References of "Patil, Nagaraj"
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See detailBioinspired redox-active catechol-bearing polymers as ultra-robust organic cathodes for lithium storage
Patil, Nagaraj ULiege; Aqil, Abdelhafid ULiege; Ouhib, Farid ULiege et al

in Advanced Materials (2017), 29(40), 1703373

Redox-active catechols are bioinspired precursors for ortho-quinones that are characterized by higher discharge potentials than para-quinones, the latter being extensively used as organic cathode ... [more ▼]

Redox-active catechols are bioinspired precursors for ortho-quinones that are characterized by higher discharge potentials than para-quinones, the latter being extensively used as organic cathode materials for lithium ion batteries (LIBs). Here, this study demonstrates that the rational molecular design of copolymers bearing catechol- and Li+ ion-conducting anionic pendants endow redox-active polymers (RAPs) with ultrarobust electrochemical energy storage features when combined to carbon nanotubes as a flexible, binder-, and metal current collector-free buckypaper electrode. The importance of the structure and functionality of the RAPs on the battery performances in LIBs is discussed. The structure-optimized RAPs can store high-capacities of 360 mA h g−1 at 5C and 320 mA h g−1 at 30C in LIBs. The high ion and electron mobilities within the buckypaper also enable to register 96 mA h g−1 (24% capacity retention) at an extreme C-rate of 600C (6 s for total discharge). Moreover, excellent cyclability is noted with a capacity retention of 98% over 3400 cycles at 30C. The high capacity, superior active-material utilization, ultralong cyclability, and excellent rate performances of RAPs-based electrode clearly rival most of the state-of-the-art Li+ ion organic cathodes, and opens up new horizons for large-scalable fabrication of electrode materials for ultrarobust Li storage. [less ▲]

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See detailMultifunctional Polyelectrolytes Bearing Pendant Catechol / Quinone for Energy and Environmental Applications
Patil, Nagaraj ULiege

Doctoral thesis (2017)

The discovery of 3,4-dihydroxyphenyl-L-alanine (L-DOPA), a catechol-functionalized amino acid as major component in mussel adhesion proteins, has triggered enormous interest in mussel-mimetic adhesives ... [more ▼]

The discovery of 3,4-dihydroxyphenyl-L-alanine (L-DOPA), a catechol-functionalized amino acid as major component in mussel adhesion proteins, has triggered enormous interest in mussel-mimetic adhesives. The design of innovative bioinspired polymers-containing catechols has rapidly gained widespread utility in the (bio)material field, ascribed to the versatility of the catechol chemistry that allows anchoring (bio)polymers, biomolecules, nanoparticles (metals and metal oxides) and other compounds onto almost any kind of surfaces without any pre-treatment. Amongst the various synthetic protocols to incorporate catechol functionalities into (bio)polymers, the radical polymerization of catechol-bearing vinyl monomers in their protected form has proven to be a versatile technique to impart intrinsic physico–chemical properties of the catechol pendants to polymers after appropriate deprotection. Importantly, the scope of applications of catechol-bearing polymers can potentially be drastically increased by developing controlled radical polymerization (CRP) techniques of their protected vinyl monomers. Indeed, these techniques will enable to precisely design the polymer with the appropriate structure, molar mass and functionality that fit at best the target application. When this thesis started in 2013, only very limited examples of functional catechol-bearing polymers prepared by CRP were reported. The aim of this PhD thesis was to develop well-defined innovative catechol-containing (co)polymers that find applications in energy storage and environmental fields by employing function-oriented macromolecular engineering approaches. In this work, numerous catechol-protected monomers have been prepared and their CRP investigated to afford well-defined (co)polymers with controlled and tunable molar masses, compositions, functionalities, and architectures (homopolymers, statistical and block copolymers). The potential of these innovative catechol-containing (co)polymers was then explored for applications in energy storage (as active-material in lithium-ion half-cells) and environment (as protein fouling/antifouling coatings). [less ▲]

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See detailInnovative polyelectrolytes/poly(ionic liquid)s for energy and environment
Ajjan, Fátima N.; Ambrogi, Martina; Tiruye, Girum Ayalneh et al

in Polymer International (2017), 66(8), 1119-1126

This manuscript presents the work carried out within the European Project RENAISSANCE-ITN, which was dedicated to the development of innovative polyelectrolytes for energy and environmental applications ... [more ▼]

