Solvent Phase Research Articles

Vibrational spectra, molecular level solvent interaction, stabilization, donor- acceptor energies, thermodynamic, non-covalent interaction and electronic behaviors of 6-Methoxyisoquinoline- anti tubercular agent

The present research is a theoretical examination of 6-methoxyisoquinoline implementing Density Functional Theory quantum mechanical approach. Structural optimization was performed to achieve a stable molecular structure with the least amount of energy. Several protic and aprotic solvent interactions were performed using the IEF polarization continuum model to examine the reactivity and stability of the molecules. Molecular interactions with solvents were investigated using UV–Visible, HOMO-LUMO, MEP, NBO, and NLO properties, which shows some changes in the compound activity at solvent phases against gas phase. The molecular interaction of π*C1–N2 to π*C5 - C10 shows the higher stabilizing energy. DMSO solvent exhibits a very low band gap energy, favors the molecule's high stability. Molecular reactivity, interactions, and optical behavior were all readily apparent. The chemical reactivity of the compound was found good in water. The percentage of PED contributions was evaluated for each mode of vibrations using vibrational spectral investigation. Topological surface analysis was used for better understanding of molecular electron density, reactive center, and steric effect. ELF, LOL, and RDG was generated for compounds with different solvents. The distance of transition and the overlapping of electron and hole were calculated using electron hole analysis. Pharmacological assessments include drug likeness, ADME, toxicity, and a pre-ADMET online tool, which supports the biological capability of the compound. Finally, molecular docking with anti-tubercular protein was performed, and a Ramachandran plot of chosen protein was shown to explore stability.

Recovery of 400 Chemicals with Three Extraction Methods for Low Volumes of Human Plasma Quantified by Instrumental Analysis and In Vitro Bioassays.

Human biomonitoring studies are important for understanding adverse health outcomes caused by exposure to chemicals. Complex mixtures of chemicals detected in blood - the blood exposome - may serve as proxies for systemic exposure. Ideally, several analytical methods are combined with in vitro bioassays to capture chemical mixtures as diverse as possible. How many and which (bio)analyses can be performed is limited by the sample volume and compatibility of extraction and (bio)analytical methods. We compared the extraction efficacy of three extraction methods using pooled human plasma spiked with >400 organic chemicals. Passive equilibrium sampling (PES) with polydimethylsiloxane (PDMS) followed by solid phase extraction (PES + SPE), SPE alone (SPE), and solvent precipitation (SolvPrec) were compared for chemical recovery in LC-HRMS and GC-HRMS as well as effect recovery in four mammalian cell lines (AhR-CALUX, SH-SY5Y, AREc32, PPARγ-BLA). The mean chemical recoveries were 38% for PES + SPE, 27% for SPE, and 61% for SolvPrec. PES + SPE enhanced the mean chemical recovery compared to SPE, especially for neutral hydrophobic chemicals. PES + SPE and SolvPrec had effect recoveries of 100-200% in all four cell lines, outperforming SPE, which had 30-100% effect recovery. Although SolvPrec has the best chemical recoveries, it does not remove matrix like inorganics or lipids, which might pose problems for some (bio)analytical methods. PES + SPE is the most promising method for sample preparation in human biomonitoring as it combines good recoveries with cleanup, enrichment, and potential for high throughput.

Theoretical study of the Cu2+-glycine interaction in ammonia and temperature effects

