Enhancing Water Treatment Performance of Porous Polysulfone Hollow Fiber Membranes through Atomic Layer Deposition.

Polysulfone (PSF) is one of the most used polymers for water treatment membranes, but its intrinsic hydrophobicity can be detrimental to the membranes' performances. By modifying a membrane's surface, it is possible to adapt its physicochemical properties and thus tune the membrane's hydrophilicity or porosity, which can achieve improved permeability and antifouling efficiency. Atomic layer deposition (ALD) stands as a distinctive technology offering exceedingly even and uniform layers of coatings, like oxides that cover the surfaces of objects with three-dimensional (3D) shapes, porous structures, and particles. In the context of this study, the focus was on titanium dioxide (TiO2), zinc oxide (ZnO), and alumina (Al2O3), which were deposited on polysulfone hollow fiber (HF) membranes via ALD using TiCl4, diethyl zinc (DEZ), and trimethylamine (TMA), respectively, and H2O as precursors. The morphology and mechanical properties of membranes were changed without damaging their performances. The deposition was confirmed mainly by energy-dispersive X-ray spectroscopy (EDX). All depositions offered great performances with a maintained permeability and BSA retention and a 20 to 40° lower water contact angle (WCA) than the raw PSF HF membrane. The deposition of TiO2 offered the best results, showing an enhancement of 50% for the water permeability and 20% for the fouling resistance of the PSF HF membranes.

Exploring Hydrogen Sources in Catalytic Transfer Hydrogenation: A Review of Unsaturated Compound Reduction.

Catalytic transfer hydrogenation has emerged as a pivotal chemical process with transformative potential in various industries. This review highlights the significance of catalytic transfer hydrogenation, a reaction that facilitates the transfer of hydrogen from one molecule to another, using a distinct molecule as the hydrogen source in the presence of a catalyst. Unlike conventional direct hydrogenation, catalytic transfer hydrogenation offers numerous advantages, such as enhanced safety, cost-effective hydrogen donors, byproduct recyclability, catalyst accessibility, and the potential for catalytic asymmetric transfer hydrogenation, particularly with chiral ligands. Moreover, the diverse range of hydrogen donor molecules utilized in this reaction have been explored, shedding light on their unique properties and their impact on catalytic systems and the mechanism elucidation of some reactions. Alcohols such as methanol and isopropanol are prominent hydrogen donors, demonstrating remarkable efficacy in various reductions. Formic acid offers irreversible hydrogenation, preventing the occurrence of reverse reactions, and is extensively utilized in chiral compound synthesis. Unconventional donors such as 1,4-cyclohexadiene and glycerol have shown a good efficiency in reducing unsaturated compounds, with glycerol additionally serving as a green solvent in some transformations. The compatibility of these donors with various catalysts, substrates, and reaction conditions were all discussed. Furthermore, this paper outlines future trends which include the utilization of biomass-derived hydrogen donors, the exploration of hydrogen storage materials such as metal-organic frameworks (MOFs), catalyst development for enhanced activity and recyclability, and the utilization of eco-friendly solvents such as glycerol and ionic liquids. Innovative heating methods, diverse base materials, and continued research into catalyst-hydrogen donor interactions are aimed to shape the future of catalytic transfer hydrogenation, enhancing its selectivity and efficiency across various industries and applications.

Molecularly imprinted polypyrrole based sensor for the detection of SARS-CoV-2 spike glycoprotein.

This study describes the application of a polypyrrole-based sensor for the determination of SARS-CoV-2-S spike glycoprotein. The SARS-CoV-2-S spike glycoprotein is a spike protein of the coronavirus SARS-CoV-2 that recently caused the worldwide spread of COVID-19 disease. This study is dedicated to the development of an electrochemical determination method based on the application of molecularly imprinted polymer technology. The electrochemical sensor was designed by molecular imprinting of polypyrrole (Ppy) with SARS-CoV-2-S spike glycoprotein (MIP-Ppy). The electrochemical sensors with MIP-Ppy and with polypyrrole without imprints (NIP-Ppy) layers were electrochemically deposited on a platinum electrode surface by a sequence of potential pulses. The performance of polymer layers was evaluated by pulsed amperometric detection. According to the obtained results, a sensor based on MIP-Ppy is more sensitive to the SARS-CoV-2-S spike glycoprotein than a sensor based on NIP-Ppy. Also, the results demonstrate that the MIP-Ppy layer is more selectively interacting with SARS-CoV-2-S glycoprotein than with bovine serum albumin. This proves that molecularly imprinted MIP-Ppy-based sensors can be applied for the detection of SARS-CoV-2 virus proteins.

Electrochemical Biosensor for the Determination of Specific Antibodies against SARS-CoV-2 Spike Protein.

