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

Reduction of a range of amido- and aryloxy-aluminum dihydride complexes, e.g. [AlH2(NR3){N(SiMe3)2}] (NR3=NMe3 or N-methylpiperidine (NMP)), with β-diketiminato dimagnesium(I) reagents, [{(ArNacnac)Mg}2] (ArNacnac=[HC(MeCNAr)2]−, Ar=mesityl (Mes) or 2,6-xylyl (Xyl)), have afforded deep red mixed valence aluminum hydride cluster compounds, [Al6H8(NR3)2{Mg(ArNacnac)}4], which have an average Al oxidation state of +0.66, the lowest for any well-defined aluminum hydride compound. In the solid-state, the clusters are shown to have distorted octahedral Al6 cores, having zero-valent Al axial sites and mono-valent AlH2− equatorial units. Several novel by-products were isolated from the reactions that gave the clusters, including the Mg−Al bonded magnesio-aluminate complexes, [(ArNacnac)(Me3N)Mg−Al(μ-H)3[{Mg(ArNacnac)}2(μ-H)]]. Computational analyses of one aluminum hydride cluster revealed its Al6 core to be electronically delocalized and to possess one unoccupied and six occupied, skeletal molecular orbitals. © 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

World University root node

Angewandte Chemie - International Edition

Magnesium(I) Reduction of Aluminum(III) Hydride Complexes: Generation of Mixed Valence Aluminum (AlI/Al0) Hydride Cluster Compounds, [Al6H8(NR3)2{Mg(β-diketiminate)}4]**

The current study aims in finding the utilization of Industrial waste such as copper and steel slags as a partial replacement material for sand in Sand Compaction Pile (SCP) in proportions of 5\%, 10\%, 15\%, 20\%, 30\%, and 40\% by weight. From the direct shear tests, it is observed that the angle of internal friction increases from 27.59 \& DEG; to 40.1 \& DEG; and 34.82 \& DEG; for copper and steel slags, respectively. The tests are done by installing the SCP in a soft clay in California Bearing Ratio mould and it is tested under soaked and unsoaked conditions. The optimum percentage found from the study for both the slag material is 30\%. Tests were also done by air-curing the composite soil within the mould for 7 days and water-curing the sample under soaked conditions for 4 days for the optimum replacement percentage.

INTERNATIONAL JOURNAL OF GEOTECHNICAL ENGINEERING

Investigating the advantage of copper and steel slags as partial replacement material in a sand compaction column in stabilizing the soft clay

Chemical synthesis of glycoconjugates is essential for studying the biological functions of carbohydrates. We herein report an efficient approach for the stereoselective synthesis of challenging α-linked glycoconjugates via a RhII/chiral phosphoric acid (CPA)-cocatalyzed dynamic kinetic anomeric O-alkylation of sugar-derived lactols via carbenoid insertion to the anomeric OH bond. Notably, we observed excellent anomeric selectivity, excellent diastereoselectivity, broad substrate scope and high efficiency for this glycosylation reaction by exploring various parameters of the cocatalytic system. DFT calculations suggested that the anomeric selectivity was mainly determined by steric interactions between the C2-carbon of the carbohydrate and the phenyl group of the metal carbenoid, while π/π interactions with the C2−OBn substituent on the carbohydrate substrate play a significant role for diastereoselectivity at the newly generated stereogenic center. © 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

Dynamic Kinetic Stereoselective Glycosylation via RhII and Chiral Phosphoric Acid-Cocatalyzed Carbenoid Insertion to the Anomeric OH Bond for the Synthesis of Glycoconjugates

ACS APPLIED NANO MATERIALS

Wearable Electrochemical Microneedle Sensors Based on the Graphene-Silver-Chitosan Nanocomposite for Real-Time Continuous Monitoring of the Depression Biomarker Serotonin

A novel dansyl-triazole-based fluorescent macrocycle with high Stokes shift and positive solvatochromism was developed. This is an excellent fluorescence sensor for selective detection of nitro-containing antibiotics and other nitro-heteroaromatics. Detection was possible in real samples/paper strips in submicromolar concentration. The interaction of the macrocycle with multiple proteins exhibited its bioactivity. © 2023 The Royal Society of Chemistry

Chemical Communications

Dansyl-triazole-based fluorescent macrocycle for selective detection of nitro-antibiotic drugs and protein interaction

This review is dedicated to the different varieties of macrocycles synthesis bearing indole units in their architecture by metal-catalyzed strategies. The progress of the new macrocyclization approaches is persisted be a keen area of research. Macrocycles contain a wide variety of molecules, and among those, heteroaryl motifs are valuable constituents that provide an attractive feature to macrocyclic systems. Indole represents one of the privileged pharmacophores against a variety of targets with various biological applications. Among the nitrogen-based heterocycles, indole plays a prominent role in organic synthesis, medicinal chemistry, pharmaceuticals, natural products synthesis, agrochemicals, dye and fragrances, and drug design. These scaffolds are widely distributed in several bioactive natural products and synthetic macrocycles constructed against a specific biochemical target and the most common constituents of naturally occurring molecules. Due to its immense importance, the progress of novel approaches for the synthesis of indole-based scaffolds has increased steadily. The majority of the macrocycles synthesis proceeds through the macrolactamization and macrolactonization, as well as the C-C bond macrocyclization process described by metal-catalyzed ring-closing metathesis (RCM) and coupling reactions. Among macrocyclizations, metal-catalyzed approaches are considered one of the most powerful tools for synthetic chemists in the design of a variety of macrocycles. This review aims to give a comprehensive insight into the synthesis of varieties of macrocycles bearing indole scaffold catalyzed by various transition metals that emerged in the literature over the last two decades. We hope that this review will persuade synthetic chemists to search for novel strategies for the C-C bond macrocyclization by metal-catalyzed protocols.

