Theory Calculations Research Articles

Absorption‐coefficient calculation of short‐wavelength photoresist materials: From EUV to BEUV and water window X‐ray

AbstractIn photolithography, shortening the exposure wavelength from ultraviolet to extreme ultraviolet (EUV, 13.5 nm) and soft X‐ray region in terms of beyond EUV (BEUV, 6.X nm) and water window X‐ray (WWX, 2.2–4.4 nm) is expected to further miniaturize the technology node down to sub‐5 nm level. However, the absorption ability of molecules in these ranges, especially WWX region, is unknown, which should be very important for the utilization of energy. Herein, the molar absorption cross sections of different elements at 2.4 nm of WWX were firstly calculated and compared with the wavelengths of 13.5 nm and 6.7 nm. Based on the absorption cross sections in these ranges and density estimation results from the density‐functional theory calculation, the linear absorption coefficients of typical resist materials, including metal‐oxy clusters, organic small molecules, polymers, and photoacid generators (PAGs), are evaluated. The analysis suggests that the Zn cluster has higher absorption in BEUV, whereas the Sn cluster has higher absorption in WWX. Doping PAGs with high EUV absorption atoms improves chemically amplified photoresist (CAR) polymer absorption performance. However, for WWX, it is necessary to introduce an absorption layer containing high WWX absorption elements such as Zr, Sn, and Hf to increase the WWX absorption.

Excited states from GW/BSE and Hartree-Fock theory: Effects of polarizability and transition type on accuracy of excited state energies.

GW and Bethe-Salpeter equation (BSE) methods are used to calculate energies of excited states of organic molecules in the Quest-3 database [Loos et al., J. Chem. Theory Comput. 16, 1711 (2020)]. The self-energy in the GW approximation is conventionally calculated using the RPA polarizability. Inclusion of a screened electron-hole interaction in the polarizability was recently shown to improve predictions of experimental ionization energies in organic molecules [C. H. Patterson, J. Chem. Theory Comput. 20, 7479 (2024)]. Self-energies from RPA or screened time-dependent Hartree-Fock (TDHF) polarizabilities in the GW/BSE method are used to calculate 141 singlet excited states in Quest-3. Theoretical best estimate excited state energies from the CC3 coupled cluster method and aug-cc-pVTZ basis sets are used to benchmark GW/BSE and CIS calculations using the same molecular geometries and basis sets. Differences between GW/BSE or CIS excited state energies and best estimate values show that there are systematic variations in the accuracies of excited state energies classified as ππ*, nπ*, πR (Rydberg), or nR character. The origin of these variations is the accuracy of self-energies of states of nonbonding vs π bonding character. In particular, N or O lone pair states require large self-energy corrections owing to strong orbital relaxation in the localized hole state, while π states have smaller corrections. Self-energies from a screened TDHF vs RPA polarizability are typically over(under)estimated for nonbonding states, leading to under(over)estimation of energies of excited states of nπ* or nR character.

Visualization and quantification of Li distribution in garnet solid electrolytes Li6.25La3Zr2Al0.25O12

Garnet-type Li7La3Zr2O12 (LLZO) is a promising solid electrolyte for all-solid-state batteries due to its structural stability and high Li+ ionic conductivity, but high-purity LLZO crystallizes in a low-conductivity tetragonal phase at room temperature (RT). Al doping stabilizes the cubic structure, yet its impact on Li+ migration is not fully understood. Using Li6.25La3Zr2Al0.25O12 (LLZAO) as a model, we conducted temperature-dependent neutron powder diffraction (NPD), neutron pair distribution function (nPDF), and density-functional theory (DFT) computations. NPD results, supported by nPDF, show Li+ ions at 24d and 96h sites, excluding 48g. Al at 24d adjusts the distribution of Li, improving ionic conductivity near RT. Maximum Entropy Method analyses indicate a temperature-driven 3D Li diffusion pathway of 24d-96h-96h-24d channels, confirmed by DFT. This work will enhance the understanding of Li diffusion and the optimization of ionic conductivity in garnet-type solid electrolytes.

