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Wearable electronic energy storage devices usually require the integration of flexible mechanisms and uncompromising electrochemistry of lithium-ion batteries (LIBs). Most of the studies in this field have mainly focused on enhancing the electrochemical properties of the material, while the significance of its flexibility and mechanical properties has been relatively ignored. In this study, the 20 wt % carbon fibers (CFs) composite N-doped flexible carbon nanofiber paper (NFCFP) was prepared through a facile PFI refiner and Bauer sieve of pulping and papermaking machinery sieve-assisted methods combined with annealing technology. The NFCFP-700 with high pyridine N content shows good ion transport and storage performance, the specific capacity remained 308 mAh⸱g−1 after 100 cycles at 0.1 C, and even at 1 C, the specific capacity of the electrode material instead increases constantly at 142 mAh⸱g−1. According to density functional theory (DFT) calculations, the coexistence of pyridine N content and defects in carbon materials was found to enhance the adsorption energy (E ad) of lithium, and the N4V2 locally show the most negative electrostatic potential (ESP) distribution, which was more favorable for the adsorption of Li+ being positively charged. This insight from DFT studies combined with experimental data emphasizes the favorable impact of pyridine N content and defects on the lithium adsorption process in carbon materials, also providing valuable information for the design and optimization of materials for lithium storage applications. [ABSTRACT FROM AUTHOR]

Given its superior structure, the abundance of surface functional groups, and low cost, cotton fiber filtration paper can be used as the support for hydrogen evolution reaction (HER) and oxygen evolution reaction catalysts (OER) instead of copper foam (CF), nickel foam (NF), or carbon cloth (CC). Herein, the chemical plating method was used to create thin self-supporting electrodes based on cotton fiber filtration paper (FP). The Co-Ni-P amorphous nanospheres can be uniformly dispersed on the self-supporting FP due to its porous structure and oxygen functional groups. The Co-Ni-P/FP electrode has an overpotential as low as 125 mV for HER and 320 mV for OER at the current density of 10 mA cm−2. Additionally, according to density functional theory (DFT) calculations, the Co atom added to the Ni-P nanosphere can lead to considerably more charge accumulation around the Co and Ni active sites, which greatly encourages the HER and OER processes. The novel porous support, FP, provides a fresh way the preparation of self-supporting electrodes. [Display omitted] • Filter paper is used to prepare the self-supporting electrode as the substrate. • The preparation method is simple and the properties are stable. • Rich oxygen-containing functional groups of FP promote deposition and dispersion. • Explore the excellent electrochemical performance of amorphous Co-Ni-P/FP by DFT. [ABSTRACT FROM AUTHOR]

[Display omitted] • Paper mill sludge-based biochar (PSBC) is synthesized for PDS activation. • High BPA removal efficiency can be achieved by the PSBC950/PDS process. • Both radical and non-radical pathways are involved in BPA degradation. • Fe(Ⅱ), O V , C O, and graphitized sp2-C with defects were identified as active sites. • The enhancement effects of C O and defects to the electron transfer were confirmed. Paper mill sludge generated from the pulp and papermaking industries has inherent iron and carbon contents. Herein, the biochar derived from paper mill sludge (PSBC) was synthesized via simple pyrolysis processes and applied as an efficient persulfate (PDS) activator for the removal of Bisphenol A (BPA) in water. The unique properties of PSBC endowed it with multiple active sites including Fe(II) species, oxygen vacancy, C O, and graphite sp2-C with defects, owing to which, the PSBC/PDS process presented satisfactory performance with BPA removal efficiency up to 98 % within 60 min. Both of the radical and non-radical pathways were revealed to be involved in the BPA degradation. Based on the results of theoretical calculation, the existences of some special structures in PSBC effectively facilitated the electron transfer process of PDS activation. The process also exhibited a high anti-interference capability to coexisting substances and the universality toward various organic contaminants degradation. And the used PSBC can be recovered by simple thermal treatment. This work provided a promising heterogeneous PDS activator with plentiful active sites and satisfactory efficiency, which can be beneficial to the cost reduction of wastewater treatment and promotes the application of paper mill sludge in the area of environmental remediation. [ABSTRACT FROM AUTHOR]

This paper analyzes the digital signal processing techniques and estimates induction motor (IM) rotational speed operating in stationary or non-stationary conditions. Rotor slot harmonics present in the stator current waveform are used to estimate the induction motor speed with a given or identified rotor slot numbers. This paper's contribution is the following: First, zoom improved short-time Chirp-Z transform is used to find supply frequency and the rotor slot harmonic frequency to improve the estimation accuracy without increasing computing complexity. Second, a technique is described that can be used to determine whether or not a motor can generate principal slot harmonics (PSH). Finally, an algorithm is designed to figure out the perfect window length and estimate the motors' speed. This proposed technique was investigated when the motor was fed by an inverter-fed supply driving a variable load and operating in non-stationary conditions. Experimental test results on 5.5 kW and 22 kW induction motors have confirmed the correctness of this method. [ABSTRACT FROM AUTHOR]

Context: The mechanisms for the formation of the first C − C bond and lower olefins on methanol to olefins (MTO) conversion on H-ZSM-5 had been focused in dispute. In this paper, density functional theory has been used to study the reaction mechanisms of methanol to olefins on ZSM-5. The configurations of reactants, intermediates, products and transition state of the numerous reactions involved in such a process have been optimized, as well as the elementary reactions related to these configurations were determined by the calculation of corresponding activation energy barriers and reaction heats. Here, two different kinds of the mechanisms were proposed for the formation of dimethyl ether (DME), one involving an associative interaction of two methanol molecules with the zeolite Brønsted acid sites and the other occurring via a surface methoxy species and a methanol molecule. A critical intermediate of the methoxy methyl cation was theoretically verified by the reaction of the methoxy species and dimethyl ether. Besides, it was found that the first intermediates containing a C − C bond were 1,2-dimethoxyethane and 2-methoxy-ethanolare, in which the former was formed from methoxy species with dimethyl ether and the latter was formed from methanol by onium ions((CH3)2O+CH2CH2OCH3), respectively. For the whole reaction mechanism, the results in this paper indicated that the ethene formation is more favorable than propylene formation due to the low activation energy barrier for ethene formation (123.49 vs. 162.09 kJ.mol−1). From these calculations, it would be concluded that ethene is the first alkene product that induces the occurrence of the hydrocarbon pool mechanism. Methods: All the periodic density function theory (DFT) calculations were performed by the Vienna Ab Initio Simulation package (VASP). The interaction between nucleus and valence electron was described using the pseudopotentials found in the projector augmented wave (PAW) method. PBE-D3 was used in the whole DFT calculations and CI-NEB was used to locate transition state. [ABSTRACT FROM AUTHOR]

[Display omitted] • Carbohydrate-based fluorometric sensors 1 and 2 have been used to detect picric acid in the aqueous medium. • The detection limits of 1 and 2 for PA were calculated to be 0.094 µM and 0.013 µM, respectively. • The DFT-supported charge transfer and µ-µ interactions explained the fluorescence quenching mechanism. • The sugar moiety plays a role in developing interaction between the sensor and PA in aqueous medium. • Both the sensors were used as naked-eye colorimetric sensors for PA in the test trips. Triazole-linked pyrene-appended inexpensive sensors 1 and 2 were synthesized from carbohydrates to instantly recognize picric acid (PA) based on a charge-transfer mechanism in the semi-water medium. Both sensors showed good selectivity and sensitivity towards PA over a wide variation of nitroaromatics in the absorbance and fluorescence methods. Moreover, sensors 1 and 2 were used for quick finding of picric acids using test strips. Interestingly, it was found that the sensitivity of 2 (LOD: 0.012 µM) is higher than 1 (LOD: 0.093 µM) might be explained by the close intramolecular space of the triazole/sugar residue and pyrene in sensor 2. The fluorescence quenching and structural features of the complexes (1-PA, 2-PA) were supported by density functional theory (DFT) calculations and spectroscopic studies. [ABSTRACT FROM AUTHOR]