In this study, we have investigated the potential energy of surfaces of the various glycine tautomers, also the interaction between Cu2+ cation with these glycine tautomers in both the gas and solvent phases and for the first time, the glycine-Cu2+(NH3)n=3−6 clusters in the gas-phase. For the studied clusters, we reported their temperature-dependent conformer distributions, along with the binding energies per ammonia molecule and clustering energies. After comparing the binding energies obtained computationally by using the DLPNO-CCSD(T)/CBS level of theory to those obtained from ten DFT functionals (M06, M06HF, M06-2X, M08HX, MN15, MN12SX, ωB97XD, PW6B95D3, TPSSH, APFD), as well as from the ab initio MP2 method, we selected the DFT functional, M08HX, in conjunction with the aug-cc-pVDZ basis set, as our method of choice. Evidence emerged from our study that the solvation medium and the presence of the Cu2+ cation influence the stability of glycine tautomers. The relative stability of Gly-Cu2+(NH3)n clusters in the gas phase is influenced by the coordination of the Cu2+ cation. The study of the relative population in the gas phase of the Gly-Cu2+(NH3)n=3−6 clusters, predicts that for cluster size n=4, the structure of the more compact penta-coordinated Cu2+ ion dominates at low temperatures. Conversely, the conformers for the less compact tetra-coordinated Cu2+ cation are prevalent at high temperatures. For cluster size n=6 with more ammonia molecules per cluster, the conformers containing the compacted is penta-coordinated Cu2+ cation, are predominant at all temperatures. Binding energies computed for ionic interactions of the Gly-Cu2+ complexes, resulted in the following values at room temperature: the binding electronic energy (ΔEn), binding enthalpy (ΔHn) and binding free energy (ΔGn) of ionic interaction are respectively -218.3, -218.4, -211.6 kcal/mol in the gas phase and -93.8, -94.9, -85.2 kcal/mol in the solvent phase. In order to extrapolate this also to the Gly-Cu2+ ammonia clusters, a suitable function of best fit was applied. The computational prediction of binding electronic energy, binding enthalpy and binding free energy, per ammonia molecule in the gas phase, at saturation, produced the values -25.9, -26.1 and -17.0 kcal/mol, respectively. We therefore recommend this function fit for further study of such systems.

Modulation of the NLO properties of p-coumaric acid by the solvent effects and proton dissociation

Solute-solvent interactions and deprotonation effects have been related to second-order nonlinear optical response modulators. This work takes advantage of sequential Monte Carlo/Quantum mechanics together with Time-Dependent Density Functional Theory, Coupled Cluster methods, and the hyper-Rayleigh scattering formalism to investigate how these effects influence the stability and optical response of p-coumaric acid (pCA) and its anionic and diionic forms. The solvent influences the chromophores in different ways, inducing bathochromic and hypsochromic solvatochromism so for the neutral pCA molecule as for its deprotonated derivatives. The results indicate a high sensitivity of the nonlinear optics (NLO) parameters with relation to proton dissociation. Ionization of the carboxyl group produces the lowest values of the first frequency-dependent hyperpolarizability (βHRS), while phenolic deprotonation leads to the highest values. The results show that proton removal can be used as a switch that modulates the NLO response within a wide range of values (159.15≤βHRS≤4393.97 au) greater than those reported for reference NLO chromophores like urea (37.3 au) and p-nitroaniline (74.3 au). Thermochemical analysis of enthalpies and Gibbs free energies indicate that both monoionic forms of the pCA molecule are the most stable in gas or water solvents. Furthermore, these structures represent the limits of NLO modulation in the gas and solvent phases. Analysis of the projected density of states and mapping of the molecular electrostatic potential indicate that increased contributions from conduction electrons found in the aromatic ring are the mechanism by which deprotonation enhances the NLO response. All the results show that ionic pCA forms are promising in the functionalization of optoelectronic devices.

Mobile Phase Aging and Its Impact on Electrospray Ionization of Oligonucleotides.

The implementation of fluoroalcohol/alkylamine mobile phase systems in oligonucleotide LC-MS provides a good balance between chromatographic separations and MS sensitivity. Since its introduction, several parameters including mobile phase composition, additive concentration, alkylamine hydrophobicity, and different fluoroalcohols have been carefully evaluated and optimized. While our understanding of this mobile phase system has increased over the years, there are challenges that continue to hinder method performance and remain poorly understood. One of these challenges is the constant loss of MS sensitivity over time, commonly termed mobile phase aging. This study investigates two aging mechanisms associated with loss of MS sensitivity: alkylamine oxidation and aggregate formation. The relationship between pH, organic solvent, oxygen, and mobile phase aging is characterized, and mitigation strategies to extend mobile phase lifetime are discussed.

