PhD Theses (Chemistry)

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    N-Propargylamines: A Key Precursor for the Construction of Functionalized Nitrogen and Sulfur Heterocycles
    (2023) Behera, Bipin Kumar
    The contents of the present thesis have been divided into five chapters based on the results achieved from the experimental works performed during the entire course of the PhD research programme. Chapter 1 highlights an overview of N-propargylamines. This includes a brief discussion about synthetic reactivity and utility of N-propargylamines. It emphasizes on its unique structure bearing both free amine and an alkyne group, thus focusing on its dual role either as nucleophile and electrophile or as N-centered radical donor and radical acceptor. Chapter 2 highlights an efficient methodology developed for the synthesis of tetra- and penta-substituted pyrroles via N-centered radical initiated oxidative self-dimerization of N-propargylamines catalyzed by silver benzoate in the presence of K2S2O8. The protocol provides a simple route for the synthesis of highly functionalized pyrroles with two carbonyl groups in the side chain. The methodology can be extended towards the synthesis of fluorescent pyrrolo[3,4-d]pyridazine derivatives. Chapter 3 represents an efficient methodology for the synthesis of both di- and trisubstituted thiazol-2-ones from N-propargylamines via [3,3]-sigmatropic rearrangement/5-exo-dig cyclization. The protocol utilizes silver(I) trifluoromethanethiolate (AgSCF3) as a C–S source and eco-friendly H2O as nucleophile under open air condition. The methodology can be extended for the synthesis of bioactive analog of thiozole-2-thione derivatives and photophysical properties have been studied for some synthesized compounds. Chapter 4 describes an efficient methodology developed for the synthesis of methylene-dihydrothiazole derivatives via Michael-addition followed by hydrothiolation of N-propargylamines. The protocol utilizes silver(I)trifluoromethanethiolate (AgSCF3) as a S source and malonate ester derivatives as nucleophiles. The reaction is compatible with many functional groups with moderated to good yield. Chapter 5 highlights a facile and efficient synthesis of structurally diversified 2-pyridones is demonstrated using the [4+2] annulation of in situ generated azadienes from N-propargylamines and active-methylene compounds. The reaction is promoted by an inorganic base giving moderate to good yields. The developed methodology is applicable for direct and formal synthesis of various bioactive molecules. The synthetic utility of the protocol was also illustrated by late stage functionalization of the products.
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    Studies Towards C-C and C-N Bond Formation using Strained Rings: A Probe for Heterocycle Formation
    (2024) Karjee, Pallab
    The thesis is organized into four chapters. The initial chapter delineates a tandem C–N bond formation for the oxidative annulation of indolines with aziridines, utilizing a combination of DDQ and NaOCl under ambient conditions. The second chapter addresses the annulative coupling of donor-acceptor cyclopropanes with cyclic secondary amines, employing Ni(OTf)2 and visible light-assisted eosin Y catalysis for tandem C–N and C–C bond formation. The third chapter focuses on the coupling of cyclic secondary amines with donor-acceptor cyclopropanes using MgI2 and Mn(OAc)3•2H2O, leading to the synthesis of fused indolizine derivatives. The fourth chapter showcases an efficient annulation of in situ formed azaoxyallyl cations with diaziridines, yielding 1,2,4-triazines at room temperature.
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    Site-Selective C-H Functionalization of Indoles: Studies towards C-C and C-N Bond Formation
    (2024) Banerjee, Sonbidya
    The thesis is structured into four chapters. The first chapter describes a Ru-catalyzed regioselective C-N bond formation of indolines and carbazole with acyl azides via C7(sp2)-H activation followed by an intramolecular C-N bond formation for the construction of 7- aminoindoline and 1-aminocarbazole scaffolds. The second chapter deals with Cu-catalyzed C7- selective C-H/N-H cross-dehydrogenative coupling of indolines and azaindoles with sulfoximines. The third chapter demonstrates a Rh-catalyzed site-selective C7 and C6 dual C-H functionalization of indolines expending 7-azabenzonorbornaiene for the formation of functionalized pyrrolocarbazoles. The fourth chapter focuses on Pd-catalyzed weak-coordination facilitated C4- selective redox-neutral nitration of indoles with tert-butyl nitrite under aerobic oxidation catalysis.
