Arrays of Plasmonic Nanoparticles Assembled on Patterns of Polymer Brushes Fabricated by Soft Lithography

This work employed end-grafted poly ethylene glycol PEG and hydroxyl-terminated poly 2-vinylpyridine P2VP polymer chains for selective immobilization and patterning of plasmonic nanoparticles NPs . A soft lithographic method which called micromolding in capillaries MIMIC used in this study. The polymers are deposited the capillary flow by the channels which formed by an elastomeric mold and substrate. The localized coatings are referred as polymer brushes and show great promise in the assembly of NPs due to the tunable interaction between the polymer chains and particles. The results show that the width of patterns defined by the channels is smaller than 1.5 µm with a length of around 0.5 cm. Also, the heights of the patterns are ~3.5 nm for P2VP and ~10 nm for PEG. The fabricated structures exhibited high levels of plasmonic activity and surface enhanced Raman scattering due to the immobilized Au NPs. The patterning polymer brushes and plasmonic NPS over large areas by a low-cost process show great promise for a variety of applications that range from molecular sensors to biotechnolog

Assembly of Plasmonic Nanoparticles on Nanopatterns of Polymer Brushes Fabricated by Electrospin Nanolithography

This paper presents electrospin nanolithography (ESPNL) for versatile and low-cost fabrication of nanoscale patterns of polymer brushes to serve as templates for assembly of metallic nanoparticles. Here electrospun nanofibers placed on top of a substrate grafted with polymer brushes serve as masks. The oxygen plasma etching of the substrate followed by removal of the fibers leads to linear patterns of polymer brushes. The line-widths as small as ∼50 nm can be achieved by precise tuning of the diameter of fibers, etching condition, and fiber-substrate interaction. Highly aligned and spatially defined patterns can be fabricated by operating in the near-field electrospinning regime. Patterns of polymer brushes with two different chemistries effectively directed the assembly of gold nanoparticles and silver nanocubes. Nanopatterned brushes imparted strong confinement effects on the assembly of plasmonic nanoparticles and resulted in strong localization of electromagnetic fields leading to intense signals in surface-enhanced Raman spectroscopy. The scalability and simplicity of ESPNL hold great promise in patterning of a broad range of polymer thin films for different applications

Fabrication of Nanopatterned Poly(ethylene glycol) Brushes by Molecular Transfer Printing from Poly(styrene-<i>block</i>-methyl methacrylate) Films to Generate Arrays of Au Nanoparticles

This article presents a soft lithographic approach using block copolymer (BCP) films to fabricate functional chemically patterned polymer brushes on the nanoscale. Hydroxyl-terminated poly­(ethylene glycol) (PEG-OH) was transfer printed from the poly­(methyl methacrylate) (PMMA) domains of self-assembled poly­(styrene-<i>block</i>-methyl methacrylate) films to a substrate in conformal contact with the film to generate patterned PEG brushes mirroring the pattern of BCP domains. A key point in the study is that the chemistry of the functional transferred brushes is different from the chemistry of either block of the copolymer; PEG-OH is miscible only in the PMMA block and therefore transferred only from PMMA domains. The functionality of the PEG brushes was demonstrated by the selective immobilization of citrate-stabilized Au NPs (15 nm) and validated the generation of high-quality chemical patterns with sub-30-nm feature sizes

Activation of epidermal growth factor receptors in triple-negative breast cancer cells by morphine; analysis through Raman spectroscopy and machine learning.

AbstractTriple negative breast cancer (TNBC) is a very aggressive form of breast cancer, and the analgesic drug morphine has been shown to promote the proliferation of TNBC cells. This article investigates whether morphine causes activation of epidermal growth factor receptors (EGFR), the roles of μ-opioid and EGFR receptors on TNBC cell proliferation and migration. While examining the changes with molecular techniques, we also aimed to investigate the analysis ability of Raman spectroscopy and machine learning-based approach. Effects of morphine on the proliferation and migration of MDA.MB.231 cells were evaluated by MTT and scratch wound-healing tests, respectively. Morphine-induced phosphorylation of the EGFR was analyzed by western blotting in the presence and absence of μ-receptor antagonist naltrexone and the EGFR-tyrosine kinase inhibitor gefitinib. Morphine-induced EGFR phosphorylation and cell migration were significantly inhibited by pretreatments with both naltrexone and gefitinib; however, morphine-increased cell proliferation was inhibited only by naltrexone. While morphine-induced changes were observed in the Raman scatterings of the cells, the inhibitory effect of naltrexone was analyzed with similarity to the control group. Principal component analysis (PCA) of the Raman confirmed the epidermal growth factor (EGF)-like effect of morphine and was inhibited by naltrexone and partly by gefitinib pretreatments. Our in vitro results suggest that combining morphine with an EGFR inhibitor or a peripherally acting opioidergic receptor antagonist may be a good strategy for pain relief without triggering cancer proliferation and migration in TNBC patients. In addition, our results demonstrated the feasibility of the Raman spectroscopy and machine learning-based approach as an effective method to investigate the effects of agents in cancer cells without the need for complex and time-consuming sample preparation. The support vector machine (SVM) with linear kernel automatically classified the effects of drugs on cancer cells with ∼95% accuracy.</div

Highly compressible binder-free sponge supercapacitor electrode based on flower-like NiO/MnO2/CNT

