Structural Chemistry Research Articles

Abstract IA014: Mechanistic insights for the advancement of PPARG inverse agonists in muscle invasive urothelial cancer

Abstract In the last decade, genetic activation of PPARG in muscle invasive urothelial cancer (MIUC) has emerged as a potential therapeutic intervention point. More than two decades ago, the first PPARG covalent inverse agonist was described. While cellularly potent, subsequent drug discovery efforts to understand and improve the pharmacology of this initial inverse agonist were largely unsuccessful until quite recently. We have recently disclosed FX-909, a covalent inverse agonist of PPARG that shows durable tumor regressions in PPARG-activated xenograft models. Detailed structural, biochemical and medicinal chemistry studies were critical to both rational and rapid evolution from previously described covalent PPARG inverse agonists to FX-909, which exhibits both superior pharmacological and in vivo properties. Mechanistic understanding of the altered conformational landscape of PPARG in MIUC integrated with detailed insights into the covalent reaction coordinate of PPARG inverse agonists enabled the design of FX-909, specifically tailored to exhibit robust “conformational biasing” that counters the PPARG conformational “activation bias” observed in MIUC. Citation Format: Jacob I. Stuckey, Jennifer Mertz, Jonathan Wilson, Yong Li, Gregg Chenail, Miljan Kuljanin, James Audia, Robert Sims. Mechanistic insights for the advancement of PPARG inverse agonists in muscle invasive urothelial cancer [abstract]. In: Proceedings of the AACR Special Conference in Cancer Research: Optimizing Therapeutic Efficacy and Tolerability through Cancer Chemistry; 2024 Dec 9-11; Toronto, Ontario, Canada. Philadelphia (PA): AACR; Mol Cancer Ther 2024;23(12_Suppl):Abstract nr IA014.

Fragmentation Considerations Using Amidoamine Oxide Homologs.

This study investigates the mass spectrometric analysis of 10 novel amidoamine oxide compounds, which are innovative hydrogelators for polar solvents. This research aims to identify characteristic fragment patterns for these amide compounds using high-resolution mass spectrometry. Methanol solutions of the compounds were analyzed in positive and negative ion modes, and MS1 and MS2 spectra at 6 collision energy levels were obtained via electrospray ionization and hybrid tandem mass spectrometry. The importance of low-intensity peaks in structure elucidation was emphasized because low-intensity fragments could provide crucial structural information, especially for compounds with similar structures. Chain-length-dependent fragmentation patterns were observed, which could aid in predicting the structures of related compounds. This research highlights the challenges of balancing informative low-intensity peaks with accurate spectral matching in databases. Based on our results, combining mass spectrometry with separation techniques, such as liquid chromatography, could enhance structural elucidation for unknown compounds. This study contributes to the broader field of mass spectrometry and structural chemistry, particularly in the analysis of amide compounds, and future directions are proposed for developing robust algorithms for selecting and interpreting low-intensity peaks to improve compound identification in complex mixtures.

In-situ doping of nitrogen and aluminum on microporous carbon for efficient dichloromethane adsorption

Chlorinated volatile organic compounds (Cl-VOCs) pollute the ecological environment and damage the human health due to their extraordinary stability. To circumvent these risks, a concise integration strategy was proposed to synthesize porous carbon (PC) by N/Al co-doping with decent surface area and concentrated micropore distribution for effective Cl-VOCs adsorption. N/Al co-doped microporous carbon (NAlPC) presented superior dichloromethane (DCM) adsorption capacity (182.50 mg/g at 0.02 kPa and 611.29 mg/g at 39.73 kPa) and outstanding recycling performance (maintaining 87 % of DCM adsorption capacity after five adsorption/desorption regeneration cycles). DCM adsorption experiments showed that pore structure and surface chemistry of NAlPC have a distinct impact on DCM adsorption behavior under different pressure. Desorption tests and theory simulations jointly proved that the introduction of N could develop the micropores of NAlPC, which is beneficial to DCM adsorption. And the doping of Al could counteract the prevention of N in the interaction between NAlPC and DCM, maintaining the powerful binding of NAlPC with DCM. This work provides a facile and economic method to prepare microporous carbon by changing its pore structure and regulating its surface chemistry to enhance the DCM adsorption force and capacity, offering a great insight to the fabrication of microporous carbon adsorbents with hierarchical pore structure and doped heterogeneous element for VOCs abatement.