DNA is continuously exposed to a variety of harmful factors, which, on the one hand, can force undesirable processes such as ageing, carcinogenesis and mutagenesis, while on the other hand, can accelerate evolutionary changes. Of all the canonical nucleosides, 2′-deoxyguanosine (dG) exhibits the lowest ionization potential, making it particularly prone to the one-electron oxidizing process. The most abundant type of nucleobase damage is constituted by 7,8-dihydro-8-oxo-2′-deoxyguanosine (OXOdG), with an oxidation potential that is 0.56 V lower than that of canonical dG. All this has led to OXOdG, as an isolated lesion, being perceived as a sink for radical cations in the genome. In this paper, a comparative analysis of the electronic properties of an OXOGC base pair within the context of a clustered DNA lesion (CDL) has been conducted. It is based on previous DFT studies that were carried out at the M06-2x/6-31++G** level of theory in non-equilibrated and equilibrated condensed phases. The results of the comparative analysis presented here reveal the following: (A) The ionization potentials of OXOG4C2 were largely unaffected by a second lesion. (B) The positive charge and spin were found predominantly on the OXOG4C2 moiety. (C) The electron-hole transfers A3T3→G4C2 and G4C2←A5T1 were found in the Marcus inverted region and were resistant to the presence of a second DNA lesion in close proximity. It can therefore be reasonably postulated that OXOGC becomes the sink for a radical cation migrating through the double helix, irrespective of the presence of other 2′-deoxyguanosine lesions in the CDL structure. [ABSTRACT FROM AUTHOR]

The development of digital techniques in control engineering leads to the creation of innovative algorithms for measuring specific parameters. In the field of electric power engineering these parameters may be amplitude, phase and frequency of voltage or current occurring in the analyzed electric grid. Thus, the algorithms mentioned, applied in relation to the quoted parameters, may provide precise and reliable measurement results in the electric grid as well as ensure better grid monitoring and security. Signal analysis regarding its identification due to the type of interference is very difficult because the multitude of information obtained is very large. In order to indicate the best method for determining errors in measuring synchronous parameters of the measured current or voltage waveforms, the authors propose in this paper a new form of one error for all testing functions, which is called an equivalent error. This error is determined for each error's value defined in the applicable standards for each of selected 15 methods. The use of the equivalent error algorithm is very helpful in identifying a group of methods whose operation is satisfactory in terms of measurement accuracy for various types of disturbances (both in the steady state and in the dynamic state) that may occur in the power grid. The results are analyzed for phasor measurement unit (PMU) devices of class P (protection) and M (measurement). [ABSTRACT FROM AUTHOR]

The gallium(III) complex of warfarin was synthesized, and its structure was determined by means of theoretical, analytical, and spectral analyses. Significant differences in the IR and Raman spectra of the complex were observed as compared to the spectra of the ligand and confirmed the suggested metal-ligand binding mode. The theoretical study of the Ga(III) complex of warfarin has been done to elucidate the structure-activity relation, inter- and intra-molecular interactions, and frontier molecular orbital energy analysis based on DFT computations. A molecular docking study has been performed to predict the biological activity of the molecule. In this paper, we report preliminary results about the cytotoxicity of the investigated compounds. The cytotoxic effects of the ligand and its Ga(III) complex were determined using the MTT method on different tumor cell lines. The screening performed revealed that the tested compounds exerted cytotoxic activity on the evaluated cell lines. [ABSTRACT FROM AUTHOR]

Delafossite CuFeO2 is widely used in the field of photocatalysis due to its narrow band gap and easy availability, while the photogenerated carriers are easy to compound due to its centrosymmetric layered structure, limiting its photocatalytic effect. In view of this, this paper focuses on another configuration of, namely β-CuFeO2, which is an intrinsic ferroelectric semiconductor with phase stability, narrow band gap, and strong polarization. We construct the [011] surface with alternating arrangement of photogenerated electron and hole generation sites, which promotes charges separation under the action of ferroelectric built-in electric field to enhance the photocatalytic performance. Based on first-principles calculations, this study identified β-CuFeO2 as a direct bandgap semiconductor with thermodynamic stability, a C-type antiferromagnetism in the magnetic ground state, and the bandgap size of 1. 37 eV, with a theoretical ferroelectric polarization intensity of 83. 46 μC/cm², which is a good photocatalyst carrier. Further, using the surface oxygen precipitation reaction (OER) as a model, unpolarized direction surfaces [100], [010] and polarized direction surfaces [001], [011] were constructed to investigate the effect of ferroelectric polarization on the OER. The results show that the surface Valance Band Maximum (VBM) redox potential of β-CuFeO2 is mostly more than the water oxidation potential (1. 23 eV) and the polarized surface is easier to form. In addition, the [011] surface with fully exposed Cu-O atoms and alternating layers of Cu, Fe atoms in the polarization direction is the most susceptible to adsorption of water molecules and has the optimal OER catalytic activity. The electronic structure analysis of the rate-determining step for the OER on the [011] surface reveals that there are two electron pockets on the *O intermediate, and one electron pocket is consumed after the reaction to produce * OOH. This is the intrinsic mechanism of the OER rate-determining step on the polarization direction [011] surface. β-CuFeO2 ferroelectric semiconductor was constructed in this work and its basic properties were calculated by theoretical simulations, and different directions of surfaces were constructed to study the effect of ferroelectric polarization on the photocatalytic OER activity, which will provide a new perspective for the design of ferroelectric photocatalysts. [ABSTRACT FROM AUTHOR]

Context: With the union of machine learning (ML) and quantum chemistry, amid the debate between machine-learned functionals and human-designed functionals in density functional theory (DFT), this paper aims to demonstrate the generation of potential energy surfaces using computations with machine-learned density functional approximation (ML-DFA). A recent research trend is the application of ML in quantum sciences in the design of density functionals such as DeepMind's Deep Learning model (DeepMind21, DM21). Though science reported the state-of-the-art performance of DM21, the opportunity to utilize DeepMind's pretrained DM21 neural networks in computations in quantum chemistry has not yet been tapped. So far in the literature, the Deep Learning density functionals (DM21) have not been applied to generate potential energy surfaces. While the superior accuracy of DM21 has been reported, there is still a scarcity of publications that apply DM21 in calculations in the field. In this context, for the first time in literature, neural density functionals inferring 2D potential energy surfaces (ML-DFA-PES) based on machine-learned DFA-based computational method is contributed in this paper. This paper reports the ML-DFA-generated PES for C4H8, H2O, H2, and H2+ by employing a pretrained DM21m TensorFlow model with cc-pVDZ basis set. In addition, we also analyze the long-range behavior of DM21 based PES to investigate the ability to describe a system at long ranges. Furthermore, we compare PES diagrams from DM21 with popular DFT functionals (b3lyp/ PW6B95) and CCSD(T). Methods: In this method, 2D potential energy surfaces are obtained using a method that relies upon the neural network's ability to accurately learn the mapping between 3D electron density and exchange–correlation potential. By inserting Deep Learning inference in DFT with a pretrained neural network, self-consistent field (SCF) energy at different geometries along the coordinates of interest is computed, and then, potential energy surfaces are plotted. In this method, first, the electron density is computed mathematically, and this computed 3D electron density is used as a ML feature vector to predict the exchange correlation potential as a ML inference computed by a forward pass of pre-trained DM21 TensorFlow computational graph, followed by the computation of self-consistent field energy at multiple geometries, and then, SCF energies at different bond lengths/angles are plotted as 2D PES. We implement this in a python source code using frameworks such as PySCF and DM21. This paper contributes this implementation in open source. The source code and DM21-DFA-based PES are contributed at https://sites.google.com/view/MLfunctionals-DeepMind-PES. [ABSTRACT FROM AUTHOR]

[Display omitted] The defects formed by N doping always coexist with pyrrole nitrogen (Po) and pyridine nitrogen (Pd), and the synergistic mechanisms of H 2 O 2 production and PMS activation between the different Po: Pd are unknown. This paper synthesized MOF-derived carbon materials with different nitrogen-type ratios as cathode materials in an electro-Fenton system using precursors with different nitrogen-containing functional groups. Several catalysts with different Po: Pd ratios (0:4, 1:3, 2:2, 3:1, 4:0) were prepared, and the best catalyst for LEV degradation was FC-CN (Po: Pd=3:1). X-ray Photoelectron Spectroscopy (XPS) and density-functional theory (DFT) calculations show that the introduction of nitrogen creates an interfacial micro-electric field (IMEF) in the carbon layer and the metal, accelerates the electron transfer from the carbon layer to the Co atoms, and promotes cycling between the Fe3+/Co2+ redox pairs, with the electron transfer reaching a maximum at Po: Pd = 3:1. FC-CN (Po: Pd=3:1) achieved more than 95 % LEV degradation in 90 min at pH = 3–9, with a lower energy consumption of 0.11 kWh m−3 order−1. and the energy consumption of the catalyst for LEV degradation is lower than that of those catalysts reported. In addition, the degradation pathway of LEV was proposed based on UPLC-MS and Fukui function. This study offers some valuable information for the application of MOF derivatives. [ABSTRACT FROM AUTHOR]

