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Ionic Liquids And Gumbos For Biomedical And Sensing Applications, Paul Kipkorir Sang Magut

LSU Doctoral Dissertations

This dissertation is a synopsis of advancements in the field of ionic liquids and a group of uniform materials based on organic salts (GUMBOS) in biomedical applications, especially with regard to cancer research. The toxicity of chemotherapeutic agents to normal tissues and drug resistance are a major concern in cancer treatment. In this dissertation, GUMBOS and nanoGUMBOS as well as ionic liquids and nanodroplets are explored as possible chemotherapeutic agents with minimal toxicity to normal cells. In the first part of my dissertation, exploitation of ionic liquid chemistry to modulate toxicity of rhodamine 6G is reported. Rhodamine 6G-based GUMBOS with …

Polymer Micro- And Nanofluidic Systems For In Vitro Diagnostics: Analyzing Single Cells And Molecules, Swathi Reddy Pullagurla

LSU Doctoral Dissertations

Polymer micro- and nanofluidic systems, with their critical dimensions, offer a potential to outperform conventional analysis techniques and diagnostic methods by enhancing speed, accuracy, sensitivity and specificity. In this work, applications of microfluidics have been demonstrated to address the existing challenges in stroke diagnosis, by mRNA expression profiling from whole blood within <20 min. A brief overview of various biomarkers for stroke diagnosis is given in chapter 1 followed by design and testing of individual microfluidic modules (chapter 2 and 3) required for the development of POC diagnostic strategy for stroke. We have designed and evaluated the performance of polymer microfluidic devices for the isolation of leukocyte subsets, known for their differential gene expression in the event of stroke. Target cells (T-cells and neutrophils) were selected from with greater purities, from 50 µl whole human blood by using affinity based capture in COC devices within a 6.6 min processing time. In addition, we have also demonstrated the ability to isolate and purify total RNA by using UV activated polycarbonate solid phase extraction platform. Polymer-based nanofluidic devices were used to study the effects of surface charge on the electrodynamic transport dynamics of target molecules. In this work, we report the fabrication of mixed-scale micro- and nanofluidic networks in poly(methylmethacrylate), PMMA, using thermal nanoimprint lithography using a resin stamp and surface modification of polymer nanoslits and nanochannels for the assessment of the associated electrokinetic parameters – surface charge density, zeta potential and electroosmotic flow. This study provided information on possible routes that can be adopted to engineer proper wall chemistry of polymer nanochannels for the enhancement or reduction of solute/wall interactions in a variety of relevant single-molecule studies.

From Micro- To Nano-Scale: Applications Of Solid-Phase Enzymatic Reactors For Biopolymer Disassembly, Nyote J. Calixte

LSU Doctoral Dissertations

The process of immobilizing enzymes onto solid supports for bioreactions has some compelling advantages compared to their solution-based counterpart including the facile separation of enzyme from products, elimination of enzyme autodigestion, and increased enzyme stability and activity. We report in this work, the immobilization of λ-exonuclease onto poly(methylmethacrylate) (PMMA) micro- and nano-pillars populated within a fluidic devices for the micro and nanoscale on-chip digestion of double-stranded DNA. Enzyme immobilization in both studies was successfully accomplished using 3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) coupling to carboxylic acid functionalized PMMA micropillars. Our micro-scale results suggest that the reaction efficiency for the catalysis of dsDNA digestion …

“Trans-Positioning” Carbons Within Strained Caged Bicyclic(S): Rom/Rcm (Ring-Opening/Ring-Closing) Metathesis And Dieckmann/Retro-Dieckmann Condensation Routes To A Cis-Decalin Infrastructure, Stefan Malone Cooper Jr

LSU Doctoral Dissertations

This dissertation describes methodology work involving a “Trans-Positioning” motif engaging strategically positioned carbons within a strained bi-carbocyclic core and on a tethered free-dangling hydrocarbon chain ultimately for skeletal rearrangement. Trans-alkenylation and trans-acylation processes are devised for investigation with bicyclo[2.2.2]octyl and bicyclo[2.2.1]heptyl strained cores. Recent advances in olefin metathesis led to an independent proposal of the now applicable, RRM (Ring-Rearranging Metathesis) for trans-alkenylation purposes. A resourceful Dieckmann/retro-Dieckmann sequence is devised for trans-acylation motives. Finally, this dissertation includes atypical diastereoselective reductions and additions which were serendipitously found with trigonal carbon atoms appended to our pertinent strained systems while in pursuit of our …

