The present paper reports the fabrication of novel types of hybrid fibrous photocatalysts by combining block copolymer (BCP) templating, sol-gel processing, and coaxial electrospinning techniques. Coaxial electrospinning produces core-shell nanofibers (NFs), which are converted into hollow porous TiO2 NFs using an oxidative calcination step. Hybrid BCP micelles comprising a single plasmonic nanoparticle (NP) in their core and thereof derived silica-coated core-shell particles are utilized as precursors to generate yolk-shell type particulate inclusions in photocatalytically active NFs. The catalytic and photocatalytic activity of calcined NFs comprising different types of yolk-shell particles is systematically investigated and compared. Interestingly, calcined NFs comprising silica-coated yolk-shells demonstrate enhanced catalytic and photocatalytic performance despite the presence of silica shell separating plasmonic NP from the TiO2 matrix. Electromagnetic simulations indicate that this enhancement is caused by a localized surface plasmon resonance and a confinement effect in silica-coated yolk-shells embedded in porous TiO2 NFs. Utilization of the coaxially electrospun TiO2 NFs in combination with yolk-shells comprising plasmonic NPs reveals to be a potent method for the photocatalytic decomposition of numerous pollutants. It is worth noting that this study stands as the first occurrence of combining yolk-shells (Au@void@SiO2) with porous electrospun NFs (TiO2) for photocatalytic purposes and gaining an understanding of plasmon and confinement effects for photocatalytic performance. This approach represents a promising route for fabricating highly active and up-scalable fibrous photocatalytic systems.

This study tackles the persistent challenge of producing highly reinforced lignin-rubber composites, emphasizing the transformation of agro-industrial residues into value-added products. To address this challenge, we introduce a novel approach termed "in-situ surface modification utilizing a thermo-chemo-mechanical approach" which incorporates the utilization of biomass-derived kraft lignin and a thermally stable organofunctional surface modifier, specifically (3-aminopropyl) triethoxysilane. The resulting material exhibits unprecedented tensile strength ( 15 MPa) along with 300 % elongation at break, while typical gum rubber offers 1-2 MPa tensile strength. Additionally, for the other tensile properties like 100 %, and 200 % tensile modulus, the improvement is 7-fold ( 5.6 MPa) and 10-fold ( 11.3 MPa), respectively. Furthermore, this composite presents a higher degree of reinforcement than a passenger car radial (PCR) tire model compound (tensile strength 14.5 MPa, 100 % tensile modulus 2.2 MPa, and 200 % tensile modulus 5.6 MPa) comprised of silica and polysulfidebased coupling agent, with exactly a similar loading of filler. The dynamic mechanical and stress relaxation behavior of the composites are critically discussed concerning the dispersion of the lignin in the sSBR/BR rubber matrix. The morphological orientation and involved chemical interaction in the presence of a surface modifier are also studied in detail. Tear fatigue analysis using pure shear specimens indicates superior fracture toughness at a lower tearing energy regime compared to silica-filled PCR tire compounds. Overall, this study showcases the potential of lignin-reinforced elastomers, offering a promising route for sustainable engineering materials and commercial viability.

In the present work, we report the fabrication and characterization of well-defined core-satellite nanostructures. These nanostructures comprise block copolymer (BCP) micelles, containing a single gold nanoparticle (AuNP) in the core and multiple photoluminescent cadmium selenide (CdSe) quantum dots (QDs) attached to the micelle's coronal chains. The asymmetric polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) BCP was employed to develop these core-satellite nanostructures in a series of P4VP-selective alcoholic solvents. The BCP micelles were first prepared in 1-propanol and subsequently mixed with AuNPs, followed by gradual addition of CdSe QDs. This method resulted in the development of spherical micelles that contained a PS/Au core and a P4VP/CdSe shell. These core-satellite nanostructures, developed in different alcoholic solvents, were further employed for the time-resolved photoluminescence analysis. It was found that solvent-selective swelling of the core-satellite nanostructures tunes the distance between the QDs and AuNPs and modulates their Förster resonance energy transfer (FRET) behavior. The average lifetime of the donor emission varied from 12.3 to 10.3 nanoseconds (ns) with the change in the P4VP-selective solvent within the core-satellite nanostructures. Furthermore, the distances between the donor and acceptor were also calculated using efficiency measurements and corresponding Förster distances. The resulting core-satellite nanostructures hold promising potential in various fields, such as photonics, optoelectronics, and sensors that utilize the FRET process.

