HOMO-LUMO Energy Levels Research Articles

Influence of bulky peripheral substituents on subphthalocyanine derivatives: Implications for photocatalytic and photoelectrochemical hydrogen production

A series of novel subphthalocyanine (SubPc) derivatives with bulky electron-donating substituents were synthesized for visible light-induced photocatalytic and photoelectrochemical hydrogen production. SubPc derivatives were decorated with bulky thiophenoxy (coded SubPc 1–2) and phenoxy (coded SubPc 3–4) substituents to compare the influence of the nature of the peripheral bulky substituents on the photophysical and photocatalytic activity of SubPc. The highest photocatalytic performance was obtained from SubPc 4, having diphenyl phenoxy substituents with an H2 production rate of 7.233 mmol g-1h−1. The photocatalytic hydrogen evolution activities of all SubPc sensitized TiO2 photocatalysts enhanced approximately four times in the presence of Pt co-catalyst. The photocatalysts showed remarkable long-term stability and reproducibility of H2 evolution over 24-hour irradiation. SubPc 4-based photocatalytic system reached a considerable catalytic activity with the H2 production of 16.022 mmol g−1 and a turnover number (TON) value of 34,089 for 24 h irradiation. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) studies were carried out to better understand the photocatalytic abilities of SubPc derivatives and develop a symbiotic connection with experimental investigations. The results highlight the importance of peripheral substituents in modifying electron density, dipole moment, and HOMO-LUMO energy levels and improving SubPc derivative light-harvesting performance. The presence of 2,6-diisopropyl on SubPc derivatives (SubPc 2 and 4) caused a significant change in the properties, resulting in favourable electron transport characteristics and, therefore, improving photocatalytic performance. Furthermore, the incorporation of TiO2, as shown in SubPc 1@TiO2 and SubPc 2@TiO2, resulted in a modest reduction in chemical hardness, implying increased charge transfer inside the molecule and, as a consequence, enhancing its efficacy as a sensitizer. These theoretical discoveries provide a solid foundation for the customized design and optimization of SubPc derivatives for effective photocatalytic applications.

Improvement the formaldehyde sensing and detection through Pt-doped graphdiyne monolayer: Quantum chemical study

One of the commonly employed chemical feedstocks is formaldehyde (CH2O), which has diverse applications in many fields. However, CH2O might have detrimental effects on human because of its toxicity. Hence, it is of utmost significance to effectively monitor and detect CH2O. Within this piece of research, the adhesion attributes of the pristine graphdiyne (PGRD) and Pt-doped GRD (Pt@GRD) for CH2O were examined through DFT calculations. Moreover, the HOMO-LUMO energy levels, electrostatic potentials, energy band structures, adhesion structure parameters, and doping site optimizations of the Pt@GRD were investigated. Based on the results, doping the Pt atom the optimal site (CII) dramatically reduced the energy gap and substantially enhanced the electrical conductance. The PGRD was not suitable for the detection of CH2O with high sensitivity since it used mainly physisorption. However, there was a robust chemical adsorption between Pt@GRD and CH2O via the chemical reaction and hybridization of the Pt-d orbital with the molecular orbital of CH2O. The performance of Pt@GRD as a novel 2D material in detecting CH2O was extremely high. The current results can provide useful insights into developing future sensors for the detection of various gasses.

Synthesis, crystal structure, DFT, Hirshfeld surface analysis, energy frameworks and in-Silico drug-targeting PFKFB3 kinase of novel triazolequinoxalin derivative (TZQ) as a therapeutic Strategy against cancer

