Molecular Modeling of Pentacyclic Aromatic Bislactam-Based Small Donor Molecules by Altering Auxiliary End-Capped Acceptors to Elevate the Photovoltaic Attributes of Organic Solar Cells.

Small-molecule (SM)-based organic solar cells (OSCs) have dominated the photovoltaic industry on account of their efficient optical and electronic properties. This quantum mechanical study addresses a DFT study of pentacyclic aromatic bislactam (PCL)-based small molecules for extremely proficient OSCs. Five novel small molecules (PCLM1-PCLM5) retaining the A-π-A-π-D-π-A-π-A arrangement were fabricated from the reference PCLR. At the MPW1PW91/6-31G** level of theory, detailed profiling of these novel molecules was performed by accurately following DFT, along with the time-dependent density functional theory (TD-DFT) hypothetical simulations to analyze the UV-visible absorption (λmax), light-harvesting efficiency (LHE), dipole moment (µ), fill factor (FF), open-circuit voltage (V OC), power conversion efficiency (PCE), frontier molecular orbitals (FMOs), binding energy (E b), density of states (DOS), electrostatic potential (ESP), and transition density matrix (TDM) plots. Alteration of peripheral acceptors in all of the molecular structures drastically modified their charge-transfer properties, such as a strong light-harvesting capability in the range of 0.9993-0.9998, reduced exciton E b (from 0.34 to 0.39 eV), a reduced bandgap (E g) in the range of 1.66-1.99 eV, an elevated λmax (775-959 nm) along with a higher µ in the solvent phase (1.934-7.865 D) when studied in comparison with PCLR, possessing an LHE of 0.9986, an E b of 0.40, an E g 2.27 eV, λmax at 662 nm, and a µ of 0.628 D. The FMO analysis revealed the uniform dispersal of charge density entirely along the highest occupied (HOMO) and lowest unoccupied (LUMO) molecular orbitals in newly constructed moieties. Electron as well as hole mobility rates, V OC, FF, and PCE of all novel molecules (PCLM1-PCLM5) were higher as compared with those of PCLR, ultimately making them exceptional candidates for solar devices. Focusing on the outcomes, terminal acceptor modification was found to be a suitable method for the development of highly tuned OSCs in the future.

Symmetrical end-capped molecular engineering of star-shaped triphenylamine-based derivatives having remarkable photovoltaic properties for efficient organic solar cells.

In the present research work, four novel triphenylamine (TPA)-based acceptor molecules have been architectured to step up the solar efficiency of organic solar cells. The four designed molecules abbreviated as T1-T4 have a common TPA donor core and different strong electron pulling peripheral acceptor groups connected through thiophene spacers. Computational simulations of T1-T4 were performed to compute and compare their optoelectronic properties with well-known reference molecule S(TPA-DPP) designated as R in the current project. For geometric optimizations of designed molecules, MPW1PW91 functional along with a basis set of 6-31G (d, p) was enforced. Assessment of the optoelectronic features of newly reported 3-D molecules (T1-T4) has been executed through density functional theory (DFT) and time-dependent density functional theory (TD-DFT) computations. Transition density matrix (TDM) and density of state (DOS) evaluations were performed for the investigation of exciton dynamics and electronic contribution between two states. All the derived molecules exhibited admirable photovoltaic features when compared to that of the reference molecule. Amidst all these newly modified molecules, T3 manifested itself as the finest candidate having the least energy band gap (1.84 eV) and the highest λmax (865 nm) in dichloromethane solvent. Also, T1 molecule has the lowest hole reorganization energy (0.0036 eV) value. These designed candidates (T1-T4) confirm that peripheral acceptor tempering is an effectual approach for the attainment of the desirable optoelectronic properties.

Synergistic end-capped engineering on non-fused thiophene ring-based acceptors to enhance the photovoltaic properties of organic solar cells.

