Waste paper derived three-dimensional carbon aerogel integrated with ceria/nitrogen-doped reduced graphene oxide as freestanding anode for high performance and durable microbial fuel cells

Bioprocess and Biosystems Engineering - Despite the green energy generation with low cost compared to conventional fuel cells, microbial fuel cells (MFCs) still suffer with anode related...     

Quantum chemical study in the direction to design efficient donor-bridge-acceptor triphenylamine sensitizers with improved electron injection

The ground state geometries have been computed by using density functional theory. The excitation energies for dye sensitizers were performed by using time dependant density functional theory. The polarizable continuum model (PCM) has been used for evaluating bulk solvent effects at all stages. The calculations have been carried out in methanol according to the experimental set up. The long-range-corrected functional (PCM-TD-LC-BLYP) underestimate the absorption spectrum of parent molecule while PCM-TDBHandHLYP is in good agreement with the experimental data. The highest occupied molecular orbital (HOMO) is delocalized on TPA moiety while lowest unoccupied molecular orbital (LUMO) is localized on anchoring group, conjugated chain and the benzene ring near to the anchoring group. The LUMO energies of all the investigated dyes are above the conduction band of TiO(2), HOMOs are below the redox couple and HOMO-LUMO energy gaps of studied dyes are smaller compared to TC4. The 1 and 3 are 7 and 12?nm blue shifted while 2 and 4 are 25 and 22?nm red shifted, respectively compared to TC4. The trend of electron injection (ΔG(inject)), relative electron injection (ΔG (r) (inject) ()), and electronic coupling constant (|VRP|) has been observed as 3?>?1?>?4?>?2?>?TC4. The improved ΔG(inject), |VRP| and light harvesting efficiency (LHE) of new designed sensitizers revealed that these materials would be excellent sensitizers. The broken coplanarity between the benzene near anchoring group having LUMO and the last benzene attached to TPA unit in 1-4 consequently would hamper the recombination reaction.     

Effect of donor strength of extended alkyl auxiliary groups on optoelectronic and charge transport properties of novel naphtha[2,1-b:6,5-b′]difuran derivatives: simple yet effective strategy

The present study spotlights the designing of new derivatives of 2,7-bis (4-octylphenyl) naphtho [2,1-b:6,5-b′] difuran (C8-DPNDF) by substituting the alkyl groups (methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups) at para position. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods are employed to optimize the molecular structures in ground and first excited states, respectively. Several electro-optical properties including hole/electron reorganization energies (λ_h/λ_e), electron affinities (EAs), ionization potentials (IPs), molecular electrostatic potentials (MEP), and frontier molecular orbitals (FMOs) have been evaluated. Furthermore their transfer integrals and intrinsic mobilities values have also been calculated. From this study, it is found that hole mobility of octyl containing derivative is raised to 4.69 cm² V^?1 s^?1. Moreover with attaching octyl group, hole transfer integral values have also been enhanced in newly designed derivatives. The balanced hole and electron reorganization energies, and improved transfer integrals lead to enhanced mobility in derivatives with octyl group, highlighting them as an efficient hole transfer material. Unlike the other electro-optical properties, the intrinsic hole mobility has increased because of transfer integral values of octyl containing derivative C8-DPNDF due to the dense and close crystal packing of C8-DPNDF. However, photostability of furan-based materials has not changed by increasing length of extended alkyl chain. Thus our present investigation highlights the importance of alkyl auxiliary groups that are often neglected/replaced with simple methyl group to save computation costs.