Structure matching mechanism of nRu/FeCo2O4 for highly‐selective oxidation of HMF toward FDCA

AbstractThe selective oxidation of 5‐hydroxymethylfurfural (HMF) toward 2,5‐furandicarboxylic acid (FDCA) offers a promising green pathway to obtain monomers for the synthesis of biodegradable plastics. However, developing a high‐selectivity catalyst and understanding the catalytic mechanism are still great challenge. Here, we synthesize a nRu/FeCo2O4 catalyst with Ru nanoparticles loaded on FeCo2O4. The nRu/FeCo2O4 presents excellent HMF oxidation activity with 100% HMF conversion efficiency and 99% FDCA yield under optimized conditions. Density‐functional theory calculations further reveal the structure matching mechanism of nRu/FeCo2O4 for high‐selective oxidation of HMF toward FDCA, that is, Ru loading in FeCo2O4 provides a more suitable structure matching configuration for adsorption of two‐side chains in HMF, which could optimize the adsorption energy and thus increase reactivity. In short, this work provides a promising structure matching strategy for designing dual‐active‐site relay catalyst to oxidize ‐CHO and C‐OH groups in HMF and thus achieve highly‐selective oxidation of HMF toward FDCA.

Correlation between Noncovalent Bond Strength and Spectroscopic Perturbations within the Lewis Base.

Me2CO was allowed to interact with 20 different Lewis acids so as to engage in various sorts of noncovalent interactions, encompassing hydrogen, halogen, chalcogen, pnictogen, and tetrel bonds. Density functional theory computations evaluated the interaction energy of each dyad, which was compared with spectroscopic, geometric, AIM, and energy decomposition elements so as to elucidate any correlations. The red shift of the C═O stretching frequency, and the changes in the nuclear magnetic resonance shielding of the O and C atoms of acetone, are closely correlated with the interaction energy so can be used to estimate the latter from experimental measurements. The standard AIM measures at the bond critical point, ρ, ∇2ρ, and V also correlate with the energy, albeit not as well as the spectroscopic parameters. The σ-hole depth on the Lewis acid is not well correlated with the energetics, due in part to the fact that electrostatics in general are not an accurate metric of bond strength.

Retraction Note: Identification and sensing of hydrogen fluoride (HF) on aluminum phosphide (Al24P24) nanocage in both gas and water phases: electronic study via density-functional theory computations.

Retraction Note: Identification and sensing of hydrogen fluoride (HF) on aluminum phosphide (Al24P24) nanocage in both gas and water phases: electronic study via density-functional theory computations.

Tailored pseudopotentials for magnesium surface core level shift calculations

In x-ray photoelectron spectroscopy (XPS), identifying the origin of peaks in the spectrum can be guided by theory calculations. With density functional theory (DFT), using pseudopotentials, one can obtain the difference in photoelectron energy for electrons originating from atoms of different environments, for example surface and bulk atoms, and thus model the surface core level shift (SCLS) energies. The focus in this work is to prepare for calculations of magnesium (Mg) 2p SCLSs in material systems where dispersion interactions play a role, primarily in Mg surface degradation and adsorption of molecules as relevant, for example, in degradable bioimplants. For SCLS DFT calculations in metallic surfaces, the state of the photoelectron must be treated as a core state. In the case of Mg, standard pseudopotentials treat the 2p state as a valence state, not a core state. We therefore need Mg pseudopotentials with the 2p electrons in the core, leaving only two electrons for the valence region (the 3s electron); Two-valence electron pseudopotentials are not common, because DFT calculations of Mg-containing materials usually are better or more easily described using 10 valence electrons. In this work, new two-electron Mg pseudopotentials are therefore created for use in dispersion-inclusive DFT calculations. To our knowledge, no such two-electron Mg pseudopotentials exist, proven to work well with the nonlocal, dispersion-inclusive, exchange-correlation functional vdW-DF-cx or similar functionals. We create a number of two-electron Mg pseudopotentials and their 2p-hole partners, and for four of the most promising we assess their performance in vdW-DF-cx. We provide results for Mg and MgO bulk phases and for the Mg(0001) surface energy, structure, and SCLS, and where possible we compare with results that we obtain by using conventional 10-electron Mg pseudopotentials, all-electron calculations, and with experiments. This work not only reports and tests the specific conditions for creating 2p Mg results, it will also, we believe, be of help in creating other similar pseudopotentials to aid the analysis of XPS spectra in other materials. Published by the American Physical Society 2024

