Binding Energy Component Research Articles

Intercalation of quaternary ammonium cations as a key factor of electron storage in MoS2 thin films

Electrochemical intercalation of cations within two-dimensional transition metal dichalcogenides presents a promising route for tailoring their optoelectronic properties. We have now succeeded in modulating the optical properties of MoS2 thin films through electrochemical intercalation of quaternary ammonium cations. The spectroelectrochemical experiments conducted with varying sizes of the intercalant revealed the size-dependent stability of the intercalated MoS2 nanosheets. The observed absorption change of the exciton bands is reversible and arises from the storage of electrons in MoS2 nanosheets and the subsequent weakening of interlayer van der Waals interactions following cation intercalation. This structural change is evidenced by the emergence of A*1g out-of-plane Raman mode. Additionally, the photoelectron spectroscopy reveals the emergence of a lower binding energy component of Mo 3d and the shift in Fermi level to higher energies, confirming the presence of stored electrons in cation intercalated-MoS2. The underlying mechanism of intercalation-induced property modifications in MoS2 discussed in the present study is useful in developing strategies for energy conversion devices.

Ab initio dispersion potentials based on physics-based functional forms with machine learning.

In this study, we introduce SAPT10K, a comprehensive dataset comprising 9982 noncovalent interaction energies and their binding energy components (electrostatics, exchange, induction, and dispersion) for diverse intermolecular complexes of 944 unique dimers. These complexes cover significant portions of the intermolecular potential energy surface and were computed using higher-order symmetry-adapted perturbation theory, SAPT2+(3)(CCD), with a large aug-cc-pVTZ basis set. The dispersion energy values in SAPT10K serve as crucial inputs for refining the abinitio dispersion potentials based on Grimme's D3 and many-body dispersion (MBD) models. Additionally, Δ machine learning (ML) models based on newly developed intermolecular features, which are derived from intermolecular histograms of distances for element/substructure pairs to simultaneously account for local environments as well as long-range correlations, are also developed to address deficiencies of the D3/MBD models, including the inflexibility of their functional forms, the absence of MBD contributions in D3, and the standard Hirshfeld partitioning scheme used in MBD. The developed dispersion models can be applied to complexes involving a wide range of elements and charged monomers, surpassing other popular ML models, which are limited to systems with only neutral monomers and specific elements. The efficient D3-ML model, with Cartesian coordinates as the sole input, demonstrates promising results on a testing set comprising 6714 dimers, outperforming another popular ML model, component-based machine-learned intermolecular force field (CLIFF), by 1.5 times. These refined D3/MBD-ML models have the capability to replace the time-consuming dispersion components in symmetry-adapted perturbation theory-based calculations and can promptly illustrate the dispersion contribution in noncovalent complexes for supramolecular assembly and chemical reactions.

Electron density-based protocol to recover the interacting quantum atoms components of intermolecular binding energy.

A new approach for obtaining interacting quantum atoms-defined components of binding energy of intermolecular interactions, which bypasses the use of standard six-dimensional integrals and two-particle reduced density matrix (2-RDM) reconstruction, is proposed. To examine this approach, three datasets calculated within the density functional theory framework using the def2-TZVP basis have been explored. The first two, containing 53 weakly bound bimolecular associates and 13 molecular clusters taken from the crystal, were used in protocol refinement, and the third one containing other 20 bimolecular and three cluster systems served as a validation reference. In addition, to verify the performance of the proposed approach on an exact 2-RDM, calculations within the coupled cluster formalism were performed for part of the first set systems using the cc-pVTZ basis set. The process of optimization of the proposed parametric model is considered, and the role of various energy contributions in the formation of non-covalent interactions is discussed with regard to the obtained trends.