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Graphical Abstract The hole and electron reorganization energies of naphtho[2,1-b:6,5-b']difuran derivatives

     

Quantum chemical investigations aimed at modeling highly efficient zinc porphyrin dye sensitized solar cells

Zinc tetraphenylporphyrin (ZnTPP) was modified by a push-pull strategy and then density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed for the resulting derivatives. The smallest HOMO-LUMO energy gaps were found in ZnTPP-6 and ZnTPP-7, which had nitro substituents and a conjugated chain, while the largest was observed for ZnTPP-5. The energy gaps of all of the systems designed in this work were smaller than that of ZnTPP. Clear intramolecular charge transfer was observed from donor to acceptor in ZnTPP-6 and ZnTPP-7, which had nitro groups at positions R8, R9, and R10, as well as in ZnTPP-3 and ZnTPP-4, which had cyano groups at those positions. The narrow band gaps (compared to that of ZnTPP) of these designed systems, where the LUMO is above the conduction band of TiO(2) and the HOMO is below the redox couple, indicate that they are efficient sensitizers. The B bands of these newly designed derivatives, except for ZnTPP-5, are redshifted compared with the B band of ZnTPP.     

Optoelectronic properties of naphtho[2, 1-b:6, 5-b′]difuran derivatives for photovoltaic application: a computational study

Some important optoelectronic properties of naphtho[2,1-b:6,5-b′]difuran (DPNDF) and its two derivatives have been limelighted by applying the density functional theory (DFT). Due to their low cost, high stability and earth abundance, the DPNDF and its derivatives are considered as potential organic semiconductor materials for their optoelectronics applications. Highly proficient derivatives are obtained systematically by attaching –CN (cyanide) to DPNDF at various sites. Our calculations indicate that DPNDF has a wide and direct band gap with an energy gap of 3.157 eV. Whereas the band gaps of its derivatives are found to be decreased by 88 meV for derivative “a” and 300 meV for derivative “b” as a consequence of p orbitals present in C and N atoms in derivative structures. The narrowing of the energy gap and density of states for the derivatives of DPNDF in the present investigation suggest that energy gap can be engineered for desirable optoelectronic applications via derivatives designing. Furthermore, their obtained results for optical parameters such as the dielectric and conductivity functions, reflectivity, refractive index, and the extinction coefficients endorses their aptness for optoelectronic applications.

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Graphical Abstract Real part of dielectric function for derivative “b”

     

Donor-enhanced bridge effect on the electronic properties of triphenylamine based dyes: density functional theory investigations

The geometries have been optimized by using density functional theory. The highest occupied molecular orbitals are delocalized on triphenylamine moiety while lowest unoccupied molecular orbital are localized on anchoring group. Intramolecular charge transfer has been observed from highest occupied molecular orbitals to lowest unoccupied molecular orbital. By replacing the vinyl hydrogens with methoxy as well as one benzene ring as bridge leads to a raised energy gap while extending the bridge decreases the energy gap compared to parent molecule. The HOMO energies bump up by extending the bridge. The LUMO energies of all the investigated dyes are above the conduction band of TiO(2) and HOMOs are below the redox couple except 3c. The distortion between anchoring group and triphenylamine can hamper the recombination reaction.     

Synthesis and Computational Exploration of Morpholine Bearing Halogenated Sulfonamides as Potential Tyrosinase Inhibitors

In the presented work, a new series of three different 4-((3,5-dichloro-2-[(2/4-halobenzyl)oxy]phenyl)sulfonyl)morpholines was synthesized and the structure of these compounds were corroborated by ¹H-NMR & ¹³C-NMR studies. The in vitro results established all the three compounds as potent tyrosinase inhibitors relative to the standard. The Kinetics mechanism plots established that compound 8 inhibited the enzyme non-competitively. The inhibition constants K_i calculated from Dixon plots for this compound was 0.0025 μM. Additionally, computational techniques were used to explore electronic structures of synthesized compounds. Fully optimized geometries were further docked with tyrosinase enzyme for inhibition studies. Reasonably good binding/interaction energies and intermolecular interactions were obtained. Finally, drug likeness was also predicted using the rule of five (RO5) and Chemical absorption, distribution, metabolism, excretion, and toxicity (ADMET) characteristics. It is anticipated that current experimental and computational investigations will evoke the scientific interest of the research community for the above-entitled compounds.