Valorizing pig hooves for activated carbon production with efficient Methyl green adsorption, DFT insights and bacterial removal via bio-adsorbent column

ABSTRACT This study describes the use of a novel activated carbon (AC) adsorbent produced from pig hoove waste for the effective removal of Methyl Green (MG) from aqueous solutions. The AC, synthesized through KOH activation, boasts a substantial surface area of 334.031 m2/g and a total pore volume of 0.007 cm³/g. Comprehensive characterization was performed using proximate and ultimate (CHNS) analysis, BET, SEM, TEM, EDX, XRD, FT-IR, XPS, TGA, particle size analysis, zeta potential and zero-point charge (pHZPC). Adsorption data fit the Langmuir isotherm model exceptionally well (R 2 = 0.99) indicating monolayer adsorption and followed pseudo-second-order kinetics implying chemisorption. The thermodynamic studies revealed that the adsorption of the MG dye is a spontaneous and endothermic phenomenon. Density Functional Theory (DFT) computations elucidated the adsorption mechanism, highlighting the critical role of oxygen functional groups. The AC’s unique properties enabled the development of a bio-adsorbent carbon column capable of removing Escherichia coli and Staphylococcus aureus from raw water samples with a 99% removal efficiency. The study also explored the potential for AC regeneration, demonstrating its versatility and sustainability for various applications. This research not only presents an efficient method for dye removal but also underlines the significance of repurposing waste materials, thereby supporting waste reduction and promoting eco-friendly practices for long-term environmental solutions and pollutant mitigation.

Regulating interlayer charge transfer in MoS2 via in-situ loading of Pd-metallene to enhance piezo-catalytic degradation efficiency: Contributions of low free energy

Molybdenum disulfide (MoS2) is a promising piezoelectric catalytic material that has garnered considerable research attention. However, its application in the water treatment field is hindered by electron/hole recombination, leading to relatively low piezoelectric efficiency. This study proposes a strategy of establishing interlayer electron bridges by anchoring Palladium metallene (Pd-ene) with ultra-high conductivity and high longitudinal strain response into MoS2, aiming to accelerate carrier migration. The Pd-ene/MoS2-3 catalyst exhibited outstanding piezoelectric catalytic activity, achieving a tetracycline degradation efficiency of 96.51 % and a Cr6+ reduction efficiency of 90.45 % within 30 min. PFM and d33 measurements indicated that the piezoelectric response signal and piezoelectric coefficient were 2.17 times and 6.4 times higher, respectively, compared to pure MoS2. Electrochemical tests revealed that the improved piezoelectric performance is primarily due to enhanced transient piezoelectric current response, reaching 5.9 mA/cm2. The presence of Pd-ene significantly boosts the catalyst’s performance in terms of current density, electrochemically active surface area, and impedance when compared to MoS2 alone. Notably, the theory calculations and quantitative experiments on radicals showed a reduction in the band gap width from 2.62 eV to 1.31 eV, creating favorable conditions for lowering the system’s free energy and facilitating the formation of H2O2. Among them, the free energy of H2O adsorption, dissociation to 2OH*, deprotolation to 2O* and desorption to O2 path decreased by 5.21, 4.96, 2.64 and 4.15 eV, respectively. This study presents an innovative strategy for enhancing the piezocatalytic activity of MoS2 and explores the application of metallene in the field of piezoelectronics.