Molecular Chain Rearrangement of Natural Cellulose‐Based Artificial Interphase for Ultra‐Stable Zn Metal Anodes

AbstractThe unstable electrolyte‐anode interface, plagued by parasitic side reactions and uncontrollable dendrite growth, severely hampers the practical implementation of aqueous zinc‐ion batteries. To address these challenges, we developed a regenerated cellulose‐based artificial interphase with synergistically optimized structure and surface chemistry on the Zn anode (RC@Zn), using a facile molecular chain rearrangement strategy. This RC interphase features a drastically increased amorphous region and more exposed active hydroxyl groups, facilitating rapid Zn2+ diffusion and homogeneous Zn2+ interface distribution, thereby enabling dendrite‐free Zn deposition. Additionally, the compact texture and abundant negatively charged surface of the RC interphase effectively shield water molecules and harmful anions, completely preventing H2 evolution and Zn corrosion. The superior mechanical strength and adhesion of the RC interphase also accommodate the substantial volume changes of Zn anodes even under deep cycling conditions. Consequently, the RC@Zn electrode demonstrates an outstanding cycling lifespan of over 8000 hours at a high current density of 10 mA cm−2. Significantly, the electrode maintains stable cycling even at a 90 % depth of discharge and ensures stable operation of full cells with a low negative/positive capacity ratio of 1.6. This study provides new solution to construct highly stable and deep cycling Zn metal anodes through interface engineering.

Catena-Poly[[di-phenyl-tin(IV)]-di-μ-iso-thio-cyanato]: an unprecedented layered coordination polymer resulting from bridging κ2 N:S thio-cyanato ligands.

In the title compound, di-phenyl-tin(IV) diiso-thio-cyanate, [Sn(NCS)2(C6H5)2] n or Ph2Sn(NCS)2, comparatively long tin-nitro-gen and short tin-sulfur bonds prove that the ambidentate iso-thio-cyanate ion acts as a bridge between two neighboring, octa-hedrally coordinated tin atoms. As a result, the mol-ecules lose their individuality in favor of a layered coordination polymer that represents a new type of mol-ecular inter-actions in the structural chemistry of diorganotin(IV) dihalides/pseudohalides. The tin atom is located on a center of inversion.

Microfluidic Precision Manufacture of High Performance Liquid Chromatographic Microspheres

AbstractA key bottleneck in developing chromatographic material is the chemically entangled control of morphology, pore structure, and material chemistry, which holds back precision material manufacture in order to pursue advanced separation performance. In this work, a precision manufacture strategy based on droplet microfluidics was developed, for production of highly efficient chromatographic microspheres with independent control over particle morphology, pore structure and material chemistry. The droplet‐synthesized microspheres display extremely narrow particle size distribution (CV<3 %), enabling a 100 % production yield due to complete elimination of sieving steps. More importantly, the size of the droplet‐synthesized microspheres is freely adjustable without the need for re‐optimizing chemical recipes or reaction conditions. The resulting materials exhibit excellent separation efficiencies, achieving a reduced plate height of hmin=1.67. This precision manufacture strategy also allows for flexible pore design and continuous pore size adjustment across three orders of magnitudes, providing a novel vehicle for resolution fine‐tuning targeting protein separation. Besides traditional silica, organic–inorganic hybrid silica, zirconia, and titania microspheres can also be precisely synthesized on the same platform, supporting various separation applications and operating conditions. Powered by precision manufacture, super‐throughput production, and versatile chemistry, the high‐performance droplet‐synthesized separation material will pave the way towards green and precision chromatographic industry.