In this study, a series of non-fused thiophene ring-based small molecular acceptors (4T1-4T7) of A-D-A type are developed by the replacement of the end-groups of the 4TR molecule. The optoelectronic characteristics of the 4TR and 4T1-4T7 molecules are investigated employing the MPW1PW91 functional with the 6-31G (d,p) basis set, and solvent-state computations are studied using the TD-SCF. All the parameters estimated in this research are improved to a substantial level for the developed molecules as compared to the 4TR molecule, e.g. all the newly developed molecules have shown a red shift in their maximum absorption (λ max) and a reduced bandgap compared to the 4TR molecule, with ranges of 646 nm to 692 nm (in chlorobenzene solvent) and 2.34 eV to 2.47 eV, respectively. The reorganization energies of electron and hole mobility for almost all developed molecules are smaller than those for the 4TR molecule, with ranges of 0.00766-0.01034 eV and 0.01324-0.01447 eV, respectively. Hence, all the modified chromophores exhibit better charge capabilities than the 4TR molecule. The charge mobility of almost all the developed molecules is improved because of their reduced reorganization energies. The 4T2 molecule has minimum RE values for both electrons (0.00766) and holes (0.01324). The V OC values of all acceptor molecules are calculated with respect to the PTB7-Th donor. An elevation in V OC and FF values is exhibited by the 4T5 and 4T7 molecules. As a result, these end-capped engineered molecules should be proposed for the future manufacturing of highly efficient organic solar cells.

End-capped group modification on cyclopentadithiophene based non-fullerene small molecule acceptors for efficient organic solar cells; a DFT approach.

Four acceptor-donor-acceptor (A-D-A) type cyclopentadithiophene core-based non-fullerene small acceptor molecules were designed with the objective to improve the proficiency of photovoltaic cells. A comprehensive density functional theory (DFT) analysis was done by employing B3LYP functional with 6-31G(d,p) basis set to study optoelectronic properties of R as well as M1-M4 molecules, while the time-dependent self-consistent field (TDSCF) was utilized to analyze their excited state calculations. Several essential characteristics must be refined in order to enhance the efficiency of small molecular acceptors, i.e., the density of states (DOS), HOMO-LUMO band gap, transition density matrix (TDM), dipole moment, reorganization energy, light-harvesting efficiency, and open-circuit voltage, etc. In comparison to the R molecule, all the derived molecules show better maximum absorption (in chloroform solvent) with a range of 886-951 nm and a smaller band gap with a range of 1.65-1.55 eV M2 retains the least exciton binding energy of 0.24 eV, and amongst all the investigated molecules M3 molecule has the least interaction coefficient values so, it possesses better charge transport probability. The reorganization energy values in eV for both electron (0.00579) and hole (0.00737) are the least for M3 molecule, so this molecule exhibits better charge mobility for electron and hole. VOC of R and M1-M4 molecule was calculated by theoretically computing the values of their complexes with PTB7-Th donor molecule.

Tuning of diphenylamine subphthalocyanine based small molecules with efficient photovoltaic parameters for organic solar cells.

In this theoretical research, four donor molecules with diphenylamine subphthalocyanine (SubPc) as a common core, flanked with various electron-withdrawing groups at the central position containing Methyl-2-cyanoacrylate in C1, 3-methyl-5-methylene-2-thioxothiazolidin-4-one in C2, 2-(2-methylene-1-oxo-1H-inden-3(2H)-ylidene) malononitrile in C3, and Methyl-2-(5-methylene-4-oxo-2-thioxothiazoliden-3-yl) acetate in C4, have been designed. To analyze photovoltaic applications of all the studied molecules (C1-C4), quantum chemical simulations i.e., absorption profiles, frontier molecular orbitals (FMOs), the density of states (DOS), transition density matrix, and open-circuit voltage, have been performed availing DFT and TD-DFT approach with selected B3LYP functional /6-31G (d,p) level of theory. Among all the substituted molecules, C3 revealed highest molar absorption coefficient (601 nm), efficient electron density transfer in FMOs, and lowest energy band gap (1.70 eV) owing to the elongated conjugation along with the compelling electron-withdrawing nature of its axial acceptor moiety. All investigated molecules showed profound peaks in the visible region of the absorption spectrum as well as had low electron and hole mobilities in contrast to that of the reference (R) molecule. The observed binding energies (in electron-volt) of C2 (0.67), C3 (0.10), and C4 (0.47) molecules are found to be lower than R. Hence, these findings reveal that all designed candidates (C1-C4) could be effective and favorable applicants to enhance the energy efficiency of small molecule (SM) based organic solar cells (OSCs).