Operando Hard X-Ray Photoelectron Spectroscopy for Observing Interfacial Electrochemical Reactions in All-Solid-State Batteries

All-solid-state lithium-ion batteries (ASS-LIBs) have been attracting wide attention for their potential superior performance, such as high safety and long cycle life compared with the conventional lithium-ion batteries with liquid organic electrolytes. However, one of the critical problems of the ASS-LIBs for wide spread applications, especially for electric vehicles, is the large interfacial resistance across the electrode/solid electrolyte (SE)1. When an electrode and SE come into contact, some mobile ions are redistributed at the interface according to their potential difference2,3. In addition, the distribution of the mobile ions and electric potential are also changed during the battery operations. Therefore, dynamic observation of their distribution across the electrode/SE interface is essential to identify and control the origin of the interfacial resistance.Hard x-ray photoelectron spectroscopy (HAXPES) is capable of nondestructive analysis of the elemental composition, oxidation states and electronic structure of sample surfaces and interfaces including those buried with over layers at depth > 10 nm[4].In this study, we developed a laboratory-based operando HAXPES system equipped with a Cr-Kα source (5414.9 eV), which enables angle-resolved measurements of and bias applications to the sample transferred without air-exposure, and applied it to the charging/discharging reactions of a LiCoO2 (LCO) positive electrode deposited on a Li6.6La3Zr1.6Ta0.4O12 (LLZT) solid electrolyte in a half cell configuration. HAXPES measurements were performed while the LCO electrode was electrically grounded to a hemispherical analyzer.The galvanostatic charge/discharge potential profiles exhibited a characteristic plateau due to delithiation of a O3-LiCoO2 at ~3.9 V vs. Li+/Li5. In the Co 2p 3/2 region of the pristine cell, a sharp intense main peak and a broad satellite peak typical to a LCO were observed. At the charged states, however, the main peak was asymmetrically broadened to the higher binding energy. The main peak was deconvoluted into two peaks at 780 eV and ~781 eV, corresponding to Co3+ ions and Co4+ ions, respectively. The full width half maximums (FWHMs) of the Co4+ ions peak increased at charged states, while that of the Co3+ ions peak was remained unchanged. Furthermore, the relative areas of satellite peak decreased at the charged states. These results suggest that Co3+ ions were oxidized to the Co4+ ions by delithiation of the LCO electrode6,7. After the subsequent discharging, the component of higher binding energy of the main peaks decreased, and the satellite peak increased. In addition, the FWHMs of the Co4+ ions peak decreased, suggesting that the Co4+ ions were reduced by lithiation into the LCO electrode during discharging. Thus, the lithiation/delithiation of LCO was successfully observed by operando HAXPES.References N. Ohta, K. Takada, L. Zhang, R. Ma, M. Osada and T. Sasaki, Advanced Materials, 18, 2226 (2006) K. Yamamoto, Y. Iriyama, T. Asaka, T. Hirayama, H. Fujita, C. A. Fisher, K. Nonaka, Y. Sugita and Z. Ogumi, Angew Chem Int Ed Engl, 49, 4414 (2010) J. Haruyama, K. Sodeyama, L. Han, K. Takada and Y. Tateyama, Chemistry of Materials, 26, 4248 (2014) N. K. F. Curran Kalha, Prajna Bhatt, et al., Journal of Physics: Condensed Matter, 33, 233001 (2021) J. N. Reimers and J. R. Dahn, The Electrochemical Society, 139, 2091 (1992) L. Dahéron, R. Dedryvère, H. Martinez, M. Ménétrier, C. Denage, C. Delmas and D. Gonbeau, Chemistry of Materials (2008) H. Kiuchi, K. Hikima, K. Shimizu, R. Kanno, F. Toshiharu and E. Matsubara, Electrochemistry Communications, 118, 106790 (2020)

Quartz Crystal Microbalance Application and In Silico Studies to Characterize the Interaction of Bovine Serum Albumin with Plasma Polymerized Pyrrole Surfaces: Implications for the Development of Biomaterials.