Overall, drug design is a dynamic and evolving field, with researchers constantly working to improve their understanding of molecular interactions, develop new computational methods, and explore innovative techniques for creating effective and safe medications. The process can involve steps such as the identification of targets, the discovery of lead compounds, lead optimization, preliminary testing, human trials, regulatory approval and finally post-marketing surveillance, all aimed at bringing a new drug from concept to market. In this article, the synthesis of the novel triazolequinoxalin (TZQ) 1-((1-hexyl-1H-1,2,3-triazol-5-yl)methyl)-3-phenylquinoxalin-2(1H)-one (4) is reported. The structure has been identified with a variety of spectroscopic methods (1H, 13C NMR, and LC-MS) and finally, the structure has been determined by X-ray diffraction (XRD) studies. The TZQ molecule has crystallized in the monoclinic space C2/c group with unit cell dimensions a = 41.201(2) Å, b = 10.6339(6) Å, c = 9.4997(4) Å, β = 93.904(4). The crystal structure is stabilized by intermolecular interactions (N–H ⋯ O and N–H … Cg) occurring within the molecule. The presence of these intermolecular interactions is evaluated through analysis of Hirshfeld surfaces (HS) and two-dimensional (2D) chemical fingerprints map. Additionally, energy frameworks were employed to identify the prevailing interaction energy influencing the molecular arrangement. Density Functional Theory (DFT) calculations were computed to establish concurrence between theoretical and experimental results. Furthermore, the HOMO-LUMO energy levels were determined using the B3LYP/6-31+G(d, p) level of theory. Finally, molecular docking was used to predict the anti-cancer activity of the compound (4) against PFKFB3 kinase and presented noticeable hydrophilic and hydrophobic interactions at the active site region.

How Matrixes Influence Room Temperature Ultralong Organic Phosphorescence: 4-Dimethylaminopyridine vs Carbazole Derivative.

How matrixes influence room temperature ultralong organic phosphorescence (RTUOP) in the doping systems is a fundamental question. In this study, we construct guest-matrix doping phosphorescence systems by using the derivatives (ISO2N-2, ISO2BCz-1, and ISO2BCz-2) of three phosphorescence units (N-2, BCz-1, and BCz-2) and two matrixes (ISO2Cz and DMAP) and systematically investigate their RTUOP properties. Firstly, the intrinsic phosphorescence properties of three guest molecules were studied in solution, in the pure powder state, and in PMMA film. Then, the guest molecules were doped into the two matrixes with increasing weight ratio. To our surprise, all of the doping systems in DMAP feature a longer lifetime but weaker phosphorescence intensity, while all of the doping systems in ISO2Cz exhibit a shorter lifetime but higher phosphorescence intensity. According to the single-crystal analysis of the two matrixes, resemblant chemical structures of the guests and ISO2Cz enable them to approach each other and interact with each other via a variety of interactions, thus facilitating the occurrence of charge separation (CS) and charge recombination (CR). The HOMO-LUMO energy levels of the guests match well with the ones of ISO2Cz, which also significantly promotes the efficiency of the CS and CR process. To our best knowledge, this work is a systematic study on how matrixes influence the RTUOP of guest-matrix doping systems and may give deep insight into the development of organic phosphorescence.

The Effect of the Interface Layer on the Electronic Parameters of the Light Emitting Electrochemical Cell (LEC) Device Based on Iridium (III) Complex that Calculated by Different Methods

We report a calculation of the electronic parameters and some optical measurement results of a light-emitting electrochemical cell (LEC), one of the most basic forms of electroluminescent films by modifying 4-(4-methoxy-N-naphthalen-1-ylanilino) benzoic acid (MA) as hole injection layer doped with an emissive layer that is ionic transition metal complex (Ir[dF(CF3)ppy]2(dtbpy))PF6-(Ir-iTMC). The electronic parameters of LEC device were computed using three different methods; Cheung and Cheung’s, Conventional Schottky and Norde, to evaluate the ideality factor (n), the barrier height () and the series resistance (Rs) of the LEC device. The formation on indium tin oxide (ITO) substrate was analyzed by Atomic Force Microscopy (AFM). The HOMO-LUMO energy level and electronic charge distribution of the MA molecule were computed theoretically using Chemissian software. The MA’s HOMO-LUMO energy level is determined to be EHOMO = −5.27 eV and ELUMO = −1.40 eV. The ITO surface has been modified with the Self-Assembled Monolayers (SAM) technique as an interlayer to improve the surface working function by simplifying hole injection from the ITO anode to the Hole Transport Layer (HTL) in the LEC. The Ir- iTMC complexes containing Π-conjugated bridging ligand shown better external quantum efficiency (EQE), reaching to 1.49%. The max luminance values of the bare-LEC and LEC-MA are measured as 145 cd m−2 and 1240 cd m−2, respectively.

