Department of Chemistry

Indian Institute of Technology Hyderabad (IITH) is a premier institute of science and technology established in 2008. IITH has been consistently ranked in the&nbsp;<a href="https://iith.ac.in/reports/" rel="noopener noreferrer">top 10 institutes</a>&nbsp;in India for Engineering&nbsp;<a href="https://www.nirfindia.org/2021/EngineeringRanking.html" rel="noopener noreferrer" target="_blank">according to NIRF</a>&nbsp;making it one of the most coveted schools for science and technology in the country.

IITH offers&nbsp;<a href="https://iith.ac.in/academics/under-graduate/">undergraduate programs</a>&nbsp;in all the classical engineering disciplines, applied sciences, design, as well as several modern interdisciplinary areas. Students are given a flexibility to explore a broad set of areas, and potentially pursue a minor or double major in a discipline that is not their own. Students who wish to seek a deeper understanding of their own discipline are strongly encouraged to get involved in cutting-edge research with the help of a faculty to mentor them, and earn an Honors in their own field.

The very foundation of IIT Hyderabad is based on&nbsp;<a href="https://iith.ac.in/research/">research and innovation</a>. The vibrant research culture is evident from the number of patents and publications that IITH produces consistently every year. IITH offers&nbsp;<a href="https://iith.ac.in/academics/programmes-offered/">graduate programs</a>&nbsp;at both a masters, and a doctoral level, in several diverse areas. There are separate programs for technology, design, science, and liberal arts. The&nbsp;<a href="https://iith.ac.in/academics/post-graduate/">MTech program</a>&nbsp;is offered in various modes and durations to cater to the ever-growing need of postgraduate level professionals in the country.

IITH encourages and supports&nbsp;<a href="https://iic-iith.netlify.app/index.html" rel="noopener noreferrer" target="_blank">innovation and entrepreneurship</a>&nbsp;at every stage. The minor program in entrepreneurship is open to all students of IITH, and many of the courses are offered by industrialists who are entrepreneurs themselves. There are various&nbsp;<a href="https://iith.ac.in/research/centres-incubators/">innovation centers and incubators</a>&nbsp;that promote entrepreneurship and help mentor young innovators. IITH has been very successful in building tie-ups with leading academic institutions around the globe.

IITH enjoys a very special relationship with Japanese universities and industries that goes beyond academic and research collaborations. In fact, some of the iconic buildings in IITH campus will carry the signature of Japanese architecture.

IITH creates a unique holistic ecosystem for education that offers interactive learning, a very flexible academic structure, cutting-edge research, strong industry collaboration, and entrepreneurship. This is an environment which enables students and faculty to translate their dreams into realities.

IIT Hyderabad

An atmospheric-pressure plasma jet (APPJ) was directly irradiated at a gas-liquid interface under ambient conditions. The reactive oxygen species (ROS) like hydroxyl radicals (•OH), hydrogen peroxide (H2O2) and ozone (O3) and also reactive nitrogen species (RNS) such as nitrogen oxides (NOx) and nitric acid (HNO3) formed during the plasma discharge were quantified under various experimental parameters. In a chemical dosimetry method, terephthalic acid (TA) was employed for the quantification of •OH and titanium sulfate was used to quantify the H2O2. Quantitative determination of NO3− was carried out by using Ion chromatography (IC). The changes in the solution pH were studied during the plasma treatment. Strong acidification along with the production of dominant reactive nitrogen species and ozone formation were observed with air. The effect of various gases, gas flow rate, various applied voltage and catalyst were studied to optimize the experimental conditions for the best performance. The influence of catalyst Fe2+ salt, TiO2 on the formation of reactive species were studied. The efficiency of the plasma device for the degradation of crystal violet (CV) was also investigated with TiO2 and Fe2+ salt. © 2022 Korean Physical Society

World University root node

Current Applied Physics

Physicochemical process of non-thermal plasma at gas-liquid interface and synergistic effect of plasma with catalyst