ORGANICS

Indole-Based Macrocyclization by Metal-Catalyzed Approaches

Despite possessing a wide spectrum of biological activities, molecular targets of EGCG remain elusive and as a result, its precise mode of action is still unknown. Herein, we have developed a novel cell-permeable and Click-able bioorthogonal probe for EGCG, YnEGCG for in situ detection and identification of its interacting proteins. The strategic structural modification on YnEGCG allowed it to retain innate biological activities of EGCG (IC50 59.52 ± 1.14 μM and 9.07 ± 0.01 μM for cell viability and radical scavenging activity, respectively). Chemoproteomics profiling identified 160 direct EGCG targets, with H:L ratio ≥ 1.10 from the list of 207 proteins, including multiple new proteins that were previously unknown. The targets were broadly distributed in various subcellular compartments suggesting a polypharmacological mode of action of EGCG. GO analysis revealed that the primary targets belonged to the enzymes that regulate key metabolic processes including glycolysis and energy homeostasis, also the cytoplasm (36 %) and mitochondria (15.6 %) contain the majority of EGCG targets. Further, we validated that EGCG interactome was closely associated with apoptosis indicating its role in inducing toxicity in cancer cells. For the first time, this in situ chemoproteomics approach could identify a direct and specific EGCG interactome under physiological conditions in an unbiased manner. © 2023 Elsevier B.V.

International Journal of Biological Macromolecules

In situ global proteomics profiling of EGCG targets using a cell-permeable and Click-able bioorthogonal probe

Breast cancer (BC) emerged as one of the life-threatening diseases among females. Despite notable improvements made in cancer detection and treatment worldwide, according to GLOBACAN 2020, BC is the fifth leading cancer, with an estimated 1 in 6 cancer deaths, in a majority of countries. However, the exact cause that leads to BC progression still needs to be determined. Here, we reviewed the role of two novel biomarkers responsible for 50–70% of BC progression. The first one is epidermal growth factor receptor (EGFR) which belongs to the ErbB tyrosine kinases family, signalling pathways associated with it play a significant role in regulating cell proliferation and division. Another one is fatty acid synthase (FASN), a key enzyme responsible for the de novo lipid synthesis required for cancer cell development. This review presents a rationale for the EGFR-mediated pathways, their interaction with FASN, communion of these two biomarkers with BC and improvements to overcome drug resistance caused by them. Graphical abstract: [Figure not available: see fulltext.] © 2023, The International CCN Society.

Journal of Cell Communication and Signaling

Role of EGFR and FASN in breast cancer progression

Catalytic oxidation using non-noble metal-based catalysts is a promising approach to mitigate pollution due to VOCs in the air. In this work, mesoporous Cu/TiO2 catalysts containing different concentrations of Cu2+ (0.2, 1, 3, and 4 wt% Cu w.r.t. Ti) were synthesized using the sol-gel technique. The catalysts were characterized using inductively coupled plasma-optical emission spectrometry, XRD, Raman spectroscopy, N2 physisorption, cyclic voltammetry, H2-TPR and electron microscopy to understand the structure and composition. The thermal catalytic gas phase oxidation of ethylene was studied by heating a mixture of ethylene (1.5 vol%) and air (5.9 vol%) in the presence of the Cu/TiO2 samples in the temperature range of 298 to 773 K. Cu/TiO2 showed a higher catalytic activity compared to TiO2 for the thermal oxidation of ethylene, indicating a strong promotion by doped copper ions. A volcanic behaviour in the catalytic activity was observed with different concentrations of Cu doping, with 1% Cu/TiO2 showing a 99.5% ethylene conversion at 673 K and 100% selectivity to CO2. The activity of 1% Cu/TiO2 remained consistent without deactivation for 24 h. At low dopant concentrations of Cu (0.2 and 1% Cu/TiO2), the reduction of Cu2+ to Cu+ was observed. An interplay of oxygen vacancies (OV), Cu+, Cu2+ and Ti4+ may be involved in controlling the activity. DRIFT studies indicated the formation of surface bidendate carbonate as a possible intermediate. © 2023 The Royal Society of Chemistry.

Catalysis Science and Technology

Oxidation of ethylene by Cu/TiO2: reducibility of Cu2+ in TiO2 as a possible descriptor of catalytic efficiency

Utilising the oxygen-vacancy-mediated reactivity of CaO/CuO and hydrazine monohydrate in isopropyl alcohol at 353 K, a variety of amino-derivatives of N-heterocycles, including pyridine, indole, quinoline, isoquinoline and benzothiazole, have been selectively synthesised by reducing their nitro analogues. It is demonstrated that CaO/CuO composite is a reusable, solvent-resilient solid reducing agent that can reduce a variety of nitro-N-heterocyclic substrates. The critical role of the structure of CaO/CuO on the nitro-reduction activity has been studied using spectroscopy and microscopy. DFT simulations indicate the facile formation of oxygen vacancies (EO,vac=−43.4 kJ/mol) on the interface of CaO/CuO surface under reducing environment. The presence of CaO facilitated a stronger interaction of the nitro-substrate on the oxygen vacant CuO (111) surface, resulting into a significantly lower activation energy (Ea=21.9 kJ/mol) for N−O dissociation. The reaction could be scaled up from 1 to 12 mmol of substrate. CaO/CuO is a reusable and a cost-effective alternative to the conventional catalyst (Pd/C, Pt/C). © 2023 Wiley-VCH GmbH.