Synthesis and Characterization of a One-Dimensional Malleable Spin-Crossover Polymer Complex Modified by Methoxy Polyethylene Glycol.

A novel one-dimensional malleable spin-crossover (SCO) complex {[Fe(MPEG-trz)3](BF4)2} has been successfully synthesized by molecular self-assembly between 4-amino-1,2,4-triazoles (MPEG-trz) grafted with a long flexible chain methoxy polyethylene glycol (MPEG) and metallic complex Fe(BF4)2•6H2O. The detailed structure information was illustrated by using FT-IR and 1H NMR measurements, while the physical behaviors of the malleable SCO complexes were systematically investigated by using magnetic susceptibility measurements using superconductivity quantum interference device (SQUID) and differential scanning calorimetry (DSC). This new metallopolymer exhibits a remarkable spin crossover transition behavior, between two spin quantum states (Fe2+ ions): high spin (HS) state (quintet state) and low spin (LS) state (singlet state), at a specific critical temperature with a slender hysteresis loop of 1 K. DFT computations revealed the partial rules of HOMO-LUMO energy levels and spin density distributions of different four-position substituted [Fe(1,2,4-triazole)3]2+ derivatives with different length of repeat units in polymer complexes. This can go a step further to depict the spin and magnetic transition behaviors of SCO polymer complexes. Furthermore, the coordination polymers possess an excellent processability due to an outstanding malleability, which can be easily shaped into a polymer film with spin magnetic switching properties.

Unprecedented formation of bis-calix[5]phyrins centrally linked with pyrene subunits

A [3+2] acid-catalyzed condensation of a tetra-functionalized pyrene fluorophore (4) with dipyrromethane dicarbinol (5) resulted in the unprecedented formation of two bis-calix[5]phyrins (bis-calix[5]-1 and bis-calix[5]-2). The solution state structure of both bis-calix[5]phyrins was found to be similar with slight variations as confirmed by NMR spectral studies. Interestingly, two different linkages between the pyrene subunits with dipyrromethane dicarbinols led to two different calix[5]phyrin systems. Although the optical features seem to be similar, the single crystal X-ray structure obtained for bis-calix[5]-1 provided the structural proof showing a non-planar, half-chair conformation with two meso-sp3 carbons. DFT studies were carried out to compare the HOMO-LUMO energy levels of both bis-calix[5]phyrins with the targetted conjugated bis-macrocycle (bis-N[Formula: see text]. Further, both the calix[5]-phyrins showed high Stokes shift (5404 cm[Formula: see text] and fluorescence quantum yield efficiency of around 90%.

Synthesis, photophysical, voltammetric, and DFT studies of 4-aminochalones

Aminochalcones, with a D-A-D architecture, were synthesized using Claisen-Schmidt condensation. The compounds were characterized by FTIR, melting point, HRMS, 1H, and 13C NMR spectroscopy and analyzed for UV–visible and fluorescence in different solvents (chloroform, acetonitrile, and methanol). All compounds showed absorption in the range of 330–420 nm and emission in the range of 400–550 nm. Both absorption and emission spectra exhibit bathochromic shifts from non-polar to polar solvents due to intramolecular charge transfer (ICT) interaction. Compounds 17 and 18 displayed mega Stokes shift (Δλ = 116–130 nm) in polar solvents giving these compounds a higher fluorescent character. Furthermore, HOMO-LUMO energy levels of compounds 17 and 18, evaluated through cyclic voltammetry, were found to be −5.10, −5.15, and −2.56, −2.99 respectively with band gap energy values 2.54–2.61 eV. The DFT and TD-DFT computations at the B3LYP functional along with a 6-31G(d,p) basis set for a comprehensive study of spectral data, molecular orbitals (HOMO, LUMO) analysis, and electrostatic potential (MEP) surfaces are also presented. The Computational studies support the experimental findings. The findings hint towards the optoelectronic efficiency of 17 and 18, and their potential for further optimization and use in optoelectronic devices.

