Unraveling the role of superalkalis in modulating the static and dynamic hyperpolarizabilities of emerging calix[4]arenes.

Calixarenes, as novel organic materials, can play a pivotal role in the development of high-performance nonlinear optical materials due to the ease of design and fabrication. In this study, DFT simulations were employed to investigate the geometric, electronic, and NLO responses of calix[4]arene doped with Li3O, Na3O, and K3O superalkalis. The computed values of the vertical ionization energies and interaction energies indicate the chemical and thermodynamic stabilities of the targeted M3O@calix[4]arene complexes. The corresponding energy gaps (2.01 to 3.49 eV) are notably reduced, indicating the semiconductor nature of the materials. Surprisingly, the M3O@calix[4]arene complexes exhibit transparency in the UV/visible range as the absorption peaks are shifted in the near infrared (NIR) region. The highest values of 5.9 × 105 a.u. and 2.3 × 108 a.u. for the respective first and second hyperpolarizabilities are observed for Na3O@calix[4]arene. Furthermore, the Na3O@calix[4]arene complex exhibits maximum values of 2.3 × 105 a.u. for second harmonic generation (SHG) and (K3O@calix[4]arene) 2.3 × 106 a.u. for the electro-optical Pockels effect (EOPE) at 1064 nm. Similarly, approximations are made for the dynamic second hyperpolarizability coefficients (EOKE and EFISHG) at different wavelengths. Notably, the Na3O@calix[4]arene complex demonstrates the highest quadratic nonlinear refractive index (n2) of 9.5 × 10-15 cm2 W-1 at 1064 nm. This research paves the way for the development of stable calix[4]arenes doped with superalkalis, leading to an improved nonlinear optical (NLO) response.

Eco-friendly synthesis of mesoporous bioactive glass ceramics and functionalization for drug delivery and hard tissue engineering applications.

Hard tissue regenerative mesoporous bioactive glass (MBG) has traditionally been synthesized using costly and toxic alkoxysilane agents and harsh conditions. In this study, MBG was synthesized using the cheaper reagent SiO2by using a co-precipitation approach. The surface properties of MBG ceramic were tailored by functionalizing with amino and carboxylic groups, aiming to develop an efficient drug delivery system for treating bone infections occurring during or after reconstruction surgeries. The amino groups were introduced through a salinization reaction, while the carboxylate groups were added via a chain elongation reaction. The MBG, MBG-NH2, and MBG-NH-COOH were analyzed by using various techniques: x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Brunauer-Emmett-Teller (BET), scanning electron microscopy and energy-dispersive x-ray spectroscopy. The XRD results confirmed the successful preparation of MBG, and the FTIR results indicated successful functionalization. BET analysis revealed that the prepared samples were mesoporous, and functionalization tuned their surface area and surface properties. Cefixime, an antibiotic, was loaded onto MBG, MBG-NH2, and MBG-NH-COOH to test their drug-carrying capacity. Comparatively, MBG-NH-COOH showed good drug loading and sustained release behavior. The release of the drug followed the Fickian diffusion mechanism. All prepared samples displayed favorable biocompatibility at higher concentration in the Alamar blue assay with MC3T3 cells and exhibited the good potential for hard tissue regeneration, as carbonated hydroxyapatite formed on their surfaces in simulated body fluid.

Exploring the Sensing Potential of g-C3N4 versus Li/g-C3N4 Nanoflakes toward Hazardous Organic Volatiles: A DFT Simulation Study.

Ab initio calculations were performed to determine the sensing behavior of g-C3N4 and Li metal-doped g-C3N4 (Li/g-C3N4) quantum dots toward toxic compounds acetamide (AA), benzamide (BA), and their thio-analogues, namely, thioacetamide (TAA) and thiobenzamide (TAA). For optimization and interaction energies, the ωB97XD/6-31G(d,p) level of theory was used. Interaction energies (Eint) illustrate the high thermodynamic stabilities of the designed complexes due to the presence of the noncovalent interactions. The presence of electrostatic forces in some complexes is also observed. The observed trend of Eint in g-C3N4 complexes was BA > TAA > AA > TBA, while in Li/g-C3N4, the trend was BA > AA > TBA > TAA. The electronic properties were studied by frontier molecular orbital (FMO) and natural bond orbital analyses. According to FMO, lithium metal doping greatly enhanced the conductivity of the complexes by generating new HOMOs near the Fermi level. A significant amount of charge transfer was also observed in complexes, reflecting the increase in charge conductivity. NCI and QTAIM analyses evidenced the presence of significant noncovalent dispersion and electrostatic forces in Li/g-C3N4 and respective complexes. Charge decomposition analysis gave an idea of the transfer of charge density between quantum dots and analytes. Finally, TD-DFT explained the optical behavior of the reported complexes. The findings of this study suggested that both bare g-C3N4 and Li/g-C3N4 can effectively be used as atmospheric sensors having excellent adsorbing properties toward toxic analytes.