Adsorption of some cationic dyes onto two models of graphene oxide

Context:The search for highly efficient adsorbent materials remains a significant requirement in the field of adsorption for wastewater treatment. Computational study can highly contribute to the identification of efficient material. In this work, we propose a computational approach to study the adsorption of four cationic basic dyes, basic blue 26 (BB26), basic green 1 (BG1), basic yellow 2 (BY2), and basic red 1 (BR1), onto two models of graphene oxide as adsorbents. The main objectives of this study are the assessment of the adsorption capacity of the graphene oxide towards basic dyes and the evaluation of the environmental and temperature effects on the adsorption capacity. Quantum theory of atoms in molecules (QTAIM) analysis has been used to understand the interactions between the dyes and graphene oxides. In addition, adsorption free energies of the dyes onto graphene oxides are calculated in gas and solvent phases for temperatures varying from 200 to 400 K. As a result, the adsorption free energy varies linearly depending on the temperature, highlighting the importance of temperature effects in the adsorption processes. Furthermore, the results indicate that the environment (through the solvation) considerably affects the calculated adsorption free energies. Overall, the results show that the two models of graphene oxide used in this work are efficient for removing dyes from wastewater.Methods:We have optimized the complexes formed by the interaction of dyes with graphene oxides at the PW6B95-D3/def2-SVP level of theory. The SMD solvation model realizes the implicit solvation, and water is used as the solvent. Calculations are performed using the Gaussian 16 suite of program. QTAIM analysis is performed using the AIMAll program. Gibbs free energies as function of temperature are calculated using the TEMPO program.

Synthesis, Computational and Antimicrobial Study of 2-(2-Hydrazinyl)thiazole Derivatives

In the present investigation, we report a combined computational and experimental study of eight thiazole derivatives (4a-4h) obtained from 3,4-dihydronaphthalen-1(2H)-one. A green chemistry protocol comprising PEG-400 and sulfamic acid was employed for the synthesis of eight diverse thiazole derivatives from 3,4-dihydronaphthalen-1(2H)-one, thiosemicarbazide and various phenacyl bromides. The synthetic strategy provides benefits like short reaction time, high yield, and non-chromatographic purification. The compounds were structurally confirmed on the basis of IR, 1HNMR and 13C NMR. The obtained thiazole derivatives were studied using the density functional theory (DFT) method employing B3LYP/6-311G(d,p) level of theory for optimization and Time-Dependent DFT (TD-DFT) approach for examining electronic energies and UV-Vis characteristics. Various computational parameters like bond length, bond angles, HOMO, LUMO, MESP, Mulliken charges, and global descriptors are obtained and discussed. The UV-Vis study the in gas phase and DMSO solvent was investigated to obtain various insights such as absorption energies oscillator strength, configurations and transitions of examined thiazole derivatives. The effect of polar solvent has augmented the absorption wavelength of all studied thiazole derivatives. The experimental and simulated UV-Vis data correlate with each other prompting the effectiveness of the computed method. The scaled and experimental wavenumbers provided the appropriate assignment of various vibrational signals. The antibacterial study was performed against E. coli, P. aeruginosa, and S. aureus which demonstrated the strong antibacterial potential against S. aureus. The antifungal study against C. albicans revealed that these compounds are poor antifungal agents. The DPPH and OH radical assays were used to establish the % radical scavenger effects and results showed that these derivatives are good antioxidant agents. The % hemolytic activity of the tested compounds showed that all compounds fall within the acceptable toxicity limit. Importantly in slico ADME and toxicity prediction studies of these compounds highlighted good ADME profile with no hepatotoxicity, immunotoxicity and cytotoxicity.

