Preparation And Application Of Hybrid Materials Based On Water-Soluble Macrocyclic Arenes Functionalized Gold Nanoparticles

Hybrid materials based on water-soluble macrocyclic arenes functionalized gold nanoparticles(AuNPs)possess the integration of unique properties relative to the individual organic/inorganic components.On the one hand,AuNPs possess many excellent properties,including high chemical stability,facile synthesis,surface functionalization,biocompatibility,tunable optical and electronic properties and so on.On the other hand,macrocyclic arenes continue to be central to supramolecular chemistry based on their recognition properties.In particular,water-soluble macrocyclic arenes have been extensively employed in different scientific areas,such as drug delivery,sensing and green catalysis,due to their rigid structures,facile functionalization,unique host–guest properties,as well as great biocompatibility.In this dissertation,hybrid materials based on water-soluble macrocyclic arenes functionalized Au NPs were fabricated utilizing water-soluble macrocyclic arenes with different structures and substituent groups through different methods.Systematic researches have been carried out on their preparations,supramolecular self-assemblies and applications in sensing,drug delivery,and green catalysis.Firstly,we constructed a smart drug delivery system,based on a quaternary ammoniumsaltfunctionalizedMSN(MSN-Q)gatedby carboxylatopillar[5]arene-modified AuNPs(CP5-AuNPs)via host–guest interactions,which responds to a competitive binding agent and temperature changes.For the first time,we achieved the combination of the host–guest properties of CP5 and the photothermal conversion capability of AuNPs in one hybrid drug delivery platform.Compared to traditional nanovalves based on host–guest interactions,this AuNPs-capped MSN-Q system,with a tunable size of AuNPs and a pore size of MSNs in conjunction with multipoint recognition,is expected to break the limitation of the cargo size and be an ideal candidate for drug delivery.Furthermore,the AuNPs-capped MSN-Q hybrid nanosystem,with tremendous latent capacity to achieve remote controlled and“ladder”pulsatile release in response to noninvasive operation,provides practical insights into the design of advanced nanocarriers towards synergistically increasing the drug delivery efficiency for chemotherapies in diseases.Secondly,we in situ prepared medium sized gold nanoparticles(AuNPs)coatedwithananoporouslayerofsyntheticmacrocycles(Carboxylatopillar[6]arene sodium salt,CP6 for short)via reversed Turvevich method for the first time.On the one hand,the rapid formation of nucleus was promoted through the reversed Turkevich method.On the other hand,the electrostatic interaction of-COO~?groups and the pillar-shaped rigid skeleton structure of CP6 not only limit the growth and aggregation of AuNPs,but also stabilize the resulting system.Significantly,label-free detection of the paraquat(methyl viologen,MV for short)was achieved via the combination of two different methods of spectral analysis utilizing the fascinating host-guest properties of AuNPs endowed by medim sized and the nanoporous layer of CP6on the AuNP surface.Furthermore,we demonstrated the catalysis ability of CP6@AuNPs for the hydrogenation of nitrophenols.Thirdly,we prepared the anionic water-soluble[2]phenyl-extended Pillar[6]arenes(AW[2]P-DeP6,AWPP6 for short)modified AuNPs(AWPP6@AuNPs)by a facile one-pot hydrothermal method for the first time.AWPP6 can be used as efficient reducing agents and optimal stabilizers for preparing AWPP6@AuNPs.In addition,TPE-4Q mediated assembly of AWPP6@AuNPs has been further investigated with the appearance of different amounts of TPE-4Q,which indicating the host-guest recognition properties of AWPP6@AuNPs have been endowed by AWPP6.Intriguingly,we demonstrated the optimal performance in label-free detection of methyl viologen of AWPP6@AuNPs and their efficient catalytic activity for the hydrogenation of nitrophenol.