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

Graphene oxide based molecular switching of ellipticine (E) has been utilized to probe its efficient loading onto graphene oxide (GO) and subsequent release to intra-cellular biomolecules like DNA/RNA. The green fluorescence of E switches to blue in GO and switches back to green with polynucleotides. The intensified blue emission of the ellipticine-GO (E-GO) complex with human serum albumin (HSA), switches to a bluish green upon addition of dsDNA. Electron microscopy reveals the formation of distinctive 3D assemblies involving GO and biomolecule(s) probably through non-covalent interactions and this is primarily responsible for the biomolcule(s) assisted fluorescence-switching of E. To our knowledge, such morphological patterning of a GO-DNA complex is very unusual, reported here the first time and could find applications in the fabrication of biomedical devices. Moreover, our approach of direct optical detection of drug loading and releasing is very cheap, appealing and will be useful for clinical trial experiments once the cytotoxicity of GO is duly taken care. © 2014 The Royal Society of Chemistry.

World University root node

Nanoscale

Loading of an anti-cancer drug onto graphene oxide and subsequent release to DNA/RNA: A direct optical detection

systematic study on the carbonylative transformation of 1-bromo-2-fluorobenzenes with various nucleophiles has been performed. Different types of double nucleophiles, such as N-N, N-C, O-C, and N-S, can be effectively applied as coupling partners. The corresponding six-membered heterocycles were isolated in moderate to good yields. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemistry - A European Journal

Palladium-Catalyzed Carbonylative Reactions of 1-Bromo-2-fluorobenzenes with Various Nucleophiles: Effective Combination of Carbonylation and Nucleophilic Substitution

We describe here a convenient and mild procedure for double carbonylation of o-dibromobenzenes with various 2-amino pyridines and naturally occurring amines, thus providing in good to excellent yields N-substituted phthalimides by using this palladium-catalyzed carbonylation procedure. Furthermore, for the first time we have applied the developed synthetic protocol for the synthesis of biologically active molecule thalidomide via a single step carbonylative cyclization reaction in excellent yield. © the Partner Organisations 2014.

Organic and Biomolecular Chemistry

Efficient palladium-catalyzed double carbonylation of o-dibromobenzenes: Synthesis of thalidomide

Purely aqueous-phase chemoselective reduction of a wide range of aromatic and aliphatic nitro substrates has been performed in the presence of inexpensive Ni- and Co-based nanoparticle catalysts using hydrazine hydrate as a reducing agent at room temperature. Along with the observed high conversions and selectivities, the studied nanoparticle catalysts also exhibit a high tolerance to other highly reducible groups present in the nitro substrates. The development of these potential chemoselective reduction catalysts also provides a facile route for the synthesis of other industrially important fine chemicals or biologically important compounds, where other highly reducible groups are present in close proximity to the targeted nitro groups. © 2014 American Chemical Society.

Inorganic Chemistry

Room-temperature chemoselective reduction of nitro groups using non-noble metal nanocatalysts in water