Energy production and environmental pollution are the two major problems the world is facing today. The depletion of fossil fuels and the emission of harmful gases into the atmosphere leads to the research on clean and renewable energy sources. In this context, hydrogen is considered an ideal fuel to meet global energy needs. Presently, hydrogen is produced from fossil fuels. However, the most desirable way is from clean and renewable energy sources, like water and sunlight. Sunlight is an abundant energy source for energy harvesting and utilization. Recent studies reveal that photoelectrochemical (PEC) water splitting has promise for solar to hydrogen (STH) conversion over the widely tested photocatalytic approach since hydrogen and oxygen gases can be quantified easily in PEC. For designing light-absorbing materials, semiconductors are the primary choice that undergoes excitation upon solar light irradiation to produce excitons (electron-hole pairs) to drive the electrolysis. Visible light active semiconductors are attractive to achieve high solar to chemical fuel conversion. However, pure semiconductor materials are far from practical applications because of charge carrier recombination, poor light-harvesting, and electrode degradation. Various heteronanostructures by the integration of metal plasmons overcome these issues. The incorporation of metal plasmons gained significance for improving the PEC water splitting performance. This review summarizes the possible main mechanisms such as plasmon-induced resonance energy transfer (PIRET), hot electron injection (HEI), and light scatting/trapping. It also deliberates the rational design of plasmonic structures for PEC water splitting. Furthermore, this review highlights the advantages of plasmonic metal-supported photoelectrodes for PEC water splitting. © 2021

Journal of Photochemistry and Photobiology C: Photochemistry Reviews

Emerging materials for plasmon-assisted photoelectrochemical water splitting

The imidazole-selone antimony(III) complexes have been described with unique bonding situations around the antimony center. The mononuclear complexes, [(L1)SbCl3] (1) and [(L2)SbCl3] (2) were isolated from the reaction between SbCl3 and corresponding symmetrically crowded, 1,3-bis(2,6-diisopropyl phenyl) imidazole selone (L1) and unsymmetrically crowded, 2,(2,6-benzhydryl-4-methyl phenyl) imidazole pyridine selone (L2), respectively. The bonding nature of 1 and 2 differ remarkably due to the unique steric hindrance around the antimony center. Besides, the lone-pair-π-hole interaction was observed in 1 and 2. The extent of Se → Sb bonding and (aryl)C → Sb bonding were further investigated by density functional theory (DFT), including natural bond orbital (NBO), natural population analysis (NPA), and electron density difference (EDD) methods. The theoretical predictions are nearly convincing with a single crystal X-ray analysis. The increasing steric bulk of the imidazole-selone from symmetric to unsymmetrical nature was found to greatly influence the donor–acceptor magnitude of Se → Sb bonding and (aryl)C → Sb bonding and lone-pair-π-hole interactions. The L2 in 2 acts as a good σ-donor and π-donor to Sb(III) compare to L1 in 1. © 2022 Elsevier Ltd

Polyhedron

Antimony(III)-selenium complexes with synergetic effect between Sb[sbnd]Se bond and Sb⋯π interactions

The batteries are energy storage device that stores intermittent energy from renewables to supply when it is desired. The marvelous aspect of today's battery industry remains to be the advancement and evolution of high-energy battery technologies. Batteries have moderate energy and power. Energy density measures how much energy is delivered by the battery in proportion to its weight and is measured in terms of Watt-hours (product of capacity (Ah) and voltage) per kilogram (Whkg−1) or per liter (WhL−1). The passage of reaching higher energy density is divided into two ways: pushing the battery's capacity further or lifting the voltage up. Because of its superior energy density, the batteries are the choice in various electrical portable devices, grids, and hybrid/electric vehicles. Energy density is very critical for the prolonged operation of the devices. This chapter provides a brief introduction to the thermodynamic aspects of high-energy-density batteries. © 2022 Elsevier Inc. All rights reserved

Encyclopedia of Energy Storage: Volume 1-4

Thermodynamic Studies on Energy Density of Batteries

Ordered supramolecular hydrogels assembled by modified aromatic amino acids often exhibit low mechanical rigidity. Aiming to stabilize the hydrogel and understand the impact of conformational freedom and hydrophobicity on the self-assembly process, two building blocks based on 9-fluorenyl-methoxycarbonyl-phenylalanine (Fmoc-Phe) gelator which contain two extra methylene units in the backbone, generating Fmoc-γPhe and Fmoc-(3-hydroxy)-γPhe are designed. Fmoc-γPhe spontaneously assembled in aqueous media forming a hydrogel with exceptional mechanical and thermal stability. Moreover, Fmoc-(3-hydroxy)-γPhe, with an extra backbone hydroxyl group decreasing its hydrophobicity while maintaining some molecular flexibility, self-assembled into a transient fibrillar hydrogel, that later formed microcrystalline aggregates through a phase transition. Molecular dynamics simulations and single crystal X-ray analyses reveal the mechanism underlying the two residues' distinct self-assembly behaviors. Finally, Fmoc-γPhe and Fmoc-(3-OH)-γPhe co-assembly to form a supramolecular hydrogel with notable mechanical properties are demonstrated. It has been believed that the understanding of the structure-assembly relationship will enable the design of new functional amino acid-based hydrogels. © 2022 The Authors. Macromolecular Rapid Communications published by Wiley-VCH GmbH.