Facile Synthesis of Gold Nanoparticles for Anticancer, Antioxidant Applications, and Photocatalytic Degradation of Toxic Organic Pollutants.

In the current study, a facile, rapid, and ecologically safe photosynthesis of gold nanoparticles (AuNPs) that remained stable for 3 months is reported to advocate the main aspects of green chemistry, such as safer solvents and auxiliaries, and the use of renewable feedstock. Zi-AuNPs were phytosynthesized by the aqueous extract of Ziziphus spina-christi leaves, and numerous techniques were employed for their characterization. The results demonstrated the successful phytofabrication of crystalline AuNPs with brownish-black color, spherical nanoparticles with a size between 0 and 10 nm, a plasmon peak at 540 nm, and a surface charge of -25.7 mV. Zi-AuNPs showed an effective photodegradation efficiency (81.14%) against malachite green and a good recycling capacity of 69.2% after five cycles of regeneration. The cytotoxicity test by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay signified a high anticancer efficiency for both Zi-AuNPs and Z. spina-christi extract against human breast cancer cells (MCF7 cell line) with IC50's of 48 and 40.25 µg/mL, respectively. Highly efficient antioxidant capabilities were proven with 2,2-diphenyl-1-picrylhydrazyl (DPPH) removal percentages of 67.5% for Zi-AuNPs and 92.34% for Z. spina-christi extract.

Synthesis, Characterization and Evaluation of Supercapacitive Response of Dodecylbenzenesulphonic Acid (DBSA) Doped Polypyrrole/Zirconium Dioxide Composites.

An in-situ chemical oxidative method was used to effectively synthesize a promising supercapacitor material based on PPy/ZrO2 composites. The synthesized materials were characterized by different analytical techniques, such as UV/visible (UV/Vis) spectroscopy, Fourier-transform infra-red spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The inclusion of ZrO2 into the PPy matrix was verified by vibrational spectra and structural analyses. The (TGA) results showed that incorporating ZrO2 into the polymeric matrix improved its thermal stability. In addition, the electrochemical properties of the synthesizedmaterials were investigated byusing cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD). The PPy/ZrO2 composite demonstrated excellent super capacitive performance, and high specific capacity of 337.83 F/g, with an exceedingly high energy density of 187.68 Wh/kg at a power density of 1000 W/kg. The composite materials maintain good stability after 1000 charge and discharge cycles, with 85% capacitance retention. The PPy/ZrO2 possesses a high capacitance, an attractive micro-morphology, and a simple synthesis method. The findings indicate that the PPy/ZrO2 composite could be a promising electrode material for high-performance supercapacitor applications.

Determination of the Tensile Properties and Biodegradability of Cornstarch-Based Biopolymers Plasticized with Sorbitol and Glycerol.

In this study, the effects of various quantities of sorbitol and glycerol plasticizers (0%, 30%, 45%, and 60%) on cornstarch-based film were examined to develop a novel polymer for usage with biodegradable materials. The film was prepared using the casting process. According to the test findings, the application of the plasticizer concentrations affected the thickness, moisture content, and water absorption of the film. When plasticizer concentrations were increased to 60%, the tensile stress and Young's modulus of plasticized films dropped regardless of plasticizer type. However, the thin film with addition of 30% sorbitol plasticizer demonstrated a steady value of Young's modulus (60.17 MPa) with an increase in tensile strength (13.61 MPa) of 46%, while the lowest combination of tensile strength and Young's modulus is the film that was plasticized with 60% glycerol, with 2.33 MPa and 16.23 MPa, respectively. In summary, the properties and performance of cornstarch-based film were greatly influenced by plasticizer types and concentrations. The finest set of features in this research appeared in the film plasticized with 30% sorbitol, which achieved the best mechanical properties for food packaging applications.