Frequency-dependent nonlinear optical response and refractive index investigation of lactone-derived thermochromic compounds.

Nonlinear optical (NLO) switchable materials play a crucial role in the fields of electronics and optoelectronics. The selection of an appropriate switching approach is vital in designing such materials to enhance their NLO response. Among various approaches, thermos-switching materials have shown a 4-fold increase in NLO response compared to other photo-switching materials. In this study, we computationally investigated the geometric, electronic, and nonlinear optical properties of reversible lactone-based thermochromic compounds using the ωB97XD/6-311+G (d,p) level of theory. Molecular orbital studies are employed to analyze the electronic properties of the close and open isomers of these compounds, while time-dependent density functional theory (TD-DFT) analysis is utilized to evaluate their molecular absorption. Our findings reveal that the π-electronic conjugation-induced delocalization significantly influences the ON-OFF switchable nonlinear optical response of the lactone-based thermochromic compounds. Notably, among all compounds, the open isomer of lactone 2 exhibits the highest hyperpolarizability value (6596.69 au). Furthermore, we extended our analysis to investigate the frequency-dependent second and third-order hyperpolarizabilities. The most pronounced frequency-dependent NLO response is observed at 532 nm. Additionally, we calculated the refractive index of these thermochromic compounds to further assess their nonlinear optical response. The open isomer of lactone 1 demonstrates the highest refractive index value (3.99 × 10-14 cm2/W). Overall, our study highlights the excellent potential of reversible thermochromic compounds as NLO molecular thermos-switches for future applications.

Alkali metals doped cycloparaphenylene nanohoops: Promising nonlinear optical materials with enhanced performance.

In the ongoing pursuit of novel and efficient NLO materials, the potential of alkali metal-doped {6}cycloparaphenylene ({6}CPP) and methylene bridged {6} cycloparaphenylene (MB{6}CPP) nanohoops as excellent NLO candidates has been explored. The geometric, electronic, linear, and nonlinear optical properties of designed systems have been investigated theoretically. All the nanohoops demonstrated thermodynamic stability, with remarkable interaction energies reaching up to -1.39 eV (-0.0511 au). Notably, the introduction of alkali metals led to a significant reduction in the HOMO-LUMO energy gaps, with values as low as 2.92 eV, compared to 6.80 eV and 6.06 eV for undoped {6}CPP and MB{6}CPP, respectively. Moreover, the alkali metal-doped nanohoops exhibited exceptional NLO response, with the K@r6-{6}CPP complex achieving the highest first hyperpolarizability of 56,221.7 × 10-30 esu. Additionally, the frequency-dependent first hyperpolarizability values are also computed at two commonly used wavelengths of 1550 nm and 1907 nm, respectively. These findings highlight the potential of designed nanohoops as promising candidates for advanced NLO materials with high-tech applications.

Decorating Mg12O12 Nanocage with Late First-Row Transition Metals To Act as Single-Atom Catalysts for the Hydrogen Evolution Reaction.

In the pursuit of sustainable clean energy sources, the hydrogen evolution reaction (HER) has attained significant interest from the scientific community. Single-atom catalysts (SACs) are among the most promising candidates for future electrocatalysis because they possess high thermal stability, effective electrical conductivity, and excellent percentage atom utilization. In the present study, the applicability of late first-row transition metals (Fe-Zn) decorated on the magnesium oxide nanocage (TM@Mg12O12) as SACs for the HER has been studied, via density functional theory. The late first-row transition metals have been chosen as they have high abundance and are relatively low-cost. Among the studied systems, results show that the Fe@Mg12O12 SAC is the best candidate for catalyzing the HER reaction as it exhibits the lowest activation barrier for HER. Moreover, Fe@Mg12O12 shows high stability (Eint = -1.64 eV), which is essential in designing SACs to prevent aggregation of the metal. Furthermore, the results of the electronic properties' analysis showed that the HOMO-LUMO gap of the nanocage is decreased significantly upon doping of Fe (from 4.81 to 2.28 eV), indicating an increase in the conductivity of the system. This study highlights the potential application of the TM@nanocage SAC systems as effective HER catalysts.