The diketopyrrolopyrrole (DPP) unit represents one of the building blocks more widely employed in the field of organic electronics; in most of the reported DPP-based small molecules, this unit represents the electron acceptor core symmetrically coupled to donor moieties, and the solubility is guaranteed by functionalizing lactamic nitrogens with long and branched alkyl tails. In this paper, we explored the possibility of modulating the solubility by realizing asymmetric DPP derivatives, where the molecular structure is extended in just one direction. Four novel derivatives have been prepared, characterized by a common dithyenil-DPP fragment and functionalized on one side by a thiophene unit linked to different auxiliary electron acceptor groups. As compared to previously reported symmetric analogs, the novel dyes showed an increased solubility in chloroform and proved to be soluble in THF as well. The novel dyes underwent a thorough optical and electrochemical characterization. Electronic properties were studied at the DFT levels. All the dyes were used as active layers in organic field effect transistors, showing balanced charge transport properties. [ABSTRACT FROM AUTHOR]

Recent evaluations of counter-based periodic testing strategies for fault detection in Microprocessor (μP) have shown that only a small set of counters is needed to provide complete coverage of severe faults. Severe faults are defined as faults that leak sensitive information, e.g., an encryption key on the output of a serial port. Alternatively, fault detection can be accomplished by executing instructions that periodically test the control and functional units of the μP. In this paper, we propose a fault detection method that utilizes an 'engineered' executable program combined with a small set of strategically placed counters in pursuit of a hardware Periodic Built-In-Self-Test (PBIST). We analyze two distinct methods for generating such a binary; the first uses an Automatic Test Generation Pattern (ATPG)-based methodology, and the second uses a process whereby existing counter-based node-monitoring infrastructure is utilized. We show that complete fault coverage of all leakage faults is possible using relatively small binaries with low latency to fault detection and by utilizing only a few strategically placed counters in the μP. [ABSTRACT FROM AUTHOR]

Interest in fullerene-based polymer structures has renewed due to the development of synthesis technologies using thin C60 polymers. Fullerene networks are good semiconductors. In this paper, heterostructure complexes composed of C60 polymer networks on atomically thin dielectric substrates are modeled. Small tensile and compressive deformations make it possible to ensure appropriate placement of monolayer boron nitride with fullerene networks. The choice of a piezoelectric boron nitride substrate was dictated by interest in their applicability in mechanoelectric, photoelectronic, and electro-optical devices with the ability to control their properties. The results we obtained show that C60 polymer/h-BN heterostructures are stable compounds. The van der Waals interaction that arises between them affects their electronic and optical properties. [ABSTRACT FROM AUTHOR]

Context: The compounds of the "565" parent ring structure have received much attention from researchers because of their excellent detonation performance. In the present study, 81 derivatives were designed by introducing different substituents based on 6-dinitrophenyl-5,6,7,8-tetrahydro-4-imidazo[4,5-e]furazano[3,4-b] pyrazine (DIOP), which is a compound of the parent ring structure of 565, and the performance of these derivatives, such as the electronic structure, energy gap, heat of formation, and detonation performance, were investigated. Among these energy-containing derivatives, the density ranges from 1.70 to 2.17 g/cm3, the detonation velocity ranges from 8.01 to 10.26 km/s, and the detonation pressure ranges from 27.99 to 49.88 GPa. Through comprehensive analysis of several properties of DIOP derivatives, it was found that the oxygen balance of derivatives with the -ONO2 group was greater than zero and close to zero, while the oxygen balance of derivatives with other groups was almost all less than zero. Among them, G8 (D = 10.1 km/s, P = 47.72 GPa), H8 (D = 10.11 km/s, P = 47.92 GPa), and I8 (D = 10.26 km/s, P = 49.88 GPa) had higher detonation velocity and pressure among all derivatives, and their impact sensitivity was better than RDX. Therefore, three potential high-energy and less sensitive energy-containing derivatives, G8, H8, and I8, were screened out. The intramolecular interactions of the three derivatives were further analyzed, and it was found that there were intensive van der Waals interactions and significant spatial steric effects within the molecules, which had a positive effect on reducing the shock sensitivity of the compounds. Moreover, the three derivatives have a large degree of stacking, which leads to a high density. Methods: All calculations in this paper are performed using Gaussian16 based on density functional theory. Firstly, the structures of the derivatives were optimized at the level of B3LYP-D3/6-311G**, and then single-site energy calculations were carried out at the level of M06-2X-D3/def2-TZVPP, to reveal the effects of single substituents versus multiple substituents and isomerism on the properties of the DIOP-based energetic derivatives. Multiwfn was used to plot the density of states (DOS) of the derivatives and to calculate the molecular surface electrostatic potential at 0.001 e/Bohr3 electron density, 0.25 Bohr lattice spacing surface. [ABSTRACT FROM AUTHOR]

In this paper, a detailed mechanism is discussed for two processes: deNOx and deN2O. An FAU catalyst was used for the reaction with Cu-Fe bimetallic adsorbates represented by a dimer with bridged oxygen. Partial hydration of the metal centres in the dimer was considered. Ab initio calculations based on the density functional theory were used. The electron parameters of the structures obtained were also analysed. Visualisation of the orbitals of selected structures and their interpretations are presented. The presented research allowed a closer look at the mechanisms of processes that are very common in the automotive and chemical industries. Based on theoretical modelling, it was possible to propose the most efficient catalyst that could find potential application in industry–this is the FAU catalyst with a Cu-O-Fe bimetallic dimer with a hydrated copper centre. The essential result of our research is the improvement in the energetics of the reaction mechanism by the presence of an OH group, which will influence the way NO and NH3 molecules react with each other in the deNOx process depending on the industrial conditions of the process. Our theoretical results suggest also how to proceed with the dosage of NO and N2O during the industrial process to increase the desired reaction effect. [ABSTRACT FROM AUTHOR]

A novel porous Ni matrix with optimal pore structure and adequate mechanical property is successfully prepared by a modified spark plasma sintering progress, while a self-supporting HER electrode of Ni 3 Se 2 @Porous Ni is subsequently obtained via a facile one-step hydrothermal synthesis. Such the Ni 3 Se 2 @Porous Ni electrode has performed a superior conductivity, excellent catalytic activity and robust durability, which can be attributed to the strong covalent bonding between Ni 3 Se 2 and Ni matrix, abundant active sites of the vertically arranged nanosheets, as well as the metallurgically bonded metal skeleton, exhibiting a fascinating potential for the industrial application. [Display omitted] Developing efficient and durable self-supporting catalytic electrodes is an important way for industrial applications of hydrogen evolution reaction. Currently, commercial nickel foam (NF)-based electrode has been widely used due to its good catalytic performance. However, the NF consisting of smooth skeleton surface and large pores not only exhibits poor conductivity but also provides insufficient space for catalyst decoration and sufficient adhesion, resulting in inadequate catalytic performance and poor durability of NF-based electrodes. In this paper, a novel three-dimensional porous Ni substrate with multangular skeleton surface and small pore structure was prepared by a modified spark plasma sintering technique, and subsequently Ni 3 Se 2 @Porous Ni electrode with a large number of Ni 3 Se 2 nanosheets uniformly distributed on the surface was obtained by one-step in-situ selenization. The electrode exhibits outstanding conductivity and catalytic hydrogen evolution reaction, providing a low overpotential of 183 mV at a current density of 100 mA cm−2. Due to the strong interfacial bonding between Ni and Ni 3 Se 2 , the Ni 3 Se 2 @Porous Ni electrode shows strong durability, which can work stably at 85 mA cm−2 for more than 200 h. This work provides an effective strategy for the rational preparation of metal substrates for efficient and durable self-supporting catalytic electrodes. [ABSTRACT FROM AUTHOR]