Theoretical study of new 3-(methylthio)-8-phenyl-8H-thieno[2,3-b]indole derivatives for application in DSSC: Solvent effect, adsorption process on the surface of TiO2

This investigation aims to elucidate the influence of chemical modifications of the π-bridge on the optoelectronic properties of a newly designed series of five dyes Di (i = 1–5). In this regard, the molecules are designed with 3-(methylthio)-8-phenyl-8H-thieno[2,3-b] indole as electron-donating fragments and cyanoacrylic acid as electron-accepting groups. To attain this goal, the optoelectronic properties of the Di dyes and the reference dye MKZ-39 were theoretically investigated in both the gas phase (GP) and Toluene solvent (TS) using Density Functional Theory (DFT). In addition, to predict the absorption spectrum and excited state properties of theoretical Di molecules, we have resorted to Time-dependent Density Functional theory (TD-DFT). Furthermore, the Monte Carlo approach was employed to theoretically evaluate the process of dye adsorption onto the surface of TiO2 (110) anatase to determine the most stable TiO2-dye-100 C7H8 complex. The results presented demonstrate that the selected dyes possess auspicious characteristics as potential promoters for solar cells, including a redshift of λMax that can reach 561 nm, a nearly complete Light-Harvesting Efficiency (LHE) of 99 %, and a higher open-circuit voltage (VOC) compared to the reference molecule. Our results could open new perspectives for further experimental research into the chemical-structural modifications of these sensitizers.

End-capped engineering of carbazole based dopant free hole transporting material with improved power conversion efficiency

Perovskite solar cells (PSCs) belonging to third-generation of solar cells are reported to have better power conversion efficiency, cost-effectiveness, and many other benefits. This computational investigation focuses on designing five indolo(3,2-b) carbazole (ICZ) central core containing small hole transport materials (HTMs) to discover photovoltaic properties as donors for perovskite solar cells accompanied by enhanced charge mobility. New HTMs with A–π–D–π–A skeleton has been designed by thiophene-bridged end-capped acceptor engineering on reference molecule (ICZ-R). Absorption spectra, frontier MOs, density of state analysis, molecular electrostatic potential surfaces, transition density matrix, non-covalent interactions, iso-surface maps, and planarity parameters were analyzed through different softwares for better-predicting performance of perovskite solar cells. All tailored HTMs showed better absorption profiles. Among them, ICZ-D3 exhibited the maximum absorbance λmax at 695 nm in dichloromethane solvent and the greatest full-width half maximum (313.93 nm). ICZ-D2 showed the lowest Eg of 1.62 eV, and the highest dipole moment (8.35 D) in the solvent phase, showing admirable solubility. Designed HTMs exhibited decelerated HOMO values (−4.62 to −5.25), lower values of binding energies (0.0323–0.388 <0.542 eV), better intrinsic charge transfer percentage (10.74–72.71%>7.88), lower hardness (0.81–1.11 <1.78 eV) and greater softness values (0.90–1.23 >0.56 eV) as compared to ICZ-R. All designed HTMs demonstrated higher estimated VOC and power conversion efficiency (PCE=11.81–25.90%) than ICZ-R, leading to fruitful applications. ICZ-D4 resulted in the highest PCE (25.90%) with better VOC (1.25 eV). These outstanding findings paved a new way to develop better-performing HTMs for PSCs.

Role of extended end-capped acceptors in non-fullerene based compounds towards photovoltaic properties

Fullerene free organic solar cells (OSCs) have found at the forefront in the photovoltaic sector due to effective optical and electronic characteristics. The quantum chemical investigation focused on the designing of pentacyclic aromatic bislactam based chromophores for highly efficient OSCs. A series of eight molecules (PCLMD1–PCLMD8) was designed from reference compound (PCLMR), with A2–π–A1–π–D–π–A1–π–A2 configuration via end group redistribution with benzothiophene based acceptors. Through benchmark study of UV–Vis between simulated and experimental values of PCLMR, MPW1PW916-31G(d,p) functional was selected of DFT approach. Various analyses such as absorption properties (UV–Vis), frontier molecular orbitals analysis (FMOs), transition density matrix (TDM), open circuit voltage (Voc) and density of state (DOS) were performed in order to explore the photovoltaic properties of above-mentioned chromophores. Modification of peripheral acceptors brought about significant changes in their charge-transfer properties. These alterations resulted in reduced exciton binding energy (Eb) ranging from 2.277 to 2.087 eV, a narrower bandgap (Eg) ranging from 1.746 to 1.868 eV and an increased maximum absorption wavelength (λmax) ranging from 829 to 882 nm in the solvent phase. These values were observed in comparison to PCLMR, which had an Eb of 2.443 eV, an Eg of 1.895 eV and λmax at 813 nm. The FMO analysis indicated a significant charge distribution across HOMO-LUMO in the designed chromophores. Furthermore, the rates of electron and hole mobility as well as the open-circuit voltage (Voc) were higher for all the benzothiophene acceptor-based molecules (PCLMD1–PCLMD8) than that of PCLMR. The analysis showed that the integration of benzothiophene acceptors with electron-withdrawing groups amplifies charge transfer towards acceptor components, leading to heightened JSC and Voc values in organic solar cells (OSCs). This phenomenon is attributed to the decrease in the energy level of the lowest unoccupied molecular orbital (LUMO), while the highest occupied molecular orbital (HOMO) remains mostly unchanged, along with the effective broadening of the absorption spectrum. Hence, it can be concluded that by employing molecular engineering with benzothiophene acceptor moieties, the efficiency of photovoltaic materials based on NF compounds could be improved.