Plasma polymerized pyrrole/iodine (PPPy/I) microparticles and bovine serum albumin (BSA) protein have shown interesting results in experimental models for the treatment of traumatic spinal cord injury. By studying the interaction between BSA and PPPy/I by a quartz crystal microbalance (QCM) and docking, we obtained important results to elucidate possible cellular interactions and promote the use of these polymers as biomaterials. These measurements were also used to characterize the adsorption process using an equilibrium constant. In addition, atomic force microscopy (AFM) was used to obtain images of the QCM surface sensors before and after BSA adsorption. Furthermore, we carried out molecular dynamics simulations and molecular docking to characterize the molecular recognition between BSA and the previously reported PPPy/I structure. For this study, we used two combinatorial models that have not been tested. Thus, we could determine the electrostatic (ΔGele) and nonelectrostatic (ΔGnonelec) components of the free binding energy (ΔGb). We demonstrated that BSA is adsorbed on PPPy/I with an adsorption constant of K = 24.35 μ-1 indicating high affinity. This observation combined with molecular docking and binding free energy calculations showed that the interaction between BSA and both combinatorial models of the PPPy structure is spontaneous.

Molecular insights in repurposing selective COX-2 inhibitor celecoxib against matrix metalloproteinases in potentiating delayed wound healing: a molecular docking and MMPB/SA based analysis of molecular dynamic simulations

Matrix metalloproteinases (MMPs) are proteolytic enzymes that play a role in healing, including reducing inflammation, promoting fibroblast and keratinocyte migration, and modifying scar tissue. Due to their pleiotropic functions in the wound-healing process in diabetic wounds, MMPs constitute a significant cause of delayed wound closure. COX-2 inhibitors are proven to inhibit inflammation. The present study aims to repurpose celecoxib against MMP-2, MMP-8 and MMP-9 through in silico approaches, such as molecular docking, molecular dynamics, and MMPB/SA analysis. We considered five selective COX-2 inhibitors (celecoxib, etoricoxib, lumiracoxib, rofecoxib and valdecoxib) for our study against MMPs. Based on molecular docking study and hydrogen bonding pattern, celecoxib in complex with three MMPs was further analyzed using 1 µs (1000 ns) molecular dynamics simulation and MMPB/SA techniques. These studies identified that celecoxib exhibited significant binding affinity −8.8, −7.9 and −8.3 kcal/mol, respectively, against MMP-2, MMP-8 and MMP-9. Celecoxib formed hydrogen bonding and hydrophobic (π–π) interactions with crucial substrate pocket amino acids, which may be accountable for their inhibitory nature. The MMPB/SA studies showed that electrostatic and van der Waal energy terms favoured the total free binding energy component, while polar solvation terms were highly disfavored. The in silico analysis of the secondary structures showed that the celecoxib binding conformation maintains relatively stable along the simulation trajectories. These findings provide some key clues regarding the accommodation of celecoxib in the substrate binding S1’ pocket and also provide structural insights and challenges in repurposing drugs as new MMP inhibitors with anti-inflammatory and anti-inflammatory wound-healing properties. Communicated by Ramaswamy H. Sarma

Formation of cesium carbonate in ion-implanted graphite, examined with dual-source x-ray photoelectron spectroscopy, density functional theory calculations and thermodynamic modelling

A sample of highly orientated pyrolytic graphite (HOPG) was implanted with Cs+ ions in order to study the effect on the graphite matrix and the chemical form of Cs once embedded. The mean implantation depth was calculated to be ∼22 nm, allowing for investigation with X-ray Photoelectron Spectroscopy, (XPS), where both a traditional Al Kα X-ray source and a higher energy Ag Lα source was used for an increased sampling depth deeper into the surface. Analysis found that there was a reduction of sp2 C–C bonding with increasing implantation dose, resulting in a total loss of sp2 character at ∼6 atomic % Cs+. A striking increase in higher binding energy components (285.8–289.4 eV) in the C 1s spectra cannot be attributed solely to the presence of C–O species, instead indicating a dramatic re-ordering of the graphitic lattice to accommodate and neutralize the embedded Cs. XPS analysis indicates the formation of cesium carbonate within the graphitic material; this is reinforced by analysis of a Cs2CO3 reference sample. Additionally, thermodynamics equilibrium simulations, supported by simplified density functional theory (DFT) calculations, are performed, leading to strong agreement with the XPS findings; that is, the most stable form of Cs within the graphite matrix is expected to be cesium carbonate (Cs2CO3), which is in thermodynamic equilibrium with degraphitised HOPG and oxygenated degraphitised HOPG.