Ice mixtures of methane and carbon monoxide were exposed to ionizing radiation in the form of energetic electrons at 5.5 K to investigate the formation of carbonyl bearing molecules in extraterrestrial ices. The radiation induced chemical processing of the mixed ices along with their isotopically labeled counterparts was probed online and in situ via infrared spectroscopy (solid state) aided with reflectron time-of-flight mass spectrometry (ReTOFMS) coupled to single photon photoionization (PI) at 10.49 eV (gas phase). Deconvolution of the carbonyl absorption feature centered at 1727 cm -1 in the processed ices and subsequent kinetic fitting to the temporal growth of the newly formed species suggests the formation of acetaldehyde (CH3CHO) together with four key classes of carbonyl-bearing molecules: (i) alkyl aldehydes, (ii) alkyl ketones, (iii) &alpha;,&beta;-unsaturated ketones/aldehydes and (iv) &alpha;,&beta;,&gamma;, &delta;-unsaturated ketones/&alpha;,&beta;-dicarbonyl compounds in keto-enol form. The mechanistical studies indicate that acetaldehyde acts as the key building block of higher aldehydes (i) and ketones (ii) with unsaturated ketones/aldehydes (iii) and/or &alpha;,&beta;-dicarbonyl compounds (iv) formed from the latter. Upon sublimation of the newly synthesized molecules, ReTOFMS together with isotopic shifts of the mass-to-charge ratios was exploited to identify eleven product classes containing molecules with up to six carbon atoms, which can be formally derived from C1-C5 hydrocarbons incorporating up to three carbon monoxide building blocks. The classes are (i) saturated aldehydes/ketones, (ii) unsaturated aldehydes/ketones, (iii) doubly unsaturated aldehydes/ketones, (iv) saturated dicarbonyls (aldehydes/ketones), (v) unsaturated dicarbonyls (aldehydes/ketones), (vi) saturated tricarbonyls (aldehydes/ketones), molecules containing (vii) one carbonyl-one alcohol (viii), two carbonyls-one alcohol, (ix) one carbonyl-two alcohol groups along with (x) alcohols and (xi) diols. Reaction pathways to synthesize these classes were derived as well. The present experiments provide clear evidence for the formation of key organic molecules-acetaldehyde, acetone, and potentially vinylalcohol-which are among the 15 carbonyl containing organic molecules detected in the interstellar medium. Despite numerous previous experimental investigations probing the effect of ionizing radiation on simple astrophysical ice representatives, our results suggest that more complex organic molecules can be formed in extraterrestrial ices than previously suggested. An outlook on further identification of individual isomers is also presented. &copy; 2014 the Owner Societies.

Physical Chemistry Chemical Physics

Infrared and reflectron time-of-flight mass spectroscopic analysis of methane (CH4)-carbon monoxide (CO) ices exposed to ionization radiation-toward the formation of carbonyl-bearing molecules in extraterrestrial ices

The formation of ketene (H2CCO) in methane-carbon monoxide (CH4-CO) ices was investigated upon its exposure to ionizing radiation in the form of energetic electrons at 5.5 K. The radiation-induced nonthermal equilibrium processing of these ices was monitored online and in situ via infrared spectroscopy complimented with post-irradiation temperature programmed desorption studies exploiting highly sensitive reflectron time-of-flight mass spectrometry (ReTOF) coupled with single photon fragment-free photo ionization (PI) at 10.49 eV. The detection of ketene in irradiated (isotopically labeled) methane-carbon monoxide ices was confirmed via the ν2 infrared absorption band and substantiated during the warm-up phase based on sublimation profiles obtained from the ReTOF-PI spectra of the corresponding isotopic masses. The experiments conducted with the mixed isotopic ices of 12CD4-13CO provide clear evidence of the formation of at least two ketene isotopomers (D2 12C13CO and D2 13C13CO), allowing for the derivation of two competing formation pathways. We have also proposed underlying reaction mechanisms to the formation of ketene based on kinetic fitting of the temporal evolution of the ketene isotopomers. © 2014. The American Astronomical Society. All rights reserved.

Astrophysical Journal

Formation of ketene (H2CCO) in interstellar analogous methane (CH4)-carbon monoxide (CO) ICES: A combined FTIR and reflectron time-of-flight mass spectroscopic study

