beyond nanometer regime. The critical methodological limitations on strain imaging of such catalysts with both large field of view and high spatial resolution obscure the mechanistic understanding of strain-performance correlations. Here, we present an optimized four-dimensional scanning transmission electron microscopy (4D-STEM) method to acquire strain mapping of both bulk and surface across particles up to 500 nm with 0.6 nm spatial resolution and 0.55% precision. We observe the ripple-like periodic strain coupled with elemental fluctuations inside a perovskite-type hydroxide CuCoSn(OH) 6 and find it correlated to electrocatalytic nitrate reduction (NO 3 – RR) absorption energy to achieve the 92.6% Faradaic efficiency and long-term test over 1000 h at membrane electrode assembly (MEA) for ammonia electrosynthesis. This universal framework design offers a practical method that not only develops an advanced measurement combining multi-modal characterization techniques but also reveals the intrinsic structure-property constitutive law of industry-level catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