Extraction of Na+ ions by dibenzo-18-crown-6 in biphasic aqueous systems of ionic liquid and chloroform

The molecular dynamics simulations were carried out to explore the extraction of Na+ ions in the ionic liquid (IL)–water, chloroform–water biphasic systems containing the crown ether: dibenzo-18-crown-6 (DB18C6) to compare organic solvents such as chloroform to ionic liquid (IL) as receiving solvent phase. The free DB18C6 was found to be highly interacted with IL as compared to chloroform. The Na+–DB18C6 complex interacts preferentially with IL at the interface. The complex has higher interaction energies with IL (-47.04 kcal/mol) as compared to chloroform (-0.11 kcal/mol). The large sharp peak height for the radial distribution function in Na+–DB18C6 complex suggests high stability and strong interaction. At the IL–water interface, it was observed that the Na+–DB18C6 complex had a lower self-diffusion coefficient (0.538 × 10−9 m2/s) than other species. The spatial distribution functions further indicated that the surfaces of Na+ were very closely distributed around the active sides of crown ether in the IL–water system whereas, in chloroform–water systems, it was distributed very far from the crown ether. The present results may help us to understand the role of solvents in heavy metal ion extraction and also in the future design of crown ethers and solvents.

Computationally design aspects of superbasic amidine-arsinine 1-oxide binary frameworks

Novel Brønsted superbases (1–10) were designed on the basis of arsinine 1-oxide core by changing the species of proton absorption site, type and situation of electron-donating substituents in the gas phase and CH3CN medium. The conjugate acids of the designed structures are stabilized through positive charge distribution and/or formation of an intramolecular hydrogen bond. To explore the various structural aspects of the designed molecules for reaching the higher basicity values in gas phase and solution phase in CH3CN solvent, proton affinity (PA), gas phase basicity (GB), pKa, and Nucleus-IndependentChemicalShifts 1 Å above the arsinine 1-oxide ring center along with zz axis (NICS(1)zz) parameters as well as natural bond orbital (NBO) charges calculated and obtained for each structure. The basicity strength of proposed structures was evaluated using B3LYP/6–311 + G(d,p) level of theory. The protonation of all designed structures was studied from both possible sites in gas and CH3CN phase and PA, GB, pKa, and NICS(1)zz values were calculated for each case. It was found that most designed compounds demonstrate superbasicity characteristics and especially amidine-arsinine 1-oxide core structure including two phosphazene electron donating groups (10) shows highest superbasicity properties. The most important finding of the study was the considerable synergistic effect between amidine and arsinine 1-oxide moieties for creating remarkable basicity strength. Aromaticity alterations of the arsinine 1-oxide ring also was monitored during protonation process.

Oligomeric and Fibrillar α-Synuclein Display Persistent Dynamics and Compressibility under Controlled Confinement.