Microfluidic Precision Manufacture of High Performance Liquid Chromatographic Microspheres.

A key bottleneck in developing chromatographic material is the chemically entangled control of morphology, pore structure, and material chemistry, which holds back precision material manufacture in order to pursue advanced separation performance. In this work, a precision manufacture strategy based on droplet microfluidics was developed, for production of highly efficient chromatographic microspheres with independent control over particle morphology, pore structure and material chemistry. The droplet-synthesized microspheres display extremely narrow particle size distribution (CV<3 %), enabling a 100 % production yield due to complete elimination of sieving steps. More importantly, the size of the droplet-synthesized microspheres is freely adjustable without the need for re-optimizing chemical recipes or reaction conditions. The resulting materials exhibit excellent separation efficiencies, achieving a reduced plate height of hmin=1.67. This precision manufacture strategy also allows for flexible pore design and continuous pore size adjustment across three orders of magnitudes, providing a novel vehicle for resolution fine-tuning targeting protein separation. Besides traditional silica, organic-inorganic hybrid silica, zirconia, and titania microspheres can also be precisely synthesized on the same platform, supporting various separation applications and operating conditions. Powered by precision manufacture, super-throughput production, and versatile chemistry, the high-performance droplet-synthesized separation material will pave the way towards green and precision chromatographic industry.

Vanadate Inclusion Leading to Red-Ox-Rich Zircon PrCrO4: Synthesis, Magnetic, and Catalytic Properties.

Rare-earth-based ternary compounds with the formula REBO4 (B = V, Cr, P, As) exhibit rich structural chemistry and associated technologically significant properties. Among the rare-earth chromates, realizing PrCrO4 in a single polymorphic modification has been challenging. Herein, we report the successful stabilization of the zircon polymorph of PrCrO4 by introducing 10 mol % of VO43- instead of CrO43- following a solution combustion method. Compositions with progressively higher amounts of vanadate have been synthesized and characterized extensively. XPS analysis of 10 and 50 mol % VO43- substituted PrCrO4 samples ascertained the existence of Pr3+/4+, Cr4+,5+, and V5+ in them, making it a red-ox-rich system. The tetragonal symmetry of PrCr0.50V0.50O4 was confirmed from the HRTEM images and SAED patterns. FTIR and Raman spectral analyses indicated distorted tetrahedral (Cr/VO4) units with a local site symmetry below D2d. Both d-d and f-f transitions of Cr4+ and Pr3+, respectively, were observed in the absorption spectra. Field and temperature-dependent magnetic measurements of PrCr0.50V0.50O4 confirmed its predominant paramagnetic behavior. The samples possessed porous morphology with a reasonable surface area. PrCr1-xVxO4 (x = 0.00-0.50) samples catalyzed the oxidation of phenol. This study demonstrated B-site tuning in ABO4 systems to select a desired polymorph preferentially.

Molecular Chain Rearrangement of Natural Cellulose-Based Artificial Interphase for Ultra-Stable Zn Metal Anodes.

The unstable electrolyte-anode interface, plagued by parasitic side reactions and uncontrollable dendrite growth, severely hampers the practical implementation of aqueous zinc-ion batteries. To address these challenges, we developed a regenerated cellulose-based artificial interphase with synergistically optimized structure and surface chemistry on the Zn anode (RC@Zn), using a facile molecular chain rearrangement strategy. This RC interphase features a drastically increased amorphous region and more exposed active hydroxyl groups, facilitating rapid Zn2+ diffusion and homogeneous Zn2+ interface distribution, thereby enabling dendrite-free Zn deposition. Additionally, the compact texture and abundant negatively charged surface of the RC interphase effectively shield water molecules and harmful anions, completely preventing H2 evolution and Zn corrosion. The superior mechanical strength and adhesion of the RC interphase also accommodate the substantial volume changes of Zn anodes even under deep cycling conditions. Consequently, the RC@Zn electrode demonstrates an outstanding cycling lifespan of over 8000 hours at a high current density of 10 mA cm-2. Significantly, the electrode maintains stable cycling even at a 90 % depth of discharge and ensures stable operation of full cells with a low negative/positive capacity ratio of 1.6. This study provides new solution to construct highly stable and deep cycling Zn metal anodes through interface engineering.

