Chemistry Commons^™

Modulation Of Hypothalamic–Limbic Circuits Regulating Appetite In Response To Health Lifestyle In Obese Adults, Nour Shakir Rezaieg, Muthanna M. Awad

Karbala International Journal of Modern Science

Background: Overeating leads to obesity a low-grade inflammatory disease. In this context, aguati-related neuropeptide (AgRP) and ghrelin are pivotal players in appetite regulation, while chemerin is an adipose tissue-secreted adipokine that contributes to low-grade inflammation associated with obesity. Objective: This study used a healthy lifestyle program designed for each obese participant to identify diet-related neuro-hormonal changes in appetite regulation. Design, Setting, and Participants: This a longitudinal quasi-experimental controlled study was conducted from 1^st December 2024, to 30^th July 2025, at University of Anbar. The sample included 100 participants, 50 obese (weight between 100–140 kg) and 50 healthy participants …

Evaluation Of Mcf-7 Breast Cancer Cell Cytotoxic And Antioxidant Activities Of Peptide Fractions From Symbiotic Bacteria Of Jellyfish Catostylus Sp., Eka Sry Wahyuni, Ahyar Ahmad, Muhammad Nasrum Massi, Sofa Fajriah, Randi Rimpung, Muh. Akbar Ardiputra, Harningsih Karim, Irda Handayani

Karbala International Journal of Modern Science

Marine-derived symbiotic microorganisms are recognized as a promising source of bioactive compounds with potential therapeutic applications, yet research on jellyfish-associated bacteria remains limited. This study examines the bioactivity of peptide fractions derived from symbiotic bacteria isolated from the jellyfish Catostylus sp., collected from the coastal waters of South Sulawesi, Indonesia, with a focus on their anticancer and antioxidant properties. Following sample collection, the symbiont bacteria were isolated, enzymatically hydrolyzed, and purified before their biological activity was evaluated. Preliminary cytotoxicity screening using the brine shrimp lethality assay revealed that the extracellular peptide fraction (5–10 kDa) and intracellular peptide fraction (3–5 kDa) …

Chasing Disinfection Byproducts Through The Pipes: How 66 Dbps Change Over Time In Chlorinated Vs. Chloraminated Distribution Systems, Erik Niehaves, Patrick T. Justen, Ashley A. Perkins, Alexandria L.B. Forster, Caroline O. Granger, Susan D. Richardson

Faculty Publications

While disinfection byproducts (DBPs) are typically measured at drinking water treatment plants, levels can change dramatically within the distribution system before reaching the consumer. In this study, the spatio-temporal trends of 66 DBPs across 9 different classes were examined in two drinking water distribution systems with similar source waters, but different pretreatments and residual disinfectants. One system uses residual chlorine in the distribution system, and the other uses chloramine, allowing for examination of how DBP concentrations change over time in distribution systems with different residual disinfectants. Four routes were sampled for each system with six time points over three days …

Optimized Photoemission From Organic Molecules In 2d Layered Halide Perovskites, Muhammad S. Muhammad, Dilruba A. Popy, Hamza Shoukat, John M. Lane, Neeraj Rai, Vojtěch Vaněček, Zdeněk Remeš, Romana Kučerková, Vladimir Babin, Chenjia Mi, Yitong Dong, Mark D. Smith, Novruz G. Akhmedov, Daniel T. Glatzhofer, Bayram Saparov

Faculty Publications

In recent years, hybrid organic–inorganic metal halides have been at the forefront of materials research. Typically, the functional (e.g., optoelectronic) properties of hybrid halides are derived from the inorganic structural part, whereas the organic structural units can add extra advantages in terms of stability, rigidity, and processability. Here, we report the design, synthesis, and characterization of two new hybrid materials in which the outstanding photophysical properties originate from the organic structural part. The new compounds, (C₁₅H16N)₂CdCl₄ and((Br)C₁₅H₁₅N)₂CdCl₄, have 2D layered Ruddlesden–Popper-type perovskite structures. These hybrids are blue-white …

Contribution To The Chemotherapy Of Human Trypanosomiasis: Design, Synthesis, And Biological Evaluation Of Dimeric 2-Nitroimidazoles Against Trypanosoma Cruzi Amastigotes And Bloodstream Trypanosoma Brucei, Afonso Santine M.M. Velez, Otavio Augusto Chaves, Carlos Serpa, Fatma M. Salem, Bibo Li Ph.D., Bin Su Ph.D., Celio Geraldo Freire-De-Lima, Debra Decote-Ricardo, Marco Edilson Freire De Lima