Tuning the optoelectronic properties of ZOPTAN core-based derivatives by varying acceptors to increase efficiency of organic solar cell.

In this theoretical study, quantum chemical analysis of five novel non-fullerene donor molecules designed from recently reported highly efficient (11.5%) donor molecule P2TBR, containing non-fused ring central thiophene-benzene-thiophene core, 2-D benzodithiophene donors, and end capped 3-methylrhodanine acceptors, has been performed to evaluate the photovoltaic parameters and their application in organic solar cells. These donor molecules consist of centrally introduced acrylonitrile acceptors in between thiophene-benzene-thiophene core of P2TBR, namely M1. Compounds M2-M5 were designed from M1 containing ZOPTAN core, through peripheral acceptor group modification by 2-methylenemalononitrile (M2), methyl 2-cyanoacrylate (M3), 2-(5,6-difluoro-2-methylene-3-oxo-2,3-dihydroinden-1-ylidene) malononitrile (M4), and 2-(3-methyl-5-methylene-4-oxothiazolidin-2-ylidene) malononitrile (M5). DFT and TD-DFT simulations of all molecules including reference were carried out using MPW1PW91 functional in conjunction with 6-31G (d, p) basis set. Optoelectronic properties, exciton dynamics, electron density distribution pattern, and charge mobility were further analyzed by absorption spectra, TDM plots, frontier molecular orbitals (FMO) analysis, and calculation of reorganization energies, respectively. Results reveal that central addition and end capped modification of acceptors in designed molecules proved to be effective strategy to finely tune the electronic and optical characteristics. Amongst all designed molecules, M4 exhibited improved opto-electronic parameters such as highest maximum absorption (695 nm) in chloroform, least band gap (2.24 eV), lowest values of λh (0.0034 eV), and λe (0.0054 eV) and lowermost binding energy (0.46 eV), because of mutual effect of extended pi-conjugation and significant electron pulling nature of terminal acceptors. Moreover, higher dipole moment, lower values of hole reorganization energy, and improved Voc of designed molecules than reference (R) make them efficient donors to enhance PCE of photovoltaic materials.

A Study on Machine Learning Methods' Application for Dye Adsorption Prediction onto Agricultural Waste Activated Carbon.

The adsorption of dyes using 39 adsorbents (16 kinds of agro-wastes) were modeled using random forest (RF), decision tree (DT), and gradient boosting (GB) models based on 350 sets of adsorption experimental data. In addition, the correlation between variables and their importance was applied. After comprehensive feature selection analysis, five important variables were selected from nine variables. The RF with the highest accuracy (R2 = 0.9) was selected as the best model for prediction of adsorption capacity of agro-waste using the five selected variables. The results suggested that agro-waste characteristics (pore volume, surface area, agro-waste pH, and particle size) accounted for 50.7% contribution for adsorption efficiency. The pore volume and surface area are the most important influencing variables among the agro-waste characteristics, while the role of particle size was inconspicuous. The accurate ability of the developed models' prediction could significantly reduce experimental screening efforts, such as predicting the dye removal efficiency of agro-waste activated carbon according to agro-waste characteristics. The relative importance of variables could provide a right direction for better treatments of dyes in the real wastewater.

Ginger (Zingiber Officinale)-derived nanoparticles in Schistosoma mansoni infected mice: Hepatoprotective and enhancer of etiological treatment.