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    Expeditious Thermal(Photo) Induced Functionalization/Annulation: En route to N-Heterocycles
    (2024) Khandelia, Tamanna
    The content of the thesis has been divided into four chapters. The thesis streamlines the synthesis of aromatic and non-aromatic N-heterocycles. It contributes towards the facile formation of C−C, C−N, C−O and C−S bonds using o-alkynylanilines, maleimides, 2-aryl quinoxalines, (benz)imidazoles, boronic acids and disulfides. Chapter I introduces transition metal induced (thermal) and photochemical construction of C−C and C−Heteroatom bonds. The mechanism involved in both transition metal induced (thermal) and photochemical approach are discussed. Both the processes are explained in details with the help of suitable examples. Chapter II describes a Cu(I) mediated cascade cyclization/annulation of unprotected o-alkynylanilines with maleimides in one-pot. The protocol offers sequential formation of one C−N and two C−C bonds to deliver fused benzo[a]carbazoles having free NH skeletons. The annulated products have been exploited towards various applications. Chapter III describes a Cu(OTf)2 mediated regioselective de-aromatized aryl-hydroxylation across C(sp2)=N bond of 2-aryl quinoxalines and bis-N-arylation of (benz)imidazoles using aryl boronic acids. For dearomative aryl-hydroxylation, the C-center should be electrophilic (ca. 0.08), N-center nucleophilic (ca. −0.50), and the C(sp2)=N bond should be polarized (Δe = 0.609).
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    Small Molecules and Porous Silica Nanoparticle Encapsulated Gd(III) and Mn(II) Complexes as MRI Contrast Agents
    (2024) Mallik, Riya
    The content of this thesis has been divided into five chapters according to the results of experimental works that have been performed during the research period. Chapter I is the intorductory chapter of the thesis that represents an overview of Gd(III) and Mn (II) based complexex and nanoparticles as alternative MRI contrast agents with enhanced relaxivity and other physiochemical properties to target various endogenous conditions.
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    Chemically Twisted Superlattices of Two-dimensional Assemblies of Copper Nanoclusters
    (2024) Das, Priya
    The organization of molecules or atoms in a hierarchical manner leads to the formation of complex superstructures with enhanced properties and functionalities, resulting in superior performance when compared to mono-morphological units. Researchers have been motivated by the impact of these achievements to explore the design and fabrication of materials with hierarchical assembly at the nanoscale level. In this regard, research on the hierarchical assembly of two-dimensional (2D) nanomaterials has led to several exciting discoveries in various fields such as energy storage, optoelectronic devices, chemical sensors, catalytic performance, membranes, and solar cells.
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    Studies Towards Stereoselective C-C/C-Heteroatom Bond Formations of Strained Rings
    (2024) Mishra, Manmath
    Chapter I. General introduction to ring opening and cyclization of D-A cyclopropanes Nitrogen- and oxygen-containing heterocycles are among the most prevalent moieties found in both pharmaceutical and naturally occurring compounds. Research and development into these compounds is of high interest and of ongoing importance in organic synthesis. Recently, C-C and C-heteroatom bonds formation by ring expansion of three-membered strained ring systems, particularly in D-A cyclopropanes have provided a great synthetic space for easy access to structurally complex scaffolds. The inherent ring strain and electrophilic character made them an attractive building blocks for the selective synthesis of five, six and seven-membered heterocycles through ring-scission. In this chapter, the studies behind the background, reactivity and synthetic methodologies of ring-opening and cyclization of D-A cyclopropanes are discussed.
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    Facile Chemical Approaches to Derive Scalable and Tolerant Liquid Repellent Surfaces
    (2024) Dhar, Manideepa
    Nature-inspired liquid-repellent surfaces, such as superhydrophobic and slippery surfaces, have gained enormous attention because of their potential applications in environmental remediation, anti-corrosion, self-cleaning, bio-medical devices and so on. In the past, several approaches were adopted to develop artificial surfaces with desired wettability. However, significant challenges, such as poor durability and mechanical and chemical robustness, continue to impede its real-world application. This synopsis report outlines the strategic utilization of a facile and catalyst-free 1, 4-conjugate addition reaction between amine and acrylate functional groups for developing liquid-repellent surfaces with enhanced robustness and durability following a simple, scalable, and rapid fabrication approach. The synopsis report entitled “Facile Chemical Approaches to Derive Scalable and Tolerant Liquid Repellent Surfaces" is divided into six chapters. Chapter 1 gives a concise overview of bio-inspired wettability, general methods adopted to develop artificial anti-wetting surfaces, existing challenges, and objectives behind this thesis work. Chapter 2 demonstrates the strategic use of a catalyst-free 1,4-conjugate addition reaction between distinct and strategically selected small molecules allowed to prepare an active deposition solution with prolonged shelf-life in various and commonly used reaction media to derive optically transparent superhydrophobic coating. Chapter 3 introduces a covalent cross-linking chemistry between selected reactants to achieve tolerant and hard superhydrophobicity. Chapter 4 demonstrates the design of chemically functionalizable coatings with a combination of a physically unclonable porous topography and distinct physiochemical properties (e.g., fluorescence, water wettability, and water adhesion) obtained through orthogonal chemical modifications (i.e., 1,4-conjugate addition reaction and Schiff-base reaction at ambient conditions) for multilevel anti-counterfeiting application. Chapter 5 accounts for the utilization of a crystalline comb-like polymer to derive a non-fluorinated, substrate-independent, and self-healable amphiphobic solid slippery coating following a simple and scalable fabrication process. Chapter 6 provides a comprehensive summary of the presented work and a future perspective of this discussed research work.
