Department of Chemistry

Indian Institute of Technology Palakkad&nbsp;(IIT Palakkad or IIT PKD) is a public autonomous&nbsp;engineering&nbsp;and&nbsp;research&nbsp;institute located in&nbsp;Palakkad,&nbsp;Kerala. It was&nbsp;one of the five new&nbsp;IITs&nbsp;proposed in the&nbsp;2014 Union budget of India. The campus was inaugurated on 3 August 2015. The institute has 94 faculty, 978 students, and 63 non-teaching staffs.

IT Palakkad currently offers four-year Bachelor of Technology (B.Tech) and two years MS programmes in 8 different engineering disciplines including&nbsp;Computer Science, Electrical, Mechanical, Civil among others.

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IIT Palakkad

We demonstrate that an in situ generated di-reduced phenalenyl (PLY) species accumulates sufficiently high energy and acts as a super electron donor to generate aryl radicals from aryl halides to accomplish Buchwald-Hartwig-type C-N cross-coupling reactions at room temperature. This catalytic protocol does not require any external stimuli such as heat, light, or cathodic current. This protocol shows a wide variety of substrate scope covering different genres of aryl and heteroaryl halides with various aromatic as well as aliphatic amines and late-stage functionalization of the well-known natural products. The control experiments, along with extensive density functional theory (DFT) calculations, unveil that the aryl radical is generated by a single electron transfer from the di-reduced PLY to the aryl halide substrate. The aryl radical acts as an electrophile and binds with amine, leading to the chemically driven radical-mediated C-N cross-coupling under transition-metal-free conditions. © 2022 American Chemical Society. All rights reserved.

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Journal of the American Chemical Society

Reduced-Phenalenyl-Based Molecule as a Super Electron Donor for Radical-Mediated C-N Coupling Catalysis at Room Temperature

The design of suitable chemical sensors for the trace detection and discrimination of chemical explosives is an important area of research in recent years. In this chapter, we have summarized the nitroaromatic sensing properties of several finite supramolecular coordination complexes. Besides, the sensing studies, in each section we have discussed the design and synthesis of luminescent metallacycles and metallacages. The existing limitations and perspectives of supramolecular coordination complexes for explosives sensing have also been stated. This chapter will be useful to the researchers working on chemical sensors and supramolecular chemistry. © 2023 Elsevier Inc. All rights reserved.

Supramolecular Coordination Complexes: Design, Synthesis, and Applications

Supramolecular coordination complexes for fluorescence sensing of nitroaromatic explosives

This chapter provides a survey on the design, synthesis, and biosensing properties of a wide variety of discrete supramolecular coordination complexes (SCCs). We have classified SCCs based on their sensing selectivity towards particular biomolecular analytes. Besides the synthesis and structural properties, a detailed discussion on the mode of binding and sensing mechanism has been highlighted under each section. This chapter will greatly benefit the researchers working in interdisciplinary areas of sciences that bridge chemistry with biology and other closely related areas of chemical sciences. © 2023 Elsevier Inc. All rights reserved.

Biosensing properties of supramolecular coordination complexes

Amino-1,8-naphthalimides are a sought-after class of materials due to their optoelectronic properties. This work demonstrates the application of CuO/CaO for a chemoselective synthesis of amino-1,8-naphthalimide fluorophores from the corresponding nitro-analogues with 100% conversion and selectivity. The reaction was completed in 10 min in isopropyl alcohol using hydrazine hydrate as a reducing agent at 80 °C. The material was characterized using XRD, FT-IR, SEM, TEM, and adsorption techniques. The product, 4-amino-1,8-naphthalimides, was characterized by using NMR (1H and 13C), LCMS, and photophysical properties were measured in DCM at 298 K. © 2022 The Author(s)

Results in Chemistry

CuO/CaO mediated synthesis of amino-1,8-naphthalimides from the nitro analogues

In this work, a composite of CuO and CaO (CuO/CaO) is prepared and demonstrated to chemically reduce nitro groups in aromatic hydrocarbons to the corresponding amines at 353 K using hydrazine monohydrate in isopropyl alcohol. The CuO/CaO was synthesized in 1:1 molar ratio of Cu to Ca by a simple sol–gel method. The CuO/CaO possesses surface oxygen vacancies and basicity which enhances the reactivity and stability in comparison to bare CuO. The active sites are probed using FT-IR, H2-TPR, XPS and CO2-TPD. Reduction of nitroarenes to aminoarenes was completed in 10–20 min with 100% selectivity. CuO/CaO was reused three successive cycles without any further treatment making it a reusable solid reagent. © 2022, Indian National Science Academy.