Synthetic Routes To Therapeutic Agents Via Masked Functionalities: From Orthogonal Peptide Crosslink To Photothermal Cancer Prodrug, Chyree Shantel Batton

LSU Doctoral Dissertations

The theonellamides are a family of compounds distinguished by their crosslinking ô-histidinoalanine (ô-HAL) residue. Part one of this dissertation details the synthesis of an orthogonally protected ô-HAL building block that will be incorporated into a total synthesis of theonellamide C. Selective deprotection of each amine and acid of this orthogonally protected building block is also demonstrated. Various reaction partners for the assembly of ô-histidinoalanine were explored. One approach involved the coupling of N-Fmoc-â-iodoalanine benzyl ester and (Nðim)-blocked histidine nucleophiles including a fused bicyclic urea and a Boc-His(Nð-Pac)-OMe. While the imidazolium salts were identified by mass spectrometry, elimination of the iodide …

Design, Synthesis, And Exploration Of A Chimeric Antioxidant And New Crosslinkers For Molecular Imprinting, Danielle Songe Meador

LSU Doctoral Dissertations

The improvement and utility of crosslinkers are important topics of molecular imprinting. Crosslinker significance is evident when molecularly imprinted polymer (MIP) composition related to performance as separation media is examined. Crosslinkers account for the bulk of MIP formulations made through traditional imprinting (80-90%) and is even greater when the One Monomer Molecularly Imprinted Polymer (OMNiMIP) approach is utilized (100%.) It is not surprising that alteration of the bulk component will result in different separation performances. Crosslinkers studied in this work were designed, synthesized, and evaluated toward improvement in OMNiMIP selectivity. In particular, functionality and number of polymerizable groups, addition of …

Reductive Alkylation Of Proteins Towards Structural And Biological Applications, Kevin Jerome Roberson

LSU Doctoral Dissertations

Nuclear magnetic resonance (NMR) spectroscopy is a proven technique for protein structure and dynamic studies, typically requiring the incorporation of stable magnetic isotopes to improve sensitivity and assign resonances. Degenerate levels of 13C-incorporation have been the biggest obstacle for mass spectrometry-assisted assignment of 13C-dimethylamine resonances in nuclear magnetic resonance spectroscopy (NMR). Reductive 13C-methylation is an alternative labeling method for proteins not amenable to bacterial host overexpression. Because reductive 13C-methylation adds sparse, isotopic labels, traditional methods of assigning the NMR signals are not applicable. The research presented in the first part of this dissertation explores several methods used to break the …

Surface Complexation Of Monosubstituted Organoarsenicals On Hematite: Atr-Ftir Investigations, Md Abdus Sabur

Theses and Dissertations (Comprehensive)

Little is known about the surface chemistry of organoarsenic compounds with iron-containing materials commonly found in geosorbents and arsenic removal technologies. In this thesis, these organoarsenicals include aliphatic and aromatic arsenicals that historically have been used as herbicides, pesticides and in the poultry feed industry, respectively. Attenuated total internal reflectance Fourier transform infrared spectroscopy has been used to study the surface interactions of organoarsenicals at the molecular level under various environmentally-relevant conditions. Kinetic and thermodynamic parameters extracted from these molecular level experiments provide trends that are not observed in any published bulk experiments. Apparent initial rates of adsorption and desorption …

Synthesis, Characterization, And Investigation Of The Catalytic Activity Of Nio, Cuo, And Nio-Cuo Nanoparticles On Silica As Surrogates Of Combustion-Generated Nanoparticles, Nuwan Nilanka Balapitiya Liyanage

LSU Doctoral Dissertations

Transition metal oxide nanoparticles contained in fly ash are known to catalyze the formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) during the waste incineration process. The potential catalytic activity of silica-supported NiO, CuO, and NiO-CuO nanoparticles for the formation of PCDD/Fs will be discussed in this dissertation. The successful synthesis of silica-supported NiO, CuO, and NiO-CuO nanoparticles as surrogates of combustion-generated nanoparticles was important to this study. The synthesis was followed by the characterization of the nanoparticle surrogates by X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDS). Finally, the catalytic …