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    Designing of hetero-bimetallic cyclic trinuclear, polymeric chains, and linear trinuclear from Cu(II), Fe(III), and Co(III) complexes using alkali, alkaline, and transition metal ions
    (2024) Chanreingam, L
    A simple ligand, which is chiral and flexible, was used to synthesize Cu(II) complexes such that the resulting complex can act as a chiral host and is flexible enough to obtain a secondary coordination sphere. Cu(II) bis complex, when reacted with K+ ion, forms a cyclic trinuclear, which resembles an inorganic crown ether. In this process, the trans-oriented Cu(II) bis complex was converted to a cis-oriented complex. An excess of [18] crown-6 was added, and the K+ was removed from the assembly, thereby obtaining a cis-oriented Cu(II) monomer. The cis-oriented disassembled Cu(II) monomer, when reacted with K+, forms back the assembly.
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    Synthesis of Furan, Pyran, Pyrrolidine, and Piperidine Scaffolds via Tandem Prins Cyclization Reactions
    (2023) Shit, Sudip
    The content of this thesis has been divided into five chapters on the basis of results of experimental work performed during the complete course of the PhD tenure. The chapter 1 describes the tandem Prins cyclization reactions and their mechanisms to construct Furan, Pyran, pyrrolidine and piperidine scafolds in brief. The chapter 2 deals with the stereoselective synthesis of hexahydrofuro[3,4-b] furan-4-ol and its dimer via tandem Prins and pinacol rearrangement. The dimer was conveniently converted into its corresponding monomer using aqueous zinc(II) chloride in THF in quantitative yields. Chapter 3 describes synthesis of spiro[furan-2,1′-isoindolin]-3′-ones from 2‑(4- hydroxybut-1-yn-1-yl)benzonitriles and aryl aldehydes under the action of triflic acid. The plausible mechanism of the reactipon has been drawn on the basis of control experiments and literature evidence. The synthetic utility of the reaction was performed using Sonogashira reaction and click reaction conditions. In chapter 4, nitrile stabilized synthesis of pyrrolidine and piperidine derivatives via tandem alkynyl aza-Prins-Ritter reactions is described. In chapter 5, regio- and chemoselective synthesis of 3-(dihydrofuran-3(2H)-ylidene)isobenzofuran-1(3H)-imines via tandem alkynyl Prins- and intramolecular oxycyclization reaction is disclosed. The methodology was extended towards synthesis of its pyran derivatives. The post synthetic applications of the reaction were extended towards synthesis of furanylidene-isobenzofuranones in excellent yields. The mechanistic investigation of the reaction was performed on the basis of controlled experiment.