Enhanced nonlinear optical response of alkalides based on stacked Janus all-cis-1,2,3,4,5,6-hexafluorocyclohexane.

Significant efforts are continuously exerted by the scientific community to explore new strategies to design materials with high nonlinear optical responses. An effective approach is to design alkalides based on Janus molecules. Herein, we present a new approach to remarkably boost the NLO response of alkalides by stacking the Janus molecules. Alkalides based on stacked Janus molecule, M-n-M' (where n = 2 & 3 while M and M' are Li/Na/K) are studied for structural, energetic, electrical, and nonlinear optical properties. The thermodynamic stability of the designed complexes is confirmed by the energetic stabilities, which range between -14.07 and -28.77 kcal/mol. The alkalide character of alkali metals-doped complexes is confirmed by the NBO charge transfer and HOMO(s) densities. The HOMO densities are located on the doped alkali metal atoms, indicating their alkalide character. The absorptions in UV-Vis and near IR region confirm the deep ultraviolet transparency of the designed complexes. The maximum first static and dynamic hyperpolarizabilities of 5.13 × 107 and 6.6 × 106 au (at 1339 nm) confirm their high NLO response, especially for K-2-M' complexes. The NLO response of alkalides based on stacked Janus molecules is 1-2 orders of magnitude higher than the alkalide based on Janus monomer. The high values of dc-Kerr and electric field-induced response e.g., max ∼107 and 108 au, respectively have been obtained. These findings suggest that our designed complexes envision a new insight into the rational design of stable high NLO performance materials.

Role of Delocalization, Asymmetric Distribution of π-Electrons and Elongated Conjugation System for Enhancement of NLO Response of Open Form of Spiropyran-Based Thermochromes.

Switchable nonlinear optical (NLO) materials have widespread applications in electronics and optoelectronics. Thermo-switches generate many times higher NLO responses as compared to photo-switches. Herein, we have investigated the geometric, electronic, and nonlinear optical properties of spiropyranes thermochromes via DFT methods. The stabilities of close and open isomers of selected spiropyranes are investigated through relative energies. Electronic properties are studied through frontier molecular orbitals (FMOs) analysis. The lower HOMO-LUMO energy gap and lower excitation energy are observed for open isomers of spiropyranes, which imparts the large first hyperpolarizability value. The delocalization of π-electrons, asymmetric distribution and elongated conjugation system are dominant factors for high hyperpolarizability values of open isomers. For deep understanding, we also analyzed the frequency-dependent hyperpolarizability and refractive index of considered thermochromes. The NLO response increased significantly with increasing frequency. Among all those compounds, the highest refractive index value is observed for the open isomer of the spiropyran 1 (1.99 × 10-17 cm2/W). Molecular absorption analysis confirmed the electronic excitation in the open isomers compared to closed isomers. The results show that reversible thermochromic compounds act as excellent NLO molecular switches and can be used to design advanced electronics.

Giant NLO response and deep ultraviolet transparency of dual (alkali/alkaline earth) metals doped C6O6Li6 electrides.

The designing of new materials having outstanding nonlinear optical (NLO) response is much needed for use in latest optics. Herein, the geometric, electronic and NLO properties of alkali and alkaline earth metals doped C6O6Li6 (alk-C6O6Li6-alkearth, alkearth = Ca, Mg, Be and alk = K, Na, Li) electrides is studied via quantum chemical approach. The interaction energies (Eint) are examined to illustrate their thermodynamic stability. The strong interaction energy of -39.99 kcal mol-1 is observed for Ca-C6O6Li6-Li electride in comparison to others. Frontier molecular orbitals (FMOs) energy gap of considered complexes is changed due to the electronic density shifting between metals and C6O6Li6 surface, which notifies the semi conducting properties of these electrides. The FMOs isodensities and natural bond orbital (NBO) charge analysis are performed to justify charge transfer between dopants and complexant. UV-Visible study also confirmed the application of these electrides as deep ultra-violet laser devices. NLO response is studied through calculation of first hyperpolarizability (ßo). The highest ßo value of 1.68 × 105 au is calculated for Mg-C6O6Li6-K electride. NLO response is further rationalized by three- and two-level models approach.