Ianthelliformisamines A-C are a novel class of bromotyrosine-derived antibacterial agents isolated recently from the marine sponge Suberea ianthelliformis. We have synthesized ianthelliformisamines A-C straightforwardly by the condensation of (E)-3-(3,5-dibromo-4-methoxyphenyl)acrylic acid and the corresponding Boc-protected polyamine followed by Boc-deprotection with TFA. Further, using this reaction protocol, a library of their analogues (39 analogues) has been synthesized by employing 3-phenylacrylic acid derivatives and Boc-protected polyamine chains through various combinations of these two fragments differing in phenyl ring substitution, double bond geometry or chain length of the central spacer of the polyamine chain (shown in red color). All the synthesized compounds (ianthelliformisamines A-C and their analogues) were screened for antibacterial activity against both Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) strains. All synthetic analogues of ianthelliformisamine A showed bacterial growth inhibition against both strains (Escherichia coli and Staphylococcus aureus), having MIC values in the range of 117.8-0.10 μM, while none of the synthetic analogues of ianthelliformisamine C as well as the parent compound showed any detectable antibacterial activity. Interestingly, some of the synthetic analogues of ianthelliformisamines A and B exerted a bactericidal effect against both E. coli and S. aureus strains, decreasing viable bacterial count by 99% at concentrations as low as 2 × MIC. This journal is © the Partner Organisations 2014.

Department of Biotechnology

Syntheses of a library of molecules on the marine natural product ianthelliformisamines platform and their biological evaluation

The dynamics of charge separation and charge recombination have been determined for lipid complexes of DNA capped hairpins possessing stilbene electron-acceptor and -donor chromophores separated by base-pair domains that vary in length and base sequence in chloroform solution by means of femtosecond time-resolved transient absorption spectroscopy. The results obtained for the DNA-lipid complexes are compared with those previously obtained in our laboratories for the same hairpins in aqueous buffer. The charge separation and charge recombination times for the lipid complexes are consistently much shorter than those determined in aqueous solution and are only weakly dependent on the number of base pairs separating the acceptor and donor. The enhanced rate constants for forward and return charge transport in DNA-lipid complexes support proposals that solvent gating is responsible, to a significant extent, for the relatively low rates of charge transport for DNA in water. Moreover, they suggest that DNA-lipid complexes may prove useful in the development of DNA-based molecular electronic devices. © 2014 American Chemical Society.

Journal of the American Chemical Society

Wirelike charge transport dynamics for DNA-lipid complexes in chloroform

Sr-doped lanthanum cobalt ferrite (La0.54Sr0.40Co0.20Fe0.80O3-δ) and lanthanum iron cobaltite (La0.54Sr0.40Fe0.20Co0.80O3-δ)-based mixed ionic and electronic conducting solid oxide fuel cell cathodes are synthesized by autocombustion technique. In order to examine the electrochemical activity including thermal matching with the adjacent cell components, a composite cathode comprising of both the ferritic and cobaltite system is prepared using mechanical mixing. Powder characterizations for cobaltite and ferritic-based perovskite revealed nanocrystallinity (15-30 nm) with particulate size ranging 50-100 nm. Anode-supported half cell with suitable doped ceria based interlayer on the top of the electrolyte and developed composite cathode augments the current density to 3.98 Acm-2 at 0.7 V at 800 °C. The oxygen reduction reaction kinetics of such composite cathode shows high exchange current density of 1.16 Acm-2 with relatively low electrode polarization of 0.02 Ωcm2 at 800 °C. The electrochemical performance is clinically correlated with the cell microstructure exhibiting minimum SrO diffusion at the electrode-electrolyte interface. © 2014 Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

International Journal of Hydrogen Energy

Nanocrystalline doped lanthanum cobalt ferrite and lanthanum iron cobaltite-based composite cathode for significant augmentation of electrochemical performance in solid oxide fuel cell

A short and generally applicable synthesis of bioactive tetracyclic natural product paracaseolide A has been accomplished employing a 'proposed' biomimetic Diels-Alder reaction as the key strategic step. The Diels-Alder precursors for this purpose were readily assembled through a versatile Suzuki coupling on preformed α-halo butenolides. The mechanistic aspects of the 'putative' biomimetic Diels-Alder reaction have been probed using computational methods, which suggest that this [4+2]-cycloaddition proceeds through a step-wise process and product profile is thermodynamically governed. © 2014 Elsevier Ltd.

Tetrahedron

Total synthesis of novel bioactive natural product paracaseolide A and analogues: Computational evaluation of a 'proposed' biomimetic Diels-Alder reaction