Identification of common genes in obesity and cancer through network interaction and targeting those genes by virtual screening approach

Obesity may have an effect on cancer outcomes, resulting in global inequalities in cancer survival and death. Microarray data analysis was done to identify differentially expressed genes (DEGs) in obese and cancer patients. Total 1977 differentially expressed genes among obesity and gastric cancer, breast cancer, pancreatic cancer, and colorectal cancer were used to build a gene interaction network, which was then analyzed by using Cytoscape software. It has been identified that JUN, CXCL12, and LEP genes show a higher degree and stress, and play an important role in obesity and cancer progression. Further, CXCL12 and LEP were taken for virtual screening study with coumarin and its derivatives to develop a drug against obesity and cancer. The interactions of CXCL12 and LEP with coumarins were studied by molecular docking and it shows good interaction as well as docking score as compared to the standard one. The ADME properties were predicted to check the drug-likeness activity of coumarins and the most of the drug-likeness activities are in admire range. The Binding free energy of the docked complex was calculated by performing MM-GBSA. The molecular docking, ADME properties prediction, and MM-GBSA was performed on Maestro 12.6. The top docked score compounds were further subjected to molecular dynamic simulation to check the stability by using GROMACS. The MM-PBSA study was performed to calculate the binding energy components as well as the energy contributions of specific amino acids. The resultant compounds could be a potent anti-obesity and anti-cancer drug. Communicated by Ramaswamy H. Sarma

Effect of H2O Molecules on the CO2 Replacement in CH4 Hydrate Behavior by Molecular Simulation

CH₄–CO₂ replacement technology has broad application prospects in reducing CO₂ emission and developing natural gas hydrate (NGH) resources. It is of great significance to study the mechanism of CH₄–CO₂ replacement. In this paper, the effect of H₂O on CH₄–CO₂ displacement behavior is studied by molecular dynamics (MD) simulation and quantum mechanics calculation. The interactions between the host and guest in cages of CH₄ hydrate are calculated using the symmetry-adapted perturbation theory method. The contribution of physical components of binding energy can be determined. The result indicates that the electrostatic interaction of H₂O–H₂O and H₂O–gas is a key factor of the CH₄–CO₂ replacement mechanism. Additionally, the microconfigurations and microstructure properties are analyzed by MD simulation in the systems containing a gas layer (CO₂ or CH₄) and a CH₄ hydrate layer. The results showed that the movement and the arrangement of H₂O molecules influence the hydrate structure due to the interaction of H₂O–gas during the replacement process. The molecular simulation suggests that the change of electrostatic interaction with H₂O molecules could improve the CH₄–CO₂ replacement efficiency, which can be favorable for the investigation of CH₄ replacement technology in NGH with CO₂ injection.

The Many-Body Expansion for Aqueous Systems Revisited: II. Alkali Metal and Halide Ion-Water Interactions.