Biological, Geological, and Environmental Faculty Publications

Effective and safe treatments for neglected tropical diseases caused by parasites, such as Chagas disease and sleeping sickness, remain lacking, posing a significant challenge for researchers worldwide. The rational design of dimeric compounds inspired solely by the pharmacophoric core of benznidazole (2-nitroimidazole) has proven to be a promising strategy for antiparasitic development. Thus, in the present work, it was increased the linker between the active units (2-nitroimidazole) to improve the interaction with TcNTR, facilitating the bioactivation of the longest dimers. Biological assays confirmed this, demonstrating that all compounds were active against replicative intracellular amastigotes of Trypanosoma cruzi (Tulahuen C2C4-LacZ). Notably, …

Antibacterial Peptides From Soybean (Glycine Max (L.) Merr.) With In Silico Study Against Escherichia Coli Bacteria, Dian Riana Ningsih, Ely Setiawan, Purwati Purwati, Zusfahair Zusfahair, Anita Hindayanti Rukmana

Karbala International Journal of Modern Science

Bioactive peptides are produced from soy milk protein hydrolysis using trypsin. The research began with the preparation and separation of soy milk protein, followed by fractionation using ammonium sulphate, protein hydrolysis, and SDS-PAGE analysis of protein hydrolysates. Fractions exhibiting the highest degree of hydrolysis were further fractionated by SPE and tested to determine the antibacterial activity Staphylococcus aureus and Escherichia coli. The peptide sequence of the active peptide as an antibacterial was identified, employing LC-HRMS. The mode of action between active peptides and bacterial membran was analysed using molecular dynamics (MD) simulation. The findings displayed that F15 contained the highest …

Sperm-Associated Antigen 6 (Spag6) As A Potential Marker Of Sperm Function In Diagnosing Male Infertility, Ibtisam A. Al-Ali,, Kawkab A. Alsaadi

Karbala International Journal of Modern Science

Background: While male infertility has become a significant global health concern, conventional analysis of semen has not made progress in the detection of contraindicated molecular biomarkers, such as sperm-associated antigen 6 (SPAG6), which is a protein involved in axonemal structure and flagellar motility.

Hypothesis: Expression of SPAG6 correlates with sperm motility and structural integrity. This means that its dysregulation may serve as a molecular indicator of impaired sperm performance.

Methods: A comprehensive review of recent studies was conducted with a focus on SPAG6’s molecular characteristics, expression patterns in normal versus abnormal spermatozoa, and the role it plays in motility-related …

Optimized Co2 Gas Sensing With Sns:Sm2o3/N-Si Nanocomposites Fabricated Via Spray Pyrolysis, Wasan A. Khalaf, Mays A. Hammadi, Mohammed J. Alsultani, Yahya R. Hathal, Mohammed O. Salman

Karbala International Journal of Modern Science

In this work, tin sulfide:samarium oxide (SnS:Sm₂O₃) composite films were deposited using a spray pyrolysis technique for room-temperature CO₂ gas sensing. X-ray diffraction (XRD) confirmed a polycrystalline SnS nature of orthorhombic-phase crystallinity at 10 at.% Sm ions, while 20 at.% Sm induced Sm₂O₃ as a separate phase. Field emission-scanning electron microscopy (FE-SEM) induced uniform grains and increased the surface roughness, enhancing gas adsorption. UV-visible absorbance revealed band-gap narrowing. Fourier transform infrared spectroscopy (FTIR) analysis revealed vibrational band shifts, confirming the structural modifications. Gas-sensing measurements demonstrated 5.72%, 19.65%, and 9.65% for pure SnS, …

Structural Characterization Of Peptide Nanoaggregates At Varying Concentrations And Their Impact On Cellular Responses, Malika Rozmetova

Theses and Dissertations

Peptide nano-assemblies can regulate cellular pathways in a structure-dependent manner. Here, we show that the enzyme-responsive peptide NapFFK(NBD)Yp forms distinct nanoscale assemblies at different concentrations, triggering differential ER stress and extracellular vesicle release in MDA-MB231 cells. These results highlight the importance of supramolecular organization in peptide–cell interactions.