Photoswitchable nonlinear optical properties of azobenzene-based supramolecular complexes: insights from density functional theory.

Density functional theory (DFT) calculations were performed for a series of supramolecular assemblies containing azobenzene (Azo-X where X = I, Br and H) and alkoxystilbazole subunits to evaluate their electronic, linear and nonlinear optical properties. These assemblies are derivatives of azobenzene, obtained by the substitution of electron-withdrawing and electron-donating groups onto the molecular skeleton. The interaction energies (Eint) of all the designed supramolecular complexes (IA-IF, IIA-IIF and IIIA-IIIF) range from -1.0 kcal mol-1 to -7.7 kcal mol-1. The electronic properties of these hydrogen/halogen bond driven supramolecular assemblies such as vertical ionization energies (VIE), HOMO-LUMO energy gap (GH-L), excitation energies, density of states (DOS) and natural population (NPA) analyses were also computed. The non-covalent interaction index (NCI) and quantum theory of atoms in molecules (QTAIM) analyses were also performed to validate the nature of inter- and intra-molecular interactions in these complexes. A substantial enhancement in the first hyperpolarizability (ß0) values of the designed supramolecular complexes was observed, which is driven by the charge transfer from the pyridyl moiety of alkoxystilbazole to Azo-X. The highest ß0 value of 1.3 × 104 au was observed for the supramolecular complex of p-nitro substituted azobenzene with alkoxystilbazole (ID complex). Moreover, the results show that the substitution of electron-withdrawing groups on Azo-X can also bring larger ß0 values for such complexes. It was confirmed on a purely theoretical basis that both the types of noncovalent interactions present and the substituent group incorporated influence the nonlinear optical (NLO) response of the systems. Furthermore, the ß0 values of the E (trans) and Z (cis) forms were compared to demonstrate the two-way photoinduced switching mechanism.

Exploring the inhibitory potential of novel piperidine-derivatives against main protease (Mpro) of SARS-CoV-2: A hybrid approach consisting of molecular docking, MD simulations and MMPBSA analysis.

In the current study, a hybrid computational approach consisting of different computational methods to explore the molecular electronic structures, bioactivity and therapeutic potential of piperidine compounds against SARS-CoV-2. The quantum chemical methods are used to study electronic structures of designed derivatives, molecular docking methods are used to see the most potential docking interactions for main protease (MPro) of SARS-CoV-2 while molecular dynamic and MMPBSA analyses are performed in bulk water solvation process to mimic real protein like aqueous environment and effectiveness of docked complexes. We designed and optimized piperidine derivatives from experimentally known precursor using quantum chemical methods. The UV-Visible, IR, molecular orbitals, molecular electrostatic plots, and global chemical reactivity descriptors are carried out which illustrate that the designed compounds are kinetically stable and reactive. The results of MD simulations and binding free energy revealed that all the complex systems possess adequate dynamic stability, and flexibility based on their RMSD, RMSF, radius of gyration, and hydrogen bond analysis. The computed net binding free energy ( Δ G b i n d ) as calculated by MMPBSA method for the complexes showed the values of -4.29 kcal.mol-1 for P1, -5.52 kcal.mol-1 for P2, -6.12 kcal.mol-1 for P3, -6.35 kcal.mol-1 for P4, -5.19 kcal.mol-1 for P5, 3.09 kcal.mol-1 for P6, -6.78 kcal.mol-1 for P7, and -6.29 kcal.mol-1 for P8.The ADMET analysis further confirmed that none of among the designed ligands violates the Lipinski rule of five (RO5). The current comprehensive investigation predicts that all our designed compounds are recommended as prospective therapeutic drugs against Mpro of SARS-CoV-2 and it provokes the scientific community to further perform their in-vitro analysis.

Surface engineered mesoporous silica carriers for the controlled delivery of anticancer drug 5-fluorouracil: Computational approach for the drug-carrier interactions using density functional theory.