Characterization Of A Water Soluble, Non-Ionic, Helical Poly(Α-Amino Acid), Wayne Huberty

LSU Doctoral Dissertations

A water soluble, non-ionic, rodlike polymer, PEGL, was synthesized and characterized in efforts to synthesize a novel model polymer to study stiff polymers in solution. The rodlike system is likely stiff due to a high relative percent helicity in water up to 50 °C, measured by circular dichroism, the observation of liquid crystalline domains in water, and from the slope measured from conformation plots supplied by GPC/MALS; however, it also apparent the system is aggregating in both a 2 mM azide solution and a buffer (200 mM NaNO3 + 20 mM NaH2PO4 + 2 mM NaN3), in corroboration of negative …

Microfluidic And Nanofluidic Devices - Mixed Scale Systems For Bioanalytical Applications, Michael David Vincent

LSU Doctoral Dissertations

Developments in the field of microfluidics and nanofluidics allow an experimenter to employ new analytical techniques. One direction in which the field is moving towards is developing new devices and or instruments on the smallest scale possible. One way in which this can be achieved is by using a combination of top-down and bottom-up technologies. Some of these top-down techniques have been used in other fields such as the use of photolithography to fabricate semiconductors. Photolithography is a top-down method used to create features normally on the micrometer scale, but in order to create nanometer size features another top-down method …

Syntheses And Characterization Of Isoporphyrins And Bodipys For Pdt And Imaging, Haijun Wang

LSU Doctoral Dissertations

This Dissertation is divided into five chapters reporting various aspects of the background to my field of study and the results obtained during my research program. Chapter 1 gives a very brief introduction to photodynamic therapy including the mechanism of the treatment, the localization of photosensitizer in tumor cells, the pathways leading to tumor death and characteristics of various photosensitizers such as porphyrin-based photosensitizers and non-porphyrin based photosensitizers. Chapter 2 reports a total synthesis of zinc(II) isoporphyrins by cyclization of b-bilene salt using á-keto esters for the macrocyclization carbon. Functionalization of the resulting zinc(II) isoporphyrins was attempted using different strategies …

Design, Synthesis, And Evaluation Of Small Molecule-Based, Profluorogenic Activatable Substrate Probes For Detection And Visualization Of Human Cancer Enzyme Nad(P)H:Quinone Oxidoreductase-1, Suraj Uditha Hettiarachchi

LSU Doctoral Dissertations

Cancer comprises many specific diseases, and it is currently responsible for millions of deaths worldwide. This broad disease profile is a great challenge for personalized oncology. Critical for the success of cancer therapy is the exploration of improved methodologies for the early detection of localized and disseminated tumor cells in patients, where bio-molecular imaging has become an indispensable tool. Being one of many different imaging techniques, optical fluorescence imaging has been translated over the years from the bench to clinical research, and it is now on the verge of being able to address some of the pressing challenges in molecular …

Gumbos- And Ionic Liquid-Coated Quartz Crystal Microbalance Sensors For Detection And Molecular Weight Determination Of Organic Vapors, Bishnu Prasad Regmi

LSU Doctoral Dissertations

There has been an ever-increasing demand for the development of high-performance sensing devices for detection and discrimination of volatile organic compounds (VOCs) present in different environments. Among a number of sensing devices currently available, sorption-based sensors are particularly attractive because they are simple and inexpensive, require low power, and are appropriate for fabrication of multisensor arrays. A sorption-based sensor is comprised of a chemically active coating immobilized on the surface of a physical transducer. The chemically active film interacts with analytes, and the transducer converts the binding event into an electrical signal. This dissertation is focused on a sorption-based sensor …

Expression Of O-Linked N-Acetylglucosamine Modified Proteins And Production And Characterization Of Chlamydia Trachomatis Ct663, Octavia Y. Goodwin