A novel benzothiophene incorporated Schiff base acting as a “turn-on” sensor for the selective detection of Serine in organic medium

A novel fluorogenic sensor N-benzo[b]thiophen-2-yl-methylene-4,5-dimethyl-benzene-1,2-diamine (BTMPD) was synthesized and characterized by using spectroscopic methods including UV–visible, FT-IR, 1H NMR, 13C NMR, and mass spectrometry. The designed fluorescent probe, owing to its remarkable properties, behaves as an efficient turn-on sensor for the sensing of amino acid Serine (Ser). Also, the strength of the probe enhances upon the addition of Ser via charge transfer, and the renowned properties of the fluorophore were duly found. The sensor BTMPD shows incredible execution potential with respect to key performance indicators such as high selectivity, sensitivity, and low detection limit. The concentration change was linear ranging from 5 × 10−8 M to 3 × 10−7 M, which is an indication of the low detection limit of 1.74 ± 0.02 nM under optimal reaction conditions. Interestingly, the Ser addition leads to an increased intensity of the probe at λ = 393 nm which other co-existing species did not. The information about the arrangement and the features of the system and the HOMO-LUMO energy levels was found out theoretically using DFT calculations which is fairly in good agreement with the experimental cyclic voltammetry results. The fluorescence sensing using the synthesized compound BTMPD reveals the practical applicability and its application in real sample analysis.

Benzodithiophene (BDT) and benzodiselenophene (BDSe) isomers’ charge transport properties for organic optoelectronic devices

This study's primary objective is to give a thorough examination of the comparative charge transport and optoelectronic characteristics of all conceivable isomers of benzodithiophene (BDT) and benzodiselenophene (BDSe). Density Functional Theory (DFT) simulations have been performed on all the possible isomers of benzodithiophene (BDT) and benzodiselenophene (BDSe) and results are compared with corresponding experimental known isomers. The absorption energies and HOMO–LUMO energy levels were predicted by Time-Dependent Density Functional Theory (TD–DFT). Electron and hole Reorganization Energies (RE), Hole Extraction Potential (HEP) and Electron Extraction Potential (EEP), Ionization Potentials (IP) and Electron Affinities (EA) of all the isomers are reported. The UV–visible absorption of BDT and BDSe isomers are between 250–417 nm and 290–445 nm respectively. Comparatively, the simulated hole and electron reorganization energy of all the BDT and BDSe isomers have low values and hence expected applications in the field of Organic Optoelectronic Devices.

Novel thiourea derivative compounds: Thermal behavior, biological evaluation, Hirshfeld surfaces and frontier orbitals analyses, in silico ADMET profiling and molecular docking studies

This work reports synthesis and structural characterization of N-(allylcarbamothioyl)-2-chlorobenzamide (HL1, C11H11ClN2OS) and N-(allylcarbamothioyl)-2-methylbenzamide (HL2, C12H14N2OS). Structural characterization studies were made via elemental analysis, FT-IR, 1H NMR and single crystal XRD techniques. Thermal behavior of the synthesized compounds were investigated via TG/DTA. The cell similarity calculation was made. The Is value for HL1 and HL2 was found to be 86.9%. The HL1 and HL2 compounds were found to be thermally stable upto 136 and 132 °C, respectively. Anticancer activity of the compounds against MCF-7 breast cancer cells was studied via cell viability test and MTT. The role and the effect of different functional groups present in the compounds on anticancer activity were investigated. The IC50 values were found to be in the range 2.59 – 7.09 µmol.L−1. The HL1 compound showed good antitumor activity at 2.59 µmol.L−1 at 48 h. The Hirshfeld surfaces analyses of the compounds were made. The HOMO-LUMO energy levels of HL1 and HL2 were calculated. The compounds were thoroughly investigated in silico for their ADMET characteristics. The physicochemical, pharmacological, and ADMET characteristics of HL1 and HL2 were investigated together with drug similarity metrics. The compounds were observed to have good drug-like property. Furthermore, molecular docking experiments were carried out to evaluate the interactions between the compoundssynthesized in this study and BRAF (V600E -protein kinase). The acquired results revealed that the synthesized compounds had high binding affinity and inhibitory effect on the BRAF (V600E) protein kinase. The synthesized compounds can be considered potent anticancer agents, according to the data obtained using both in vitro and in silico techniques.