Introduction: Drug delivery systems are the topmost priority to increase drug safety and efficacy. In this study, hybrid porous silicates SBA-15 and its derivatives SBA@N and SBA@3N were synthesized and loaded with an anticancer drug, 5-fluorouracil. The drug release was studied in a simulated physiological environment. Method: These materials were characterized for their textural and physio-chemical properties by scanning electron microscopy (SEM), nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), small-angle X-ray diffraction (SAX), and nitrogen adsorption/desorption techniques. The surface electrostatics of the materials was measured by zeta potential. Results: The drug loading efficiency of the prepared hybrid materials was about 10%. In vitro drug release profiles were obtained in simulated fluids. Slow drug release kinetics was observed for SBA@3N, which released 7.5% of the entrapped drug in simulated intestinal fluid (SIF, pH 7.2) and 33% in simulated body fluid (SBF, pH 7.2) for 72 h. The material SBA@N presented an initial burst release of 13% in simulated intestinal fluid and 32.6% in simulated gastric fluid (SGF, pH 1.2), while about 70% of the drug was released within the next 72 h. Density functional theory (DFT) calculations have also supported the slow drug release from the SBA@3N material. The release mechanism of the drug from the prepared carriers was studied by first-order, second-order, Korsmeyer-Peppas, Hixson-Crowell, and Higuchi kinetic models. The drug release from these carriers follows Fickian diffusion and zero-order kinetics in SGF and SBF, whereas first-order, non-Fickian diffusion, and case-II transport were observed in SIF. Discussion: Based on these findings, the proposed synthesized hybrid materials may be suggested as a potential drug delivery system for anti-cancer drugs such as 5-fluorouracil.

Therapeutic potential of oxo-triarylmethyl (oxTAM) as a targeted drug delivery system for nitrosourea and fluorouracil anticancer drugs; A first principles insight.

In this study, oxygenated triarylmethyl (oxTAM) is investigated by DFT calculations as a drug carrier framework for Nitrosourea (NU) and Fluorouracil (FU) drugs. Based on the adsorption analysis i.e., energies and distances between interacting atoms, it is found that oxTAM exhibits excellent carrier abilities for the delivery of FU (-1.53 eV & 2.00 Å) and NU (-1.33 eV & 2.12 Å) drugs. NCI and QTAIM results indicate the presence of hydrogen bonding in drug-carrier complexes. The values of dipole moment and global chemical descriptors show the significant reactivity of oxTAM for NU and FU drugs. Based on electronic property analysis, FU@oxTAM has a higher adsorption trend for complexation with oxTAM as compared to NU@oxTAM. Moreover, FU can easily release from the carrier due to the decreasing adsorption stability after protonation under an acidic environment as well as a short recovery time observed for the oxTAM carrier surface. Keeping in view all the above parameters, we inferred that oxTAM can serve as a potential drug delivery system for anticancer drugs including, Nitrosourea and Fluorouracil drugs.

Task-specific polymeric membranes to achieve high gas-liquid mass transfer.

In the current study, Polyimide (P84)-based polymeric membranes were fabricated and used as spargers in the bubble column reactor (BCR) to get a high gas-liquid mass transfer (GL-MT) rate of oxygen in water. Different polymeric membranes were fabricated by incorporating polyvinyl pyrrolidone (PVP) as a porogen and a Zeolitic Imidazolate Framework (ZIF-8) to induce high porosity and hydrophobicity in the membranes. The GL-MT efficiency of membranes was evaluated by measuring the overall volumetric mass transfer coefficient (kLa) of oxygen in air. The kLa of O2 (in air) was measured by supplying the gas through a fixed membrane surface area of 11.94 cm2 at a fixed gas flow rate of 3L/min under atmospheric pressure. The results revealed that adding porogen and ZIF-8 increased the porosity of the membranes compared to the pure polymeric membranes. In comparison, the ZIF-8 (3 wt%) based membrane showed the highest porosity (80%), hydrophobicity (95° contact angle) and kLa of oxygen in air (241.2 h-1) with 78% saturation in only 60 s. ZIF-8 based membranes showed the potential to increase the amount of dissolved oxygen in BCR by reducing the bubble size, increasing the number of bubbles, and improving the hydrophobicity. The study showed that ZIF-8 based membrane diffusers are expected to produce high GL-MT in microbial syngas fermentation. To the best of our knowledge, this is the first study on the fabrication and application of polymeric membranes for GL-MT applications. Further research should be conducted under real fermentation conditions to assess the practicality of the system to support substrate utilization, microbial growth, and product formation.