LSU Doctoral Dissertations

O-linked â-N-acetylglucosamine is a regulatory post translational modification. This modification occurs on nearly all functional classes of proteins, in the nucleus and cytoplasm. O-GlcNAc is added to serine or threonine by O-GlcNAc transferase and removed by O-GlcNAcase. Previous attempts to study O-GlcNAc-modified proteins have resulted in low yields, making 3-dimensional structure determination impossible. In this dissertation O-GlcNAc transferase will be co-expressed with domains of human cAMP responsive element-binding protein (CREB1) and Abelson tyrosine-kinase 2 (ABL2) in E. coli, to produce O-GlcNAc-modified protein. The O-GlcNAc-modified protein was expressed in a variety of E. coli cell lines at a variety of conditions, …

Bio-Imprinted Hydro-Gels (Bigs) For Protein And Virus Detection, Wei Bai

LSU Doctoral Dissertations

Detection of bio-markers at low concentration is becoming a more and more important topic in scientific research due to its importance in applications crucially related to people’s life like medical diagnosis, environment protection and national security. In the past decades, as the improvement of the modern analytical technologies progressed, plenty of methodologies have been developed to realize the fast and accurate detection of bio-markers in liquid media. However, some drawbacks still remain like the expensive cost, high requirement of operational environment, and need for skilled operators. Here, a new kind of aptamer-based bio-imprinted hydrogel sensor (BIG) with specific macroscopic volume …

The Contribution Of Fly Ash Components To Pcdd/F Formation, Phillip M. Potter

LSU Doctoral Dissertations

Chlorinated aromatics undergo surface-mediated reactions with metal oxides to form environmentally persistent free radicals (EPFRs) which can further react to produce polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Previous work using laboratory-made fly ash surrogates composed of transition metal oxides deposited on silica powder has confirmed their ability to mimic fly ash in the production of PCDD/Fs. However, little is known about the propensity of alumina and aluminosilicates to form PCDD/Fs. Cooperative catalysis between transition metals in the formation of PCDD/Fs has also seen little research. A fly ash sample containing both alumina and mullite, an aluminosilicate, was tested for PCDD/F formation …

Synthesis, Characterization, And Theoretical Studies Of Fluorescent Gumbos And Nanogumbos, Chengfei Lu

LSU Doctoral Dissertations

In this dissertation, novel fluorescent materials, which are referred to as a group of uniform materials based on organic salts (GUMBOS) are synthesized, characterized, and studied for different applications. GUMBOS are solid state organic salts having melting points from 25°C to 250°C. Similar to ionic liquids, GUMBOS are highly tunable and can be designed for specific applications by incorporating multiple-functions into a single ion pair by selection of cation-anion combinations. Chapter 2 is a discussion of the synthesis and characterization of a PEGylated IR786 GUMBOS. These GUMBOS are prepared by a two-step synthesis procedure followed by a facile anion exchange …

Stability Of High Band Gap P3ht: Pcbm Organic Solar Cells Using Tiox Interfacial Layer, Kurniawan Foe, Gon Namkoong, Matthew Samson, Enas M. Younes, Ilho Nam, Tarek M. Abdel-Fattah

Electrical & Computer Engineering Faculty Publications

We fabricated a poly [3-hexylthiophene] (P3HT) and [6,6] -phenyl-C61-butyric acid methyl ester (PC₆₁BM with the TiO_x layer. We found that a solution based TiO_x coated at a spin speed of 3000 rpm improved the photon absorption of the active layer. An optimized TiO_x layer was also used as the interfacial layer to investigate the stability of P3HT: PC₆₁BM OPC. After 70 days of storage, we observed that the short-circuit current density (J_SC) dropped by 16.2%, fill factor (FF) dropped by 10.6%, and power conversion efficiency (PCE) dropped approximately by 25%, while …

A Computational Study Of Small Gold Clusters With H2s, Thiols, H2o, And Alcohols, Silvija C. Smith

Theses and Dissertations (Comprehensive)

Alkane thiols, RSH, are commonly used in aqueous solution to stabilize and prevent aggregation of gold clusters, Au_n. Initially a RSH-Au_n complex is formed and, subsequently, there is hydrogen atom transfer to form a RSAu_nH complex. We examine the rate of this reaction for small neutral gold clusters, with n=1-2 and short-chain thiols with R = H, CH₃, and CH₃CH₂, using transition state theory. The comparison of DFT (with the functionals, BP86 and M06-2X), and MP2 was performed. A pseudopotential was employed to account for the large relativisitic effects …

Generation Of Diverse Molecular Complexity From Cyclooctatetraene, Mohamed Fawzy El Mansy

Dissertations (1934 -)

ABSTRACT

GENERATION OF DIVERSE MOLECULAR COMPLEXITY

FROM CYCLOOCTATETRAENE

Mohamed F. El Mansy, B.Sc, M.Sc.