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    Design, Synthesis and Investigations of Liquid Crystalline Organic Semiconductors
    (2023) Vishwakarma, Vinod Kumar
    This thesis entitled “Design, Synthesis and Investigations of Liquid Crystalline Organic Semiconductors” describes simple and straightforward synthetic pathways, characterizations and applications of new LC/non-LC organic materials, with their potential applications in acid sensing, optoelectronic devices mainly OLEDs and OFETs applications. A brief overview of the chapters is given. Chapter 1, gives a general introduction to liquid crystals, characterization techniques and their applications. Chapter 2a addresses the synthesis and characterization of pyrazino[2,3-g]quinoxaline (PQ) derivatives where the central pyrazino[2,3-g]quinoxaline central core is substituted with eight peripheral flexible tails of varying lengths. The compounds with very short/branched peripheral chains did not stabilize any liquid crystalline phase, while the medium to long-chain homologs exhibited columnar phases. All the compounds exhibited a high molar extinction coefficient and bright greenish-yellow emission behavior in solution and solid state. One of the columnar liquid crystalline materials was used in the fabrication of host-guest OLED exhibited higher efficiency and bright green emission. Chapter 2b describes the sensing ability of the pyrazino[2,3-g]quinoxaline derivative to volatile trifluoroacetic acid in trace amounts (in parts per billion levels). The reversible detection of acid-sensing behavior was visually perceivable in both solutions as well as in the drop-casted film on a TLC paper-based strip. Chapter 3 explains new design strategies for the synthesis of donor-acceptor-donor pyrazino[2,3-g]quinoxaline carbazole derivatives with straight chain and branched alkyl peripheral chains. The electron-donating carbazole moieties that have been placed in the periphery showed a strong electron-donating ability, high molar extinction coefficients and lower band-gap, bright emission behavior in solution and solid-state, along with positive solvatochromism. One of the branched chain compounds was used in yellow and white OLEDs device fabrications. Chapter 4 describes the detailed synthesis of naphthalene and perylene-based imidazole derivatives with a new donor-π-acceptor-π-donor architecture containing ten flexible chains for solution-processable organic field effect transistor (OFETs) applications. These compounds showed a wide range of columnar LC behavior. One of these naphthalene and perylene bisimide derivatives were evaluated for their application in OFET devices exhibited high hole mobility values.
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    Stimuli-responsive Turn-on Fluorogenic Donors of Hydrogen Sulfide (H2S) and the Prodrugs of Anti-cancer Compounds
    (2023) Mahato, Sulendar K
    The dissertation entitled “Stimuli-responsive Turn-on Fluorogenic Donors of Hydrogen Sulfide (H2S) and Prodrugs of Anti-Cancer Compounds” consists of four chapters based on the results of experimental works performed during the complete course of Ph.D. research tenure.
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    Stereospecific Opening and Cyclization of the Strained Ring Systems for the Synthesis of Six-Membered Heterocycles
    (2022) Das, Bijay Ketan
    The thesis is divided into four chapters. The first chapter describes the general introduction to the opening and cyclization of the strained ring system for the synthesis of six-membered heterocycles. The second chapter focuses on the synthesis of piperazines and tetrahydropyrazines through stereospecific ring-opening and cycloisomerization of aziridines with N-propargylamines. Third chapter covers stereospecific synthesis of substituted 1,4-oxazine via Zn/Ag Relay catalyzed ring opening/hydroalkoxylation of oxiranes with N-propargylamines. Chapter four deals with the stereospecific assembly of tetrahydroquinolines via tandem ring-opening/oxidative cyclization of donor-acceptor cyclopropanes with N-alkyl anilines.
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    Application of Modified Smooth Exterior Scaling Method to Study Auger and Shape Resonances in Different Atomic and Molecular Systems
    (2024) Banuary, Mwdansar
    This thesis focuses on the application of modified smooth exterior scaling (MSES) as an efficient method to impose outgoing boundary conditions in e-atom and e-molecule scattering resonances. This is the first time that the MSES method has been applied to calculate energies and widths of Auger and shape resonances in three-dimensional many-body electron systems. MSES converts the divergent resonance wave functions into square integrable ones thereby making the study of temporary bound states (resonance states) amenable to bound state electronic structure methods. The main objective of this thesis is to formulate the MSES method in bivariational SCF and electron propagator methods.