The limits of copper oxidation states from density functional theory computations: Fluoro-copper complexes, [CuFn]x, where n = 1 through 6 and x = 3+ through 5−

Density functional theory calculations, at the ωB97X-D/6-311+G* level of theory, were performed on homoleptic fluoro-copper complexes [CuFn]x, n = 1 through 6 and x = 3+ through 5−, to determine the highest positive and lowest negative copper oxidation states that can be supported in these complexes. Only singlet and doublet spin states were investigated. All fluoro-copper stoichiometries stabilized copper(III) or greater. However, some stoichiometries stabilized oxidation states up to copper(VI), and the greatest positive copper oxidation state was copper(VIII) in the distorted octahedral [CuF6]2+ cation. Oxidation states as negative as copper(–IV) in the diatomic [CuF]5− anion and copper(–III) in the triatomic [CuF2]5− were also observed as optimized minima, although no negative oxidation states were calculated to exist for fluoro-copper complexes containing more than two fluorine atoms. No singlet or doublet fluoro-copper complexes with charges more positive than 3+, more negative than 5−, or of Cu(VII), could be optimized.

Using a Single-Atom FeN4 Catalyst on Defective Graphene for the Efficient Reduction of NO to Alanine: A Computational Study

The use of a single-atom FeN4 catalyst on defective graphene (Fe-NC) has recently emerged as an effective method for the synthesis of amino acids. Herein, we investigated the mechanism of alanine formation on FeN4-doped graphene using comprehensive density functional theory (DFT) computations. The alanine formation reaction begins with the activation of NO molecules on the surface, followed by their reaction with hydrogen atoms provided in the system. The computational results show that NO molecules can be effectively activated on Fe-NC, facilitating the subsequent alanine formation at a relatively lower potential. The potential-limiting step in alanine production involves either the formation of HNO* or HNOH* intermediates on Fe-NG, as the free energy changes (ΔG) in these two elementary steps are nearly equivalent. Notably, the formation of HNO* exhibits a higher activation energy (Ea) compared to HNOH* formation. This study provides valuable insights into the C–N coupling reaction and the mechanism of amino acid synthesis on single-atom catalysts.

Modulating the Iron Microenvironment for a Cooperative Interplay Between Fe-N-C Single Atoms and Fe3C Nanoclusters on the Oxygen Reduction Reaction.

The coexistence of single atoms and nanoparticles is shown to increase the oxygen reduction performance in Fe-N-C electrocatalysts, but the mechanisms underlying this synergistic effect remain elusive. In this study, model Fe-N-C electrocatalysts with controlled ratios of FeN4 sites and Fe3C nanoclusters is systematically designed and synthesized. Experiments and density functional theory (DFT) computations reveal that Fe3C nanoclusters near FeN4 sites modulate the electron density of the Fe single-atom microenvironment through an electron withdrawing effect. This substantially alters the oxygen reduction reaction (ORR) mechanisms and boosts the catalytic performance of FeN4 sites. This study provides fundamental insights into the dynamic catalytic impact of single atoms and nanoparticle coexistence in advanced Fe-N-C electrocatalysts for the ORR, paving the way for further refinement through various combinations.

Advanced Techniques for High-Performance Fock Matrix Construction on GPU Clusters.