The roles of α-synuclein in neurotransmitter release in brain neurons and in the Parkinson's disease condition have challenged comprehensive description. To gain insight into molecular mechanistic properties that actuate α-synuclein function and dysfunction, the coupled protein and solvent dynamics of oligomer and fibril forms of human α-synuclein are examined in a low-temperature system that allows control of confinement and localization of a motionally sensitive electron paramagnetic resonance spin probe in the coupled solvent-protein regions. The rotational mobility of the spin probe resolves two distinct α-synuclein-associated solvent components for oligomers and fibrils, as for globular proteins, but with dramatically higher fluidities at each temperature, that are comparable to low-confinement, aqueous-cryosolvent mesophases. In contrast to the temperature-independent volumes of the solvent phases that surround globular and condensate-forming proteins, the higher-fluidity mesophase volume of α-synuclein oligomers and fibrils decreases with decreasing temperature, signaling a compression of this phase. This unique property and thermal hysteresis in the mobilities and component weights, together with previous high-resolution structural characterizations, suggest a model in which the dynamically disordered C-terminal domain of α-synuclein creates a compressible phase that maintains high fluidity under confinement. Robust dynamics and compressibility are fundamental molecular mechanical properties of α-synuclein oligomers and fibrils, which may contribute to dysfunction and inform about function.

Greener and Whiter Analytical Chemistry Using Cyrene as a More Sustainable and Eco-Friendlier Mobile Phase Constituent in Chromatography.

Cyrene (dihydrolevoglucosenone) was evaluated for the first time as a potential sustainable mobile phase solvent in reversed-phase chromatography. As a benign biodegradable solvent, Cyrene is an attractive replacement to classical non-green organic chromatographic solvents such as acetonitrile and a modifier, co-eluent to known green solvents such as ethanol. Compared to ethanol, Cyrene is less toxic, non-flammable, biobased, biodegradable, and a cheaper solvent. A fire safety spider chart was generated to compare the properties of Cyrene to ethanol and show its superiority as a greener solvent. Cyrene's behavior, advantages, and drawbacks in reversed-phase chromatography, including the cut-off value of 350 nm, elution power, selectivity, and effect on the column, were investigated using a model drug mixture of moxifloxacin and metronidazole. A monolithic C18 (100 × 4.6 mm) column was used as a stationary phase. Different ratios of Cyrene: ethanol with an aqueous portion of sodium acetate buffer mobile phases were tested. A mobile phase consisting of Cyrene: ethanol: 0.1 M sodium acetate buffer pH 4.25 (8:13:79, v/v/v) was selected as the most suitable mobile phase system for separating and simultaneously determining metronidazole and moxifloxacin. The greenness and whiteness of the method were evaluated using the qualitative green assessment tool AGREE and the white analytical chemistry assessment tool RGB12. Further potentials of Cyrene as a solvent or modifier in normal phase chromatography, liquid chromatography-mass spectrometry, and supercritical fluid chromatography are discussed.

Potential energy surfaces of the [formula omitted] clusters in solution phase

In the present work, we have studied the effects of the implicit solvent on the structural and energetic parameters of Cu2+(MeOH)n=1-8 clusters. Initially, we explored the potential energy surfaces (PESs) obtained in the solution phase using the functional DFT M06-2X method, in conjunction with the 6–31++G** Pople basis set, and compared them with isomers of the same complexes optimized in the gaseous phase. The implicit solvent is described here by the polarized continuum model of integral equation formalism (IEF-PCM). Subsequently, we reported the temperature dependence and the binding electronic energies per methanol molecule. Our investigations reveal that the 6- and 5-coordinate isomers occupy the ground states on the PESs of the Cu2+(MeOH)n=1-8 clusters. The stability rules of the Cu2+ ion established in the gas phase are best adhered to in the implicit solvent. Regarding the temperature dependence of the solution phase conformer distribution, symmetric and compact structures, as well as those with a high coordination number (CN), dominate the population of the Cu2+(MeOH)n=1-8 clusters at all temperatures. Notably, the populations of clusters with sizes n=7-8 are exclusively dominated by hexa-coordinated structures at all temperatures, while penta- and tetra-coordinated isomers are disadvantaged. For the determination of the binding electronic energy, using a function fit, we computed these energies to be -1589kJ mol−1 in the implicit solvent and -7150kJ mol−1 in the gaseous phase. This significant difference is attributable to the interactions between the methanol molecules and the implicit solvent, which are present in the solvent phase but absent in a gaseous medium. This difference is further supported by the analysis of the Wiberg bond index of the metal–ligand interactions of the clusters in the two media.

