A new stream of donor- π -acceptor (D- π -A) type arylborane-arylamine based donor contributors namely (BN1, BN2, BN3, BN4, BN5) have been drafted by substituting the terminal ...2,4,6-tris-(trifluoromethyl)phenyl groups of reference B4N2-FMes (designated as BNR in the current study) with thiophene followed by W1 (4-(5-methylthiophen-2-yl)benzothiadiazole), W2 (2-(3-methyl-5-methylene-4-oxothiazolidin-2-ylidene)malononitrile), W3 (3-methyl-5-methylene-2-thioxothiazolidin-4-one), W4 (2-methylenemalononitrile), W5 (2-cyanoacrylicaidmethylester) acceptor moieties respectively. The computational characterization was performed via reliable density functional theory at B3LYP/6–31G (d,p). The optoelectronic parameters of newly planned molecules have been cross-checked with the reference (BNR). The newly planned (BN1-BN5) conjugated macrocycles have manifested outperformed results. Amongst all, BN4 has displayed the lowest band gap (2.07 eV), highest λmax (672 nm) in dichloromethane (DCM), highest ionization potential (IP) and electron affinity (EA) owing to its functionalization with cyano (CN) containing strong electron pulling moieties. Out of all reported molecules, BN1 has explored the lowest reorganization energy (RE) value for the electron (λ- = 0.00224 eV) and hole (λ+ = 0.00266 eV) demonstrating its augmented charge transition. BN1 is characterized by the highest dipole moment (6.31 D) in DCM addressing its enhanced solubility. Amongst all, BN4 has explored the highest VOC (1.51 eV) due to its low-lying HOMO. To sum up, the thiophene bridged end-capped acceptor alteration approach has been proved persuasive in providing the gateway to devise optimistic photovoltaic materials. All currently planned donor contributors (BN1-BN5) ought to be targeted to assemble upcoming proficient organic solar cells (OSCs).
Display omitted
•Five small donor molecules (BN1-BN5) have been designed for photovoltaic applications.•All the devised molecules have manifested lower band gap and higher λmax than the model (BNR).•The newly introduced acceptor moieties have displayed paramount charge mobility.
•Geometric parameters are calculated by DFT; HOMO-LUMO gap energy was obtained as 5.5713 eV.•Strong hyperconjugative intramolecular interactions were observed in the NBO analysis.•In solvents title ...compound have stability, compactness and reduced structural fluctuations.•Drug likeness studies show biological activity as a potential therapeutic candidate.
In this work, 3-(3-(4-Chlorophenyl)-1-phenyl-1H-pyrazol-4-yl)-5-ethoxy-4H-1,2,4-triazole compound has been synthesized and experimentally (FT-IR and 1H and 13CNMR) evaluated. .Density Functional Theory (DFT) is applied to investigate solvent solutes using a variety of solvents. The computed frequencies have been scaled. In global reactive parameters solvents significantly altered the molecule's characteristics behaviour, gas and water has high electrophilicity index which trigger its biological activity. The description focuses on how electron fragments influence the stimulation of electron states. From p*(C23-C24) to p*(C20-C25) and p*(C21-C22), the energy stabilised is 246.13 and 170.28 kcal/mol it is a significant stabilizing energy. Molecular Electrostatic Potential (MEP) shows that vast majority of each positive domain is near hydrogen atoms; almost all of the negative domain is close to NN atoms in both the gas and solvent phases. TDM (Transition Density Matrices) analysis presents graphical representations that depict the ability to transmit charges. Average local Ionization Energy (ALIE) scrutiny uses the colour blue to symbolize the stable sigma bonds, commonly linked to hydrogen atoms that generate protons. The choice of solvent significantly impacts its overall characteristics and chemical activity. In the topological aspect (with solvents), the most fragile acquaintances, binding zones, or the density of electron variations were all detected. Furthermore, a significant relationship exists between the electrical features of solvents and their polarization. According to Lipinski's rule of five, using a pill-sized quantity of such chemicals is generally safe. We also examined the molecule's biological activity by docking an adenogenic receptor. The anti-adenosine replicating protein (1Y56) binds most strongly (-7.10 kcal/mol) and interacts with other molecules in the most non-covalent ways.