Unravelling the effect of donor-π-acceptor architecture in designing 1,3-indanedione based sensitizers for DSSC applications

• 1,3-indanedione-based electron-acceptor group has been employed in designing new sensitizers and theoretical calculations of the nine sensitizers, that are designed based on D-π-A architecture, were performed at DFT and TDDFT level. • HOMO-LUMO energy levels of the designed dyes are matching with the energy levels of titania and redox couples. • Frontier molecular orbital (FMO) analysis revealed intra-molecular charge transfer from the electron-donor to the 1,3-indanedione electron-acceptor. • Two-fold enhancement of dipole moment was observed in all sensitizers upon binding on (TiO 2 ) 9 nanocluster. • The simulated electronic spectra of free dyes and Dye@TiO 2 encompass the entire visible region. • Phenoxazine (POZ) and phenothiazine (PTZ) electron-donor moieties significantly improved the chemical reactivity and photophysical properties and therefore, corresponding RK4 and RK5 sensitizers are better than others. • The D-π-A architecture is found to be better than D-π-A-D architecture in the case of 1,3-indanedione-based sensitizers. Molecular engineering plays a vital role in the design of efficient organic sensitizers for DSSC applications. The study highlights the density functional theory calculations of nine organic sensitizers, designed based on a new 1,3-indanedione electron-acceptor cum anchoring group. The new sensitizers (RK1-9) have been designed by tailoring a modified 1,3-indanedione electron-acceptor with conventional electron-donors in the form of D-π-A architecture. Geometry optimization studies reveal that the RK7 & RK8 molecules have more twisted geometries. Similarly, the RK5 dye has the smallest energy gap of 2.34 eV compared to other dyes. LUMO energy levels of all the designed dyes are positive, found above the conduction band energy level, and the HOMO energy levels were more negative than the redox potentials. Calculated electrochemical parameters suggest that the dyes RK1-5 and RK9 inject the electrons efficiently into the conduction band of TiO 2 . Further, the Gibbs free energies of the dyes indicate that the RK4 and RK5 dyes regenerate much faster than the other dyes. The electronic absorption spectra of the RK dyes were steadily shifting towards the longer wavelength region with solvent polarity and further red-shifts upon adsorbing on the (TiO 2 ) 9 nanocluster. The LUMO and LUMO+1 wave functions of the RK dye@(TiO 2 ) 9 complexes are confined to the (TiO 2 ) 9 nanocluster, suggesting effective intramolecular charge transfer upon photo-excitation. Overall, the computational study demonstrates the significance of the 1,3-indanedione electron-acceptor and o the D-π-A architecture in the molecular design of new organic sensitizers for DSSC applications.