The increasing demand for flexible electronics encourages the innovative and functional designs of electrode materials with high performance and compressibility. In this work, we report a compressible supercapacitor electrode which is prepared by coating electrically active NiO/MnO2/carbon nanotube (CNT) composite onto a sponge. A cube of sugar was used as the template to obtain the sponge through infiltration and cross-linking of polydimethylsiloxane (PDMS). NiO/MnO2/CNT was deposited on the PDMS sponge to generate substantial amount of interface, resulting in a specific capacitance of 23 F/g at 0.1 A /g in a three-electrode system and 1.32 F/g at 0.5 mA in a symmetric supercapacitor. The proposed system exhibits excellent cycling stability with capacitance retention over 10.000 cycles. The strong adhesion of the binary metal oxides and carbon material onto the porous nonconductive sponge enables mechanical stability under compression-release cycles. Our study indicates that this electrode is a promising candidate for applications in flexible electronics. Furthermore, this research might guide the development of flexible, high-performance, and low-cost electrodes, which will be useful in wearable energy storage systems. (C) 2022 Published by Elsevier B.V

Plasmonic assemblies of gold nanorods on nanoscale patterns of poly(ethylene glycol) : application in surface-enhanced Raman spectroscopy

Approaches are needed for the tailored assembly of plasmonic building blocks on the surface of substrates to synergistically enhance their properties. Here we demonstrate selective immobilization and assembly of gold nanorods (NRs) on substrates modified and patterned with end-grafted poly(ethylene glycol) (PEG) layers. The ligand exchange from the initial cetyltrimethylammonium bromide to sodium citrate was necessary for the immobilization of gold NRs onto PEG grafted substrates. Linear nanopatterns of PEG were fabricated using electrospun nanofibers as masks in oxygen plasma etching. The selective immobilization of citrate-stabilized gold NRs with a length of ∼50 nm and a width of 20 nm on the nanopatterned PEG layers led to linear and registered arrays of rods. The number of gold NRs per line depended on the width of the patterns and approached 1 when the width of the patterns was comparable to the length of the rods. The confinement of the binding regions led to a ∼3 fold increase in the number of gold NRs immobilized per unit area. The selective and dense immobilization of gold NRs on the nanoscale patterns of PEG resulted in spatially defined and strong surface-enhanced Raman scattering activity enabling detection of molecules at concentrations as low as 1 nM

Assembly of Plasmonic Nanoparticles on Nanopatterns of Polymer Brushes Fabricated by Electrospin Nanolithography

This paper presents electrospin nanolithography (ESPNL) for versatile and low-cost fabrication of nanoscale patterns of polymer brushes to serve as templates for assembly of metallic nanoparticles. Here electrospun nanofibers placed on top of a substrate grafted with polymer brushes serve as masks. The oxygen plasma etching of the substrate followed by removal of the fibers leads to linear patterns of polymer brushes. The line-widths as small as ∼50 nm can be achieved by precise tuning of the diameter of fibers, etching condition, and fiber-substrate interaction. Highly aligned and spatially defined patterns can be fabricated by operating in the near-field electrospinning regime. Patterns of polymer brushes with two different chemistries effectively directed the assembly of gold nanoparticles and silver nanocubes. Nanopatterned brushes imparted strong confinement effects on the assembly of plasmonic nanoparticles and resulted in strong localization of electromagnetic fields leading to intense signals in surface-enhanced Raman spectroscopy. The scalability and simplicity of ESPNL hold great promise in patterning of a broad range of polymer thin films for different applications

SERS-active linear barcodes by microfluidic-assisted patterning

Abstract Simple, low-cost, robust, and scalable fabrication of microscopic linear barcodes with high levels of complexity and multiple authentication layers is critical for emerging applications in information security and anti-counterfeiting. This manuscript presents a novel approach for fabrication of microscopic linear barcodes that can be visualized under Raman microscopy. Microfluidic channels are used as molds to generate linear patterns of end-grafted polymers on a substrate. These patterns serve as templates for area-selective binding of colloidal gold nanoparticles resulting in plasmonic arrays. The deposition of multiple taggant molecules on the plasmonic arrays via a second microfluidic mold results in a linear barcode with unique Raman fingerprints that are enhanced by the underlying plasmonic nanoparticles. The width of the bars is as small as 10 μm, with a total barcode length on the order of 100 μm. The simultaneous use of geometric and chemical security layers provides a high level of complexity challenging the counterfeiting of the barcodes. The additive, scalable, and inexpensive nature of the presented approach can be easily adapted to different colloidal nanomaterials and applications

Scalable Fabrication of MXene-PVDF Nanocomposite Triboelectric Fibers via Thermal Drawing

In the data-driven world, textile is a valuable resource for improving the quality of life through continuous monitoring of daily activities and physiological signals of humans. Triboelectric nanogenerators (TENG) are an attractive option for self-powered sensor development by coupling energy harvesting and sensing ability. In this study, to the best of the knowledge, scalable fabrication of Ti3C2Tx MXene-embedded polyvinylidene fluoride (PVDF) nanocomposite fiber using a thermal drawing process is presented for the first time. The output open circuit voltage and short circuit current show 53% and 58% improvement, respectively, compared to pristine PVDF fiber. The synergistic interaction between the surface termination groups of MXene and polar PVDF polymer enhances the performance of the fiber. The flexibility of the fiber enables the weaving of fabric TENG devices for large-area applications. The fabric TENG (3 x 2 cm(2)) demonstrates a power density of 40.8 mW m(-2) at the matching load of 8 M omega by maintaining a stable performance over 12 000 cycles. Moreover, the fabric TENG has shown the capability of energy harvesting by operating a digital clock and a calculator. A distributed self-powered sensor for human activities and walking pattern monitoring are demonstrated with the fabric