Unraveling the impact of polar solvation on the molecular geometry, spectroscopy (FT-IR, UV, NMR), reactivity (ELF, NBO, HOMO-LUMO) and antiviral inhibitory potential of Cissampeline by molecular docking approach

Cissampeline, a highly promising natural substance derived from medicinal plants of the Cissampelos genus, has recently garnered significant interest due to its potent antiviral properties against a broad spectrum of viral infections. In this comprehensive study, we employed gd3bj-B3LYP/def2svp level of theory to investigate the impact of polar solvation on the molecular structure, dynamical stability, spectroscopy, nature of bonding, and antiviral inhibitory potential of Cissampeline. Our results demonstrated excellent agreement between the theoretically characterized structure and the experimentally determined one. Interestingly, we observed that in the absence of a solvent environment, the gas phase exhibited shorter bond angles compared to when different solvents were utilized, indicating reduced solvent interactions. Regarding solvation dynamics, we found that the total energy of the structure, when optimized in different solvents, followed the order DMSO > MeOH > Water > Gas, with corresponding total final energies of 1736.599 > 867.932 > 837.760 > 413.989 kcal/mol, respectively. Furthermore, NBO analysis revealed the strength of electron delocalization, with the order of perturbation energies being DMSO > MeOH > H2O > Gas phase, measured at 626.07 > 241.40 > 238.65 > 72.93 kcal/mol, respectively. Particularly noteworthy was the σ-σ* transition in the DMSO solvent phase, displaying the highest perturbation energy of 626.07 kcal/mol. FMO analysis provided insights into the energy levels of the studied species, with values of 4.5432 eV for Gas, 4.5250 eV for MeOH, 4.5247 eV for H2O, and 4.5242 eV for DMSO, respectively. Regarding the interaction of Cissampeline with amino acid residues, we found that the ligand exhibited the highest binding affinity with 3MX2 at -7.7 kcal/mol, followed by CMPL + 3T5N at -7.3 kcal/mol, and CMPL + 3MX5 at -6.0 kcal/mol. In comparison, the standard drug RIBAV only displayed successful interaction with 3MX2, showing the least binding affinity at -5.8 kcal/mol. This study showed highlights the remarkable potential of Cissampeline as an effective antiviral agent and sheds light on the importance of considering solvation effects in molecular investigations.

Molecular structure solvent–solute, electronic, topology and dynamics simulation studies on 2-[[1-(cyclopropyl methoxy)-4-hydroxy-2-oxoquinoline-3-carbonyl] amino] acetic acid- an effective CKD drug

The current theoretical work analyzes the optimal structure and vibrational assignments of 2-[[1-(cyclopropyl methox)-4-hydroxy-2-oxoquinoline-3-carbonyl] amino] acetic acid (2C2O), examined theoretically through DFT method. PED values were calculated, and vibrational assignments have been determined. Studies employing FT-IR and FT-Raman methods were explored in both experimental and theoretical scenarios. By using Gaussian 09W, structural optimization, and bond parameters are examined. MEP differentiates nucleophilic and electrophilic sites and establishes a molecules 3-dinemsional charge distribution using gas and solvent phases. Global descriptors and band gap energies are provided using the Frontier Molecular Orbital(FMO) study. The electron delocalization resulting from hyperconjucation can be understood by using the NBO method. The TD-DFT technique and IEFPCM model were utilized to stimulate the UV spectra of the title compound. FUKUI function used to trace the area of reactive sites. Topological explorations were scrutinized using the Multiwave function. The title chemical exhibits a promising pharmacological profile. In this research, we assess its bioactivity and drug likeness. Molecular docking using Autodock technique reveals the compounds inhibiting effect on receptors. Analysis of the protein–ligand complexes stability was done using MD simulations.

