Overview: The Potential of silanes for chromate replacement in metal finishing industries

Trialkoxysilanes (or silanes) have emerged as a very promising alternative for chromates in metal finishing industries. Compared to the conventional chromating processes, the major merits of silane-based surface treatments include: eco-compliance, easy-control processing, comparable corrosion protection of metals as well as paint adhesion to a variety of topcoats. In this overview paper, we report the recent status of silane studies including results of corrosion performance tests, the mechanism of corrosion protection of metals by silanes and the themal stabilities of silane films. We also address the new fields that we are beginning to explore such as nano-structured silane films, “self-healing” silane films, and “super-primers”.     

Acid–base chemistry at the single ion limit

We present the results of acid–base experiments performed at the single ion (H⁺ or OH⁻) limit in ∼6 aL volume nanopores incorporating electrochemical zero-mode waveguides (E-ZMWs). At pH 3 each E-ZMW nanopore contains ca. 3600H⁺ ions, and application of a negative electrochemical potential to the gold working electrode/optical cladding layer reduces H⁺ to H₂, thereby depleting H⁺ and increasing the local pH within the nanopore. The change in pH was quantified by tracking the intensity of fluorescein, a pH-responsive fluorophore whose intensity increases with pH. This behavior was translated to the single ion limit by changing the initial pH of the electrolyte solution to pH 6, at which the average pore occupancy 〈n〉_pore ∼3.6H⁺/nanopore. Application of an electrochemical potential sufficiently negative to change the local pH to pH 7 reduces the proton nanopore occupancy to 〈n〉_pore ∼0.36H⁺/nanopore, demonstrating that the approach is sensitive to single H⁺ manipulations, as evidenced by clear potential-dependent changes in fluorescein emission intensity. In addition, at high overpotential, the observed fluorescence intensity exceeded the value predicted from the fluorescence intensity-pH calibration, an observation attributed to the nucleation of H₂ nanobubbles as confirmed both by calculations and the behavior of non-pH responsive Alexa 488 fluorophore. Apart from enhancing fundamental understanding, the approach described here opens the door to applications requiring ultrasensitive ion sensing, based on the optical detection of H⁺ population at the single ion limit.

Visualizing dynamic change in the number of protons during electroreduction of protons in attoliter volume zero-mode waveguides.     

Elucidation of Binding Mechanism of Photodynamic Therapeutic Agent Toluidine Blue O with Chicken Egg White Lysozyme by Spectroscopic and Molecular Dynamics Studies

The nature of binding mechanism of toluidine blue O (TBO) with chicken egg white lysozyme was studied comprehensively by various spectroscopic and computational methods. Both steady state and time‐resolved fluorescence studies unambiguously point to the prevalence of static quenching mechanism in lysozyme–TBO system. Thermodynamic parameters revealed that the association of TBO with lysozyme was a spontaneous process in which hydrophobic and hydrogen bond interactions played a pivotal role in the binding process. The secondary and tertiary conformational changes of lysozyme in the presence of TBO were unraveled using absorption, Fourier transform infrared spectroscopy (FT‐IR) and circular dichroism (CD) techniques. Molecular docking studies of lysozyme–TBO system substantiated the findings of site marker experiment and revealed TBO adjacent to Trp‐63 and Trp‐108 residues of lysozyme. Molecular dynamics (MD) simulation studies of lysozyme–TBO system indicate a stable and effective complexation of TBO with lysozyme. It is hoped that the results presented here will enable further understanding of TBO toxicity.     

Binder-less and free-standing Co–Fe metal nanoparticles-decorated PVdF-HFP nanofiber membrane as an electrochemical probe for enzyme-less glucose sensors

Co–Fe bimetallic nanoparticles-affixed polyvinylidene fluoride-co-hexafluoropropylene (PVdF-HFP) nanofiber membrane is fabricated using the electrospinning and chemical reduction techniques. The semicrystalline polymeric backbone decorated with the highly crystalline Co–Fe bimetallic nanoparticles enunciates the mechanical integrity, while the incessant and swift electron mobility is articulated with the consistent dissemination of bimetallic nanoparticles on the intersected and multi-layered polymeric nanofibers. The diffusion and adsorption of glucose are expedited in the extended cavities and porosities of as-formulated polymeric nanofibers, maximizing the glucose utilization efficacy, while the uniformly implanted Co⁴⁺/Fe³⁺ active centers on PVdF-HFP nanofibers maximize the electrocatalytic activity toward glucose oxidation under alkaline regimes. Thus, the combinative sorts including nanofiber and nanocomposite strategies of PVdF-HFP/Co–Fe membrane assimilate the enzyme-less electrochemical glucose detection concerts of high sensitivity (375.01 μA mM^?1 cm^?2), low limit of detection (0.65 μm), and wide linear range (0.001 to 8 mM), outfitting the erstwhile enzyme-less glucose detection reports. Additionally, the endowments of high selectivity and real sample glucose-sensing analyses of PVdF-HFP/Co–Fe along with the binder-less and free-standing characteristics construct the state-of-the-art paradigm for the evolution of affordable enzyme-less electrochemical glucose sensors.

     

Lefschetz fixed point theory on fibrations

For a fibre preserving map ϕ: E → E on a fibration (E, π, B), we construct a grading preserving map T(ϕ, π) between H*(E) and H*(B) that generalizes the Lefschetz number. If T(ϕ, π) is an isomorphism between H ⁰(E) and H ⁰(B), then π restricts to a surjective local diffeomorphism on each connected component of the fixed point set of ϕ under a transversality condition. This yields a characterization for the bundle H → G → G/H to be trivial when π ₁ (G/H) = 0.     