Peripherally mixed halogenated boron subphthalocyanines

The goal of this study was to develop mixtures of peripherally halogenated boron subphthalocyanines (BsubPcs) to explore these macrocycles as mixed alloys for applications within the organic electronic space. These halogenated BsubPc mixtures were synthesized by reacting mixtures of commercially available phthalonitriles, namely 4,5-dichlorophthalonitrile (Cl2-pn), 4,5-difluorophthalonitrile (F2-pn), tetrachlorophthalonitrile (Cl4-pn), and tetrafluorophthalonitrile (F4-pn), with boron trichloride (BCl[Formula: see text] to achieve mixed halogenation upon formation of the BsubPcs. More specifically, as named, Cl2-pn + F2-pn and Cl4-pn + F4-pn mixtures were used to form Cl-Cl[Formula: see text]F[Formula: see text]BsubPc and Cl-Cl[Formula: see text]F[Formula: see text]BsubPc, respectively. To establish a firm synthetic methodology, the reaction kinetics of forming the BsubPc mixtures from their respective phthalonitrile mixtures were compared to the kinetics of the standard procedures forming the individual BsubPcs, for example, Cl-Cl[Formula: see text]BsubPc from Cl4-pn. As we use BCl3 to form the BsubPcs, the axial bond is in general chloride, but we observed again random fluoride axial exchange, and therefore moved to the second step to have complete axial fluorination. Crude mixed halogenated BsubPcs were sublimed at high purities to enable physical characterization, including a study of UV-Vis absorption spectra differentiation, and cyclic (CV) and differential pulse voltammograms (DPV) electrochemical differentiation. We also did density functional theory (DFT) calculations for points of physical properties comparison. The comparison points are together with fully peripherally chlorinated Cl[Formula: see text]BsubPcs and fluorinated F[Formula: see text]BsubPcs. Given the outcomes, we foresee in future studies the ability to tune different ratios of peripherally halogenated BsubPc mixtures via synthetic tools, to enable tuning of the HOMO LUMO energy levels, which could consequently tune their application and performance in organic electronics.

High-performance non-fullerene acceptor-analogues designed from dithienothiophen [3,2-b]-pyrrolobenzothiadiazole (TPBT) donor materials.

Density functional theory (DFT) method was employed to investigate the electronic structure properties, excited state dynamics, charge transfer, and photovoltaic potential of benzo [1,2,5] thiadiazole fused to 3,7-dimethyl-3a,6,7,7b-tetrahydro-5H-thieno[2',3':4,5]thieno[3,2-b]pyrrole to form 3,9,12,13-tetramethyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2″,3″:4,5]pyrrolo[3.2-g]thieno[2',3':4,5]thieno[3,2-b]indole as the acceptor (A), bridge with thiophene as π-spacer to the donor moieties (D) which are 2,3-dihydrobenzo [b]thiophene-6-carboxylic acid (M4) and functionalized R, M1, M2, M3, and M5 to give a D-π-A-π-D. Here is the reverse combination for our molecules: the A-π-D-π-A type of chromophore configuration. It is also observed that tuning the dono-bridge configuration significantly increases the ease of charge transfer as the energy gap decreases in the order of 1.29 eV in M4 < 1.59 eV in M3 < 1.67 eV < 1.99 in M2 and 2.06 eV. The reorganization energy (RE) of M3 (0.0031) and M5 (0.0031) indicates an increase in the order of M3 > M5 > R > M2 > M4 > M1. The HOMO-LUMO indicates that the reactivity decreased, while the stability increased for the reference R at 0.990 eV, compared to the designed molecules M1-M5, with M1 being the least stable at 0.970 eV, while M4 exhibited the highest stability at 1.550 eV. The stability of the designed molecule decreased in the order of M4:1.550 > M3:1.257 > M5:1.197 > M2:1.010 > M1:0.970. Therefore, all results point to the electron-deficient core as an effective end-capped electron acceptor in M1-M5 compounds. As the ideal pair for successfully optimizing optoelectronic properties by reducing the HOMO-LUMO energy levels, reorganization energy, and binding energy and enhancing the absorption maximum and open-circuit voltage values in these designed molecules. DFT and TDDFT calculations were performed with Gaussian 16 program. The modelled compounds were optimized fully using the CAM-B3LYP, WB97XD, B3LYP, and MPW1PW91 functionals with the 6-31 G (d,p) basis set. The graphs for the density of states were plotted using the PyMOlyze software. Other molecular properties like the transition density matrix (TDM) and electron density difference maps (EDD) were rendered via the Multiwfn software.