We present a detailed study of the many-body expansion (MBE) for alkali metal and halide ion-water interactions and quantify the effect of these ions on the strength of the surrounding aqueous hydrogen bonding environment. Building on our previous work on neutral water clusters [J. P. Heindel and S. S. Xantheas, J. Chem. Theor. Comput. 16 (11), 6843-6855 (2020)], we carry out the MBE for the alkali metal and halide ion-water clusters, Z+/-(H2O)9, where Z = Li+, Na+, K+, Rb+, Cs+, F-, Cl-, Br-, and I- and compare them with the results for a pure water cluster with the same number of "bodies", viz., (H2O)10. The 2-B ion-water (I-W) interaction accounts for a larger percentage of the total cluster binding energy compared to a pure water cluster of the same size, with the total 3-B term being smaller and of opposite sign (repulsive), whereas higher order terms are essentially negligible. The same oscillating behavior around zero for the MBE terms higher than the 5-B with a basis set that was reported for water clusters is also observed for the ion-water clusters considered here, with the basis set superposition error (BSSE) corrections amending this as in the water cluster case. A remarkable, linear anticorrelation between the total 2-B (I-W), the total 2-B (W-W), and also the 3-B (W-W-W) interactions is found, quantifying the effect of the different ions in disrupting and altering (weakening) the neighboring hydrogen bonded water network: stronger (I-W) interactions result in weaker (W-W) interactions. Additional linear correlations across the two series of alkali metals and halide ions were found between the 3-B (I-W-W) and the 2-B (I-W) as well as between the 3-B (I-W-W) and the 3-B (W-W-W) interactions, suggesting the existence of previously unrealized underlying physics governing these 2-B intermolecular and 3-B collective interactions. Our results further suggest a universal behavior of the two different families of ions (alkali metals and halides) for both the correlations of the various components of the total binding energies and the estimate of the 2-B BSSE correction, which is reported to follow a common profile for ion-water and water-water interactions when cast in terms of reduced distances and energies of the respective dimers. We expect the current results that quantify the interplay between ion-water and water-water interactions in aqueous clusters to impact the development of classical, ab initio-based force fields for monatomic ion solvation, whereas the insights into the nature of the BSSE to be critical in future ab initio-based, many-body molecular dynamics studies.

Jahn–Teller distorted Cu1−xNixCr2O4 (x = 0, 0.5, 1) nanoparticles

In this report, x-ray photoelectron spectroscopy data for three types of Cu-doped nickel chromite nanoparticles are presented. CuCr2O4, Cu0.5Ni0.5Cr2O4, and NiCr2O4 were prepared using the citric acid-assisted sol-gel method. All samples were amorphous after the initial gel preparations were dried, but after calcination at temperatures higher than 700 °C, the samples crystallized in a spinel structure. X-ray diffraction patterns for the samples were well fitted with the I41/amd space group. Survey scans were conducted as well as detailed scans of Cu 2p, Ni 2p, Cr 2p, and O 1s levels. The O 1s core level was well-fitted with three components, including lattice oxygen (low binding energy) and two higher binding energy components, which corresponded to surface-absorbed hydroxyl groups originating from water and alcohol used in the synthesis of the particles. The line shape of the Cu 2p core level was compatible with mixed 2+ and 1+/0+ oxidation states for Cu ions in these nanoparticles. The strong intensity of the high binding energy satellite indicated that the majority of the Cu 2p ions were in 2+ oxidation state. Finally, Ni 2p showed a mixed 3+/2+ oxidation state for Ni ions in these nanoparticles.

An interfacial chemistry study of methylene diphenyl diisocyanate and tantalum for heat exchanger applications

The interactions between oxidised tantalum and methylene diphenyl diisocyanate (MDI) have been investigated by X‐ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (ToF‐SIMS). Thin (approximately 2 nm) and thick layers of polymeric MDI were deposited on tantalum; one set was cured at 200°C, the other dried at ambient temperature (20°C). The thick layers serve as a characteristic pMDI layer, and thin layers contain information relating to the nature of interfacial bonding. By careful fitting of the N1s region contributions relating to interfacial bonding have been established. All spectra show an Nδ+ contribution indicative of acid–base bonding; in the case of the thick films, this is of an intermolecular nature whereas in the thin films, the more intense contribution is a result of such forces between pMDI and substrate. This is confirmed by ToF‐SIMS. A lower binding energy component at ca 396 eV on the air‐dried thin layer of pMDI is the result of a formal reaction between pMDI and tantalum yielding a nitride‐like species in the N1s spectrum.

Unusual Complexes of P(CH)3 with FH, ClH, and ClF.

