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In the present work, we have studied the influence of gold nanoparticles (AuNPs) on the photoluminescence (PL) behavior of cadmium selenide (CdSe) quantum dots (QDs) confined in spatially separated soft nanoscale cylindrical domains. These cylindrical domains, in the form of hairy core‐shell nanofibers, were fabricated via cooperative self‐assembly of polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) block copolymer (BCP) mixed with pre‐synthesized CdSe QDs and AuNPs. The CdSe QDs and AuNPs were simultaneously incorporated in the P4VP cylindrical domains of the self‐assembled BCP structure. It was found that the confinement imposed by the nanometer‐sized cylindrical core resulted in the localization of the CdSe QDs and AuNPs in close proximity. Notably, it was observed that the PL intensity of the CdSe QDs could be manipulated by varying the amount of AuNPs present in the cylinder core. Interestingly, in the presence of a very low fraction of AuNPs, the PL intensity of the CdSe QDs increased compared to the AuNPs‐free system. However, further increase in the fraction of AuNPs led to gradual quenching of the photoluminescence intensity. The PL enhancement and quenching plausibly was due to the interplay between the energy transfer due to surface plasmon coupling and FRET/electron transfer from QDs to the AuNPs. The resulting functional nanofibers could have potential applications in sensing, bioimaging, and optoelectronic devices. [ABSTRACT FROM AUTHOR]

In the present study, we demonstrate the fabrication of multifunctional nanofibers, loaded with CdSe quantum dots (QDs) and sulforhodamine 101 (S101) dye, via the self-assembly process of a polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP). The CdSe QDs and S101 dye were simultaneously incorporated in the cylindrical domains, constituted of P4VP blocks, of the self-assembled BCP structure. The cylindrical domains subsequently were isolated as individual nanofibers via the selective-swelling approach. The confinement imposed due to the nano-dimension geometry of the cylindrical domains enabled the QDs and S101 dye to localize within their Förster radius enabling an efficient fluorescence resonance energy transfer (FRET) between them. The mean lifetime of donor emission varied from 4.56 to 3.38 ns with the change in the ratio of S101 dye and CdSe QDs within the nanofibers. Furthermore, using efficiency measurements and the corresponding Förster distances, donor–acceptor distances were determined. Moreover, the kinetics of energy transfer from CdSe QDs to S101 was studied by the Poisson binding model, to understand the interactions between CdSe QDs and S101 dye molecules. The numbers of dye molecules per CdSe QD were determined, by assuming random distribution of S101 dye molecules around the CdSe QDs in the nanofibers. The results showed that the number of dye molecules per QD increased with increasing concentration of dye molecules in the nanofibers. The resulting multifunctional nanofibers could have potential applications in optoelectronics, photonics and sensors which utilize the FRET process. [ABSTRACT FROM AUTHOR]

We investigate the self-assembly of a cylinder-forming polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) mixed with trioctylphosphine oxide (TOPO) capped cadmium selenide (CdSe) quantum dots (QDs). The QDs were found to be enthalpically compatible with the P4VP chains via ligand displacement of TOPO from the QD surface. However, the QDs were found to localize preferentially at the PS/P4VP interphase plausibly to gain translational entropy in order to further lower the energetics of the self-assembled structure. Interestingly, the morphological transformation observed with increasing weight fraction of the QDs in the BCP/QD composite was driven by the migration of the displaced TOPO from the QD surface to the PS phase, effectively increasing its total volume fraction. Hence, the PS-b-P4VP BCP with PS as the minority block displayed lamellar morphology in its composite with QDs. Furthermore, the preferred localization of the QDs at the PS/P4VP interface led to the formation of a trilayer lamellar morphology which was deduced from the suppression of the primary scattering peak, relative to higher order peaks in the SAXS data. The morphological transformation was accompanied by a significant increase in the domain spacing due to excessive stretching of the longer P4VP chains of the asymmetric block copolymer. However, in the PS-b-P4VP/CdSe composites with P4VP as the minority block, cylindrical morphology was retained and the domain spacing decreased due to dominance of the co-surfactant effect as well as interfacial localization of CdSe QDs. We also demonstrate that these PS-b-P4VP/CdSe self-assembled hybrid materials could further be used to obtain isolated core–shell nanoobjects, such as nanofibers and nanosheets, containing CdSe QDs. The nanoobjects so obtained exhibited photoluminescence properties typical of CdSe quantum dots. These photoluminescent polymer nanoobjects could have potential applications in biological targeting and fluorescence labeling. [ABSTRACT FROM AUTHOR]