In this article, we report the development of an electrochemical biosensor for the determination of the SARS-CoV-2 spike protein (rS). A gold disc electrode was electrochemically modified to form the nanocrystalline gold structure on the surface. Then, it was further altered by a self-assembling monolayer based on a mixture of two alkane thiols: 11-mercaptoundecanoic acid (11-MUA) and 6-mercapto-1-hexanol (6-MCOH) (SAMmix). After activating carboxyl groups using a N-(3-dimethylaminopropyl)-N'-ethyl-carbodiimide hydrochloride and N-hydroxysuccinimide mixture, the rS protein was covalently immobilized on the top of the SAMmix. This electrode was used to design an electrochemical sensor suitable for determining antibodies against the SARS-CoV-2 rS protein (anti-rS). We assessed the association between the immobilized rS protein and the anti-rS antibody present in the blood serum of a SARS-CoV-2 infected person using three electrochemical methods: cyclic voltammetry, differential pulse voltammetry, and potential pulsed amperometry. The results demonstrated that differential pulse voltammetry and potential pulsed amperometry measurements displayed similar sensitivity. In contrast, the measurements performed by cyclic voltammetry suggest that this method is the most sensitive out of the three methods applied in this research.

Optical-Fiber Microsphere-Based Temperature Sensors with ZnO ALD Coating-Comparative Study.

This study presents the microsphere-based fiber-optic sensor with the ZnO Atomic Layer Deposition coating thickness of 100 nm and 200 nm for temperature measurements. Metrological properties of the sensor were investigated over the temperature range from 100 °C to 300 °C, with a 10 °C step. The interferometric signal was used to monitor the integrity of the microsphere and its attachment to the connecting fiber. For the sensor with a 100 nm coating, a spectrum shift of the reflected signal and the optical power of the reflected signal were used to measure temperature, while only the optical power of the reflected signal was used in the sensor with a 200 nm coating. The R2 coefficient of the discussed sensors indicates a linear fit of over 0.99 to the obtained data. The sensitivity of the sensors, investigated in this study, equals 103.5 nW/°C and 19 pm/°C or 11.4 nW/°C for ZnO thickness of 200 nm and 100 nm, respectively.

Polyvinyl Chloride Modified Carbon Paste Electrodes for Sensitive Determination of Levofloxacin Drug in Serum, Urine, and Pharmaceutical Formulations.

Levofloxacin (LF) is a medically important antibiotic drug that is used to treat a variety of bacterial infections. In this study, three highly sensitive and selective carbon paste electrodes (CPEs) were fabricated for potentiometric determination of the LF drug: (i) CPEs filled with carbon paste (referred to as CPE); (ii) CPE coated (drop-casted) with ion-selective PVC membrane (referred to as C-CPE); (iii) CPE filled with carbon paste modified with a plasticizer (PVC/cyclohexanone) (referenced as P-CPE). The CPE was formulated from graphite (Gr, 44.0%) and reduced graphene oxide (rGO, 3.0%) as the carbon source, tricresyl phosphate (TCP, 47.0%) as the plasticizer; sodium tetrakis[3,5-bis(trifluoromethyl)phenyl] borate (St-TFPMB, 1.0%) as the ion exchanger; and levofloxacinium-tetraphenylborate (LF-TPB, 5.0%) as the lipophilic ion pair. It showed a sub-Nernstian slope of 49.3 mV decade-1 within the LF concentration range 1.0 × 10-2 M to 1.0 × 10-5 M, with a detection limit of 1.0 × 10-5 M. The PVC coated electrode (C-CPE) showed improved sensitivity (in terms of slope, equal to 50.2 mV decade-1) compared to CPEs. After the incorporation of PVC paste on the modified CPE (P-CPE), the sensitivity increased at 53.5 mV decade-1, indicating such improvement. The selectivity coefficient (log KLF2+,Fe+3pot.) against different interfering species (Na+, K+, NH4+, Ca2+, Al3+, Fe3+, Glycine, Glucose, Maltose, Lactose) were significantly improved by one to three orders of magnitudes in the case of C-CPE and P-CPE, compared to CPEs. The modification with the PVC membrane coating significantly improved the response time and solubility of the LF-TPB within the electrode matrix and increased the lifetime. The constructed sensors were successfully applied for LF determination in pharmaceutical preparation (Levoxin® 500 mg), spiked urine, and serum samples with high accuracy and precision.

Enhanced sieving from exfoliated MoS2 membranes via covalent functionalization.