Ab initio MP2/aug’-cc-pVTZ calculations have been performed to determine the structures and binding energies of complexes formed by phosphatetrahedrane, P(CH)3, and HF, HCl, and ClF. Four types of complexes exist on the potential energy surfaces. Isomers A form at the P atom near the end of a P-C bond, B at a C-C bond, C at the centroid of the C-C-C ring along the C3 symmetry axis, and D at the P atom along the C3 symmetry axis. Complexes A and B are stabilized by hydrogen bonds when FH and ClH are the acids, and by halogen bonds when ClF is the acid. In isomers C, the dipole moments of the two monomers are favorably aligned but in D the alignment is unfavorable. For each of the monomers, the binding energies of the complexes decrease in the order A > B > C > D. The most stabilizing Symmetry Adapted Perturbation Theory (SAPT) binding energy component for the A and B isomers is the electrostatic interaction, while the dispersion interaction is the most stabilizing term for C and D. The barriers to converting one isomer to another are significantly higher for the A isomers compared to B. Equation of motion coupled cluster singles and doubles (EOM-CCSD) intermolecular coupling constants J(X-C) are small for both B and C isomers. J(X-P) values are larger and positive in the A isomers, negative in the B isomers, and have their largest positive values in the D isomers. Intramolecular coupling constants 1J(P-C) experience little change upon complex formation, except in the halogen-bonded complex FCl:P(CH3) A.

Harmonic phase transition in solids under high pressures

The binding energy of atoms in substances exceeds the energy of the harmonic vibrator owing to the anharmonicity (Fig. 1). Experiments show reduction of the anharmonic component of binding energy in solids under high pressures. These data allow us to determine values of pressures when the coefficients of thermal expansions become equal to zero, i.e. when the harmonic phase transition occurs.

Multiferroic nanoparticles of Ni doped CoCr2O4: An XPS study

Three spinel compounds, namely CoCr2O4, (Co0.75Ni0.25)Cr2O4, and (Co0.5Ni0.5)Cr2O4 were investigated using x-ray photoelectron spectroscopy techniques. These compounds were synthesized using sol-gel techniques. The gel was dried and subsequently calcined at 600 °C to achieve crystallinity and the correct cubic phase. The survey scans of the analyzed samples with detailed spectra of the Co 2p, Ni 2p, Cr 2p, O 1s, and the valence band were collected. The core levels are found to be asymmetric and have multiple components. Ni and Co have 2+/3+ oxidation states, whereas Cr prefers 3+ oxidation state. The O 1s core level demonstrates three components. The low binding energy component refers to the lattice oxygen atoms, whereas the two high binding energy components correspond to the surface adsorbed hydroxyl groups resulting from water and the alcohol used for the synthesis of these nanoparticles. The data emanating from this study are reported.

Graphene Grown from Flat and Bowl Shaped Polycyclic Aromatic Hydrocarbons on Cu(111).

The growth of carbon layers, defective graphene, and graphene by deposition of polycyclic aromatic hydrocarbons (PAHs) on Cu(111) is studied by scanning tunneling microscopy and X-ray photoelectron spectroscopy. Two different PAHs are used as starting materials: the buckybowl pentaindenocorannulene (PIC) which contains pentagonal rings and planar coronene (CR). For both precursors, with increasing sample temperature during deposition, porous carbon aggregates (350 °C), dense carbon layers (400-450 °C), disordered defective graphene (500 °C-550 °C), and extended graphene (≥600 °C) are obtained. No significant differences for defective graphene grown from PIC and CR are observed. C 1s X-ray photoelectron spectra of PIC and CR derived samples grown at 350-550 °C exhibit a characteristic C-Cu low binding energy component. Preparation at ≥600 °C eliminates this C-Cu species and only C-C bonded carbon remains.