This Article presents two optimized multi-GPU algorithms for Fock matrix construction, building on the work of Ufimtsev and Martinez [ J. Chem. Theory Comput. 2009, 5, 1004-1015] and Barca et al. [ J. Chem. Theory Comput. 2021, 17, 7486-7503]. The novel algorithms, opt-UM and opt-Brc, introduce significant enhancements, including improved integral screening, exploitation of sparsity and symmetry, a linear scaling exchange matrix assembly algorithm, and extended capabilities for Hartree-Fock caculations up to f-type angular momentum functions. Opt-Brc excels for smaller systems and for highly contracted triple-ζ basis sets, while opt-UM is advantageous for large molecular systems. Performance benchmarks on NVIDIA A100 GPUs show that our algorithms in the EXtreme-scale Electronic Structure System (EXESS), when combined, outperform all current GPU and CPU Fock build implementations in TeraChem, QUICK, GPU4PySCF, LibIntX, ORCA, and Q-Chem. The implementations were benchmarked on linear and globular systems and average speed ups across three double-ζ basis sets of 1.4×, 8.4×, and 9.4× were observed compared to TeraChem, QUICK, and GPU4PySCF respectively. An increased average speedup of 2.1× over TeraChem is observed when using four A100 GPUs. Strong scaling analysis reveals over 91% parallel efficiency on four GPUs for opt-Brc, making it typically faster for multi-GPU execution. Single-compute-node comparisons with CPU-based software like ORCA and Q-Chem show speedups of up to 42× and 31×, respectively, enhancing power efficiency by up to 18×.

Friction mechanisms of WS2 in humid environments: Investigating H2O adsorption via DFT computations and sliding friction experiments

Tungsten disulfide is increasingly used for space and nuclear applications owing to its low friction in vacuum, but the friction increases drastically in humid environments. The increased friction has been conventionally attributed to the oxidation of WS2. This study investigated the frictional behaviour of WS2 in humid atmospheres through sliding friction experiments combined with density functional theory computations. The results showed that the increased friction can be attributed to the formation of O-H···S type interfacial hydrogen bonds between WS2 layers by adsorbed H2O, without significant oxidation. This interaction led to enhanced interlayer bonding and adhesion, consequently elevating friction. This study provides atomistic insights into the friction mechanism of WS2 and design guidelines for thin films operatable in humid environments.

The effect of the oxygen dangling on the thermoelectric properties of organic Thienoisoindigo single-molecule junction.

Theoretical investigation for thermoelectric characteristics of organic Thienoisoindigo single-molecule is carried out using the first-principles calculations based on the density functional theory. It reveals that modifying the position or removing oxygen atoms significantly alters the thermoelectric properties. Transmission coefficient calculations show that the lowest unoccupied molecular orbital (LUMO) dominates across all molecular configurations. Repositioning oxygen atoms increases the bandgap from 1.14 to 1.53 eV, while the complete removal of oxygen further increases to 1.8 eV. This change leads to the disruption of constructive quantum interference, which is replaced by destructive one. The electrical conductance is similarly affected by changes in oxygen atom positioning, with values shifting from 1.06 to 1.63. Molecules without oxygen atoms exhibit lower conductance compared to those with dangling oxygen, resulting in reduced semiconductor-like behavior and enhanced insulating properties. The Seebeck coefficient remains stable at 2.99 V/K when oxygen atoms are repositioned. However, the removal of one oxygen atom changes the coefficient to a positive value (290.14 V/K), causing the molecule to transition from n-type to p-type behavior. The complete absence of oxygen atoms returns the Seebeck coefficient to a negative value ( 256.08 V/K), switching the molecule back to n-type conduction. This investigation was achieved by applying the SIESTA software through density functional theory (DFT) computations. To account for exchange and correlation effects, we use a double-zeta polarized (DZP) basis set in conjunction with the generalized gradient approximation (GGA-PBE) to determine the ideal ground-state atomic locations. By combining the Hamiltonian of each system with the quantum transport code GOLLUM, we can calculate the transmission coefficient, projected density of states, electrical conductance, and Seebeck coefficient to examine the thermoelectric characteristics of the molecular junction.