Display omitted
•The study explores incorporating varying thiazole concentrations into PCL biodegradable polymer.•The studied composites were prepared via the solution casting route.•XRD showed 55 % crystallinity at ...0.03 dye loading, indicating thiazole integration and ordering.•Antibacterial tests exhibited marked growth inhibition of both gram bacteria.
Polycaprolactone (PCL) is a biodegradable polymer widely used for medical implants and devices due to its biocompatibility, processability, and tunable degradation behavior. This study explores the incorporation of a thiazole-based antimicrobial compound into PCL at varying concentrations to develop new composite materials with both biodegradability and antibacterial function. Samples were solution cast and characterized using techniques like X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, UV–vis spectroscopy, antibacterial assays, and computational density functional theory (DFT) modeling. XRD showed up to 54 % crystallinity at the highest 0.03 g dye loading, indicating the thiazole impacted ordering and lamellar packing. FTIR and DFT calculations demonstrated multiple possible intermolecular bonding modes between the compounds. UV–vis spectra revealed the superimposed absorptions of the PCL matrix and emergent thiazole chromophore. Antibacterial tests exhibited marked growth inhibition of both gram-positive and gram-negative bacteria proportional to the thiazole concentration. The customizable PCL-thiazole blends offer biocompatible materials with functional antibacterial behavior for specialized applications in biomedicine.
Display omitted
Display omitted
On the basis of the thiophene-containing and furan-containing complexes, we design four complexes by introducing thiazole, isothiazole, oxazole, isoxazole on main ligands. The ...electronic structure, absorption and emission spectra, charge injection/transport properties, absorption and phosphorescence properties have been investigated by density functional theory (DFT) and time-dependent density functional theory (TDDFT). Introducing S atom to substitute O atom could enhance HOMO energy level, blueshift emission wavelength, decrease ΔES1- T1 value. The introduction of N atom on furan ring and thiophene ring could decrease HOMO and LUMO energy levels and energy gaps, blueshift emission wavelength, decrease ΔES1- T1 value, enhance electron transport ability. Introducing thiazole could decrease hole injection ability and ΔES1- T1, and then may have higher ΦPL. Isoxazole and isothiazole groups could facilitate the electron transition from HOMO to LUMO and enhance hole injection ability. Thiazole and isothiazole groups could increase absorption peak strength and hole transport ability.
Theoretical calculations unveil the charge redistribution over abundant interfaces and the enhanced electronic states of Ru/RuS2 heterostructure. The resulting surface electron‐deficient Ru sites ...display optimized adsorption behavior toward diverse reaction intermediates, thereby reducing the thermodynamic energy barriers. Experimentally, for the first time the laminar Ru/RuS2 heterostructure is rationally engineered by virtue of the synchronous reduction and sulfurization under eutectic salt system. Impressively, it exhibits extremely high catalytic activity for both OER (201 mV @ 10 mA cm−2) and HER (45 mV @ 10 mA cm−2) in acidic media due to favorable kinetics and excellent specific activity, consequently leading to a terrific performance in acidic overall water splitting devices (1.501 V @ 10 mA cm−2). The in‐depth insight into the internal activity origin of interfacial effect could offer precise guidance for the rational establishment of hybrid interfaces.
Profiting from the rearranged charge density around the abundant interface and the enhanced electronic states, in acidic media, the Ru/RuS2 heterostructure exhibits prominent catalytic activity toward oxygen and hydrogen evolution reactions, and consequent remarkably high overall water splitting performance, demonstrating promising application prospect for industrial proton exchange membrane‐water electrolysis.
Display omitted
•The drug carrier ability of B3O3 toward Foscarnet is investigated via DFT.•The interaction is characterized by the geometric, energetic, electronic, and optical analyses.•Widely ...accepted ωB97XD/6-31+G(d,p) method of DFT is adopted for geometric analysis whereas for electronic properties B3LYP/6-31+G (d,p) method is used.•NCI and QTAIM analyses confirmed the nature of interactions.