Flux Crystal Growth Of Potassium Lanthanide Double Vanadates With Lanthanide-Dependent Coordination Number Variance, Hunter B. Tisdale, Hans Conrad Zur Loye

Faculty Publications

A series of potassium rare earth double vanadates is presented. Single crystals of double vanadates with stoichiometry K₃Ln(VO₄)₂ (Ln = La, Pr, Nd, and Sm) and crystallizing in the glaserite structure type were synthesized via a molten alkali chloride/fluoride flux reaction. Different structures were observed depending on the constituent rare earth: K₃La(VO₄)₂ crystallizes in an as-of-yet unreported modification of the typical glaserite structure in the space group P2₁/c, likely due to its larger ionic size that results in an increase in the lanthanide coordination number …

The Chemistry Of Red Lipstick: The Impact Red Lipstick Has On Society, Lilliana Weldeslassie

Electronic Theses & Dissertations (2024 - present)

Cosmetic chemistry is deeply embedded in everyday life, shaping the products people use from morning to night. Among these, red lipstick stands out as a formulation that blends complex chemistry with a cultural meaning. This thesis examines the scientific foundations of red lipstick through its chemical composition, pigment structure, toxicological history, analytical methods, and evolving sustainability practices. Historically, red lipsticks relied on high-risk ingredients such as lead, mercury, and other toxic metals, reflecting an era before chemical safety and regulatory oversight were incorporated.²¹ Modern formulations have established safer synthetic dyes, natural waxes, plant-based oils, and stabilizers created to optimize …

Bio-Orthogonal Chemistry-Based Strategy To Turn-On And Turn-Off Crispr-Cas9 Gene Editing In Solution And In Live Cells, Bhoomika Pandit

Electronic Theses & Dissertations (2024 - present)

The CRISPR–Cas9 system is a widely popular tool for genome engineering. There is a strong interest in developing tools for temporal control of CRISPR-Cas9 activity to address some of the challenges and to broaden the scope of potential applications. In this thesis I describe two biorthogonal based approaches to either Turn-ON and Turn-OFF CRISPR-Cas9 gene editing.

In first project work I describe a bio-orthogonal chemistry-based approach to Turn-ON Cas9 nuclease activity with temporal precision. We report a TCO-acylimidazole reagent that acylates 2′-OH groups of RNA. Poly-acylation (“cloaking”) of RNA was optimized in vitro using a model 18-nt oligonucleotide, as well …

Photo And Spatial Control Of Rna Structures And Functions: Exploring Positional Effects And Photo-Responsiveness Of Azobenzene Modified Nucleotides, Jinxi Du

Electronic Theses & Dissertations (2024 - present)

RNA molecules perform many important biological functions by forming complex three-dimensional structures stabilized by base pairing, tertiary interactions, and metal ion coordination. Because RNA function depends strongly on its structure, methods that allow reversible control of RNA conformation and activity are important for understanding RNA behavior and for potential therapeutic applications. However, achieving reversible and site-specific control of RNA structure, especially at the single-nucleotide level, remains challenging. In this dissertation, I developed and applied azobenzene-modified nucleotides as a chemical tool to enable optical and spatial control of RNA structure and function.

The first part of this dissertation focuses on establishing …

Advancing Lipidomics Through Fluoroalcohol-Induced Multiphase Fractionation And Orthogonal Lc×Lc–Ms Detection, Md Al Amin

Chemistry & Biochemistry Dissertations

Comprehensive characterization of the lipidome remains a significant analytical challenge due to the immense structural diversity, wide dynamic range, and complex physicochemical continuum of lipid species. Conventional extraction methods, such as those by Bligh–Dyer and Folch, and one-dimensional liquid chromatography (1D-LC) often fail to resolve this complexity, leading to chromatographic overlap, severe ion suppression, and limited coverage of low-abundance or highly hydrophobic species. This dissertation addresses these bottlenecks by establishing a separation-driven analytical framework that integrates novel fluoroalcohol-induced multiphase systems (FAiTPS) with orthogonal multidimensional liquid chromatography–mass spectrometry (LC×LC–MS).