This manuscript presents the work carried out within the European Project RENAISSANCE-ITN, which was dedicated to the development of innovative polyelectrolytes for energy and environmental applications. Within the project different types of innovative polyelectrolytes were synthesized such as poly(ionic liquid)s coming from renewable or natural ions, thiazolium cations, cathechol functionalities or from a new generation of cheap deep-eutectic monomers. Further, macromolecular architectures such as new poly(ionic liquid) block copolymers and new (semi)conducting polymer/polyelectrolyte complexes were also developed. As the final goal, the application of these innovative polymers in energy and environment was investigated. Important advances in energy storage technologies included the development of new carbonaceous materials, new lignin/conducting polymer biopolymer electrodes, new iongels and single-ion conducting polymer electrolytes for supercapacitors and batteries and new poly(ionic liquid) binders for batteries. On the other hand, the use of the innovative polyelectrolytes into sustainable environmental technologies led to the development of new liquid and dry water, new materials for water cleaning technologies such as floculants, oil absorbers, new recyclable organocatalysts platform and multifunctional polymer coatings with antifouling and antimicrobial properties. All in all this article demonstrates the potential of the poly(ionic liquid)s for high-value applications in Energy & Enviromental areas. [less ▲]

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See detailMultifunctional poly(ionic liquid)s: from synthesis to applications in energy and environment
Detrembleur, Christophe ULiege; Patil, Nagaraj ULiege; Debuigne, Antoine ULiege et al

Conference (2017, May 24)

Poly(ionic liquid)s (PILs) are a subclass of polyelectrolytes that gained an enabling role in many fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids ... [more ▼]

Poly(ionic liquid)s (PILs) are a subclass of polyelectrolytes that gained an enabling role in many fields of polymer chemistry and material science. PILs combine the unique properties of ionic liquids with the flexibility and properties of macromolecules, and provide novel attractive functions. Recently, the precision design of novel PILs by controlled/living polymerization (CLP) techniques was intensively searched for developing emerging applications. This talk will first discuss recent routes for the precision synthesis of all vinyl-imidazolium based (co)polymers in water or in organic media under non-demanding experimental conditions. We will then describe the preparation of innovative redox and surface active PILs, and show the potential of these PILs in battery applications and for multifunctional coatings. More specifically, we will show how macromolecular engineering can be exploited for designing innovative polymer cathodes for ultra-high performance Li storage with unprecedented performances (high capacities and ultra-long life-span over more than 3000 cycles at an extreme current-rate). This innovative and effective molecular design for polymer cathodes opens up new horizons in developing an economical and environmentally benign platform for large-scalable fabrication of high performance batteries. [less ▲]

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See detailSurface- and redox-active multifunctional polyphenol-derived poly(ionic liquid)s: controlled synthesis and characterization
Patil, Nagaraj ULiege; Cordella, Daniela; Aqil, Abdelhafid ULiege et al

in Macromolecules (2016), 49(20), 7676-7691

Combining the redox activity and remarkable adhesion propensity of polyphenols (such as catechol or pyrogallol) with the numerous tunable properties of poly(ionic liquid)s (PILs) is an attractive route to ... [more ▼]

Combining the redox activity and remarkable adhesion propensity of polyphenols (such as catechol or pyrogallol) with the numerous tunable properties of poly(ionic liquid)s (PILs) is an attractive route to design inventive multifunctional macro-molecular platforms. In this contribution, we describe the first synthesis of a novel family of structurally well-defined PILs functionalized with catechol/pyrogallol/phenol pendants by organometallic-mediated radical polymerization (OMRP) using an alkyl−cobalt(III) complex as initiator and mediating agent. The living character of the chains is also exploited to produce di-and triblock PILs, and the facile counteranion exchange reactions afforded a library of PILs-bearing free phenol/catechol/pyrogallol moieties. Electrochemical investigations of catechol/pyrogallol-derived PILs in aqueous medium demonstrated the characteristic catechol to o-quinone transformations, whereas, quasi-reversible doping/undoping with supporting electrolyte cations (Li + /tetrabutylammonium +) has been observed in organic media, suggesting a bright future for this new family of redox-active PILs as cathode material for secondary energy storage devices. Also, pendant catechol/pyrogallol groups mediated sustained anchoring onto the gold surface conferred PILs properties to the interface. As a proof-of-concept, both the adsorption and inhibition of proteins on polymer modified surfaces have been demonstrated in real time using the quartz crystal microbalance with dissipation technique. The exquisite physicochemical tunability of these innovative surface-and redox-active PILs makes them excellent candidates for a broad range of potential applications, including " smart surfaces " and electrochemical energy storage devices. [less ▲]

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See detailPolymers bearing pendant catechols for organic electrode-active materials in lithium-ion batteries
Patil, Nagaraj ULiege; Cordella, Daniela ULiege; Aqil, Abdelhafid ULiege et al

Conference (2016, May 23)

Herein, we describe the synthesis and organometallic-mediated radical polymerization of 1-vinyl-3-alkylimidazolium-type monomers bearing pendant catechols in its protected version, using a presynthesized ... [more ▼]