Pyridoxal and pyridoxal 5′-phosphate are aldehyde forms of B6 vitamin that can easily be transformed into each other in the living organism. The presence of a phosphate group, however, provides the related compounds (e.g., hydrazones) with better solubility in water. In addition, the phosphate group may sometimes act as a binding center for metal ions. In particular, a phosphate group can be a strong ligand for a gold(III) ion, which is of interest for researchers for the anti-tumor and antimicrobial potential of gold(III). This paper aims to answer whether the phosphate group is involved in the complex formation between gold(III) and hydrazones derived from pyridoxal 5′-phosphate. The answer is negative, since the comparison of the stability constants determined for the gold(III) complexes with pyridoxal- and pyridoxal 5′-phosphate-derived hydrazones showed a negligible difference. In addition, quantum chemical calculations confirmed that the preferential coordination of two series of phosphorylated and non-phosphorylated hydrazones to gold(III) ion is similar. The preferential protonation modes for the gold(III) complexes were also determined using experimental and calculated data. [ABSTRACT FROM AUTHOR]

Context: Herein, we compare and contrast the dual roles of Cun clusters (n = 3, 5, and 7 atoms) in scavenging or generating RO• free radicals from ROH at the theoretical levels (where R = H, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, and phenyl). This investigation is performed in water media to mimic the actual environment in the biological system. In the presence of the Cun clusters, bond dissociation energy (BDE) of RO–H and R–OH is reduced. This is clear evidence for the increased possibility of both the RO–H and R–OH bonds breakage and scavenging of RO• radicals. The nature of anchoring bonds responsible for the interaction of Cun clusters with ROH and RO• are interpreted using the quantum theory of atoms in molecules (QTAIM) and the natural bond orbital (NBO) analysis. The DFT results indicate that the O•⋅⋅⋅•Cu bond is stronger and has more covalent character in RO•⋅⋅⋅•Cun radical complexes than in ROH⋅⋅⋅•Cun. Therefore, the interactions of Cun clusters with RO• radicals (antioxidant) are more pronounced than their interactions with ROH non-radicals (pro-oxidant). Methods: The GAMESS software package was utilized in this paper. The B3LYP and M06 functions with the 6–311 + + G(d,p), and LANL2DZ/SDD basis sets was used to perform the important geometrical parameters of RO•⋅⋅⋅•Cun and ROH⋅⋅⋅•Cun, binding energy (Eb), and bond dissociation energy (BDE). [ABSTRACT FROM AUTHOR]

Context: Due to their unique photophysical properties, organic charge transfer crystals are becoming promising materials for next-generation optoelectronic devices. This research paper explores the impact of s-block metals on a charge transfer crystal of indol-2-one for enhanced nonlinear optical (NLO) responses with efficient energetic offsets. The study reveals that alkali metals can enhance NLO performance due to their free electrons. Method: The Perdew-Burke-Ernzerhof functional of DFT with dispersion correction (D3) was used, and the λmax values ranged between 596 and 669 nm, with the highest value for dichloromethane (DCM). Leveraging the unique properties of metals allowed for the development of nonlinear optical materials with improved performance and versatility. Softness (σ) values provide insight into electron density changes, with higher values indicating a greater tendency for changes and lower values indicating the opposite. The NLO results for the chromophores MMI1–MMI6 show varying linear polarizability (< α0 >) along with their first (β0) and second (γ0) hyperpolarizabilities. Chromophore MMI4 stands out with the highest NLO performance, having two potassium (K) atoms. Its < α0 > , β0, and γ0 values of 4.19, 7.09, and 17.43 (× 10−24 e.s.u), respectively, indicate a significant enhancement in NLO response compared to the other chromophores. The transitions involving (O20)LP → (C3-N5)π* and (O19)LP → (N12-C13)π* exhibit the highest level of stabilization, followed by (O23)π → (C10-C11)π*, while (C6-N12)π → (C6-C7)π* shows the lowest level of stabilization for chromophore MMI4. The present research work is facile in its nature, and it can be helpful for synthetic scientist to design the new materials for uniting crystal properties with metal doping for efficient NLO devices. [ABSTRACT FROM AUTHOR]

Calcium ferrite containing aluminum (CFA) is a precursor of the low-temperature bonding phase in the sintering process of iron ore fines for blast furnace ironmaking. Thus, improving the formation of CFA at lower temperature is very important for saving energy, improving efficiency and production. In this paper, the formation process of CFA was investigated at 1200 °C by reactions of alumina (Al2O3), respectively with a mixture of calcium oxide (CaO) and hematite (Fe2O3) and monocalcium ferrite (CF) as a recognized initial product, as well as reaction of Al-containing hematite (Hss) with CF. The result confirmed that CF is an intermediate product formed easily in the sintering process, and it may react with excessive Fe2O3 to generate an alpha-calcium iron oxide (Ca2Fe15.50O25) as a new phase. It was found that CFA can be formed directly by reactions of CF with Hss and Ca2Fe15.50O25 with Al2O3, while the reaction of CF with Al2O3 is more helpful in generating Ca2Fe15.5O25 rather than CFA, simultaneously forming a calcium aluminum oxide (CaAl2O4, CA; CaAl4O7, CA2). It was revealed that the appearance of CA and CA2 is a main reason to hinder CFA formation in the sintering process of iron ore fines. [ABSTRACT FROM AUTHOR]

The basis set issue has always been one of the most important factors of accuracy in the quantum chemical calculations of NMR chemical shifts. In a previous paper, we developed new pecS-n (n = 1, 2) basis sets purposed for the calculations of the NMR chemical shifts of the nuclei of the most popular NMR-active isotopes of 1–2 row elements and successfully approbated these on the DFT calculations of chemical shifts in a limited series of small molecules. In this paper, we demonstrate the performance of the pecS-n (n = 1, 2) basis sets on the calculations of as much as 713 1H and 767 13C chemical shifts of 23 biologically active natural products with complicated stereochemical structures, carried out using the GIAO-DFT(PBE0) approach. We also proposed new alternative contraction schemes for our basis sets characterized by less contraction depth of the p-shell. New contraction coefficients have been optimized with the property-energy consistent (PEC) method. The accuracies of the pecS-n (n = 1, 2) basis sets of both the original and newly contracted forms were assessed on massive benchmark calculations of proton and carbon chemical shifts of a vast variety of natural products. It was found that less contracted pecS-n (n = 1, 2) basis sets provide no noticeable improvement in accuracy. These calculations represent the most austere test of our basis sets as applied to routine calculations of the NMR chemical shifts of real-life compounds. [ABSTRACT FROM AUTHOR]

Based on the reported research, hydroxyl radicals can be rapidly transformed into carbonate radicals in the carbonate–bicarbonate buffering system in vivo. Many of the processes considered to be initiated by hydroxyl radicals may be caused by carbonate radicals, which indicates that lipid peroxidation initiated by hydroxyl radicals can also be caused by carbonate radicals. To date, theoretical research on reactions of hydrogen abstraction from and radical addition to polyunsaturated fatty acids (PUFAs) of carbonate radicals has not been carried out systematically. This paper employs (3Z,6Z)-nona-3,6-diene (NDE) as a model for polyunsaturated fatty acids (PUFAs). Density functional theory (DFT) with the CAM-B3LYP method at the 6-311+g(d,p) level was used to calculate the differences in reactivity of carbonate radicals abstracting hydrogen from different positions of NDE and their addition to the double bonds of NDE under lipid solvent conditions with a dielectric constant of 4.0 (CPCM model). Grimme's empirical dispersion correction was taken into account through the D3 scheme. The energy barrier, reaction rate constants, internal energy, enthalpy and Gibbs free energy changes in these reactions were calculated With zero-point vibrational energy (ZPVE) corrections. The results indicated that carbonate radicals initiate lipid peroxidation primarily through hydrogen abstraction from diallyl carbon atoms. The reaction of hydrogen abstraction from diallyl carbon atoms exhibits the highest reaction rate, with a reaction rate constant approximately 43-fold greater than the second-ranked hydrogen abstraction from allyl carbon atoms. This process has the lowest energy barrier, internal energy, enthalpy, and Gibbs free energy changes, indicating that it is also the most spontaneous process. [ABSTRACT FROM AUTHOR]