Use of green analysis methods to determine the ionization constant values of isoxazolyl penicillins

In this study, an environmentally friendly analysis of penicillinase-resistant antibiotics oxacillin, dicloxacillin, and cloxacillin was carried out by liquid chromatography methods using ethanol solvent that is not harmful to human health and the environment. Ionization constant (wwpKa) values of isoxazolyl penicillins in ethanol–water binary mixtures containing 20–35% (v/v) ethanol at 37 °C were obtained by green reverse phase liquid chromatography and micellar liquid chromatography methods known as green chromatography. The developed methods are based on a model that relates the chromatographic behavior of the identified analytes to pH. The linear relationship between the microscopic solvatochromic parameter ETN and the retention values of the compounds was determined depending on the change of organic solvent in the mobile phase. Using the obtained chromatographic data, conditions that ensure the simultaneous separation of the compounds for both methods were determined. The relationship between the calculated sspKa values and the macroscopic properties of ethanol was investigated. The agreement between the pKa (wwpKa) values in the water medium determined by this approach was determined by t-test at a 95% confidence level for both methods. The wwpKa values of the compounds at 25 °C were also estimated using Abraham solute parameters without any experimental work.

Synthesis, characterization, pharmaceutical evaluation, molecular docking and DFT calculations of a novel drug (E)-5-bromo-3-(phenylimino) indolin-2-one

Herein, one-pot synthesis of (E)-5-bromo-3-(phenylimino)indolin-2-one (5BPI molecule), density function theory for validation of the synthesized molecule, and biological activities, have been reported. Anticancer activity of the synthesized (E)-5-bromo-3-(phenylimino)indolin-2-one compound from National Cancer Institute, USA, was evaluated. However, antimicrobial nature of the molecule against 1NCO, 7C2N, 3DRA, and 4YNU proteins was also demonstrated using molecular docking as a preliminary investigation that showed the binding with ligand possess very low binding affinity as −6.22, −6.51, −5.59, and −7.45 kcal/mol, respectively. Density Functional Theory was effectively used to analyse the stability of the molecular structure under optimized circumstances, for comparative studies involving experimental and theoretical data for the gas and solvent phases. According to this analysis, UV–Vis spectra, band gap energy, nonlinear optical properties, molecular electrostatic potential, electron localization function, localized orbital locator, and reduced density gradient were illustrated in different solvents. In addition, natural bond orbital analysis was conveyed to the largest second-order perturbation energy that corresponded to electron delocalization from the donor and acceptor interaction. As a consequence, it was clearly demonstrated by the compound's drug-likeness, ADMET characteristics, docked complexes' released energies, and anticancer activity that it may be employed as a lead molecule to treat different carcinomas after the more potent alterations in their skeleton prompted by chemical reactions.

Investigation on the electronic detection of letrozole drug in gas and solvent phases by metal oxide nanoclusters

Chemical sensors could pioneer great utilities in point-of-care diagnostic medical devices. Understanding the detection and adsorption processes of drug molecules on the surface of nanoclusters is essential to their usage in medical engineering. Therefore, density functional theory (DFT) calculations have been utilized to investigate the adsorption and detection behavior of letrozole (LET) on the surface of some metal oxide nanoclusters (Be12O12, Mg12O12, and Ca12O12) to screen the promising nanoclusters. The adsorption energy calculations for the most stable complexes indicated are stable in gas phases. Thermodynamic analysis indicated adsorption processes of LET are spontaneous and exothermic. After the adsorption, the LUMO-HOMO energy gap (Eg) for all metal oxide-LET complexes was reduced, with the largest decrease (−33.14% and −38.75%) found in the Be12O12 and Ca12O12 complexes. This decrease can be presumed as a signal for LET detection. Furthermore, the Be12O12 and Ca12O12 nanoclusters indicated a suitable short recovery time for the desorption of LET drug molecule. The solvent phase (water as a solvent phase) calculation indicated the structures are stable in the water and similar to the gas phase Be12O12 and Ca12O12 nanoclusters can detect the LET. Thus, it can be concluded that the Be12O12 and Ca12O12 nanoclusters are appropriate candidates for LET detection and these nanoclusters can be used in sensor devices.