Nanolaminate membranes made of two-dimensional materials such as graphene oxide are promising candidates for molecular sieving via size-limited diffusion in the two-dimensional capillaries, but high hydrophilicity makes these membranes unstable in water. Here, we report a nanolaminate membrane based on covalently functionalized molybdenum disulfide (MoS2) nanosheets. The functionalized MoS2 membranes demonstrate >90% and ~87% rejection for micropollutants and NaCl, respectively, when operating under reverse osmotic conditions. The sieving performance and water flux of the functionalized MoS2 membranes are attributed both to control of the capillary widths of the nanolaminates and to control of the surface chemistry of the nanosheets. We identify small hydrophobic functional groups, such as the methyl group, as the most promising for water purification. Methyl- functionalized nanosheets show high water permeation rates as confirmed by our molecular dynamic simulations, while maintaining high NaCl rejection. Control of the surface chemistry and the interlayer spacing therefore offers opportunities to tune the selectivity of the membranes while enhancing their stability.

ZnO ALD-Coated Microsphere-Based Sensors for Temperature Measurements.

In this paper, the application of a microsphere-based fiber-optic sensor with a 200 nm zinc oxide (ZnO) coating, deposited by the Atomic Layer Deposition (ALD) method, for temperature measurements between 100 and 300 °C, is presented. The main advantage of integrating a fiber-optic microsphere with a sensing device is the possibility of monitoring the integrity of the sensor head in real-time, which allows for higher accuracy during measurements. The study has demonstrated that ZnO ALD-coated microsphere-based sensors can be successfully used for temperature measurements. The sensitivity of the tested device was found to be 103.5 nW/°C when the sensor was coupled with a light source of 1300 nm central wavelength. The measured coefficient R2 of the sensor head was over 0.99, indicating a good fit of the theoretical linear model to the measured experimental data.

Enhanced visible light photocatalysis by TiO2-BN enabled electrospinning of nanofibers for pharmaceutical degradation and wastewater treatment.

Boron nitride (BN) nanosheets are promising support materials for catalysts. A series of TiO2-BN enabled electrospun nanofibers were synthesized for the photocatalytic treatment of ibuprofen and secondary wastewater effluent under visible light. X-ray photoelectron spectroscopy confirmed the existence of B-O-Ti bonds between the BN nanosheets and TiO2 nanofibers, resulting in energy rearrangement, narrowed band gaps, and enhanced light utilization efficiency of the TiO2-BN nanocomposites in the visible light spectrum. Transient photocurrent measurements revealed that the BN enhanced the transport of photogenerated holes from the bulk TiO2 nanofibers to its surface, resulting in more efficient separation and less recombination of the charge carriers. A kinetic study of ibuprofen degradation indicated the enhanced photocatalytic performance of TiO2-BN catalysts with a higher BN content in the nanocomposites. The kinetic rate constant of the TiO2-10% BN catalysts was 10 times higher than that of the pure TiO2 nanofibers. The degradation of organic contaminants in wastewater followed the same trend as ibuprofen and improved with increasing BN content. The stability of the TiO2-BN nanocomposites as an effective solar photocatalyst was demonstrated by multiple cycles of wastewater treatment. The results proved that TiO2-BN is an appealing photocatalyst under visible light.

Impact of Polyelectrolyte Multilayers on the Ionic Current Rectification of Conical Nanopores.

Single conical nanopores were functionalised layer by layer with weak polyelectrolytes. We studied their influence on the ionic diode properties We have considered different couples of polyelectrolytes: poly-l-lysine/poly(acrylic acid) and poly(ethyleneimine)/poly(acrylic acid) as well as the influence of cross-linking. The results show that the nanopores decorated with poly(ethyleneimine)/poly(acrylic acid) exhibit an interesting behavior. Indeed, at pH 3, the nanopore is open only at the low salt concentration, while at pH 7, it is already open. The nanopores functionalized with poly-l-lysine/poly(acrylic acid) do not show an inversion of ionic transport properties with the pH as expected. After cross-linked to prevent large conformational changes, the ionic diode properties are dependent on the pH.

Porous Gelatin Membrane Obtained from Pickering Emulsions Stabilized by Graphene Oxide.

This article presents a novel procedure for preparing porous membranes from water-soluble polymers involving the formation of a Pickering emulsion. Gelatin is a biodegradable biopolymer obtained by the partial hydrolysis of collagen. A biopolymer such as gelatin is capable of adsorbing at an oil/water interface, resulting in decreased interfacial energy. Hence, gelatin is widely employed as an alternate for synthetic surfactants to stabilize emulsions in the food industry. However, high-molecular-weight gelatin leads to large emulsion droplets and poor emulsion stability. The amphoteric nature of graphene oxide (GO) nanosheets was helpful in stabilizing the oil/water interface and allows for the preparation of a stable gelatin/GO emulsion. Membranes fabricated using gelatin/GO have a uniformly distributed porous structure. However, prepared membranes are highly hydrosoluble, so the membranes were cross-linked without affecting their morphology. XRD results evidenced that gelatin effectively exfoliated the graphite oxide which is essential to stabilizing the emulsion. Fabricated gelatin/GO membranes possess uniformly distributed pores and are highly stable in aqueous solution. Pure water filtration tests were conducted on the membranes. The permeability results proved that the membranes fabricated by a Pickering emulsion are promising materials for filtration.