Ionic liquids (ILs) are green solvents involved in chemical reaction and separation processes. In this paper, four ILs-based metal catalysts were prepared by dissolving four transition metal chlorides into 1-butyl-3-methylimidazolium chloride ([Bmim]Cl). Their catalytic performance was measured, and the catalytic mechanism was studied via density functional theory (DFT) based on the analysis of the Mayer bonding order, Mulliken charge, molecular electrostatic potential (ESP), electron localization function (ELF), and partial density of states (PDOS). The results show that the catalytic activity follows the order [Bmim]Cl-RuCl3 > [Bmim]Cl-AgCl > [Bmim]Cl-CuCl2 > [Bmim]Cl-CuCl. [Bmim]Cl helps to dissolve and activate HCl, and the metal chlorides can greatly reduce the activation energy of the reaction. This study provides new insights into the catalytic mechanism of IL, transition metals, and their synergistic effect from a microscopic point of view and sheds light on the development of new catalysts for acetylene hydrochlorination. [ABSTRACT FROM AUTHOR]

Context: Boron-based nanostructures hold significant promise for revolutionizing hydrogen storage technologies due to their exceptional properties and potential in efficiently accommodating and interacting with hydrogen molecules. In this paper, boron-based Bn (n = 3–14) nanoclusters decorated with alkaline earth metals (AEM = Ca and Be) were investigated for hydrogen storage applications based on density function theory (DFT) calculations. To evaluate H2 adsorption capability, the adsorption energies, frontier molecular orbitals (FMOs), natural bond orbital (NBO), and quantum theory of atoms in molecule (QTAIM) analysis are performed. The primary aim of this research work is to achieve targeted value of 5.5 wt% set by the US Department of Energy (DOE) for the year 2025. The results revealed that B5Ca2, B6Ca2, and B10Ca2 structures have the ability to hold up to 12H2 molecules with gravimetric capacities of 15.20, 14.21, and 8.60 wt%, respectively, when compared to other boron structures decorated with calcium. Similarly, for Be-decorated structure, B3Be2 structure can accommodate 3H2 molecules with gravimetric capacity of 10.59 wt%. The result of this study indicates that AEM-decorated Bn nanoclusters hold great promise as potential materials for hydrogen storage. Methods: Density functional theory (DFT) approach at ωB97XD/6-311++G(d,p) level of theory is employed to investigate the possibility of storing H2 molecules on alkaline earth metal (AEM = Ca and Be)-decorated Bn (n = 3–14) nanoclusters. All DFT computations were performed using Gaussian 09 software. To calculate frontier molecular orbitals (FMOs) and quantum theory of atoms in molecule (QTAIM) analysis, we have used GaussView and Multiwfn software, respectively. [ABSTRACT FROM AUTHOR]

Secure transmission of images over wireless communications systems can be done using RSA, the most known and efficient cryptographic algorithm, and OFDMA, the most preferred signal processing choice in wireless communications. This paper aims to investigate the performance of OFDMA system for wireless transmission of RSA-based encrypted images. In fact, the performance of OFDMA systems; based on different signal processing techniques, such as, discrete sine transforms (DST) and discrete cosine transforms (DCT), as well as the conventional discrete Fourier transforms (DFT) are tested for wireless transmission of gray-scale images with/without RSA encryption. The progress of transmitting the image is carried by firstly, encrypting the image with RSA algorithm. Then, the encrypted image is modulated with DFT-based, DCT-based, and DST-based OFDMA systems. After that, the modulated images are transmitted over a wireless multipath fading channel. The reverse operations will be carried at the receiver, in addition to the frequency domain equalization to overcome the channel effect. Exhaustive numbers of scenarios are performed for study and investigation of the performance of the different OFDMA systems in terms of PSNR and MSE, with different subcarriers mapping and modulation techniques, is done. Results indicate that the ability of different OFDMA systems for wireless secure transmission of images. However, the DCT-OFDMA system showed superiority over the DST-OFDMA and the conventional DFT-OFDMA systems. [ABSTRACT FROM AUTHOR]

Shellac is a natural resin composed of a complex mixture of hydroxy aliphatic acids, primarily aleuritic acid (AA), and sesquiterpenoid acids such as jalaric acid (JA). The paper puts forth valuable information on the polymerization mechanism considering AA and JA using Gaussian 16.0 software. Computations of energy, thermochemical values, and molecular orbital coefficients have been done using both Hartree-Fock (HF) and Density Functional Theory (DFT) to establish the mechanism. Global reactivity parameter study revealed that monomers of the shellac are hard whereas the polymer units are soft. HOMO-LUMO, ESP and theoretical FTIR results are coherent with the previously reported works for the prediction of possible polymeric species present in the shellac along with their thermodynamic stability. This is the first attempt to predict the linkages in shellac resin. This study helps understand the mechanism of formation of lac polymer and also highlights the associated properties of shellac. [ABSTRACT FROM AUTHOR]

Gold(III) complexes with different ligands can provide researchers with a measure against pathogenic microorganisms with antibiotic resistance. We reported in our previous paper that the UV-Vis spectra of different protonated species of complexes formed by gold(III) and five hydrazones derived from pyridoxal 5′-phosphate are similar to each other and to the spectra of free protonated hydrazones. The present paper focuses on the reasons of the noted similarity in electron absorption spectra. The geometry of different protonated species of complexes of gold(III) and hydrazones (15 structures in total) was optimized using the density functional theory (DFT). The coordination polyhedron of gold(III) bond critical points were further studied to identify the symmetry of the gold coordination sphere and the type of interactions that hold the complex together. The UV-Vis spectra were calculated using TD DFT methods. The molecular orbitals were analyzed to interpret the calculated spectra. [ABSTRACT FROM AUTHOR]

Context: Nanomaterials enjoy a great surface-to-surface area ratio, small size, extremely high stability, satisfactory bio-compatibility, improved permeability, specificity in receptor targeting, and tunable lifetime. This paper investigates alkali metal-doped borospherenes M@C4B32 (in which M denotes K, Na, and Li) as a highly efficient alternative for the delivery of drugs using density functional theory (DFT) calculations. A borospherene with a B36 nanocage doped with four C atoms (i.e., C4B32) recently showed promising performance. Therefore, the present work investigates C4B32 nanoclusters doped with alkali metals for the effective delivery of drugs. Methods: This paper primarily seeks to evaluate the interaction between thioguanine (TG) as a cancer drug and pristine M@C4B32 through DFT (PBE/6–31 + G (d)) calculations. The UV–Vis spectroscopy indicated a redshift in the complex electronic spectra to higher wavelengths (i.e., lower energy levels). Hence, K@C4B32 was concluded to be effective in TG delivery. [ABSTRACT FROM AUTHOR]

Boron presents an important role in chemistry, biology, and materials science. Diatomic transition-metal borides (MBs) are the building blocks of many complexes and materials, and they present unique electronic structures with interesting and peculiar properties and a variety of bonding schemes which are analyzed here. In the first part of this paper, we present a review on the available experimental and theoretical studies on the first-row-transition-metal borides, i.e., ScB, TiB, VB, CrB, MnB, FeB, CoB, NiB, CuB, and ZnB; the second-row-transition-metal borides, i.e., YB, ZrB, NbB, MoB, TcB, RuB, RhB, PdB, AgB, and CdB; and the third-row-transition-metal borides, i.e., LaB, HfB, TaB, WB, ReB, OsB, IrB, PtB, AuB, and HgB. Consequently, in the second part, the second- and third-row MBs are studied via DFT calculations using the B3LYP, TPSSh, and MN15 functionals and, in some cases, via multi-reference methods, MRCISD+Q, in conjunction with the aug-cc-pVQZ-PPM/aug-cc-pVQZB basis sets. Specifically, bond distances, dissociation energies, frequencies, dipole moments, and natural NPA charges are reported. Comparisons between MB molecules along the three rows are presented, and their differences and similarities are analyzed. The bonding of the diatomic borides is also described; it is found that, apart from RhB(X1Σ+), which was just recently found to form quadruple bonds, RuB(X2Δ) and TcB(X3Σ−) also form quadruple σ2σ2π2π2 bonds in their X states. Moreover, to fill the gap existing in the current literature, here, we calculate the TcB molecule. [ABSTRACT FROM AUTHOR]