Macromolecular Rapid Communications

Exploiting Minimalistic Backbone Engineered γ-Phenylalanine for the Formation of Supramolecular Co-Polymer

Despite the fundamental clinical importance of amyloid fibril formation, its mechanism is still enigmatic. Crystallography of minimal amyloid models was a milestone in the understanding of the architecture and biological activities of amyloid fibers. However, the crystal structure of ultimate dipeptide-based amyloids is not yet reported. Herein, we present the crystal structure of a typical amyloid-forming minimal dipeptide, Ac-Phe-Phe-NH2 (Ac-FF-NH2), showing a canonical β-sheet structure at the atomic level. The simplicity of the structure helped in investigating amyloid-inhibition using crystallography, never previously reported for larger peptide models. Interestingly, in the presence of an inhibitor, the supramolecular packing of Ac-FF-NH2 molecules rearranged into a supramolecular 2-fold helix (21 helix). This study promotes our understanding of the mechanism of amyloid formation and of the structural transitions that occur during the inhibition process in a most fundamental model. © 2021 Wiley-VCH GmbH

Angewandte Chemie - International Edition

Inhibitor-Mediated Structural Transition in a Minimal Amyloid Model

Two novel mononuclear heteroleptic Ru(II) photosensitizers with 2-(1H-benzo[d]imidazol-2-yl)quinoline derivatives were designed and successfully synthesized. The facile synthesis and their photophysical properties are investigated. Both the Ru(II) complexes i.e., [RuII(bpy)2(L1)](ClO4) : [1](ClO4) and [RuII(bpy)2(L2)](ClO4)2 : [2](ClO4)2 {L1 = 2-(1H-benzo[d]imidazol-2-yl)quinoline and L2 = 2-(1-methyl-1H-benzo[d]imidazol-2-yl)quinoline} have been meticulously characterized by different spectroscopic and analytical techniques such as FT–IR, 1H NMR, ESI mass spectra, UV–vis and fluorescence spectroscopy, etc. Molecular structures of [1](ClO4) and [2](ClO4)2 have been determined by a single-crystal X-ray structure diffraction study. Redox and spectral properties of the synthesized Ru(II) complexes were examined along with their corresponding ligands and compared with the classic homoleptic [RuII(bpy)3](PF6)2. The effects on substituents in the ligand backbone were scrutinised. The emission behaviour of both [1](ClO4) and [2](ClO4)2 revealed relatively long-lived emissive 3MLCT and bathochromic shift (~ 715 nm) while compared with [RuII(bpy)3](PF6)2 (~ 605 nm). Fairly weak quantum yields for [1](ClO4) and [2](ClO4)2 : ∼ 0.00299 and ∼ 0.00295 with half-lives 181.57 ns and 198.89 ns, respectively, suggested different non-radiative emission pathways. Additionally, for [1](ClO4) and [2](ClO4)2, electrochemical reduction of carbon dioxide (CO2) in dry acetonitrile solvent was performed and showed great promises for future designing of electrochemical reduction of CO2. Graphical abstract: Two mononuclear heteroleptic Ru(II) photosensitizers [1](ClO4) and [2](ClO4)2 containing 2-(1H-benzo[d]imidazol-2-yl)quinoline ligand were synthesized and investigated via FT–IR, 1H NMR, ESI mass spectra, UV–vis, time-resolved photoluminescence spectroscopy, X-ray structure, etc. Both [1](ClO4) and [2](ClO4)2 showed great promises for electrochemical reduction of carbon dioxide in dry acetonitrile.[Figure not available: see fulltext.] © 2022, Indian Academy of Sciences.

Department of Physics

Journal of Chemical Sciences

Synthesis, characterization, structural and photophysical properties of heteroleptic ruthenium complexes containing 2-(1H-benzo[d]imidazol-2-yl)quinoline ligand towards electrocatalytic CO2 reduction