Shedding light on static and dynamic hyperpolarizabilities of thia[7&8]circulenes, toward their NLO applications.

Herein, we examined the nonlinear optical properties of thia[7&8]circulenes (1-18). Circulenes are the building blocks of various nanomaterials such as graphene, nanotubes, and fullerenes. Many studies on circulenes have focused on the aromaticity of circulenes, but less attention has been paid on optoelectronics properties. Carbon atoms of the [7&8]circulenes are replaced with multiple sulfur atoms to designed thia[7&8]circulenes (1-18). These circulenes (1-18) are thermodynamically, kinetically, and chemically stable. Nonlinear optical (NLO) response is evaluated through static and frequency-dependent first and second hyperpolarizability values. The static first hyperpolarizability (ßo) of these compounds ranges between 0.00 and 496 au. The frequency-dependent coefficients for all thia[7&8]circulenes show remarkable enhancement at 532 and 1064 nm, respectively. The nonlinear refractive index is increased up to 1.13 × 10-14 au for circulene 9 at 532 nm. These findings successfully demonstrated that nonlinear optical response of thia[7&8]circulenes can be increased by decorating multiple sulfur atoms. The unsymmetrical distribution of sulfur atoms is more effective in enhancing nonlinear optical response.

Benchmark Density Functional Theory Approach for the Calculation of Bond Dissociation Energies of the M-O2 Bond: A Key Step in Water Splitting Reactions.

A very fascinating aspect in quantum chemical research is to determine the accurate and cost-effective methods for the calculation of electronic and structural properties through a benchmark study. The current study focuses on the performance evaluation of density functional theory methods for the accurate measurement of bond dissociation energies (BDEs) of chemically important M-O2 bonds in water splitting reactions. The BDE measurement has got noteworthy attention due to its importance in all areas of chemistry. For BDE measurements of M-O2 bonds in five metal complexes with oxygen molecules, 14 density functionals (DFs) are chosen from seven classes of DFs with two series of mixed basis sets. A combination of pseudopotential and Pople basis sets [LANL2DZ & 6-31G(d) and SDD & 6-31+G(d)] are used as a series of mixed basis sets. The B3LYP-GD3BJ functional with LANL2DZ & 6-31G(d) gives outstanding results due to low deviations, error, and the best Pearson's correlation (R) between the experimental and theoretical data. Our study suggested an efficient, low-cost, precise, and accurate B3LYP-GD3BJ/LANL2DZ & 6-31G(d) level of theory for BDE of the M-O2 bond, which may be useful for chemists working in the field of energy generation and utilization.

Exploring the potential of highly selective deep eutectic solvents (DES) based membranes for dehydration of butanol via pervaporation.

N-butanol has unique physicochemical and combustion properties, similar to gasoline, which makes it an environmentally friendly alternative to conventional fuels. To improve the efficiency, the dehydration of butanol is necessary. This paper aims to investigate the performance of Deep Eutectic Solvents (DESs) based membranes for the dehydration of n-butanol by the pervaporation process. Three DES with different combinations of hydrogen bond donors and acceptors, i.e., DL-menthol: Lauric acid (DES), DL-menthol-Palmitic acid (DES), and [TETA] Cl: Thymol (DES), were used. We hypothesized that (i) incorporation of hydrophobic DES would increase the hydrophobicity of the membranes; (ii) specific functional groups (phenolic group, amine group) in DESs would enhance the butanol-philic character of membranes, and (iii) hydrophobic DESs would increase the butanol separation efficiency and permeability of membranes. FTIR analysis and physicochemical parameters of the resultant liquid mixture validated the DESs' production. The DESs were then filled into the permeable support, resulting in supported liquid membranes (SLMs). An additional layer of polydimethylsiloxane (PDMS) was coated directly on the DES-PSf layer to prevent leaching out of DES. A feed containing a 6 wt % aqueous solution of butanol under varying temperatures was studied. The results showed that among all membranes, [TETA] Cl: Thymol DES-based membrane showed the highest sorption of 36% at room temperature. The introduction of DES in membranes resulted in a remarkable increase in the separation factor while sustaining a reasonable flux. Among all the membranes, the DL-menthol: Lauric acid (DES) based membrane exhibited the highest separation factor of 57 with a total flux of 0.11 kg/m2. h. Significantly high butanol-water separation was attributed to the low viscosity and high butanol solubility of the chosen DES, which makes it a suitable substitute to conventional ILs.