Optoelectronic design and charge transport properties of Benzodifuran (BDF) isomers for organic electronic devices: DFT/TD-DFT insights

The primary goal of this work is to provide a comprehensive analysis of the charge transport and optoelectronic characteristics of all the isomers of benzodifuran (BDF) for organic electronic devices in order to suggest qualified materials/candidates for organic photovoltaic devices. Density functional theory (DFT) calculations were performed for all possible isomers of BDF and results are compared with corresponding experimental known isomers. Time Dependent-Density Functional Theory (TD-DFT) is used for the calculation of the absorption and HOMO-LUMO energy levels. To characterize the electronic charge transport state in these isomers, the ionization potentials (IP), reorganization energies (hole and electron), and electron affinities (EA) of all the isomers are investigated. Comparatively, all the BDF isomers are having low electron and hole reorganization energies and hence they can be used in the organic electronic material fabrication.

Computational and experimental investigation on biological and photophysical properties of high yielded novel aryl-substituted pyrazolone analogue

A series of new aryl-substituted pyrazolone derivatives 5(a-h) were synthesised via the Baylis-Hillman acetate reaction with pyrazolones and tested for antifungal, antibacterial, and antioxidant properties in vitro. Among the tested molecules 5d and 5e show good in vitro antifungal and antibacterial activities due to the presence of fluorine, which enhances the absorption rate by increasing lipid solubility and improves the pharmacological activity. It is also evident from the results obtained from structure-activity relationship (SAR) studies. Further, the photophysical properties of synthesized compounds were theoretically estimated using the ab-intio technique. The ground state optimization and HOMO–LUMO energy levels are calculated using the DFT-B3LYP-6-311 basis set. Using the theoretically estimated HOMO–LUMO value, global chemical reactivity descriptor parameters are estimated, and the result shows that compounds 5d and 5e have a higher electronegative and electrophilicity index than other molecules. Overall results suggest that, fluorine substituted pyrazolone derivatives show good photophysical, SAR, and biological properties.

Water-soluble β-cyclodextrin based turn-on amplifying fluorescent probes for sensitive and selective detection of Hg2+/Hg+ ions

In this work, fluorescent β- cyclodextrin (β-CD) based probes containing naphthalimide group were synthesized to realize the specific recognition of Hg2+/Hg+ in aqueous system. Firstly, three small fluorescent molecules (N1, N2 and N3) with -NH2 groups were synthesized from 4-bromo-1, 8-naphthalene anhydride. Secondly, CHCCH2- group was introduced into β-CD by Williamson ether formation reaction. Finally, the target probes (β-CD-PI, β-CD-PY and β-CD-TP) were obtained by Amino-Yne click reaction. These probes can efficiently recognize Hg2+/Hg+. β-CD-PI emits bright yellow fluorescence after binding with Hg2+/Hg+, which is a turn-on fluorescent probe. When the Hg2+/Hg+ concentration exceeds 26 μM, the fluorescence intensity amplifies sharply (20 folds). The hydrophobic parts of the probes aggregated together to form a micelle-like structure due to complexation with Hg2+/Hg+, resulting in special micelle-sensitizing properties. Meanwhile, the HOMO-LUMO energy levels of the probes were calculated by cyclic voltammetry (CV). The probe is expected to be used for the detection of Hg2+/Hg+ in aqueous solutions without any organic solvents.

Modifying transparent electrode with conjugated organic semiconductor hole transport material as interface for enhancing performance of organic solar cell

