Correlation between photophysical properties and lasing performances of Rhodamine-19 in three types of sol–gel glass hosts

Rhodamine-19 (Rh-19) incorporated three types of sol–gel samples (mentioned as dope route-I, dope route-II and dip method) were prepared by using two different methods of dye impregnation. The photophysical properties of all the three types of Rh-19 incorporated sol–gel solids were studied by using the UV–Visible absorption and the fluorescence spectroscopy. A single photon counting technique was used to estimate the lifetime of fluorescent species. From the study of fluorescence spectra, the coexistence of dimers (fluorescent and non-fluorescent both) and monomer of Rh-19 was observed. The photophysical properties of Rh-19 were found to be the best in dip sample, medium in dope route-II sample and low in dope route-I sample. After studying photophysical properties, the samples were subjected to laser study under nitrogen laser pumping at 337.1 nm at the rate of 1.5 Hz in transverse dye laser cavity. The highest laser efficiency and photostability of the dye were observed in dip sample, medium in dope route-II sample and small in dope route-I sample. A comparison between photophysical properties and laser performance of these materials showed a very good correlation.     

Optimization of anionic conductivity through the coexistence of ionomer cluster and backbone-backbone morphologies in anion exchange membranes

Random copolymers of poly(4-vinylpyridine) and polyisoprene were synthesized, and subsequently quaternized with 1-alkylbromides. The number of carbons on the pendant side-chain of the resultant comb-shaped polymer, n, ranged from 2–8. The comb-shaped polymers were crosslinked employing thiol-ene chemistry to give mechanically robust ion conducting membranes. Analysis by wide and medium-angle X-ray scattering show three morphology regimes that are dependent on the number of carbons on the pendant side-chains. When n = 2, ionomer cluster morphology was dominant, when n = 8 backbone-backbone morphology was dominant, and when n = 3–6, the membrane showed a coexistence of both ionomer cluster and backbone-backbone morphologies. Evaluation of the water uptake of the membranes showed a maximum water uptake per cation of 9.5 when n = 5 at 95% relative humidity (RH) and 60°C. Conductivity of the samples characterized by electrochemical impedance spectroscopy showed bromide conductivity as high as 110 mS/cm when n = 3 at 95% RH and 90°C.     

Surface-Active Fluorinated Quantum Dots for Enhanced Cellular Uptake

Fluorescent nanoparticles, such as quantum dots, hold great potential for biomedical applications, mainly sensing and bioimaging. However, the inefficient cell uptake of some nanoparticles hampers their application in clinical practice. Here, the effect of the modification of the quantum dot surface with fluorinated ligands to increase their surface activity and, thus, enhance their cellular uptake was explored.     

Nuclear Uptake of Gold Nanoparticles Deduced Using Dual‐Angle X‐Ray Fluorescence Mapping

Studies into the cell nucleus' incorporation of gold nanoparticles (AuNPs) are often limited by ambiguities arising from conventional imaging techniques. Indeed, it is suggested that to date there is no unambiguous imaging evidence for such uptake in whole cells, particularly at the single nanoparticle level. This shortcoming in understanding exists despite the nucleus being the most important subcellular compartment in eukaryotes and gold being the most commonly used metal nanoparticle in medical applications. Here, dual‐angle X‐ray flouresence is used to show individually resolved nanoparticles within the cell nucleus, finding them to be well separated and 79% of the intranuclear population to be monodispersed. These findings have important implications for nanomedicine, illustrated here through a specific exemplar of the predicted enhancement of radiation effects arising from the observed AuNPs, finding intranuclear dose enhancements spanning nearly five orders of magnitude.     

Mussel-inspired polydopamine functionalized recyclable coconut shell derived carbon nanocomposites for efficient adsorption of methylene blue

Relatively cheap or at no cost, easily available, renewable agricultural waste has been given a new purpose. Using coconut shells as the raw material, and being obtained from agricultural, industry by-products, or even waste materials were used as carbon resource. Acid etching coconut shells carbon (AC) rendered micro/nanoscale hierarchical structures and made the surface available for further modification. Then, the surface of acidified coconut shell carbon was engineered via mussel inspired chemistry. The polydopamine functionalized AC composites (AC-PDA) were applied for efficient removal of methylene blue (MB) dye. Further, the surface morphology, and chemical structure were evaluated by means of scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FT-IR). Through the combination of acid etching and mussel inspired chemistry, organic functional groups can be successfully introduced onto the surface of the coconut shells carbon. The improvement of adsorption capacity of AC-PDA compared with AC is probably due to the increased number of active binding sites resulting from surface modification and formation of new functional groups.     