One pot synthesis of UiO-66@IL composite for fabrication of CO2 selective mixed matrix membranes.

In this study, a facile and extensible one pot approach was utilized to synthesize ionic liquid inside a porous metal organic framework (UiO-66). Different characterization techniques were used to confirm the successful synthesis of UiO-66@IL composite. The MMMs were characterized and tested for CO2 separation from CH4 or N2 at ambient and elevated temperatures. SEM images exhibited well dispersion of the filler particles with no notable defect even at high loadings. Single and mixed gas permeation results indicated significant performance (CO2 permeability: 143 Barrer and CO2/CH4, CO2/N2 selectivity: 28.32, 61.11 respectively) by enhancing the permeability of CO2 by 74% and selectivity to 31% and 26% for CO2/CH4 and CO2/N2 compared with neat Pebax®1657 membrane.

Mixed superalkalis are a better choice than pure superalkalis for B12N12 nanocages to design high-performance nonlinear optical materials.

Mixed superalkali clusters are a source of excess electrons, as their vertical ionization energies (2.81-3.36 eV) are much lower than those of alkali metals (even cesium (∼3.85 eV)) and the superalkali Li3O (3.42 eV). In the present work, the geometric, electronic, and nonlinear optical (NLO) properties of mixed superalkali cluster-doped B12N12 nanocages are studied theoretically. All complexes, A-G, have very high interaction energies (-98.02 to -123.13 kcal mol-1) and are thermodynamically stable when compared to previously reported Li3O@B12N12 (-92.71 kcal mol-1). The designed complexes have smaller HOMO-LUMO energy gaps (3.36-4.27 eV) than pristine B12N12 (11.13 eV). Charge transfer in the complexes is studied through natural population analysis and non-bonding interactions are evaluated through quantum theory of atoms in molecules (QTAIM) and non-covalent interaction analyses. These complexes have absorption maxima (1076-1486 nm) in the near-infrared region (NIR) and they are transparent in the UV region. The first hyperpolarizability of complex C is 1.7 × 107 au, which is much higher than the value of 3.7 × 104 au for a pure Li3O superalkali-doped B12N12 complex calculated at the same level of theory, as reported by Sun et al. (Dalton Trans., 2016, 45, 7500-7509). The large second hyperpolarizability values also reflect the enhanced nonlinear optical response. The best computed values for the electro-optical Pockels effect, second harmonic generation, and hyper-Rayleigh scattering are 3.29 × 1010 au, 1.17 × 1010 au, and 6.71 × 106 au, respectively. Furthermore, the electro-optic dc-Kerr effect and electric-field-induced second harmonic generation have maximum values of 3.96 × 1011 au and 3.46 × 1010 au at 1064 nm. There are enhancements in the quadratic nonlinear refractive index (n2) values for complexes A-G, with a highest n2 value of 3.35 × 10-8 cm2 W-1 at 1064 nm. These results suggest that mixed-superalkali-doped B12N12 nanoclusters are potential candidates when designing high-performance NLO materials.

Computational investigation of a covalent triazine framework (CTF-0) as an efficient electrochemical sensor.

In the current study, a covalent triazine framework (CTF-0) was evaluated as an electrochemical sensor against industrial pollutants i.e., O3, NO, SO2, SO3, and CO2. The deep understanding of analytes@CTF-0 complexation was acquired by interaction energy, NCI, QTAIM, SAPT0, EDD, NBO and FMO analyses. The outcome of interaction energy analyses clearly indicates that all the analytes are physiosorbed onto the CTF-0 surface. NCI and QTAIM analysis were employed to understand the nature of the non-covalent interactions. Furthermore, SAPT0 analysis revealed that dispersion has the highest contribution towards total SAPT0 energy. In NBO analysis, the highest charge transfer is obtained in the case of SO3@CTF-0 (-0.167 e-) whereas the lowest charge transfer is observed in CO2@CTF-0. The results of NBO charge transfer are also verified through EDD analysis. FMO analysis revealed that the highest reduction in the HOMO-LUMO energy gap is observed in the case of O3 (5.03 eV) adsorption onto the CTF-0 surface, which indicates the sensitivity of CTF-0 for O3 analytes. We strongly believe that these results might be productive for experimentalists to tailor a highly sensitive electrochemical sensor using covalent triazine-based frameworks (CTFs).