In this study, B3O3 quantum dot is investigated via density functional theory (DFT) calculations as an antiviral drug carrier toward Foscarnet. Geometric analysis is carried out to find stable orientations of interaction between Foscarnet drug and the B3O3 quantum dot. As a result, three stable orientations are proposed. The Eint of the most stable orientation is –32.63 kcal/mol whereas the BSSE corrected energy is −26.98 kcal/mol. Noncovalent interaction index (NCI) and quantum theory of atoms in molecules (QTAIM) analyses are employed to understand the nature and the type of interactions taking place between drug and the B3O3 quantum dot. Their results indicated the presence of hydrogen bonding in the most stable complex (orientation A). The HOMO-LUMO analysis is performed to study the electronic properties of the interacting moieties. The lowest Egap is observed in case of orientation A. The value of dipole moments and chemical descriptors showed the significant activity of B3O3 quantum dot toward Foscarnet drug molecule. The overall findings from this study suggest the B3O3 quantum dot as a potential drug carrier system for antiviral drugs.
•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.
Display omitted
•Density Functional Theory (DFT) framework has been used to explore XCdCl3 (X = Na, K, Rb and Cs) chloroperovskites.•Single-crystal elastic constant and associated mechanical ...parameters indicate that all of the compounds are mechanically stable, ductile, and soft.•All the chloroperovskites are found as semiconducting nature with an indirect bandgap energy.•Bandgap energies are preferable for visible light absorption and their application in photovoltaic technology.•Optical parameter analysis consisted of the electronic band structure analysis.
The structural, elastic, mechanical and optoelectronic properties of XCdCl3(X = Na, K, Rb and Cs) chloroperovskites have been investigated by using the Density Functional Theory (DFT) framework through the CASTEP code. The GGA, GGA-U and LDA functionals have been used to explore XCdCl3 (X = Na, K, Rb and Cs) chloroperovskites. All of the computational results of structural parameters are in good accord with the available experimental data, indicating that our work is reliable. The elastic stiffness constants Cij use the essential circumstances to show that the XCdCl3 perovskite structures are mechanically stable. The elastic modulus and other reliable features indicate the XCdCl3 chloroperovskites are mechanically ductile and soft. All the materials exhibit indirect bandgap and their bandgap energy decrease with X-site cation variation from Na to Cs. Optical conductivity and absorption for visible and ultraviolet imply their wide application in photovoltaic technology.
A magnesium‐catalyzed hydroboration of alkynes providing good yields and selectivities for a wide range of terminal and symmetrical and unsymmetrical internal alkynes has been developed. The ...compatibility with many functional groups makes this magnesium catalyzed procedure attractive for late stage functionalization. Experimental mechanistic investigations and DFT calculations reveal insights into the reaction mechanism of the magnesium catalyzed protocol.
MgBu2 proved to be an efficient catalyst for the hydroboration of terminal and internal alkynes, achieving good yields and selectivities. The compatibility with many functional groups makes the Mg‐catalyzed hydroboration of alkynes very attractive as a late stage functionalization procedure. Moreover, experimental investigations together with DFT calculations provide insight into the reaction mechanism.
•A Novel layer-stacked well designed and highly crystalline 2D MOF named as Co3(HADQ)2 MOF.•This Unique MOF features Co-N4 motifs along with pyridinic Nitrogen (total N content: 28.6 at. %) as the ...active sites for ORR.•Outclass most of the electrocatalysts with a high activity (E1/2 = 0.836 V vs. RHE, n = 3.93, and jL = 5.31 mAcm−2) in acidic media.•Exceptionally electrochemical stability up to 20,000 cycles for ORR in an acidic media at 0.29 pH.
Efficient and robust electrocatalysts for acidic Oxygen reduction reaction (ORR) is crucial for the proton exchange membrane hydrogen fuel cells. However, the current electrocatalysts suffer from the stability issues in the acidic enviorment during ORR. Herein, we introduce a new layer-stacked two-dimensional (2D) metal-organic framework (MOF), Co3(HADQ)2 (HADQ = 2,3,6,7,10,11-hexaamine dipyrazino quinoxaline), synthesized for the first time. This novel MOF material shows the extremely high conductivity of 8,385.744 S/m with extraordinary activity (E1/2 = 0.836 V vs. RHE, n = 3.93, and jL = 5.31 mAcm−2) and an exceptional stability (up to 20,000 cycles) as the electrocatalyst for ORR in an acidic media (pH = 0.29), outperforming most of the state of the art Metal-N-C and single-atom electrocatalysts for acidic ORR. Density functional theory calculations indicate that the Co-sites are the active sites. We propose that Co3(HADQ)2 is a promising model catalyst for mechanistic studies of acidic ORR, due to its well defined and tunable structure.
PDF