BACKGROUND: Nanotechnology has been manufactured from medicinal plants to develop safe, and effective antischistosmal alternatives to replace today's therapies. The aim of the study is to evaluate the prophylactic effect of ginger-derived nanoparticles (GNPs), and the therapeutic effect of ginger aqueous extract, and GNPs on Schistosoma mansoni (S. mansoni) infected mice compared to praziquantel (PZQ), and mefloquine (MFQ). METHODOLOGY/PRINCIPAL FINDINGS: Eighty four mice, divided into nine different groups, were sacrificed at 6th, 8th, and 10th week post-infection (PI), with assessment of parasitological, histopathological, and oxidative stress parameters, and scanning the worms by electron microscope. As a prophylactic drug, GNPs showed slight reduction in worm burden, egg density, and granuloma size and number. As a therapeutic drug, GNPs significantly reduced worm burden (59.9%), tissue egg load (64.9%), granuloma size, and number at 10th week PI, and altered adult worm tegumental architecture, added to antioxidant effect. Interestingly, combination of GNPs with PZQ or MFQ gave almost similar or sometimes better curative effects as obtained with each drug separately. The highest therapeutic effect was obtained when ½ dose GNPs combined with ½ dose MFQ which achieved 100% reduction in both the total worm burden, and ova tissue density as early as the 6th week PI, with absence of detected eggs or tissue granuloma, and preservation of liver architecture. CONCLUSIONS/SIGNIFICANCE: GNPs have a schistosomicidal, antioxidant, and hepatoprotective role. GNPs have a strong synergistic effect when combined with etiological treatments (PZQ or MFQ), and significantly reduced therapeutic doses by 50%, which may mitigate side effects and resistance to etiological drugs, a hypothesis requiring further research. We recommend extending this study to humans.

Synthesis of bioactive quinazolin-4(3H)-one derivatives via microwave activation tailored by phase-transfer catalysis.

A series of nine new 2,3-disubstituted 4(3H)-quinazolin-4-one derivatives was furnished starting from the 2-propyl-4(3H)-quinazo-line-4-one (2). The reinvestigation of the key starting quinazolinone 2 was performed under microwave irradiation (MW) and solvent-free conditions. Combination of MW and phase-transfer catalysis using tetrabutylammonium benzoate (TBAB) as a novel neutral ionic catalyst was used for carrying out N-alkylation and condensation reactions of compound 2 as a simple, efficient and eco-friendly technique. The structure of the synthesized compounds was elucidated using different spectral and chemical analyses. In vitro antimicrobial activity of the compounds was investigated against four bacterial and two fungal strains; very modest activity was achieved. Some of the synthesized compounds were screened for their antitumor activity against different human tumor cell lines. The screened compounds exhibited a significant antitumor activity on some of the cancer cell lines, melanoma (SK-MEL-2), ovarian cancer (IGROV1), renal cancer (TK-10), prostate cancer (PC-3), breast cancer (MCF7) and colon cancer (HT29). The most active, even more active than the reference 5-fluorouracil, were found to be ethyl 4-[(4-oxo-2-propylquinazolin-3(4H)-yl)methyl]benzoate (3c), 3-{2-[6-(pyrrolidin-1-yl-sulfonyl)-1,2,3,4-tetrahydroquinoline]-2-oxoethyl}-2-propylquinazolin--4(3H)-one (3e), N'-[(E)-(2H-1,3-benzodioxo-5-yl)methylidene]-2-(4-oxo-2-propylquinazolin-3(4H)-yl)acetohydrazide (10a), N'-[(E)-(4-hydroxyphenyl)methylidene]-2-(4-oxo-2-propylquinazo-lin-3(4H) -yl)acetohydrazide (10b) and N'-[(E)-(4-nitrophenyl)methyl idene]-2-(4-oxo-2-propylquinazolin-3(4H)-yl)acetohydrazide (10c).

Optical study of a static benzoxazinone derivative doped poly (vinyl) pyrrolidone - Poly(vinyl) alcohol blend system.

Blends with composition 50/50(wt/wt%)poly(vinyl)alcohol (PVA)/poly(vinyl) pyrrolidone (PVP) doped with different weight ratios from benzoxazinone derivative (BZ) were prepared by casting solution technique. The optical absorption was recorded at room temperature in the wavelength range of 190-1100nm. Tauc's plots revealed direct allowed transition with optical band gap, Eopt, of 5.20eV for blend film. Under addition of benzoxazinone, the optical energy value decreased until 2.60eV for 12wt% BZ blend system. Optical parameters such as refractive index, dielectric constant, dielectric loss and color constants were determined. Benzoxazinone molecules have a significant effect on optical parameters.