Spinel oxide enables high-temperature self-lubrication in superalloys

The ability to lubricate and resist wear at temperatures above 600 °C in an oxidative environment remains a significant challenge for metals due to their high-temperature softening, oxidation, and rapid degradation of traditional solid lubricants. Herein, we demonstrate that high-temperature lubricity can be achieved with coefficients of friction (COF) as low as 0.10-0.32 at 600-900 °C by tailoring surface oxidation in additively-manufactured Inconel superalloy. By integrating high-temperature tribological testing, advanced materials characterization, and computations, we show that the formation of spinel-based oxide layers on superalloy promotes sustained self-lubrication due to their lower shear strength and more negative formation and cohesive energy compared to other surface oxides. A reversible phase transformation between the cubic and tetragonal/monoclinic spinel was driven by stress and temperature during high temperature wear. To span Ni- and Cr-based ternary oxide compositional spaces for which little high-temperature COF data exist, we develop a computational design method to predict the lubricity of oxides, incorporating thermodynamics and density functional theory computations. Our finding demonstrates that spinel oxide can exhibit low COF values at temperatures much higher than conventional solid lubricants with 2D layered or Magnéli structures, suggesting a promising design strategy for self-lubricating high-temperature alloys.

Simultaneous visualization of lipid droplets and tracking of the endogenous hypochlorous acid in psoriatic mice models with a novel fluorescent probe in a wash-free fashion

Psoriasis is an autoimmune inflammation-related disease accompanied by a variety of complications. Reactive oxygen species (ROS) are modulators of inflammation, and their excessive production caused by oxidative/anti-oxidative imbalance has been observed in psoriatic patients. Hypochlorous acid (HOCl) is a ROS produced by myeloperoxidase (MPO) from chloride ions (Cl-) and hydrogen peroxide (H2O2). Endogenous HOCl has recently been studied as a potential biomarker of psoriasis underlying the necessity for the development of efficient analytical tools for its detection and real time monitoring. Herein, we designed a novel highly sensitive and selective coumarin-based fluorescent probe for HOCl detection, named CN2-CF3-S. The probe itself featured negligible fluorescence because of the heavy atom effect of the thiocarbonyl group. However, upon responding to HOCl a conversion to sulfur-free derivative CN2-CF3-O occurs, resulting in a dramatical fluorescent enhancement setting the detection limit for HOCl of 3.2 nM. The HOCl-recognition mechanism could be ascribed to the HOCl-triggered oxidative desulfurization process that agrees with liquid chromatography-mass spectrometry (LC-MS) analysis and density functional theory (DFT) computations. The probe’s design incorporated a synergistic combination of two structural features for efficient lipid droplets (LDs)-targeting imaging. An efficient push–pull system reinforced by the presence of two strongly electron-donating dimethylamino groups equipped CN2-CF3-O with pronounced solvatochromism realized through the enhanced blue-shifted emission in non-polar media. Meanwhile, the presence of trifluormethylphenyl moiety at the acceptor side led to an increased lipophilicity. The CN2-CF3-S probe has been successfully utilized to track the endogenous HOCl in cells and on skin of the psoriatic mice in a wash-free manner. As a result, we have demonstrated that the concentration of HOCl in skin might correlate positively with the degree of inflammation in psoriasis. Thus, CN2-CF3-S constitutes the first example of LDs-imaging fluorescent probe for detecting the psoriasis-linked HOCl, offering a convenient tool for further in-depth investigation of psoriasis pathophysiology.

Coupled Perturbed Approach to Dual Basis Sets for Molecules and Solids. II: Energy and Band Corrections for Periodic Systems.