Herein, we describe the synthesis and organometallic-mediated radical polymerization of 1-vinyl-3-alkylimidazolium-type monomers bearing pendant catechols in its protected version, using a presynthesized alkyl‒cobalt(III) complex as monocomponent initiator/mediating agent in a controlled fashion. A neat post-polymerization deprotection, followed by facile anion exchange reactions afforded a novel multi-functional poly(ionic liquids)-bearing free catechol functionalities. Prototype Lithium-ion battery, consisting a binder- and current collector-free electroactive polymer-supported buckypaper as the composite cathode, delivered an impressive specific capacity in the range of 199–230 mA h g‒1, relatively at high discharge potential = 3.2–3.4 V (vs Li/Li+), as calculated from CV and galvanostatic charge-discharge experiments. The superior electrochemical performance of the composite cathode consisting of PIL-catechols active-material, in comparison with poly(dopaminde acrylamide) is ascribed to the intrinsic Li-ion conductivity and enhanced surface activity of the imidazolium backbone with TFSI counteranion, compared to the acrylamide backbone. [less ▲]

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See detailOrganometallic-mediated radical polymerization, a versatile tool for the precision synthesis of unprecedented copolymers
Detrembleur, Christophe ULiege; Cordella, Daniela ULiege; Demarteau, Jérémy ULiege et al

Conference (2015, December 17)

Controlled radical polymerization techniques give access to innovative (multi)functional polymeric materials for advanced applications. Organometallic-mediated radical polymerization (OMRP) is one of ... [more ▼]

Controlled radical polymerization techniques give access to innovative (multi)functional polymeric materials for advanced applications. Organometallic-mediated radical polymerization (OMRP) is one of these techniques that enable the preparation of unprecedented copolymers, and is based on the temporary deactivation of the propagating chains by a transition metal complex. The strength of the carbon-metal bond at the polymer chain-end is dictating the reactivity of the system. One of the most efficient OMRP process involves the commercially available Co(acac)2. Recent studies have demonstrated that the system reactivity is easily modulated by the addition of some molecules able to coordinate the cobalt complex, by tuning the temperature, or by UV irradiation. The facile modulation of the C-Co bond strength has enabled to control the polymerization of monomers of opposite reactivity, such as vinyl esters and acrylates, and to synthesize novel well-defined (co)polymers under very mild experimental conditions. In this talk, we will discuss some recent breakthroughs in the field that illustrate the huge potential of the process for the design of unique functional macromolecules. More precisely, we will describe the first control of the copolymerization of ethylene with a series of functional vinyl monomers under mild experimental conditions that leads to random copolymers with ethylene content up to 60 mol% and negligible chain branching. The first one-pot synthesis of novel ethylene-based block copolymers will also be discussed. Additionally, we will demonstrate the implementation of the OMRP process to aqueous based media by describing, amongst other examples, the precision synthesis of innovative functional (telechelic) poly(ionic liquid)s (PILs) in water. [less ▲]

Detailed reference viewed: 78 (9 ULiège)
See detailControlled synthesis of multi-functional polymers bearing pendant catechols for surface modifications
Patil, Nagaraj ULiege; Aqil, Abdelhafid ULiege; Jérôme, Christine ULiege et al

Poster (2015, June)

Poly(ethylene glycol) (PEG)-based polymers have been widely employed in anti-fouling coating applications due to their robust bio-relevant properties including water solubility and biocompatibility ... [more ▼]

Poly(ethylene glycol) (PEG)-based polymers have been widely employed in anti-fouling coating applications due to their robust bio-relevant properties including water solubility and biocompatibility. However, limited by its poor adhesion towards surfaces, demands an addition modification strategies. Mussel adhesive proteins (MAPs) are potential models for adhesive polymers, which exhibits underwater adhesion towards dissimilar materials under environmentally challenging conditions. Most often experimentally simple, but structurally complex poly(dopamine) has been used as an analogues of MAPs for metal chelation, cross-linking and surface binding purposes. Inspired by MAPs, we have developed catechol-bearing copolymers for surface adhesion of stainless steel. This study describes the synthesis and reversible addition−fragmentation chain transfer (RAFT) polymerization of mussel-inspired acetonide-protected dopamine (meth)acrylamide monomers (ADA and ADMA). A series of well-defined P(PEGAm-b-ADAn) and P(ADMAn-b-PEGMAm) copolymers across a range of molar masses (13−42 kg/mol) with low molar mass dispersities (Đ = 1.12−1.25) were reported for the first time. Post polymerization TFA treatment yields block copolymers bearing free –catechol units in quantitative yields (>95%). The self-assembling nature of amphiphilic block-copolymers was studied by 1H-NMR, DLS and TEM. Surface functionalization and anti-fouling experiments were performed in real time using quartz crystal microbalance coupled with dissipation (QCM-D). The copolymer upon oxidation yields reactive quinones, which can be exploited to cross-link with chitosan (also, polymers with free –NH2 and –SH groups), thereby producing nano(macro)gels. In general, these novel class of block copolymeric ligand systems can be foreseen as versatile ingredients in material chemistry to obtain biocompatible multifunctional systems, benefited by high water solubility with inherent stealth ability and protein-repellency, as well as effective chelating groups, and may find application for a variety of biomedical fields, of which we have illustrated an important example. [less ▲]