Marquette University, 2014

The use of simple hydrocarbons as starting materials for the synthesis of complex molecules relies on efficient methods for oxidation, functionalization or rearrangement. For example, various researchers have explored cyclopentadiene or cycloheptatriene as precursors for the preparation of a wide variety of drug candidates, natural products and synthetic products. The purpose of this research is to explore methods to transform the simple hydrocarbon, cyclooctatetraene (COT) into complex target molecules.

Tricarbonyl (cyclooctatetraene)iron, readily prepared from COT, reacts with a variety of electrophiles to form …

Time-Dependent Regulation Of Apoptosis By Aen And Bax In Response To 2-Aminoanthracene Dietary Consumption, Worlanyo E. Gato, Dale B. Hales, Stacey R. Mcgee, Jay C. Means

Chemistry: Faculty Publications (1990-2023)

Background/Objective: The modulation of the toxic effects of 2-aminoanthracene (2AA) on the liver by apoptosis was investigated. Fisher-344 (F344) rats were exposed to various concentrations of 2AA for 14 and 28 days. The arylamine 2AA is an aromatic hydrocarbon employed in manufacturing chemicals, dyes, inks, and it is also a curing agent in epoxy resins and polyurethanes. 2AA has been detected in tobacco smoke and cooked foods.

Methods: Analysis of total messenger ribonucleic acid (mRNA) extracts from liver for apoptosis-related gene expression changes in apoptosis enhancing nuclease (AEN), Bcl2-associated X protein (BAX), CASP3, Jun proto-oncogene (JUN), murine double minute-2 p53 …

Synthesis And Characterization Of Zinc Sulfide/Zinc Oxide Semiconductor Nanoparticles, Daniel Alan Hall

All Master's Theses

ZnS/ZnO semiconductor nanoparticles have been synthesized with L-cysteine and sodium polyphosphate capping agents using a colloidal synthesis method. The nanoparticles were characterized through the use of fluorescence spectroscopy, ultraviolet/visible (UV /Vis) spectroscopy, and X-ray diffraction (XRD) instrumentation. Introduction of oxygen during the synthesis reaction increases the intensity of the nanoparticle fluorescence and causes a blue shift in emissions which becomes more pronounced with longer exposure to oxygen. Growth of the ZnO shell around the ZnS particles alters the composition from a ZnS nanoparticle to a ZnS/ZnO nanoparticle as seen by an increase in absorbance from 350nm to 450nm which indicates …

Synthesis Of Novel Triazoles Bearing 1,2,4-Oxadiazole And Phenylsulfonyl Groups By 1,3-Dipolar Cycloaddition Of Some Organic Azides And Their Biological Activities, Yaşar Dürüst, Hamza Karakuş, Muhsi̇ne Zeynep Yavuz, Ali̇ Akçahan Gepdi̇remen

Turkish Journal of Chemistry

1,3-Dipolar cycloaddition of 5-azidomethyl-3-p-substituted phenyl-1,2,4-oxadiazoles to phenyl vinyl sulfone and bismaleimide gives rise straightforwardly to 1-((3-(p-substituted) phenyl-1,2,4-oxadiazol-5-yl)methyl)-4-(phenylsul\-fonyl)-4,5-dihydro-1H-1,2,3-triazoles and bisdihydropyrrolo[3,4-d][1,2,3]triazole-4,6(3aH,5H)-diones. The structures of the new cycloadducts were elucidated by means of IR, NMR (^1H, ^{13}C, 2D), mass spectra, and physical characteristics (mp and R_f values). In addition, anticancer activities of the cycloadducts against MCF-7 cells were also investigated.