Optimizing Fe-N-C Electrocatalysts for PEMFCs: Influence of Constituents and Pyrolysis on Properties and Performance

Proton exchange membrane fuel cells (PEMFCs) are promising alternative technologies with applications in stationary power systems, vehicles, and portable electronics due to their low temperature operation, fast start-up, and environmental advantages. However, the high cost of platinum-based catalysts, in particular for the oxygen reduction reaction (ORR) of the cathode side, prevents their widespread incorporation. Fe-N-C electrocatalysts have emerged as viable alternatives to platinum. In this study, different precursor components were investigated for the way that they affect the pyrolysis process, which is crucial for tailoring the final catalyst properties. In particular, carbon allotropes such as carbon Vulcan, Ketjenblack, and carbon nanotubes were selected for their unique structures and properties. In addition, various sources of iron (FeCl2, FeCl3, and K[Fe(SCN)4]) were evaluated. The influence of the pyrolysis atmosphere on the resulting Fe-N-C catalyst structures was also assessed. Through an integrated structure and surface chemistry analyses, as well as electrochemical tests with rotating disk electrode experiments in acidic media, the ORR performance and stability of these catalysts were defined. By examining the relationships between carbon sources and iron precursors, this research provides valuable information for the optimization of Fe-N-C catalysts in fuel cell applications.

One-step green synthesis of multi-morphological carbon nanotube forests for superior microwave absorption and electrocatalysis

Porous carbon materials with multiscale distinctive morphologies hold significant promise in electromagnetic wave stealth/protection and catalysis; however, formidable challenges are highly verbose and resource/time-consuming fabrication processes. Here, we report a one-step solvent/template-free self-expanding carbonization strategy for rapidly fabricating porous carbon foams (Ni/CNT) with zero-dimensional (0D) nanoparticles, one-dimensional (1D) nanotube forests, and three-dimensional (3D) hollow microvesicles. Owing to the multi-morphological structure and low-density feature, the resulting porous carbon foam Ni/CNT-800 achieves a minimum reflection loss of −56.48 dB and an effective bandwidth of 5.44 GHz at a low filler loading of only 9 wt%. Moreover, altering the electronic structure and surface chemistry of carbon foam by phosphorus doping enables a highly reduced durable overpotential (η) of 275 mV for oxygen evolution reaction. This work emphasizes a straightforward strategy for the facile design and efficient fabrication of carbon-based materials with unique multiscale porous morphologies, customizable functions, and various applications.

Optical absorption studies of pulsed-laser-engineered silver nanospheres and their enhanced catalytic performance in the degradation of toxic methylene blue dye

Pulsed laser ablation in liquid is an environment-friendly and one of the fastest physical routes to synthesize surfactant-free and stable metal/metal oxide nanoparticles with high purity and no harmful residues. In this study, we report the synthesis of silver nanospheres (AgNSs) using the nanosecond pulsed laser ablation in liquid (PLAL) technique resulting in the formation of a colloidal solution. Investigation of the optical properties using UV–Vis spectroscopy revealed the effects of laser wavelength, frequency, fluence, ablation time, and re-irradiation on the light absorption of the produced silver nanospheres. Physicochemical characterizations included FE-SEM, XRD, DLS, FTIR, and XPS techniques to evaluate the size, morphology, crystal structure, size distribution, zeta potential, and surface chemistry. FE-SEM studies revealed the formation of well-dispersed spherical Ag nanospheres with an average particle size of 209 nm without any agglomeration. DLS measurements showed high stability with a recorded zeta potential value of −38.27 (+/−1.81) mV and a wider size distribution. The XRD analysis indicated a face-centered cubic crystal structure with the formation of an oxide layer over the metallic silver core. The presence of silver and oxygen was confirmed through XPS studies with binding energies at 368.1 eV and 374.1 eV and oxide formation on the surface of Ag NSs. Finally, the catalytic activity of the Ag colloid was examined for the degradation of the toxic methylene blue dye. The results revealed an excellent catalytic response with 90 % of the dye degraded in just 15 min of reaction time. The kinetics of the degradation process were studied with a rate constant of 0.054/min−1 showcasing the effectiveness of the pulsed laser-synthesized silver colloidal nanomaterial as a sustainable approach for environmental remediation.