Mononuclear Co(ii) complexes [CoII(L)Cl2]; 1, [CoII(L)(bpy)Cl]PF6; 2, [CoII(L)(phen)Cl]PF6; 3 and [CoII(L)(pic)Cl]; 4, (where L = N,N-bis(pyridin-2-ylmethyl)aniline, bpy = 2,2′-bipyridine, phen = 1,10-phenanthroline, pic = picolinic acid) were systematically synthesized and characterized by different analytical and spectroscopic methods. All the complexes were structurally identified by single-crystal X-ray diffraction analysis. Penta-coordinated complex 1 adopted a distorted trigonal bipyramidal geometry, whereas hexacoordinated complexes 2-4 have distorted octahedral geometry. The interactions of salmon sperm DNA (ss-DNA) with our synthesized complexes 1-4 were investigated by absorbance and fluorescence spectroscopy. All the complexes are very susceptible to DNA binding and exhibited binding affinities (Kb) in the order of ∼104 M−1, indicating their strong interaction with ss-DNA. The Stern-Volmer constant (Ksv) ranged from 0.46 ± 0.01 × 104 to 1.08 ± 0.04 × 104 M−1, suggesting weak or moderate binding with DNA. Agarose gel electrophoresis revealed the DNA cleavage activity in vitro for 2-4, which could efficiently cleave the supercoiled plasmid DNA without any external agents; however, with the addition of H2O2, the cleavage property was enhanced. Live-cell imaging and other biochemical assays demonstrated the ability of Co(ii) complexes 1-4 to induce significant cytotoxicity in A549 lung cancer cells with IC50 values of 32.14 ± 1.3 μM, 3.14 ± 0.16 μM, 15.78 ± 0.72 μM and 18.45 ± 0.92 μM, and in MDA-MB-231 breast cancer cells with IC50 values of 20.42 ± 0.92 μM, 0.41 ± 0.02 μM, 2.31 ± 0.12 μM and 9.67 ± 0.35 μM, respectively. © 2022 The Royal Society of Chemistry.

Department of Biotechnology

Dalton Transactions

Mononuclear Co(ii) polypyridyl complexes: synthesis, molecular structure, DNA binding/cleavage, radical scavenging, docking studies and anticancer activities

In this report, CuBi2O4/Co3O4 has been used for the electrochemical detection of glucose. Herein, CuBi2O4 nanorods and Co3O4 has been hybridized with CuBi2O4 to form CuBi2O4/Co3O4 nanocomposite hydrothermally. CuBi2O4 and CuBi2O4/Co3O4 electrodes are fabricated by using drop casting method. Structural, morphological studies of CuBi2O4/Co3O4 and electrochemical characterizations pertaining to its performance in comparison to CuBi2O4 for electrochemical detection of glucose are performed and discussed elaborately. The detailed mechanism involved in the electrochemical detection of glucose is proposed. The electrode has shown the sensitivity of 49 μA mM−1 cm−2 with a limit of detection (LOD) of 0.136 μM. DFT calculations are performed on the optimized molecules involved in the electrochemical detection of glucose confirming CuBi2O4/Co3O4 acting as electron donor while glucose as electron acceptor. Further, natural bond orbital (NBO) for charge distribution calculations and ESP mappings for the optimized molecules are performed to understand nucleophilic/electrophilic positions. This study reveals that CuBi2O4 and its modifications are promising materials for the electrochemical detection of glucose. Further, the role of Co3O4 in improving the sensitivity and electrochemical performance for detection of glucose has been discussed. © 2022 Wiley-VCH GmbH.

Department of Electrical Engineering

ChemElectroChem

Co3O4 and CuBi2O4 Hybrid Nanostructures for Efficient Nonenzymatic Glucose Detection in Human Blood and Serum Samples with Mechanistic Insights

The search for extremely narrow-band new red emitters is essential for smart displays and lighting applications. Herein, we report the synthesis of a series of red-emitting Eu3+-substituted Li3BaSrY3(WO4)8 and solid-solution (Li3BaSrY0.3Eu2.7(WO4)8−y(MoO4)y) phosphors with a stratified scheelite structure and the systematic investigation of their optical properties. All the compositions show broad absorption (charge transfer (O2− → M6+)) extended up to the blue region along with strong characteristic Eu3+ excitation lines. The phosphor compositions exhibit proficient narrow-band red emission (quantum yield up to 85%; full width at half maximum (FWHM) = 6 nm; CIE colour coordinates x = 0.65, y = 0.35, i.e. approaching the NTSC standard for red colour) of exceptional colour purity (94% to 98%), and this host supports heavy trivalent Eu activation (showing zero concentration quenching of the emission (Eu-rich lattice)). The dominating electric dipole (5D0 → 7F2, red emission) transition shows Eu3+-ion occupancy in the non-centrosymmetric site in the host lattice. The selected composition shows better absolute quantum efficiencies compared to commercial phosphors. The presently synthesized phosphors have proven to be thermally stable against the temperature quenching effect. The fabricated red LED showed excellent performance, colour purity, LER and CIE values. The excellent optical properties, quantum yield and thermal stability make the phosphor applicable as a red component in solid-state lighting devices and as a light source for plant growth applications. © 2022 The Royal Society of Chemistry.