Proceedings of the Indian National Science Academy

CuO/CaO as a solid reducing reagent for nitroarenes: combined effect of oxygen vacancies and surface basicity

The design of suitable fluorescent chemosensors for trace detection and quantification of biologically relevant analytes has attracted significant research focus in the past decades. Zinc(II) ion is the second most abundant transition metal cations present in the human body and it is a “Life-Saving Commodity” that exhibits essential cellular functions in various metabolic processes. A wide variety of small-molecular-based fluorescent chemosensors have been designed and successfully employed for the trace sensing and quantification of Zn(II) ions both in vitro and in vivo. Among the various small molecular fluorophores, the amino-1,8-naphthalimide-based chemosensors have got special research interest because of their easy synthesis, facile structure, functional tunability, and interesting photophysical properties. In this review article, we exemplified the advancements made in the use of amino-1,8-naphthalimide-based fluorescent chemosensors for selective sensing and quantification of Zn(II) ions. We detailed the design, fluorescence sensing properties, and bioimaging application of various amino-1,8-naphthalimide-based chemosensors. © 2022 Elsevier Ltd

Tetrahedron Letters

Amino-1,8-naphthalimide-based fluorescent chemosensors for Zn(II) ion

Electrocatalyzed oxidative B−H nitrogenations of nido-carborane (nido-7,8-C2B9H12−) with N-heterocycles have been established, enabling the preparation of various N-substituted nido-carboranes without chemical oxidants or metal catalyst under ambient conditions. The electrolysis manifold occurred with high levels of efficiency as well as chemo- and position- selectivity, employing sustainable electricity as the sole oxidant. The strategy set the stage for a user-friendly access to novel amino acid and fluorogenic boron-dipyrrin (BODIPY)-labeled nido-carborane hybrids. © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

Fulltext

Angewandte Chemie - International Edition

Electrochemical B−H Nitrogenation: Access to Amino Acid and BODIPY-Labeled nido-Carboranes

Indole dearomatization is an important strategy to access indolines: a motif present in a variety of natural products and biologically active molecules. Herein, a method for transition-metal catalyzed regioselective dearomative arylboration of indoles to generate diverse indolines is presented. The method accomplishes intermolecular dearomatization of simple indoles through a migratory insertion pathway on substrates that lack activating or directing groups on the C2- or C3-positions. Synthetically useful C2- and C3-borylated indolines can be accessed through a simple change in N-protecting group in high regio- and diastereoselectivities (up to >40:1 rr and >40:1 dr) from readily available starting materials. Additionally, the origin of regioselectivity was explored experimentally and computationally to uncover the remarkable interplay between carbonyl orientation of the N-protecting group on indole, electronics of the C2-C3 π-bond, and sterics. The method enabled the first enantioselective synthesis of (-)-azamedicarpin. ©

Nickel-Catalyzed Dearomative Arylboration of Indoles: Regioselective Synthesis of C2- And C3-Borylated Indolines

The development of suitable chemical sensors for the selective detection and quantification of antibiotics has aroused tremendous research interests in recent years because of their serious menace to the environment. The excessive accumulation, through high human consumption and animal activities, of antibiotics in the soil can trigger pernicious effects on the living systems and it necessitates the development of suitable sensors. Among the various detection methods that are currently available, the fluorescent technique has become an alternative and effective method for the identification of antibiotics. In recent years, a variety of fluorescent sensors have been designed concerning the discriminative sensing of antibiotics both in solution and vapor-phase. In this review article, we attempted to systematically summarize a report on the recent advancements accomplished in the use of luminescent metal–organic frameworks (LMOFs) as fluorescent sensors for the discriminative sensing of different types of antibiotics. The LMOFs based fluorescent sensors described in this article are grouped according to their sensing propensity towards the particular type of antibiotics. Finally, the article provides a prospect on the advantages and existing challenges in antibiotics detection using LMOFs based fluorescent sensors and the future direction of this field has also been stated. © 2021 Elsevier B.V.

Coordination Chemistry Reviews

Recent advances in luminescent metal–organic frameworks (LMOFs) based fluorescent sensors for antibiotics

SIRT5 is a member of the sirtuin family of NAD+-dependent protein lysine deacylases implicated in a variety of physiological processes. SIRT5 removes negatively charged malonyl, succinyl, and glutaryl groups from lysine residues and thereby regulates multiple enzymes involved in cellular metabolism and other biological processes. SIRT5 is overexpressed in human breast cancers and other malignancies, but little is known about the therapeutic potential of SIRT5 inhibition for treating cancer. Here we report that genetic SIRT5 disruption in breast cancer cell lines and mouse models caused increased succinylation of IDH2 and other metabolic enzymes, increased oxidative stress, and impaired transformation and tumorigenesis. We, therefore, developed potent, selective, and cell-permeable small-molecule SIRT5 inhibitors. SIRT5 inhibition suppressed the transformed properties of cultured breast cancer cells and significantly reduced mammary tumor growth in vivo, in both genetically engineered and xenotransplant mouse models. Considering that Sirt5 knockout mice are generally normal, with only mild phenotypes observed, these data establish SIRT5 as a promising target for treating breast cancer. The new SIRT5 inhibitors provide useful probes for future investigations of SIRT5 and an avenue for targeting SIRT5 as a therapeutic strategy. © 2021, The Author(s), under exclusive licence to Springer Nature Limited part of Springer Nature.