Polymerized ionic liquid (PIL)-based ionic chiral block copolymers (BCPs*) were synthesized by functionalization of a poly(4-vinyl pyridine) segment in poly(styrene)-block-poly(4-vinyl pyridine) (PS-b-P4VP) block copolymer. Because of the ease of the ion exchange reaction with the quaternized PIL block, chirality was induced with l-/d-histidine, which acted as chiral auxiliaries, via ion-exchange reaction. Interestingly, the self-assembled helical nanofibrils of BCPs* divulged the reversal of handedness with respect to intrinsic chirality at the molecular level. Remarkably, a similar reversal of handedness was also observed at the quaternary phase. This peculiar behavior of reversal of handedness was correlated to the molecular packing of helical chains according to a cholesteric hard-core model of liquid crystals possessing a large helical pitch to helix diameter (P/d) ratio, where P and d denote the helical pitch and helix diameter, respectively.

We investigate the encapsulation of polymer-tethered nanoparticles (NPs) inside block copolymer (BCP) micelles, which turns to the mutual stabilization of BCP micelles and NPs by each other. It has been demonstrated, for the first time, that in the presence of cosolvent, which is selective for the core-forming block, the encapsulation of polymer-tethered NPs into the core of preformed BCP micelles is feasible. Furthermore, interestingly, in a certain range of cosolvent volume fraction, NP/BCP hybrid micelles comprising a single NP in the micelle core could be obtained. Significantly, in the presence of cosolvent the NP-loaded hybrid micelles remain intact, whereas the NP-free (empty) micelles undergo further transformations. The experimental observations are additionally supported by the results obtained from the molecular dynamic simulation. In particular, our modeling recognizes mechanisms for the formation of NP/BCP hybrids, which include a one-by-one adsorption of individual BCP chains onto the NP surface, fusion of NP with the preformed BCP micelles, or a combination of both mechanisms. The present work provides new opportunities for the fabrication of BCP-based hybrid nanomaterials having potential applications in drug delivery, diagnostics, catalysis, energy harvesting materials, optical devices, etc.

Imprint lithography has emerged as a reliable, reproducible, and rapid method for patterning colloidal nanostructures. As a promising alternative to top-down lithographic approaches, the fabrication of nanodevices has thus become effective and straightforward. In this study, a fusion of interference lithography (IL) and nanosphere imprint lithography on various target substrates ranging from carbon film on transmission electron microscope grid to inorganic and dopable polymer semiconductor is reported. 1D plasmonic photonic crystals are printed with 75% yield on the centimeter scale using colloidal ink and an IL-produced polydimethylsiloxane stamp. Atomically smooth facet, single-crystalline, and monodisperse colloidal building blocks of gold (Au) nanoparticles are used to print 1D plasmonic grating on top of a titanium dioxide (TiO2) slab waveguide, producing waveguide-plasmon polariton modes with superior 10 nm spectral line-width. Plasmon-induced hot electrons are confirmed via two-terminal current measurements with increased photoresponsivity under guiding conditions. The fabricated hybrid structure with Au/TiO2 heterojunction enhances photocatalytic processes like degradation of methyl orange (MO) dye molecules using the generated hot electrons. This simple colloidal printing technique demonstrated on silicon, glass, Au film, and naphthalenediimide polymer thus marks an important milestone for large-scale implementation in optoelectronic devices.

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.

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@TiO2 porous nanofibers was investigated using a model reaction of catalytic reduction of 4-nitrophenol and Congo red dye in the presence of NaBH4. The Au@TiO2 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.

We investigated the micellar behavior of a series of asymmetric polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymers in different P4VP-selective alcoholic solvents. The micellar behavior was further correlated with the spectroscopic ellipsometry results obtained on swelling of PS and P4VP polymer films in the corresponding solvent vapors. The time-resolved (in situ) dynamic light scattering (DLS) measurements, in combination with (ex situ) electron microscopy imaging, revealed information about the aggregation state of PS-b-P4VP BCP in different alcohols and the effect of heat treatment. The ellipsometry measurements allowed us to estimate the difference in solvent selectivity toward PS/P4VP pair. Both DLS and ellipsometric studies suggested that less polar alcohols (i.e., 1-propanol, 1-butanol, and 1-pentanol) are likely to be close to each other in terms of their selectivity toward PS/P4VP pair, whereas more polar ethanol and methanol show the highest and the lowest affinity toward P4VP, respectively.