Indium tin oxide (ITO) is used as a substrate was covered with 4-[4-(4-methoxy-N-naphthalen-2-ylanilino) phenyl] benzoic acid (MNA) as a self-assembled monolayer (SAM). Poly(3-hexylthiophene) (P3HT) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6) C61 (PCBM) were mixed and used as a donor–acceptor in organic solar cell (OSC). The MNA (SAM) layer is used as an interface instead of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS) for hole injection. The HOMO-LUMO energy level of MNA-SAM molecule and the electronic charge distribution were calculated theoretically using Chemissian software. The HOMO-LUMO energy level of the MNA is calculated as EHOMO = −5.10 eV and ELUMO = −1.60 eV. The OSC modified with MNA showed an efficient performance in the absence of PEDOT: PSS as hole transport layer. The annealing of the ITO/SAM/P3HT: PCBM films at different temperatures are also investigated to study the effect of reducing defects. The interface structures of the organic semiconductor layer on ITO were characterized by Atomic Force Microcopy (AFM). In addition, Kelvin Probe Microscopy (KPM) is used to understand how the annealing changes the surface potential energy of the ITO/SAM substrate. Using the KPM method, which measures the surface potential energy of the films, the energy bands of the ITO were increased to maximum 5.09 eV. The ITO/SAM/P3HT: PCBM film's surface potential was determined to be 0.18 eV after being annealed at 80 °C. The surface potential of the modified films was discovered to be 0.33 V and 0.39 V when the annealing temperature was raised from 80 °C to 120 °C and 160 °C. The maximum device efficiency was demonstrated by the ITO/SAM/P3HT: PCBM film after an hour of annealing at 160 °C.

Highly Luminescent MOF and Its In Situ Fabricated Sustainable Corn Starch Gel Composite as a Fluoro-Switchable Reversible Sensor Triggered by Antibiotics and Oxo-Anions.

Frequent use of antibiotics and the growth of industry lead to the pollution of several natural resources which is one of the major consequences for fatality to human health. Exploration of smart sensing materials is highly anticipated for ultrasensitive detection of those hazardous organics. The robust porous hydrogen bonded network encompassing a free-NH2 moiety, Zn(II)-based metal-organic framework (MOF) (1), is used for the selective detection of antibiotics and toxic oxo-anions at the ppb level. The framework is able to detect the electronically dissimilar antibiotic sulfadiazine and nitrofurazone via fluorescence "turn-on" and "turn-off" processes, respectively. The antibiotic-triggered reversible fluoro-switching phenomena (fluorescence "on-off-on") are also observed by using the fluorimetric method. An extensive theoretical investigation was performed to establish the fluoro-switching response of 1, triggered by a class of antibiotics and also the sensing of oxo-anions. This investigation reveals that the interchange of the HOMO-LUMO energy levels of fluorophore and analytes is responsible for such a fluoro-switchable sensing activity. Sensor 1 showed the versatile detection ability which is reflected by the detection of a carcinogenic nitro-group-containing drug "roxarsone". In view of the sustainable environment along with quick-responsive merit of 1, an in situ MOF gel composite (1@CS; CS = corn starch) is prepared using 1 and CS due to its useful potential features such as biocompatibility, toxicologically innocuous, good flexibility, and low commercial price. The MOF composite exhibited visual detection of the above analytes as well as antibiotic-triggered reversible fluoro-switchable colorimetric "on-off-on" response. Therefore, 1@CS represents a promising smart sensing material for monitoring of the antibiotics and oxo-anions, particularly appropriate for the real-field analysis of carcinogenic drug molecule "roxarsone" in food specimens.

The effect of nitrogen-rich ionic liquid [EMIMDCA] on the electronic structure of solid polymer electrolyte (PEO-LiTFSI).

In our work, the ab-initio methods based on density functional theory (DFT) formalism are used to investigate the effect of nitrogen-rich ionic liquid (EMIMDCA; 1-ethyl-3-methylimidazolium dicyanamide) on the electronic structure of SPE (solid polymer electrolyte) (PEO-LiTFSI) electrolyte with B3LYP method and LANL2DZ basis set. The differences in energy levels of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), i.e., energy gap ([Formula: see text]) of the PEO, [EMIMDCA], SPE, and ionogel (IG), are found 5.74, 6.59, 3.25, and 2.80eV, respectively. In SPE, the reduced band gap ([Formula: see text]) is due to the transportation of cation of LiTFSI (Li+ ion). Finally, the reduced band gap of IG confirms that IL enhances the transportation of cation of LiTFSI (Li+ ion) through the oxygen atom of PEO. The global and local chemical descriptors and electrochemical stability windows (ESWs) are calculated using the HOMO-LUMO energy levels. Partial charge analysis is studied by Mulliken population analysis and molecular electrostatic potential surface.