Competition & UV254 projection in odorants vs natural organic matter adsorption onto activated carbon surfaces: Is the chemistry right?

Powdered activated carbon (PAC) adsorption remains an indispensable method for addressing odor problems in drinking water. While natural organic matter (NOM) is ubiquitous and competes strongly in deteriorating odorant adsorption capacity, it can also serve as a promising indicator for predicting odorant adsorption through online measurement. However, the impact of PAC surface chemistry on NOM competition and feasibility of prediction across various adsorbents are not well understood. Here, we examined the role of PAC properties (pore structure and surface chemistry) in the competitive adsorption between odorants and NOM components, aligned with the applicability assessment of using NOM optical properties for odorant adsorption projection across various PAC samples. Chemical oxidation and thermal treatment achieved considerable changes in surface functional group composition, alongside minimal changes in pore structure, of two typical PAC products with microporous/mesoporous pore characteristics. The effect of NOM interference on the reduction of odorant adsorption exhibited a similar level regardless of the PACs with different pore structure (average pore size of 1.7 nm vs. 4.2 nm). Surface modification increased the equilibrium adsorption capacity (qe50) of odorants by 15.1% to 146.4% (thermal treatment) or decreased by -81.3% to -34.1% (chemical oxidation), respectively, but minimal changes in odorant-NOM selectivity. For various odorants, hydrophobicity (log D) influenced the adsorption capacity while the structural flexibility (reflected by the rotatable bonds) affected the vulnerability of odorant adsorption to NOM competition. It was found for the first time that four-parameter Richards model (RMSE = 2.6%) is superior to the linear model (RMSE = 12.5%) or logarithmic model (RMSE = 77.6%) to describe the S-shape UV254 projection curves associated with odorant adsorption on PAC. Moreover, the feasibility was confirmed to use UV254 projection curves of pristine PAC fitted with the Richard model to predict the odorant adsorption on surface-modified PAC in two different surface waters (RMSE 9.2% and 7.4%, respectively). This study provides insight into the role of PAC surface chemistry and pore characteristics in odorant adsorption in NOM-containing waters and enhances the feasibility of the NOM surrogate model for odorant monitor and control during PAC adsorption.

The Synthesis, Structure, and Supramolecular Chemistry of Anthracene Rings and Cages

The Synthesis, Structure, and Supramolecular Chemistry of Anthracene Rings and Cages

Order evolution from a high‐entropy matrix: Understanding and predicting paths to low‐temperature equilibrium

AbstractInterest in high‐entropy inorganic compounds originates from their ability to stabilize cations and anions in local environments that rarely occur at standard temperature and pressure. This leads to new crystalline phases in many‐cation formulations with structures and properties that depart from conventional trends. The highest‐entropy homogeneous and random solid solution is a parent structure from which a continuum of lower‐entropy offspring can originate by adopting chemical and/or structural order. This report demonstrates how synthesis conditions, thermal history, and elastic and chemical boundary conditions conspire to regulate this process in Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O, during which coherent CuO nanotweeds and spinel nanocuboids evolve. We do so by combining structured synthesis routes, atomic‐resolution microscopy and spectroscopy, density functional theory, and a phase field modeling framework that accurately predicts the emergent structure and local chemistry. This establishes a framework to appreciate, understand, and predict the macrostate spectrum available to a high‐entropy system that is critical to rationalizing property engineering opportunities.