Study On Transportation Of Phenol Through A Nanotubule Membrane, Yue Liu, Li Xie, Xiaoxue Fan, Dingyan Fan, Shasheng Huang

Turkish Journal of Chemistry

Gold nanochannels were prepared by plating electrolessly gold within the pores of polycarbonate filter membranes (PCTMs). These PCTMs with cylindrical Au nanotubules of uniform radius and high density can be used as a convenient model system to investigate the mechanism of particle transport through nanotubules. The transport properties of phenol through a modified Au nanotubule membrane were studied. The permeate flux of phenol transport through the nanotubule membrane can be spatially and temporally manipulated by controlling the magnitude and direction of the current applied across the separation cell, and the electroosmotic flow (EOF) was investigated by measuring the flux of …

Calixcephems: Clustered Cephalosporins Analogous To Calixpenams As Novel Potential Anti-Mrsa Agents, Fazel Nasuhi Pur, Karim Akbari Dilmaghani

Turkish Journal of Chemistry

Two novel clusters of cephalosporin based on calixarene were synthesized directly or by ring expansion of the penicillin arms of calixpenams to the corresponding cephem arms via sulfoxide intermediates. Antibiotic tests showed that calixcephems have a noteworthy increase in antibacterial activity against methicillin-resistant strains of Staphylococcus aureus (MRSA) with respect to parent calixpenams and their corresponding single cephems.

Microwave-Assisted Synthesis Of Novel Nonperipherally Substituted Metallophthalocyanines Bearing (7-(Trifluoromethyl)Quinolin-4-Yl)Oxy Groups, Di̇dem Evren, Hacer Yasemi̇n Yeni̇lmez, Ayfer Kalkan Burat

Turkish Journal of Chemistry

The synthesis, characterization, and spectroscopic properties of novel nonperipherally tetrasubstituted metallophthalocyanines (zinc, cobalt, copper, manganese, and indium) bearing 4 (7-(trifluoromethyl)quinolin-4-yl)oxy units has been reported. The new compounds have been characterized using UV-Vis, IR, ^1H NMR, ^{13}C NMR, ^{19}F NMR, and mass spectroscopic data. The absorption properties of these new complexes were compared to those of peripherally substituted phthalocyanine derivatives. Based on the structural, spectroscopic, and absorption studies, it was found that the substitution effect altered the electronic structures significantly. The results provide useful information to understand the effect of peripheral or nonperipheral substitution on the properties of this macrocyclic ring. …

The Synthesis Of A Bisbenzothiophene (Bbt) Based Organic Semiconductor With Increased Function And Increased Solubility, Mary England

Senior Honors Theses

Organic semiconductors are growing in applications for use in modern technology.¹ The main interest in these molecules can be attributed to their low cost (compared to silicon) and their ability to be used on flexible substrates. There are four features that make a good organic semiconductor. First, the molecule should be conjugated, having alternating single and double bonds (lone electron pairs act similarly to double bonds). Secondly, the molecule should be planar, or flat, in shape. Thirdly, the molecule should have a narrow band gap to increase the overall conductivity. Lastly, the molecule should be soluble to ease application. …

The Effects Of Coal Mining On Health In Appalachia : Global Context And Social Justice Implications, Adrienne Schmidt

Honors Theses

The purpose of this report is to investigate the environmental and health effects of coal mining in the Appalachian region of the United States in the context of global natural resource extraction, explore existing regulation for the reduction of negative environmental health effects of mining in Appalachia, and explore the social justice implications of current mining practices. The research for this report was limited to literature published in English. It was found that there are widespread negative health effects of mining in Appalachia due to environmental toxins, a toxic social environment of limited economic opportunity, and occupational health hazards. The …

Anchoring The Potential Energy Surfaces Of Homogenous And Heterogenous Dimers Of Formaldehyde And Thiofomaldehyde, Christina M. Holy

Honors Theses

This work characterizes five stationary points of the formaldehyde dimer, (CH2O)2, two of which are minima, seven newly-identified stationary points of the formaldehyde/thioformaldehyde (mixed) dimer, CH2O/CH2S, four of which are minima, and five newly-identified stationary points of the thioformaldehyde dimer, (CH2S)2 , three of which are minima. Full geometry optimizations and corresponding harmonic vibrational frequencies were performed on CH2O and CH2S as well as each of the dimer configurations (Figures 3-5). The computations were carried out with second order Møller-Plesset perturbation theory (MP2), with the heavy-auc-cc-pVTZ (haTZ) basis set. Additionally, thirteen density functional theory methods were employed: B3LYP, B3LYP-D3, B3LYP-D3(BJ), …