Preparation and Characterization of Chitosan Thin Films on Mixed-Matrix Membranes for Complete Removal of Chromium

Herein we present a new approach for the complete removal of Cr^VI species, through reduction of Cr^VI to Cr^III, followed by adsorption of Cr^III. Reduction of chromium from water is an important challenge, as Cr^IV is one of the most toxic substances emitted from industrial processes. Chitosan (CS) thin films were developed on plain polysulfone (PSf) and PSf/TiO₂ membrane substrates by a temperature-induced technique using polyvinyl alcohol as a binder. Structure property elucidation was carried out by X-ray diffraction, microscopy, spectroscopy, contact angle measurement, and water uptake studies. The increase in hydrophilicity followed the order: PSf < PSf/TiO₂ < PSf/TiO₂/CS membranes. Use of this thin-film composite membrane for chromium removal was investigated with regards to the effects of light and pH. The observations reveal 100 % reduction of Cr^VI to Cr^III through electrons and protons donated from OH and NH₂ groups of the CS layer; the reduced Cr^III species are adsorbed onto the CS layer via complexation to give chromium-free water.     

An Unexpected Role of Hyaluronic Acid in Trafficking siRNA Across the Cellular Barrier: The First Biomimetic,Anionic, Non‐Viral Transfection Method

Circulating nucleic acids, such as short interfering RNA (siRNA), regulate many biological processes; however, the mechanism by which these molecules enter the cell is poorly understood. The role of extracellular‐matrix‐derived polymers in binding siRNAs and trafficking them across the plasma membrane is reported. Thermal melting, dynamic light scattering, scanning electron microscopy, and computational analysis indicate that hyaluronic acid can stabilize siRNA via hydrogen bonding and Van der Waals interactions. This stabilization facilitated HA size‐ and concentration‐dependent gene silencing in a CD44‐positive human osteosarcoma cell line (MG‐63) and in human mesenchymal stromal cells (hMSCs). This native HA‐based siRNA transfection represents the first report on an anionic, non‐viral delivery method that resulted in approximately 60 % gene knockdown in both cell types tested, which correlated with a reduction in translation levels.     

Biogenic synthesis from <Emphasis Type="Italic">Prunus</Emphasis> × <Emphasis Type="Italic">yedoensis</Emphasis> leaf extract,characterization, and photocatalytic and antibacterial activity of TiO<Subscript>2</Subscript> nanoparticles

Green synthesis of TiO₂ nanoparticles (NPs) from Prunus × yedoensis leaf extract (PYLE), and their application for removal of phosphate and their antibacterial activity, were studied for the first time. NPs were obtained using a green chemistry approach from 0.1 M TiO₂ and PYLE at ratio of 1:1 (v/w). Initial confirmation of production of TiO₂ NPs was provided by a color change from white to light yellow, then calcination was performed at 500 °C for 1 h. The TiO₂ NPs were characterized using various analytical techniques such as ultraviolet–visible (UV–Vis) spectroscopy, X-ray diffraction analysis, Fourier-transform infrared spectroscopy, Raman spectroscopy, UV–Vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. The results indicated that the optimal amount of TiO₂ NPs for removal of phosphate was 10 mg/l (10 ppm) with duration of 25 min. Furthermore, the antibacterial activity of TiO₂ NPs was also investigated using two different bacteria (Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli) in aqueous medium. The results revealed highly efficient sunlight-driven photocatalytic and antibacterial activity of TiO₂ NPs.     

Nondoped blue fluorescent OLED based on cyanophenanthrimidazole‐styryl‐triphenylamine/carbazole materials

New 2‐(4′‐9H‐carbazole‐9‐yl)‐styryl‐1H‐phenathro[9,10‐d]imidazole‐1‐yl)benzonitrile (SPICN‐Cz) and 4‐(2‐(4‐(diphenylamino)phenyl‐styryl‐1H‐phenathro[9,10‐d]imidazole‐1‐yl)benzonitrile (SPICN‐TPA) have been synthesised, and their photophysical, electrochemical, and electroluminescent properties were analysed in comparison with their cyano‐free parent compounds, SPI‐Cz, and SPI‐TPA. Solvatochromic effects show the transformation of an excited state character from locally excited (LE) state to charge transfer (CT) state. Using time‐dependent density functional theory calculation, the excited state properties of these donor‐acceptor blue emissive materials have been analysed. Their excited state properties have been tuned by replacing the strong donor triphenylamine to weak donor carbazole to achieve the combination of high photoluminance efficiency locally excited (LE) component and high exciton‐utilizing CT component in one excited state. Hybridization processes between LE and CT components of SPICN‐Cz and SPICN‐TPA in the emissive state have been discussed. The nondoped organic light emitting diode device based on SPICN‐Cz exhibit better electroluminescent performances than those of SPICN‐TPA–based device: high external quantum efficiency of 2.58 %, current efficiency of 2.90 cd A^‐1, and power efficiency of 2.26 lm W^‐1 with Commission Internationale de l'Éclairage (CIE) coordinates of (0.15, 0.12). The excited state modulation and the composition of LE and CT states in the donor‐acceptor system could be useful to design low‐cost, high‐efficiency fluorescent organic light emitting diode materials.