Toward a Self-consistent Evaluation of Gas Dwarf Scenarios for Temperate Sub-Neptunes

Abstract The recent JWST detections of carbon-bearing molecules in a habitable-zone sub-Neptune have opened a new era in the study of low-mass exoplanets. The sub-Neptune regime spans a wide diversity of planetary interiors and atmospheres not witnessed in the solar system, including mini-Neptunes, super-Earths, and water worlds. Recent works have investigated the possibility of gas dwarfs, with rocky interiors and thick H2-rich atmospheres, to explain aspects of the sub-Neptune population, including the radius valley. Interactions between the H2-rich envelope and a potential magma ocean may lead to observable atmospheric signatures. We report a coupled interior-atmosphere modeling framework for gas dwarfs to investigate the plausibility of magma oceans on such planets and their observable diagnostics. We find that the surface–atmosphere interactions and atmospheric composition are sensitive to a wide range of parameters, including the atmospheric and internal structure, mineral composition, volatile solubility and atmospheric chemistry. While magma oceans are typically associated with high-temperature rocky planets, we assess if such conditions may be admissible and observable for temperate sub-Neptunes. We find that a holistic modeling approach is required for this purpose and to avoid unphysical model solutions. Using our model framework, we consider the habitable-zone sub-Neptune K2-18 b as a case study and find that its observed atmospheric composition is incompatible with a magma ocean scenario. We identify key atmospheric molecular and elemental diagnostics, including the abundances of CO2, CO, NH3, and, potentially, S-bearing species. Our study also underscores the need for fundamental material properties for accurate modeling of such planets.

Harnessing Novel Reduced Graphene Oxide-Based Aerogel for Efficient Organic Contaminant and Heavy Metal Removal in Aqueous Environments.

Ensuring clean water sources is pivotal for sustainable development and the well-being of communities worldwide. This study represents a pioneering effort in water purification, exploring an innovative approach utilizing modified reduced graphene oxide (rGO) aerogels. These advanced materials promise to revolutionize environmental remediation efforts, specifically removing organic contaminants from aqueous solutions. The study investigates the exceptional adsorption properties of rGO-aerogel, enhanced with cysteamine, to understand its efficacy in addressing water pollution challenges. The characterization methods utilized encompass various analytical techniques, including FE-SEM, BET, FTIR, TGA, DSC, XPS, NMR, and elemental analysis. These analyses provide valuable insights into the material's structural modifications and surface chemistry. The research comprehensively explores the intricacies of adsorption kinetics, equilibrium, and isothermal study to unravel the underlying mechanisms governing contaminant removal. MO and Ni2+ exhibited adsorption of 542.6 and 150.6 mg g-1, respectively, at 25 °C. Ni2+ has unveiled the highest removal at pH 5, and MO has shown high removal in a wide pH range (pH 4-7). Both contaminants have shown fast adsorption kinetic performance on an rGO-aerogel surface. This study aims to identify the synergistic effect of cysteamine and rGO in aerogel formation to remove heavy metals and organic contaminants. These findings mark a significant stride in advancing sustainable water-treatment methods and pioneering in synthesizing innovative materials with versatile applications in environmental contexts, offering a potential solution to the global water pollution crisis.

Synthesis, structure, and solution chemistry of mixed-ligand oxidovanadium(IV) complexes incorporating ONO donor hydrazone ligands