Glycosylated Cell‐Penetrating Poly(disulfide)s: Multifunctional Cellular Uptake at High Solubility

The glycosylation of cell‐penetrating poly(disulfide)s (CPDs) is introduced to increase the solubility of classical CPDs and to achieve multifunctional cellular uptake. With the recently developed sidechain engineering, CPDs decorated with α‐d ‐glucose (Glu), β‐d ‐galactose (Gal), d ‐trehalose (Tre), and triethyleneglycol (TEG) were readily accessible. Confocal laser scanning microscopy images of HeLa Kyoto cells incubated with the new CPDs at 2.5 μm revealed efficient uptake into cytosol and nucleoli of all glycosylated CPDs, whereas the original CPDs and TEGylated CPDs showed much precipitation into fluorescent aggregates at these high concentrations. Flow cytometry analysis identified Glu‐CPDs as most active, closely followed by Gal‐CPDs and Tre‐CPDs, and all clearly more active than non‐glycosylated CPDs. In the MTT assay, all glyco‐CPDs were non‐toxic at concentrations as high as 2.5 μm . Consistent with thiol‐mediated uptake, glycosylated CPDs remained dependent on thiols on the cell surface for dynamic covalent exchange, their removal with Ellman's reagent DTNB efficiently inhibited uptake. Multifunctionality was demonstrated by inhibition of Glu‐CPDs with d ‐glucose (IC₅₀ ca. 20 mm ). Insensitivity toward l ‐glucose and d ‐galactose and insensitivity of conventional CPDs toward d ‐glucose supported that glucose‐mediated uptake of the multifunctional Glu‐CPDs involves selective recognition by glucose receptors at the cell surface. Weaker but significant sensitivity of Gal‐CPDs toward d ‐galactose but not d ‐glucose was noted (IC₅₀ ca. 110 mm ). Biotinylation of Glu‐CPDs resulted in the efficient delivery of streptavidin together with a fluorescent model substrate. Protein delivery with Glu‐CPDs was more efficient than with conventional CPDs and remained sensitive to DTNB and d ‐glucose, i.e., multifunctional.     

The Remarkable Effect of Halogen Substitution on the Membrane Transport of Fluorescent Molecules in Living Cells

Small‐molecule‐based fluorescent probes have become important tools in biology for sensing and imaging applications. However, the biological applications of many of the fluorescent molecules are hampered by low cellular uptake and high toxicity. In this paper, we show for the first time that the introduction of halogen atoms enhances the cellular uptake of fluorescent molecules and the nature of halogen atoms plays a crucial role in the plasma membrane transport in mammalian cells. The remarkably higher uptake of iodinated compounds compared to that of their chloro or bromo analogues suggests that the strong halogen bonding ability of iodine atoms may play an important role in the membrane transport. This study provides a novel strategy for the transport of fluorescent molecules across the plasma membrane in living cells.     

Stimuli‐responsive polymer nanocomposites based on styrene‐butadiene rubber and bacterial cellulose whiskers

Water‐induced mechanically adaptive rubber nanocomposites were prepared by mixing bacterial cellulose whiskers (BCWs) suspension with styrene‐butadiene rubber (SBR) latex, followed by evaporation method. The structure, morphology, dynamic mechanical properties, water stimuli‐responsive behavior, and biodegradability of SBR/BCWs nanocomposite films were investigated. The results showed that the hydrophilic whiskers had a significant reinforcement effect on the storage modulus of SBR matrix, which originated from the formation of a rigid three‐dimensional filler network within matrix by strong hydrogen bonding between whiskers. The SBR/BCWs nanocomposites showed pronounced water stimuli‐responsive behavior compared with neat SBR. The storage modulus of SBR/BCWs nanocomposite could be decreased by 99.2% after equilibrium water swelling. This remarkable water‐triggered modulus change is attributed to the disentanglement of BCWs network via competitive hydrogen bonding with water.