This paper deals with the evaluation of novel imidazole molecules for their antimicrobial and larvicidal activities. A series of imidazole derivatives 1(a–f) and 2(a–e) were prepared by the Mannich base technique using a Cu(II) catalyst. The Cu(phen)Cl2 catalyst was found to be more effective than other methods. FTIR, elemental analyses, mass spectrometry, 1H NMR, and 13C NMR spectroscopy were performed to elucidate the structures of the synthesised compounds. Antimicrobial and larvicidal activities were investigated for all compounds. The antibacterial activity of compounds (2d) and (2a) were highly active in S.aureus (MIC: 0.25 μg/mL) and K.pneumoniae (MIC: 0.25 μg/mL) compared to ciprofloxacin. Compound (1c) was significantly more effective than clotrimazole in C.albicans (MIC: 0.25 μg/mL). Molecular docking studies of compound 2d showed a higher binding affinity for the 1BDD protein (− 3.4 kcal/mol) than ciprofloxacin (− 4.4 kcal/mol). Compound 1c had a higher binding affinity (− 6.0 kcal/mol) than clotrimazole (− 3.1 kcal/mol) with greater frontier molecular orbital energy and reactivity properties of compound 1c (∆E gap = 0.13 eV). The activity of compound 1a (LD50: 34.9 μg/mL) was more effective in the Culex quinquefasciatus than permethrin (LD50: 35.4 μg/mL) and its molecular docking binding affinity for 3OGN protein (− 6.1 kcal/mol). These newly synthesised compounds can act as lead molecules for the development of larvicides and antibiotic agents. [ABSTRACT FROM AUTHOR]

The NiCo-LDH was prepared as a precursor via co-precipitation method and subsequently phosphated into NiCoP nanosheets with a 2D structure. By modifying ZnCdS with 2D NiCoP, the activity of the composite to split water and produce hydrogen under visible light was enhanced. By adjusting the morphology of NiCoP, the recombination of photogenerated carriers is more effectively inhibited, and more catalytic active sites are exposed, which provides a new idea for the preparation of two-dimensional transition metal phosphides. [Display omitted] • A facile approach for synthesizing 2D transition metal phosphide nanosheets is presented. • The ZnCdS photocatalyst decorated by NiCoP nanosheet exhibits 17.3 times higher hydrogen production capacity compared to ZnCdS. • NiCoP accelerates the separation and migration of electron-hole pairs of ZnCdS, Co as the active site can more effectively promote the photocatalytic water splitting reaction. The unique characteristics and diverse applications of 2D transition metal phosphides have aroused significant interest. In this paper, we successfully prepared 2D NiCoP modified ZnCdS composite. The NiCoP nanosheets were successfully obtained by phosphating layered double hydroxide (LDH) precursor. The results show that the ZnCdS-8%NiCoP has the highest photocatalytic performance among all the composite photocatalysts with the H 2 evolution rate of 1370.1 µmol h−1, which is 17.9 folds higher than obtained with pure ZnCdS. Detailed analysis reveal that NiCoP nanosheets functions as an excellent electron acceptor, speeding up the directed migration of electrons. Furthermore, the rational mechanism of photocatalytic has been presented based on density function theory (DFT) calculations, which is well congruent with experimental results. Our research offers a simple, environmentally benign, and scalable technique for making highly effective photocatalysts, as well as a novel perspective on transition metal phosphides rational design. [ABSTRACT FROM AUTHOR]

An accelerated thermal aging process was used to simulate the condition of paper insulation in transformer oil-paper systems. Optical parameters of the insulation paper after various aging intervals were analyzed with terahertz time-domain spectroscopy (THz-TDS) over the range 0.1~1.8 THz. The result shows that the paper had seven absorption peaks at 0.19, 0.49, 0.82, 1.19, 1.43, 1.53, and 1.74 THz, and density functional theory of B3LYP/6-311G+ (d, p) was used to simulate the molecular dynamics of the repeating component (cellobiose) of the cellulose paper. Theoretical spectra were consistent with experiment, which had absorption peaks at 0.18, 0.82, 1.47, and 1.53 THz in the same frequency range. At the same time, the paper samples after various aging intervals had different refractive indexes, and least squares fitting revealed a linear relationship between the degree of polymerization and the refractive index of the paper. Hence, this paper demonstrates that THz-TDS could be used to analyze the aging condition of transformer insulation paper and provides the theoretical and experimental basis for detection. [ABSTRACT FROM AUTHOR]

[Display omitted] • A novel chromogenic azo-azomethine chemosensor, namely 2-((E)-(2-(benzo[ d ]thiazol-2-yl)hydrazineylidene)methyl)-4-((E)-phenyldiazenyl)phenol (referred to as L), was rationally designed and synthesized. • L could sense cyanide ion without interference of other anions. • Sensing mechanism of cyanide sensing was confirmed by 1H NMR and DFT calculations. • Reversibility and reusability of the sensor was confirmed by paper strip experiment. • The practical applicability of the probe for cyanide detection in environmental sample have been achieved. A novel chromogenic azo-azomethine chemosensor, namely 2-((E)-(2-(benzo[ d ]thiazol-2-yl) hydrazineylidene)methyl)-4-((E)-phenyldiazenyl)phenol (referred to as L), was rationally designed and synthesized. The molecular structure of L was established using various spectroscopic and spectrometry techniques including NMR, FT-IR and mass. The spectral profile including absorption and fluorescence were recorded in solvents of varying polarity. The sensor responsiveness towards different anions was evaluated visually and established using UV–vis spectroscopy and NMR studies. A binary solution of DMSO/H 2 O (6:4, v:v) was used for anion recognition studies. A color change from colorless to yellow was noticed upon addition of CN– ion to the probe (L) solution. The developed probe was found to be very sensitive towards CN– ion with a detection limit of 21 nM. Benesi-Hildebrand plot revealed a binding constant of 1.2*103 M-2and the binding stoichiometry of 1:2 was confirmed using Job's plot. 1H NMR studies were utilised to ascertain the recognition mechanism which revealed the CN– ion assisted deprotonation of N-H and O-H group of L. The recognition mechanism established using NMR technique has been supported theoretically by DFT based studies. Additionally, cost-effective paper strips coated with L has been proved to be a convenient tool for detecting CN– ion in aqueous solutions. The reversibility and reusability of the developed probe was also investigated in both solution as well as solid state using trifluoroacetic acid (TFA) without any loss of the sensitivity of the developed probe. Moreover, the developed probe recognises cyanide ion in environmental samples with around 100 % recovery. The practical application of the Logic gate response of L was confirmed by paper strip experiment. [ABSTRACT FROM AUTHOR]

• It is shown that the tautomeric state plays a crucial role for the optical properties of azo dyes. • Currently there is no suitable DFT approach to predict the optical spectra of tautomeric azo dyes. • Do not neglect the tautomeric state. In a paper of Zhu and co-workers ("Study of the electronic effect and quantitative spectra predictions of o-methoxyanilineterminated monoazonaphthols: a combined experimental and DFT study" by Guoxun Zhu, Yan Lin, Wenxian Zhou, Huacan Song and Zhengquan Li, RSC Advances, 2023, 13 , 33736), the authors derived a protocol for the absorption spectra prediction is sulphonated azo naphthols assuming that they exist as single azo tautomers. However, as it is well known before and as shown by the available experimental data and the calculations, performed in this note, the studied dyes exist almost solely in hydrazone tautomeric form, which unavoidably affects the conclusions and linear relations made in the original paper. A detailed benchmarking on the spectra prediction, involving 39 density functionals (33 of them hybrid and 6 – pure) indicates that there is no a functional correctly predicting the absorption spectra of the tautomers in azo naphthols. [ABSTRACT FROM AUTHOR]