Fabrication of block copolymer (BCP) template-assisted nano-catalysts has been a subject of immense interest in the field of catalysis and polymer chemistry for more than two decades now. Different methods, such as colloidal route, on-substrate methods, bulk self-assembly approaches, combined approaches, and many others have been used to prepare such nano-catalysts. The present review focuses on the advances made in this direction using diblock, triblock, and other types of BCP self-assembled structures. It will be shown how interestingly, researchers have exploited the features of tunable periodicity, domain orientation, and degree of lateral orders of self-assembled BCPs by using fundamental approaches, as well as using different combinations of simple methods to fabricate efficient catalysts. These approaches allow for fabricating catalysts that are used for the growth of single- and multi-walled carbon nanotubes (CNTs) on the substrate, size-dependent electrooxidation of the carbon mono oxide, cracking of 1,3,5-triisopropylbenzene (TIPB), methanol oxidation, formic acid oxidation, and for catalytic degradation of dyes and water pollutants, etc. The focus will also be on how efficient and ease-of-use catalysts can be fabricated using different BCP templates, and how these have contributed to the fabrication of different nano-catalysts, such as nanoparticle array catalysts, strawberry and Janus-like nanoparticles catalysts, mesoporous nanoparticles and film catalysts, gyroid-based bicontinuous catalysts, and hollow fiber membrane catalysts. [ABSTRACT FROM AUTHOR]

The quest to decode the evolution of homochirality of life on earth has stimulated research at the molecular level. In this study, handed mirror symmetry breaking, and molecular parity violation hypotheses of systematically designed π-conjugated rotamers possessing anthracene and bianthracene core were evinced via circularly polarized luminescence (CPL) and circular dichroism (CD). The CPL signals were found to exhibit a (−)-sign, and a handed dissymmetry ratio, which increased with viscosity of achiral solvents depending on the rotation barrier of rotamers. The time-resolved photoluminescence spectroscopy and quantum efficiency measurement of these luminophores in selected solvents reinforced the hypothesis of a viscosity-induced consistent increase of the (−)-sign handed CPL signals. [ABSTRACT FROM AUTHOR]

Catalytically active porous and hollow titania nanofibers encapsulating gold nanoparticles were fabricated using a combination of sol-gel chemistry and coaxial electrospinning technique. We report the fabrication of catalytically active porous and hollow titania nanofibers encapsulating gold nanoparticles (AuNPs) using a combination of sol-gel chemistry and coaxial electrospinning technique. The coaxial electrospinning involved the use of a mixture of poly(vinyl pyrrolidone) (PVP) and titania sol as the shell forming component, whereas a mixture of poly(4-vinyl pyridine) (P4VP) and pre-synthesized AuNPs constituted the core forming component. The core-shell nanofibers were calcined stepwise up to 600 °C which resulted in decomposition and removal of the organic constituents of the nanofibers. This led to the formation of porous and hollow titania nanofibers, where the catalytic AuNPs were embedded in the inner wall of the titania shell. The catalytic activity of the prepared Au@TiO 2 porous nanofibers was investigated using a model reaction of catalytic reduction of 4-nitrophenol and Congo red dye in the presence of NaBH 4 . The Au@TiO 2 porous and hollow nanofibers exhibited excellent catalytic activity and recyclability, and the morphology of the nanofibers remained intact after repeated usage. The presented approach could be a promising route for immobilizing various nanosized catalysts in hollow titania supports for the design of stable catalytic systems where the added photocatalytic activity of titania could further be of significance., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Core/intermediate/shell (C/I/S) structures with Type-I emission are well-known and are gaining immense importance due to their superior luminescence properties. Here, we report a unique C/I/S structure composed of CdSe/CdS/ZnSe that exhibits both Type-I and Type-II phenomena. The structures have been well characterized using a combination of optical and structural techniques. The photoluminescence (PL) and photoluminescence excitation (PLE) data indicate the formation of a combined Type-I and Type-II structure in one material, results supported by simple theoretical calculations. Single particle fluorescence reveals colocalization of both the emissions. The X-ray diffraction (XRD) and transmission electron microscopy (TEM) results confirm the structure of these particles. The time-resolved fluorescence studies show the possibility of tuning the lifetime of these materials by changing the Type-I/Type-II thickness ratios. It is possible to form these two separate excitons in the same system separated by a CdS intermediate layer that acts both as a barrier and an active member of the Type-II system allowing the generation and recombination of two excitons, in violation of Kasha's rule.