Thermodynamic analysis of remote substrate binding energy in 3α-hydroxysteroid dehydrogenase/carbonyl reductase catalysis

The binding energy of enzyme and substrate is used to lower the activation energy for the catalytic reaction. 3α-HSD/CR uses remote binding interactions to accelerate the reaction of androsterone with NAD+. Here, we examine the enthalpic and entropic components of the remote binding energy in the 3α-HSD/CR-catalyzed reaction of NAD+ with androsterone versus the substrate analogs, 2-decalol and cyclohexanol, by analyzing the temperature-dependent kinetic parameters through steady-state kinetics. The effects of temperature on kcat/Km for 3α-HSD/CR acting on androsterone, 2-decalol, and cyclohexanol show the reactions are entropically favorable but enthalpically unfavorable. Thermodynamic analysis from the temperature-dependent values of Km and kcat shows the binding of the E-NAD+ complex with either 2-decalol or cyclohexanol to form the ternary complex is endothermic and entropy-driven, and the subsequent conversion to the transition state is both enthalpically and entropically unfavorable. Hence, solvation entropy may play an important role in the binding process through both the desolvation of the solute molecules and the release of bound water molecules from the active site into bulk solvent. As compared to the thermodynamic parameters of 3α-HSD/CR acting on cyclohexanol, the hydrophobic interaction of the B-ring of steroids with the active site of 3α-HSD/CR contributes to catalysis by increasing exclusively the entropy of activation (ΔTΔS‡ = 1.8 kcal/mol), while the BCD-ring of androsterone significantly lowers ΔΔH‡ by 10.4 kcal/mol with a slight entropic penalty of −1.9 kcal/mol. Therefore, the remote non-reacting sites of androsterone may induce a conformational change of the substrate binding loop with an entropic cost for better interaction with the transition state to decrease the enthalpy of activation, significantly increasing catalytic efficiency.

Reproducing ensemble averaged electrostatics with Super-Gaussian-based smooth dielectric function: application to electrostatic component of binding energy of protein complexes

Reproducing ensemble averaged electrostatics with Super-Gaussian-based smooth dielectric function: application to electrostatic component of binding energy of protein complexes

Insights into the structural/conformational requirements of cytotoxic oxadiazoles as potential chemotherapeutic target binding agents

A few novel previously synthesized 2,5-disubstituted 1,3,4-oxadiazoles with cytotoxic activity (1–17) were subjected to combined docking/quantum mechanical studies against chemotherapeutic targets. Selected macromolecular targets were those that were previously known to be inhibited by 1,3,4-oxadiazoles. Within this work, favorable binding modes/affinities of the oxadiazoles toward validated cancer targets were elucidated. Some oxadiazole structures exhibited ΔGbs comparable to or stronger than crystallographic ligands that were previously demonstrated to inhibit such targets. On the basis of obtained results, a general structure activity/binding relationship (SAR/SBR) was developed and a few 2,5-disubstituted 1,3,4-oxadiazole structures were proposed and virtually validated as potential cytotoxic candidates. To get more insight into structure binding relationship of candidate molecules within best correlated targets, docked conformation of the best in silico in vitro correlated oxadiazole structure was analyzed in terms of intermolecular binding energy components by functional B3LYP in association with split valence basis set using polarization functions (Def2-SVP). We believe that such modeling studies may be complementary to our previous results on the synthesis and cytotoxicity assessment of novel 1,3,4-oxadiazole derivatives through extending the scope of privileged structures toward designing new potential anti-tumor compounds.

Chemical state analysis, optical band gap, and photocatalytic decolorization of cobalt-doped ZnO nanospherical thin films by DC/RF sputtering technique

We have used direct current radio frequency (DC/RF) sputtering to deposit cobalt- incorporated zinc oxide (Co:ZnO) thin films on glass substrate. The x-ray diffraction (XRD) was applied for structural observation while topography was examined by atomic force microscopy (AFM). The optical studies were carried out by UV–vis absorption spectroscopy. The elemental composition was performed via x-ray photoelectron spectroscopy (XPS). The chemical state studies were also investigated. The shifting of XRD pattern towards higher diffraction angle confirmed successful incorporation. The optical observation showed “d–d” electron transition during the thin film deposition. The photocatalytic response was carried through the degradation of methylene blue (MB). The improved photocatalytic behavior of Co:ZnO thin films were attributed to the high binding energy component (HBEC) of oxygen vacancies. We have also proposed the tentative mechanism of cobalt incorporation into ZnO through XPS finding. We also checked the stability of deposited thin films. Co:ZnO thin films are new attractive candidates for degradation of waste dyes.