Context: Dihydroxylammonium 5,5'-biotetrazolium-1,1'-diolate (TKX-50) has two important properties of typical azole energy-containing ionic salts, including high energy and safety. Therefore, in today's era where more emphasis is placed on explosive performance and explosive detonation control conditions, TKX-50 is a very important object of research, and its reaction process in the initial stage of detonation is gradually receiving more and more attention from researchers in the field of energy-containing materials research. Methods: In this paper, based on first-principles density-functional theory (DFT), the mechanism of chemical bond breakage of TKX-50 under pressure was determined based on the analysis of the strength and stability of chemical bonds inside the TKX-50 molecules using Raman spectroscopy relative intensity analysis. The results show that TKX-50 is dominated by N–H bond breaking and followed by H–O bond breaking in the initial reaction stage. These reactions lead to the reorganization and structural changes within the molecule, which eventually lead to the decomposition of TKX-50. [ABSTRACT FROM AUTHOR]

This review considers the works that focus on various aspects of the theoretical description of nanohelicenes (other equivalent names are graphene spirals, graphene helicoid, helical graphene nanoribbon, or helical graphene)—a promising class of one-dimensional nanostructures. The intrinsic helical topology and continuous π-system lead to the manifestation of unique optical, electronic, and magnetic properties that are also highly dependent on axial and torsion strains. In this paper, it was shown that the properties of nanohelicenes are mainly associated with the peripheral modification of the nanohelicene ribbon. We have proposed a nomenclature that enables the classification of all nanohelicenes as modifications of some prototype classes. [ABSTRACT FROM AUTHOR]

This paper presents two mechanisms for the deNOx process and for the deN2O process (in two variants). The processes were carried out on a clinoptilolite zeolite catalyst with a deposited Cu–Cu monometallic dimer and Cu–Zn bimetallic dimer with bridged oxygen between the metal atoms. Analyses were performed for hydrated forms of the catalyst with a hydrated bridging oxygen on one of the metal atoms. Calculations were performed using DFT (density functional theory) based on an ab initio method. The analyses included calculations of the energies of individual reaction steps and analysis of charges, bond orders and bond lengths as well as HOMO, SOMO and LUMO orbitals of selected steps in the mechanism. Based on the results obtained, it was determined that the most efficient catalyst for both processes is a Cu–Zn bimetallic catalyst with a bridged hydroxyl group. It shows higher efficiency in the limiting step (formation of the -N2H intermediate product) than the previously studied FAU and MFI zeolites with a Cu–Zn bimetallic dimer. In addition, the possibility of using the catalytic system from the deNOx process in the deN2O process was presented, which can benefit SCR installations. In addition, it was proved that the order of adsorption of NO and N2O has significance for further steps of the deN2O process. In order to improve the comparison of FAU, MFI and CLI zeolite catalysts with a Cu–Zn dimer, further studies on the deN2O mechanism for the first two zeolites are needed. This study allows us to propose a bimetallic catalyst for the deNOx and deN2O processes. [ABSTRACT FROM AUTHOR]

Decaying DC (DDC) offset current mitigation is a vital challenge in phasor current estimation since it causes malfunctioning/maloperation of measurements and protection systems. Due to the inductive nature of electric power systems, the current during fault inception cannot change immediately and it contains a transient oscillation. The oscillatory component acts similar to an exponential DC signal and its characteristics depend on the X/R ratio of the system, fault location, and fault impedance. DDC attenuates accurate phasor estimation, which is pivotal in protection systems. Therefore, the DDC must be eliminated from the fault current (FC) signal. This paper presents an overview of DDC mitigation methods by considering different groups—before the discrete Fourier transform (pre-DFT), after the discrete Fourier transform (post-DFT), the least square-based (LS-based), and other methods. Through a comprehensive review of the existing schemes, the effects of noise, harmonics, multiple DDCs (MDDCs), and off-nominal frequency (ONF) on the accuracy of DDC estimation, were recognized. A detailed discussion (along with some simulation results) are presented to address the main advantages/disadvantages of the past studies. Finally, this paper presents a few suggestions for future researchers, for researchers to investigate more implementable solutions in this field. [ABSTRACT FROM AUTHOR]

This paper studies the mechanism of electrochemically induced carbon–bromine dissociation in 1-Br-2-methylnaphalene in the reduction regime. In particular, the bond dissociation of the relevant radical anion is disassembled at a molecular level, exploiting quantum mechanical calculations including steady-state, equilibrium and dissociation dynamics via dynamic reaction coordinate (DRC) calculations. DRC is a molecular-dynamic-based calculation relying on an ab initio potential surface. This is to achieve a detailed picture of the dissociation process in an elementary molecular detail. From a thermodynamic point of view, all the reaction paths examined are energetically feasible. The obtained results suggest that the carbon halogen bond dissociates following the first electron uptake follow a stepwise mechanism. Indeed, the formation of the bromide anion and an organic radical occurs. The latter reacts to form a binaphthalene intrinsically chiral dimer. This paper is respectfully dedicated to Professors Anny Jutand and Christian Amatore for their outstanding contribution in the field of electrochemical catalysis and electrosynthesis. [ABSTRACT FROM AUTHOR]

Etidronic acid (1-Hydroxyethylidene-1,1-diphosphonic acid, HEDP, H4L) is a proposed decorporation agent for U(VI). This paper studied its complex formation with Eu(III), an inactive analog of trivalent actinides, over a wide pH range, at varying metal-to-ligand ratios (M:L) and total concentrations. Combining spectroscopic, spectrometric, and quantum chemical methods, five distinct Eu(III)−HEDP complexes were found, four of which were characterized. The readily soluble EuH2L+ and Eu(H2L)2− species with log β values of 23.7 ± 0.1 and 45.1 ± 0.9 are formed at acidic pH. At near-neutral pH, EuHL0s forms with a log β of ~23.6 and, additionally, a most probably polynuclear complex. The readily dissolved EuL− species with a log β of ~11.2 is formed at alkaline pH. A six-membered chelate ring is the key motif in all solution structures. The equilibrium between the Eu(III)–HEDP species is influenced by several parameters, i.e., pH, M:L, total Eu(III) and HEDP concentrations, and time. Overall, the present work sheds light on the very complex speciation in the HEDP–Eu(III) system and indicates that, for risk assessment of potential decorporation scenarios, side reactions of HEDP with trivalent actinides and lanthanides should also be taken into account. [ABSTRACT FROM AUTHOR]

A density functional theory (DFT) calculation is carried out in this work to investigate the effect of vacancies on the behavior of Al(111)/6H SiC composites. Generally, DFT simulations with appropriate interface models can be an acceptable alternative to experimental methods. We developed two modes for Al/SiC superlattices: C-terminated and Si-terminated interface configurations. C and Si vacancies reduce interfacial adhesion near the interface, while Al vacancies have little effect. Supercells are stretched vertically along the z-direction to obtain tensile strength. Stress–strain diagrams illustrate that the tensile properties of the composite can be improved by the presence of a vacancy, particularly on the SiC side, compared to a composite without a vacancy. Determining the interfacial fracture toughness plays a pivotal role in evaluating the resistance of materials to failure. The fracture toughness of Al/SiC is calculated using the first principal calculations in this paper. Young's modulus (E) and surface energy (Ɣ) is calculated to obtain the fracture toughness (KIC). Young's modulus is higher for C-terminated configurations than for Si-terminated configurations. Surface energy plays a dominant role in determining the fracture toughness process. Finally, to better understand the electronic properties of this system, the density of states (DOS) is calculated. [ABSTRACT FROM AUTHOR]