The core of this research is the development and physicochemical characterization of …

Exploring The Limitations Of Substrate Scope In Dimethylallyltryptophan Synthases, Evan T. Miller

Theses and Dissertations--Pharmacy

Natural products (NPs), are the largest source of bioactive compounds in Nature, and are essential to the treatment of human disease. Nearly 50% of drugs approved for use from 1981 to 2019 owe some aspect of their development to NPs, either in terms of their structure, pharmacophore, or mechanism of action. However, NPs are difficult to structurally optimize. Chemoenzymatic methods for NP derivatization have been increasingly seen as practical alternatives to traditional synthetic methods. Prenyltransferases (PTs) are involved in the primary and secondary metabolism of plants, bacteria, and fungi, and they are key enzymes in the biosynthesis of many clinically …

Climate And Environmental Controls On Forest Soil Organic Matter Cycling, Genevieve Goebel

Dartmouth College Ph.D Dissertations

Climate change factors act on the soil environment in complex ways, known to disturb soil organic carbon (C). Rising global temperatures and alterations to regional precipitation and nitrogen deposition regimes may contribute to the intensification of global change by accelerating the rate of biological decomposition and CO2 efflux to the atmosphere. The magnitude and endurance of the disturbance to soil organic C across landscapes and throughout time that climate change factors may pose to soil C cycling are not comprehensively understood. These knowledge gaps in our field make it challenging to anticipate how soil environments and the vast ecosystems that …

Biochemical Investigations Of F420-Dependent Glucose-6-Phosphate Dehydrogenase From Cryptosporangium Arvum, Sarah T. Al-Noubani

2026 Spring Honors Capstones Projects

F₄₂₀-dependent glucose-6-phosphate dehydrogenase (FGD) catalyzes the conversion of glucose-6-phosphate to 6-phosphogluconolactone using the deazaflavin, Cofactor F₄₂₀. FGD from Mycobacterium tuberculosis has been investigated due to its health relevance to prodrug activation. More recently, FGD from Cryptosporangium arvum (Cryar- FGD) has been investigated due to its broader substrate specificity toward multiple sugar phosphates. Kinetic and NMR studies have shown that Cryar-FGD has dual catalytic activity as a dehydrogenase and isomerase. Further investigations are being conducted on Cryar-FGD to characterize key residues involved in catalysis.

To investigate the catalytically active residues of Cryar-FGD, …

Characterization Of Phytoplankton-Excreted Metabolites Mediating Carbon Flux Through The Surface Ocean, Yuting Zhu, Hanna S. Anderson, Eli Salcedo, Samuel E. Miller, Krista Longnecker, Melissa C. Kido Soule, Sheean T. Haley, Gretchen J. Swarr, Rogier Braakman, Sonya T. Dyhrman, Elizabeth B. Kujawinski

Chemistry & Biochemistry Faculty Publications

The marine labile dissolved organic carbon (DOC) pool is a dynamic reservoir of thousands of molecules that cycles approximately one-quarter of Earth’s primary production within days to weeks. After excretion by phytoplankton and other microbes, metabolites are rapidly consumed, resulting in low standing concentrations (picomolar to low nanomolar). Despite the decades-long search for labile DOC sources and molecular identities, marine phytoplankton exometabolomes are not well characterized, largely due to difficulties in measuring small polar molecules in saline water. Here, we profiled the exometabolomes of six axenic phytoplankton species representing key functional groups including a diatom (Thalassiosira pseudonana CCMP1335), a …

Land Use Influences Dissolved Organic Matter Composition In The U.S. Coastal Critical Zone Network, Aleksandar I. Goranov, Elizabeth V. Whitney, Brian R. Moyer, Katherine L. Tully, Patrick G. Hatcher, Yu-Ping Chhin

Chemistry & Biochemistry Faculty Publications

Coastal watersheds are highly productive biogeochemical systems supporting robust coastal fisheries and contributing significantly to the marine gross primary production flux. These ecosystems are comprised of civil infrastructure, farms, forests, and marshes, and their diversity is reflected in the quantity and quality of dissolved organic matter (DOM). Here, we assess the role of farming in influencing DOM from surface waters of six coastal tidal creeks adjacent to forest and farm sites in the US Critical Zone Network. Molecular fingerprinting using electrospray ionization - Fourier transform - ion cyclotron resonance - mass spectrometry revealed that farm-influenced DOM was enriched in nitrogen-, …

The Forensic Implications Of Hydrochloric Acid (Hcl) Exposure On Dna Preservation In Human Teeth, Shaelyn Lee Zimmerman

Graduate Student Theses, Dissertations, & Professional Papers

Identity is a human right, and forensic anthropological methods are often aimed at returning identity to decedents. Three main pathways are used for the identification of human remains: fingerprints, dental records, and DNA analysis. Identification efforts may be hindered when perpetrators attempt to obscure the victim’s identity. In cases where corrosive substances, such as hydrochloric acid (HCl) are used, dental comparison and fingerprinting often fail and genetic analysis becomes the best chance of achieving personal identification.