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    N- and O- Donor Ligands for Fluorometric and Colorimetric Detection of Metal Ions
    (2024) Bhattacharya, Araghini
    This Thesis contains five chapters. Chapter 1 is the introduction which describes the contribution of metals in our daily lives and their adverse effects on human beings when exposed to excess amounts along with a brief elaboration of different detection techniques. Some recent developments in devising fluorescent and colorimetric probes are also discussed. In Chapter 2 the 2,4,5-tris(2-pyridyl)imidazole (L1H) molecule has been evaluated as a probe for dual sensing of Hg2+ and Cu2+ ions in EtOH/HEPES buffer medium (5 mM, pH = 7.34, 1:1, v/v). Probe L1H shows a good sensitive and selective turn off response in the presence of both Hg2+ and Cu2+ ions, which is comprehensible under long UV light. Its sensitivity was evaluated in different pH medium and in presence of other metal ions. Paper strip experiments and in-vitro cell imaging was done to know the sensitivity of the probe towards the metal ions in different environment. Chapter 3 describes the probe 2,6-di(2-pyridyl)-1,5-dihydroimidazo[4,5-f]benzimidazole (L2H2) and its sensing application towards metal ions. This probe could detect Zn2+ and Cd2+ ions in three different aqueous systems viz., water, DMSO/HEPES buffer (1:1, pH = 7.34, rt), and DMSO/water (1:1, rt). In water a “turn-on” response was observed for both metal ions, whereas in the latter two solvent systems, a ratiometric change in fluorescence maximum was observed. The detection limit of this probe was as low as 0.3 μM and 0.62 μM (in water) for Zn2+ and Cd2+ ions, respectively. In Chapter 4 synthesis and evaluation of a novel probe N'-(pyren-1-ylmethylene)benzo[d]imidazo[2,1-b]thiazole-2-carbohydrazide (L3H) as metal ion sensor was explored. It was found to be able to nanomolar detection of Pd2+ and Ni2+ ions by colorimetric change. This probe was also able to detect the presence of Pd2+ ions in drug samples and APIs without any major interference. LOD values were calculated to be 46.1 to 93.9 nM (4.9 to 6.0 ppb) for PdCl2 and 10.6 to 19.6 nM (1.1 to 2.1 ppb) for Pd(PPh3)2Cl2 and 9.301 nM for NiCl2 solutions. It also showed extremely good recovery of Pd2+ in presence of all the drug molecules. In Chapter 5 another novel ligand L4H based on 2,7-dichlorofluorescein was synthesized and evaluated for sensing applications. It was found to be able to detect Co2+ and Cu2+ ions differentially by different colouration of the solution in presence of these two metal ions. In situ Cu-complex of the ligand was utilised for quantification of amino acids like BSA and HSA proteins. Its differential selectivity paved the for molecular logic gate application.
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    Computational investigation of excited state processes in ESIPT-based systems and vinylene-linked thiophene pyrrole
    (2024) Mawa, Ibanrishisha
    The thesis focuses on understanding the mechanistic pathway in systems undergoing excited state intramolecular proton transfer and cis-trans isomerization. Unveiling the mechanism of these processes at an atomistic scale is of utmost importance as it would add to our understanding and assist in designing materials with better performance. These kinds of processes are observed in our everyday life such as the vision process in retinal chromophores, vitamin D production in humans on exposure to sunlight and mutation during DNA replication, etc. The application part of systems undergoing photoinduced processes are realized in the design and development of certain materials such as optoelectronic devices. The thesis has three working chapters. The first work is based on 1-hydroxy-2-acetonaphthone (HAN) due to the unsettled issues regarding the proton transfer process. In addition, the process of full photocycle including the non-radiative relaxation pathways is proposed. The second work highlights the effect of implicit solvents on the photoinduced processes in nitrile-substituted 2-(oxazolinyl)-phenols. Additionally, the mechanisms behind these two regiomers’ weakly emissive properties in the solvent phases are investigated. My last work involves the exploration of photoisomerization pathways in vinylene-linked thiophene-pyrrole system. Considering the computational cost for the dynamics study in the excited state, we have employed single-reference method such as time-dependent density functional theory (TDDFT) and algebraic diagrammatic construction scheme of second order (ADC(2)). However, multi-reference studies are also incorporated in our study wherever the single-reference methods fail.
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    Properties and Potential Applications of Biomimetic and Bio-derived Nanofluidic Systems
    (2021) Konch, Tukhar Jyoti
    The branch of fluid dynamic that explore the flow of liquid in structure constrained to nanometer size regime (1-100nm) is defined as nanofluidic. Fluidic transport in and around nanofluidic structures is dominated by interactions of otherwise weak effects such as the formation of electrical double layers (EDL), attractive or repulsive forces of charged species, and entropic barriers. Typically, transport of charged species through nanometer-sized channels are dominated by the overlapping electrical double layers. One of the major difficulties in designing nanofluidic devices is the inherent complexity. The overall transport characteristics are determined by the interplay of various nanoscale or even molecular level physical, geometric, and chemical factors. Biological ion channels, however, are known for their capability of elaborately manipulating these factors to regulate the transmembrane ionic flow, which plays a crucial role in a number of physiological processes. Mimicking the biological systems researchers has tried to demonstrate its artificial counterparts. In light of this feature, various ion-channel-mimetic smart 1D nanofluidic systems have been developed that can reproduce functions analogous to its parent biological systems. Although systematic research in single-pore devices makes the physical picture of this nanofluidic process much clear, it is still far from competent for practical applications. Toward practical applications, one major challenge is to extrapolate individual nanofluidic devices to macroscopic platform in a cost-efficient way. Interestingly solution to the above mentioned dilemma was also resolved from natural inspirations in the form of lamellar microstructure of nacre, in which soft materials (polysaccharides and proteins) are sandwiched between hard inorganic layers (aragonite platelets), forming an alternatively arranged layered structure. This novel method of material designing and large-scale integration of individual artificial nanofluidic channels into a macroscopic platform give birth a new research filed known as the 2D nanofluidics. Via a simple vacuum filtration process, colloidal dispersions of individual 2D nanosheets can be reassembled into a densely stacked multi-layered structure. The interstitial space between opposite 2D nanosheets can be treated as lamellar channels for mass and charge transport.