Genetic information stored in a DNA base sequence is continuously exposed to harmful factors. It has been determined that 9 × 104 different DNA damage events occur in a single human cell every 24 h. Of these, 7,8-dihydro-8-oxo-guanosine (OXOG) is one of the most abundant and can undergo further transformations towards spirodi(iminohydantoin) (Sp). Sp is highly mutagenic in comparison to its precursor if not repaired. In this paper, the influence of both Sp diastereomers 4R and 4S as well as their anti and syn conformers on charge transfer through the double helix was taken into theoretical consideration. In addition, the electronic properties of four modelled double-stranded oligonucleotides (ds-oligos) were also discussed, i.e., d[A1Sp2A3oxoG4A5] * [T5C4T3C2T1]. Throughout the study, the M06—2X/6—31++G** level theory was used. Solvent–solute non-equilibrated and equilibrated interactions were also considered. The subsequent results elucidated that the 7,8-dihydro-8-oxo-guanosine:cytidine (OXOGC) base pair is the settled point of a migrated radical cation in each of the discussed cases, due to its low adiabatic ionization potential, i.e., ~5.55 [eV]. The opposite was noted for excess electron transfer through ds-oligos containing anti (R)-Sp or anti (S)-Sp. The radical anion was found on the OXOGC moiety, whereas in the presence of syn (S)-Sp or syn (R)-Sp, an excess electron was found on the distal A1T5 or A5T1 base pair, respectively. Furthermore, a spatial geometry analysis of the discussed ds-oligos revealed that the presence of syn (R)-Sp in the ds-oligo caused only a slight deformation to the double helix, while syn (S)-Sp formed an almost ideal base pair with a complementary dC. The above results are in strong agreement with the final charge transfer rate constant, as calculated according to Marcus' theory. In conclusion, DNA damage such as spirodi(iminohydantoin), especially when becoming part of clustered DNA damage, can affect the effectiveness of other lesion recognition and repair processes. This can lead to the acceleration of undesired and deleterious processes such as carcinogenesis or aging. However, in terms of anticancer radio-/chemo- or combined therapy, the slowing down of the repair machinery can result in increased effectiveness. With this in mind, the influence of clustered damage on charge transfer and its subsequent effect on single-damage recognition by glycosylases justifies future investigation. [ABSTRACT FROM AUTHOR]

Natural products remain one of the major sources of coveted, biologically active compounds. Each isolated compound undergoes biological testing, and its structure is usually established using a set of spectroscopic techniques (NMR, MS, UV-IR, ECD, VCD, etc.). However, the number of erroneously determined structures remains noticeable. Structure revisions are very costly, as they usually require extensive use of spectroscopic data, computational chemistry, and total synthesis. The cost is particularly high when a biologically active compound is resynthesized and the product is inactive because its structure is wrong and remains unknown. In this paper, we propose using Computer-Assisted Structure Elucidation (CASE) and Density Functional Theory (DFT) methods as tools for preventive verification of the originally proposed structure, and elucidation of the correct structure if the original structure is deemed to be incorrect. We examined twelve real cases in which structure revisions of natural products were performed using total synthesis, and we showed that in each of these cases, time-consuming total synthesis could have been avoided if CASE and DFT had been applied. In all described cases, the correct structures were established within minutes of using the originally published NMR and MS data, which were sometimes incomplete or had typos. [ABSTRACT FROM AUTHOR]

Iron is one of the essential metals required by almost all living organisms. However, nature has certain constraints in distributing this element among tissues. Since polymeric oxide-bridged Fe (III) is the prominent source of Fe (III) ions, the insolubility of Fe (III) ions in aqueous systems reduces the direct uptake by cells. Secondly, the free-Fe entities which generate .OH radicals pave the way to the destruction of the cells. Hence, a protective coordination environment via sophisticated chemical systems is required for the acquisition of Fe, its successive transport, storage, and effective utilization in various tissues. Siderophores are polydentate ligands used by bacterial cells for Fe acquisition, with a relatively high affinity for Fe (III) ions. Secreted from the bacterial cells into the external aqueous medium, they sequester Fe to give a soluble complex which re-enters the organism at a specific receptor. Once it gets inside the cell, the Fe is released from the complex and utilized for essential biochemical reactions. The medicinal applications of these natural ligands, developing progressively in various research groups, necessitate the theoretical aspects of their coordination chemistry. This research paper deals with the coordination chemistry of one of the siderophores, cepabactin (Cep). The chemical computations confirm that the FeIII(Cep)3 complex is octahedral and high spin. The oxygen atoms of Cep, which are hard and negatively charged, thus act as electron donors in the FeIII(Cep)3 complex formation. This in turn makes the siderophores relatively less attractive towards Fe (II) ions. [ABSTRACT FROM AUTHOR]

Context: In recent years, fluorescent probe technology has received more and more attention. However, the photophysical and photochemical properties of probe molecules still need to be further explored. This paper presents the excited state intramolecular proton transfer (ESIPT) processes and photophysical properties of the probe molecule 4-bromo-2-((E)-((Z)-((5-bromo-1H-indol-2-yl) methylene) hydrazono) methyl) phenol (BHPL) and its four derivatives (BHPL2, BHPL3, BHPL4, and BHPL5). Infrared spectra and geometric structure analyses revealed that introducing the –NH2 group on the benzene ring with the hydroxyl group will enhance the intramolecular hydrogen bond, which benefits the ESIPT process. Combining their absorption and fluorescence spectra, it can be concluded that BHPL2 and BHPL4 are both excellent probe candidates due to their large Stokes shift. The hole and electron and root mean square displacement analyses manifest that the fluorescence quenching of BHPL4 may be due to the intramolecular charge transfer process. Potential energy curves of BHPL and its four derivatives noted that ESIPT process of the BHPL2 is the most favorable to occur. The frontier molecular orbital and NBO analyses indicated that besides introducing electron-donating groups to reduce the energy gap and enhance fluorescence emission, introducing double electron-withdrawing groups can also achieve this effect, explaining why the energy barrier of ESIPT process for BHPL2 is lower than BHPL5. This work would provide the theoretical basis for designing novel fluorescence probes with more prominent properties. Methods: The ground (S0) and excited (S1) state structures of all compounds were optimized by density functional theory (DFT) and time-dependent (TDDFT) method, with B3LYP/6-311+G(d,p) level, respectively. The infrared spectra and potential energy curves were simulated at the same theoretical level. The reduced density gradient scatter plots and interaction region indicator isosurfaces were drawn using Multiwfn and VMD programs. The absorption and fluorescence spectra were simulated by the TDDFT/B3PW91/6-311+G(d,p) method. All the calculations in this work are carried out in Gaussian 16 program package. [ABSTRACT FROM AUTHOR]

MoO3 and MoO2 systems have attracted particular attention for many widespread applications thanks to their electronic and optical peculiarities; from the crystallographic point of view, MoO3 adopts a thermodynamically stable orthorhombic phase (α-MoO3) belonging to the space group Pbmn, while MoO2 assumes a monoclinic arrangement characterized by space group P21/c. In the present paper, we investigated the electronic and optical properties of both MoO3 and MoO2 by using Density Functional Theory calculations, in particular, the Meta Generalized Gradient Approximation (MGGA) SCAN functional together with the PseudoDojo pseudopotential, which were used for the first time to obtain a deeper insight into the nature of different Mo–O bonds in these materials. The calculated density of states, the band gap, and the band structure were confirmed and validated by comparison with already available experimental results, while the optical properties were validated by recording optical spectra. Furthermore, the calculated band-gap energy value for the orthorhombic MoO3 showed the best match to the experimental value reported in the literature. All these findings suggest that the newly proposed theoretical techniques reproduce the experimental evidence of both MoO2 and MoO3 systems with high accuracy. [ABSTRACT FROM AUTHOR]

Test sets that target standard fault models may not always be sufficient for detecting all defects. To evaluate test sets for the detection of unmodeled defects, n-detect test sets (which detect all modeled faults at least n times) have previously been proposed. Unfortunately, n-detect test sets are often prohibitively long. In this paper, we investigate the ability of shadow flip-flops connected into a MISR (Multiple Input Signature Register) to detect stuck-at faults fortuitously multiple times during scan shift. We explore which flip-flops should be shadowed to increase the value of n for the least detected stuck-at faults for each circuit studied. We then identify which circuit characteristics are most important for determining the cost of the MISR needed to achieve high values of n. For example, circuits that contain a few flip-flops with upstream fault cones that cover a large percentage of all faults in the circuit can often achieve high n-detect coverage fortuitously with a low-cost MISR. This allows a DFT engineer to predict the viability of this MISR-based approach early in the design cycle. [ABSTRACT FROM AUTHOR]

In this paper, the molecular and electronic structure of curcumin is studied. High-symmetric gas-phase tautomers and their deprotonated forms in various symmetry groups are identified. The stability of lower-symmetry structures was explained by using the Pseudo-Jahn-Teller (PJT) effect. This effect leads to stable structures of different symmetries for the neutral enol and keto forms. The presented analysis demonstrated the potential significance of the PJT effect, which may modulate the setting of electronic and vibrational (vibronic) energy levels upon photodynamic processes. The PJT effect may rationalize the photoprotection action and activity of naturally occurring symmetric dyes. [ABSTRACT FROM AUTHOR]