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See detailMussel-inspired protein-repelling ambivalent block copolymers: controlled synthesis and characterization
Patil, Nagaraj ULiege; Falentin-Daudré, Céline; Jérôme, Christine ULiege et al

in Polymer Chemistry (2015), 6(15), 2919-2933

This paper describes the reversible addition–fragmentation chain transfer (RAFT) polymerization of mussel-inspired acetonide-protected dopamine (meth)acrylamide monomers (ADA and ADMA) and its ... [more ▼]

This paper describes the reversible addition–fragmentation chain transfer (RAFT) polymerization of mussel-inspired acetonide-protected dopamine (meth)acrylamide monomers (ADA and ADMA) and its implementation to the synthesis of innovative ambivalent block copolymers. They consist of a hydro- phobic poly((meth)acrylamide) block functionalized by catechols and a hydrophilic segment of a poly- ((meth)acrylate) bearing pendent PEG chains. For the first time, a series of well-defined P(PEGAm-b-ADAn) and P(ADMAn-b-PEGMAm) diblock copolymers across a range of molar masses (13–42 kg mol−1) with low molar mass dispersities (Đ = 1.12 − 1.25) were reported. Post polymerization, trifluoroacetic acid (TFA) treatment yields block copolymers bearing free-catechol units in quantitative yields (>95%) with a slight noticeable hydrolysis of pendent-PEG units (2%–4%). The self-assembly of the amphiphilic block copoly- mers into spherical micelles was demonstrated by 1H NMR, DLS and TEM imaging techniques. Real-time quartz crystal microbalance with dissipation monitoring (QCM-D) studies revealed that free-catechol groups were necessary for a strong anchoring onto gold and stainless steel surfaces because acetonide- protected and catechol-oxidized block copolymers completely desorbed from the surface in the rinsing step. The ambivalent nature of catechol functionalized block copolymers was studied by bovine serum albumin (BSA) adsorption on polymer modified surfaces, which displayed improved resistance against BSA adsorption, when compared to an unmodified surface. [less ▲]

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See detailSurface-immobilised anti-fouling block-copolymers: synthesis and characterization
Patil, Nagaraj ULiege; Detrembleur, Christophe ULiege; Jérôme, Christine ULiege

Poster (2014, May 20)

Poly(ethylene glycol) (PEG)-based polymers have been widely employed in anti-fouling coating applications due to their robust bio-relevant properties including water solubility and biocompatibility ... [more ▼]

Poly(ethylene glycol) (PEG)-based polymers have been widely employed in anti-fouling coating applications due to their robust bio-relevant properties including water solubility and biocompatibility. However, limited by its poor adhesion towards surfaces, demands an addition modification strategies. Mussel adhesive proteins (MAPs) are potential models for adhesive polymers, which exhibits underwater adhesion towards dissimilar materials under environmentally challenging conditions. Most often experimentally simple, but structurally complex poly(dopamine) has been used as an analogues of MAPs for metal chelation, cross-linking and surface binding purposes. Inspired by MAPs, we have developed catechol-bearing copolymers for surface adhesion of stainless steel. This study aims at developing novel catechol-bearing, PEG-based block-copolymers by reversible addition-fragmentation chain transfer (RAFT) polymerization technique. PEGA used as macro-RAFT to prepare acetonide-protected catechol as second block. Deprotection of acetonide groups under acidic conditions produced functional block-copolymer with free catechols as pendant moieties. The self-assembling nature of amphiphilic block-copolymers was studied by 1H-NMR, DLS and TEM. Surface functionalization and anti-fouling experiments were performed in real time using quartz crystal microbalance coupled with dissipation (QCM-D). The copolymer upon oxidation yields reactive quinones, which can be exploited to cross-link with chitosan (also, polymers with free –NH2 and –SH groups), thereby producing nano(macro)gels. Benefited from inherent anti-microbial and anti-oxidative properties of chitosan and catechol-respectively, could result in potential materials for water purification systems, food packaging and medical devices. [less ▲]

Detailed reference viewed: 236 (13 ULiège)