Previous studies have shown teeth are an excellent source of DNA. Large, multi-rooted teeth, such as molars, are often preferred because they contain the …

An Investigation Into The Potential Role Of Thioester Bonds In Prebiotic Atp Synthesis, Adam J. Ruf

Williams Honors College, Honors Research Projects

In this project I will attempt to show a potential prebiotic pathway for the synthesis of ATP. This pathway involves the use of thioester bond containing molecules, as derivatives of these bonds have been shown to exhibit enzyme-like catalytic properties. Nuclear magnetic resonance spectroscopy will be utilized to characterize each step of the pathway to ensure it is successful.

Pipeline Corrosion And Relevant Microbial Influence, Renee E. Bamberger

Williams Honors College, Honors Research Projects

This study investigated the role of microbial activity and oxygen availability in the corrosion of carbon steel pipelines with a focus on microbially influenced corrosion (MIC). Sediment collected from Old Woman Creek, Ohio, was used to simulate natural soil conditions, and carbon steel coupons were incubated under four treatments: nonsterile oxic, nonsterile anoxic, autoclaved oxic, and autoclaved anoxic over 85 days. Corrosion was assessed through mass loss measurements and the analysis of pH, sulfate, chloride, and dissolved iron concentrations. The greatest mass loss was observed in autoclaved oxic conditions, contrary to the initial hypothesis that microbial activity would greatly enhance …

Absolute Quantification And Identification Of Rna From Rna-Lipid Nanoparticles Using High Resolution Mass Spectrometry, Jason C. Funderburk

Theses and Dissertations

RNA therapeutics are a rising drug category with potential use for a range of conditions encompassing infectious diseases to therapies for cancer, diseases, and genetic disorders. RNA-lipid nanoparticles (RNA-LNPs) are the prominent delivery method for these therapeutics approved products include mRNA vaccines and polyneuropathy treatments. The emergency use authorizations and orphan drug status of current RNA-LNP drugs has allowed approval without finalization of the regulatory analytical procedures for quality monitoring. The objective of the study was to develop an LC-MS assay to simultaneously measure identity and concentration of two therapeutically relevant intact RNA constructs extracted from RNA-LNPs to enhance quality …

31p Solution Nmr Investigation Of Abasic Dna, Clarissa R. Krimmel

Graduate Theses/Dissertations

Base excision repair (BER) mechanisms fix single base lesions in DNA, such as T:G mismatches. During the base excision repair mechanism, an abasic site (AP site) is formed as an intermediate. AP sites are unstable and highly mutagenic; they can stop DNA replication. This research investigates how the conformational properties of abasic sites in DNA affect the binding recognition of enzymes involved in DNA repair mechanisms, including BER. Three different abasic sequences are being analyzed for this research project. A second project looks at the effects of a naturally occurring purine derivative, hypoxanthine, on the DNA backbone. These hypoxanthine lesions …

Synthesis And Characterization Of Succinate Dehydrogenase Inhibitors H2/Z14 And C6/Z96 In Order To Combat Small Cell Lung Cancer, Lauren M. Graves

Honors Undergraduate Theses

The use of ubiquinone inhibitors to combat cancer is a recent development in medicinal science and procedures to efficiently synthesize these drugs remain limited. C6/Z96 and H2/Z14, two succinate dehydrogenase inhibitors, have been previously tested in vitro against NSCLC with positive results. Their similarity to ubiquinone is what makes them a strong candidate for a succinate dehydrogenase inhibitor at the ubiquinone binding site. The heterocyclic scaffolds and substituents are proposed to bind strongly through a combination of electronics, hydrogen-bonding, and fit, allowing them to bind well and prove to be more favorable than ubiquinone when competing for the Q-site. By …

Fumigant Toxicity Of Essential Oils From Chemotypes Of Curry Tree (Murraya Koenigii) Against Adult African Malaria Mosquito (Anopheles Gambiae Sensu Stricto), Clarence M. Mang’Era, Fathiya M. Khamis, Ahmed Hassanali, Paul O. Mireji