When trying to reach convergence of quantum chemical calculations toward the complete basis set limit, crystalline solids generally prove to be more challenging than molecules. This is due both to the closer packing of atoms─hence, to linear dependencies─and to the problematic behavior of Ewald techniques used for dealing with the infinite character of Coulomb sums. Thus, a dual basis set approach is even more desirable for periodic systems than for molecules. In such an approach, the self-consistent procedure is implemented in a small basis set, and the effect of the enlargement of the basis set is estimated a posteriori. In this paper, we extend to crystalline solids our previous coupled perturbed dual basis set approach [J. Chem. Theory Comput. 2020, 16, 1, 340-353] in which the basis set enlargement is treated as a perturbation. Among the notable features of this approach are (i) the possibility of obtaining not only a correction to the energy but also to energy bands and electron density; (ii) the absence of a diagonalization step for the full Fock matrix in the large basis set; and (iii) the possibility of extrapolating low order perturbation energy corrections to infinite order. We also present here the first periodic implementation of the dual basis set method of Liang and Head-Gordon [J. Phys. Chem. A 2004, 108, 3206-3210]. The effectiveness of both approaches is, then, compared on a small, but representative, set of solids.

Anti-Amyloid Aggregation and Anti-Hyperglycemic Activities of Novel Ruthenium Uracil Schiff Base Compounds.

The formation and characterization of new diamagnetic ruthenium uracil mono-imine compounds: [(η6-p-cymene)RuII(L)Cl][BF4] (L=H2urpda=5-((pyridin-2-yl)methyleneamino)-6-aminouracil) for 1, urdpy=6-amino-1,3-dimethyl-5-((pyridin-2-ylmethylene)amino)uracil) for 2 or urqda=5-((quinolin-2-yl)methyleneamino)-6-aminouracil) for 3); cis-[Ru(bipy)2(urpy)](BF4)2 (4) (urpy=5-((pyridin-2-yl)methyleneamino)uracil) and cis-[Ru(bipy)2(dapd)] (5) (H2dadp=5,6-diaminouracil) are described. A ruthenium(IV) uracil Schiff base compound, trans-[Ru(urpda)(PPh3)Cl2] (6) was also formed. Various physicochemical techniques were utilized to characterize the novel ruthenium compounds. Similarly, the stabilities of 1-3 and 6 monitored in chloro-containing and the non-coordinating solvent, dichloromethane show that they are kinetically inert, whereas, in a high nucleophilic environment, the chloride co-ligands of these ruthenium complexes were rapidly substituted by DMSO. In contrast, the substitution of the labile co-ligands for these ruthenium complexes by DMSO molecules in a high chloride content was suppressed. Solution chemical reactivities of the different ruthenium complexes were rationalized by density functional theory computations. Furthermore, the binding affinities and strengths between BSA and the respective ruthenium complexes were monitored using fluorescence spectroscopy. In addition, the in vitro anti-diabetic activities of the novel metal complexes were assessed in selected skeletal muscle and liver cell lines.

Complexation by γ-cyclodextrin as a way of improving anticancer potential of sumanene

Biological applications of sumanene buckybowl molecule have been widely discussed over the years yet remain still unexplored experimentally. On the other hand, creating cyclodextrin-containing supramolecular assemblies was demonstrated to be a powerful tool in terms of designing effective systems for medicinal chemistry purposes. Here, we show that sumanene molecule exclusively forms 1:1 host-guest complexes with γ-cyclodextrin (γCD) or (2-hydroxypropyl)-γ-cyclodextrin (HP-γCD), as revealed by extensive spectroscopic studies supported with density functional theory (DFT) computations. Based on our preliminary biological studies, we discovered that the formation of such complexes resulted in the improvement of anticancer properties of sumanene, expressed by high cell viabilities in vitro of healthy human mammary fibroblasts (HMF) together with low viabilities of human breast adenocarcinoma cells (MDA-MB-231). Improved pharmacokinetic (ADME-Tox) properties for sumanene@γCD and sumanene@HP-γCD complexes in comparison to native sumanene were also supported by in sillico modeling studies. This work provides the method how to focus the cytotoxic action of sumanene toward cancer cells using supramolecular assembly strategy, paving the way to the further exploration of biological properties of sumanene-containing supramolecular systems with bioactive features and applications of this buckybowl in general.