Four mixed-ligand oxidovanadium(IV) complexes, [VIVO(L1-4)(phen)], 1-4, incorporating tridentate dibasic ONO donor hydrazone ligands (H2L1-4, general abbreviation H2L) derived from the condensation of 2-picolinyl hydrazide with 2-hydroxy acetophenone and its 5-substituted derivatives as primary ligands and 1,10-phenanthroline (phen) as auxiliary ligand have been synthesized in excellent yields. The complexes were characterized by elemental analyses, magnetic susceptibility measurements, and various spectral (e.g. IR, UV–Vis and EPR) studies. The molecular structure of one of the four complexes has been determined by single-crystal X-ray diffractometry. In 1, the hydrazone ligand is meridionally disposed of, coordinating through one enolic-O, one phenolic-O, and one imine-N. The other basal position is occupied by one pyridine-N of the phen moiety. The axial positions are occupied by one oxido-O atom and the other pyridine-N atom of the phen moiety. The complexes are paramagnetic with one unpaired electron (μeff ≈ 1.73 BM), suggesting no interaction with the neighboring molecules and are EPR active. The complexes display two d-d transitions, one near 725 and the other near 840 nm due to d xy → d xz , d yz and d xy → d x 2 − y 2 transitions, respectively. The other d-d transition associated with d xy → d z 2 transition was not observed as it falls in the UV region, which is masked by highly intense intra-ligand transitions. The complexes display one-electron oxidation peaks in the +0.75 to +0.89 V vs. Ag/AgCl region in the CH3CN solution that show a linear relationship with the Hammett parameter (σ) of the substituents in the aryloxy ring.

Tailoring Hematite Photoanodes for Improved PEC Performance: The Role of Alcohol Species Revealed by SHAP Analysis.

We explore the synergistic effects of TiO2 underlayers and varied alcohol species in the precursor solutions on the photoelectrochemical (PEC) performance of hematite photoanodes. Utilizing a robust machine learning (ML) framework combined with comprehensive analytical data sets, we systematically investigate how these modifications influence key physical and chemical properties, directly impacting the efficiency of water splitting processes. Our approach employs an ML model that integrates SHapley Additive exPlanations (SHAP) to quantitatively assess the impact of each dominant descriptor selected in the analytical data on the PEC performance, and they were combined with the SHAP values' dependence on the experimental operations. Specifically, we focus on the type of alcohol (methanol, ethanol, butanol, and 2-ethyl-1-butanol) used in the precursor solutions as the experimental operation, examining their effects on the dominant descriptors selected in the analytical data. The results from the SHAP analysis reveal that different alcohol species significantly alter the physicochemical properties at the hematite/TiO2 interface and in bulk hematite. These changes are primarily manifested in the modulation of the density of states and resistance to promote the charge carrier transport. For example, ethanol and butanol were found to enhance the electron density of states at the interface, which correlates with higher photocurrent outputs and improved PEC activity. In contrast, methanol showed a less pronounced effect, suggesting a nuanced interaction between the alcohol molecular structure and hematite surface chemistry. These findings not only underscore the importance of tailored precursor solution chemistry for enhancing PEC performance but also highlight the power of ML tools in uncovering the underlying physical and chemical mechanisms that govern the behavior of complex material systems. This study sets a foundational approach where ML can bridge the gap between empirical observations and theoretical understanding, leading to the rational design of energy materials.

A-Site Cation Chemistry in Halide Perovskites.

Metal halide perovskites are an important class of semiconductors now being implemented as photovoltaic absorbers and explored for light emission, among other device applications. The semiconducting properties of halide perovskites are deeply intertwined with their composition and structure. Specifically the symmetry, tilting, and distortions of the metal halide octahedra impact the band structure and other optoelectronic properties. In this review, we examine the various compositions of monovalent A-site cations in three-dimensional (3D) halide perovskites AMX3 (M = divalent metal; X = halide). We focus on how the A-site cation templates the inorganic metal-halide perovskite framework, resulting in changes in the crystal structure symmetry, as well as M-X bonding parameters, summarized in a comprehensive table of AMX3 structures. The A-site cation motion, effects of alloying, and 2D Ruddlesden-Popper perovskite structures with unique A-site cations are further overviewed. Correlations are shown between these A-site cation dominated structural parameters and the resulting optoelectronic properties such as band gap. This review should serve as a reference for the A-site cation structural chemistry of metal halide perovskites and inspire continued research into less explored metal halide perovskite compositions and structures.