All Peer-Reviewed Publications

The toxicity of fumigant formulations of essential oils (EOs) from curry tree (Murraya koenigii (L.) Spreng (Rutaceae)) against African malaria adult mosquito (Anopheles gambiae sensu stricto (Giles, 1902) (Diptera: Culicidae: Culicini)) was evaluated to identify most effective chemotype of the curry tree against the mosquitoes. Ninety-two compounds (91.78%–96.47% coverage) in the EO profiles were identified, among which EO isolated from curry tree chemotype from Kibwezi was most toxic. This chemotype had a median lethal dose (LD50) of 3.6 × 10⁻³ mg/cm³ (95% CI: 2.70–4.58) and a lethal time (Ti50) of 1.91 ± 0.086 h (p < 0.001). The equivalent LD50 of EOs of chemotypes from Mombasa, Makindu, and Malindi in Kenya was 4.9 × 10⁻³, 6.6 …

Design, Syntheses And Biological Applications Of Fluorescent Probes For Nad(P)H, Hsa And Cellular Microenvironment Sensing, Adenike M. Olowolagba

Dissertations, Master's Theses and Master's Reports

Fluorescent probes have emerged as powerful tools for investigating complex biological processes due to their high sensitivity, selectivity, and capability for real-time, non-invasive imaging. In particular, the detection of key biomolecules such as NAD(P)H, viscosity-related parameters, human serum albumin (HSA), and pH is essential for understanding cellular metabolism, redox homeostasis, and disease progression. In Chapter 2, three coumarin-based fluorescent probes (A–C) were designed, synthesized, and characterized for monitoring NAD(P)H levels in living cells. Probes A and B feature coumarin–cyanine hybrid structures linked via vinyl and thiophene bridges to 3-quinolinium acceptors, respectively, while probe C incorporates a dicyano moiety to replace …

Integration Of Islamic Values In Mathematics Learning, Ai Mulya, Surya Faradiba

Jurnal Pendidikan Sains

This study aims to identify the integration of Islamic values in mathematics learning and its contribution to student character development. The method used is a systematic literature study by reviewing relevant accredited scientific articles. The results of the study indicate that the integration of Islamic values is carried out through the preparation of Islamic-context-based mathematics problems, linking concepts to verses of the Qur'an and hadith, the application of ethnomathematics with Islamic cultural nuances, and the introduction of Islamic economic concepts. The dominant values that emerge include honesty, responsibility, discipline, justice, and piety. These findings indicate that the integration of Islamic …

Understanding The Fidelity And Specificity Of Dna Polymerase I, Bill R. Miller Iii, Andrew V. Yeager, Jake A. Collins, Alexis Blake, Elise Tate, Carol A. Parish, Eugene Y. Wu

Chemistry Faculty Publications

High-fidelity DNA polymerases employ complex mechanisms to catalyze template-dependent DNA synthesis while quickly discarding mismatches. Atomic-level structural details about short-lived states during nucleotide discrimination are necessary to gain insight into the kinetic checkpoints that contribute to fidelity. We performed microsecond molecular dynamics simulations of DNA polymerase I, large fragment, from Bacillus stearothermophilus (Bacillus fragment, or BF) in complex with a template guanine and a mismatched thymidine triphosphate to observe the early events in the process of selection against a mismatch. Although the nucleobases formed a wobble base pair early, the mismatched pair was blocked from fully entering the active site …

Energetics And Kinetics Of Alkali Ion Exchange In Analcime, Jinyi Liu, An T. Ta, R. Seaton Ullberg, Jean Wilfried Hounfodji, Michael Badawi, Hans Conrad Zur Loye, Simon R. Phillpot

Faculty Publications

We employ density functional theory calculations to investigate the energetics and diffusion mechanisms of alkali metal ions (Na⁺, K⁺, Rb⁺, and Cs⁺) within the analcime framework. While Na⁺preferentially adsorbs at the center of the 8-member ring, DFT calculations show that larger ions, such as Cs⁺, occupy the center of the cage due to steric constraints. The computed exchange energies indicate that exchange of Na⁺by Cs⁺is thermodynamically favorable. Migration energy barriers, determined using the climbing image nudged elastic band method, show that Na⁺is …