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    Transition-Metal Catalyzed Regioselective C-C/C-Heteroatom Bond Formations: Access to Functionalized Arenes and Heterocycles
    (2022) Sarkar, Tanumay
    The thesis is divided into four chapters. The first chapter illustrates a Ru(II)-catalyzed siteselective C-H acyloxylation of N-aryl-2-pyrimidines with carboxylic acids as the acyl source. The second chapter describes a Ni(II)-catalyzed oxidative C-H heteroarylation of arenes with azoles utilizing a removable oxazoline-based directing auxiliary. The third chapter deals with the Bi(III)- catalyzed annulation of 2-naphthols with N-sulfonylaziridines. The fourth chapter demonstrates (3+3)-cycloaddition of aziridines with diaziridines for the stereospecific synthesis of triazines under Fe(III)-catalysis.
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    Ipso Nucleophilic Substitution on Electron Deficient Arene Systems
    (2024) Mondal, Sandip
    The thesis entitled, “Ipso Nucleophilic Substitution on Electron Deficient Arene Systems” mainly focused on the development of greener and transition metal free methodologies for various alkylation reactions. The contents of the thesis have been divided into five chapters based on the results of experimental works performed during the research period.
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    Design of Coatings Embedded with Tolerant, Tailored and Responsive Underwater Oil Wettability and Oil Adhesion
    (2023) Borbora, Angana
    The anti-oil wettability of various naturally existing underwater creatures has inspired researchers to develop artificial super oil repellent interfaces for multiple applications in engineering, healthcare, and environmental remediation. In the past, several approaches were adopted to artificially fabricate underwater oil-repellent surfaces, formally known as underwater superoleophobicity, by co-optimizing hydrophilic chemical composition and rough micro/nano-structures on their surface. However, the earlier reported approaches in deriving underwater superoleophobicity were unable to associate some other essential properties, such as, physical and chemical durability, adaptive tuning of oil adhesion, and transparency in the prepared surfaces. Here, a facile 1, 4-conjugate addition reaction is exploited to derive covalently crosslinked chemically reactive coatings on various surfaces loaded with residual chemical functionalities that provide the opportunity to embed underwater superoleophobicity through appropriate post-covalent modifications. While the covalent crosslinking tailored mechanical property, the adequate chemical post-modification customized oil adhesion and optical transparency. The thesis entitled “Design of Coatings Embedded with Tolerant, Tailored and Responsive Underwater Oil Wettability and Oil Adhesion” is presented in six chapters. Chapter 1 introduces bio-mimicked underwater superoleophobic surfaces, the existing challenges associated with conventional artificial fabrication approaches, and the objectives of the thesis work. Chapter 2 demonstrates the fabrication of a dually reactive multilayer coating following the 1, 4-conjugate addition reaction and the post-covalent modification of the multilayer coating to immobilize highly sensitive bare micro-meter sized nematic liquid crystal (LC) droplets underwater for single LC droplet based repetitive sensing application. Chapter 3 accounts for the utilization of the dually reactive multilayer coating to develop various responsive underwater superoleophobic surfaces via post-modifications and their adaptive oil adhesion for sensing different amphiphilic (cationic, anionic and facial) molecules. Chapter 4 demonstrates the rational functionalization of the dual reactive multilayer coating to depict the highly selective raising of the oil contact angle (OCA) and rolling of a beaded oil droplet underwater in the presence of targeted and relevant toxic chemicals. Chapter 5 introduces a covalently crosslinked and chemically reactive sol-gel conversion process through the 1, 4-conjugate addition reaction to achieve a substrate-independent, mechanically durable, and optical transparent coating embedded with underwater superoleophobicity. Moreover, this approach allows to modulate mechanical property of highly deformable objects. Chapter 6 provides a brief summary and the future outlook of the work presented here.