Unexpected ionic transport behavior in hydrophobic and uncharged conical nanopores.

We investigated ionic transport behavior in the case of uncharged conical nanopores. To do so, we designed conical nanopores using atomic layer deposition of Al2O3/ZnO nanolaminates and then coated these with trimethylsilane. The experimental results are supported by molecular dynamics simulations. The ionic transport reveals an unexpected behavior: (i) a current rectification and (ii) a constant conductance at low salt concentration which are usually reported for charged conical nanopore. To explain these results, we have considered different assumptions: (i) a default of functionalization, (ii) the adsorption anion and (iii) the slippage. The first one was refuted by the study of the poly-l-lysine transport through the nanopore. To verify the second assumption, we investigate the effect of pH on the current rectification and the molecular dynamics simulations. Finally our study demonstrates that the unexpected ionic transport is provided to a predominant effect of slippage due to the water organization at the solid/liquid interface.

Inverse Pickering Emulsion Stabilized by Exfoliated Hexagonal-Boron Nitride (h-BN).

The formation of inverse Pickering emulsions using exfoliated hexagonal boron nitride (h-BN) as an effective particulate stabilizer without using any surfactants is reported for the first time. The stability and the type of h-BN Pickering emulsions formulated with different BN concentrations and by varying oil/water (o/w) ratios are studied and discussed. First the emulsion structure is analyzed microscopically through optical and epifluorescence microscopy and macroscopically by the study of the rheological behavior. The average droplet size decreases with h-BN concentration whereas the emulsions achieve good stability at 2 wt % BN concentrations and for a 1:1 o/w ratio. In all formulations, the emulsions are of water-in-oil (w/o) type due mainly to the hydrophobicity of h-BN.

Diffusion dynamics of latex nanoparticles coated with ssDNA across a single nanopore.

The fundamental understanding of the transport mechanisms of objects across a single nanopore is one key point to develop Coulter counters at the nanoscale for macromolecule or nanoparticle detection. In this area, nanoparticles have been less investigated than biomacromolecules such as DNA or proteins due to their self-aggregation in the presence of salts. In this work, the transport of modified latex nanoparticles across solid-state nanopores was investigated. To prevent their aggregation, their surface was modified with a low molecular weight single strand DNA coating. Then the coated nanoparticles were successfully detected across a single pore material in 200 mM NaCl buffer. The experimental capture rate was compared to that of the predictive model. It reveals that the nanoparticle entrance inside the nanopore is mainly governed by diffusion and required a weak energy. For relative current blockades, the predictive model should take into account both the nanopore shape and the additional charge due to ssDNA coating.

Optical, electrical and magnetic properties of lanthanum strontium manganite La1-xSrxMnO3 synthesized through the citrate combustion method.

Generally, strontium-doped lanthanum manganites (LSM) are materials connected ordinarily as cathodes in the solid oxide fuel cell (SOFC). In this study, the structural, optical, electrical and magnetic properties of La1-xSrxMnO3 (x = 0.2, 0.5, 0.8) synthesized using an organic acid precursor strategy were investigated, based on using citric acid as a fuel. Evidently, the results disclosed that a pure single monoclinic LSM phase was obtained from the thermally treated precursors annealed at 1000 °C with an annealing time of 2 h. The microstructure of the formed sample relied on the Sr2+ ion content. Moreover, a good optical transparency of 45-60% in a wide range of wavelengths between 800 and 1800 nm for all samples substituted by Sr2+ ions was performed. The optical band gap energy was increased from 2.09 to 2.76 eV by increasing the Sr2+ ion molar ratios. The trend in the calculated refractive index, the high frequency dielectric constant (εα) and the static dielectric constant (ε0) of all the produced samples can be linked to an increase in the Sr2+ ion concentration. Moreover, the magnetic properties were enhanced with increasing Sr2+ ion content.

Low-Coherence Interferometric Fiber-Optic Sensors with Potential Applications as Biosensors.

Fiber-optic Fabry-Pérot interferometers (FPI) can be applied as optical sensors, and excellent measurement sensitivity can be obtained by fine-tuning the interferometer design. In this work, we evaluate the ability of selected dielectric thin films to optimize the reflectivity of the Fabry-Pérot cavity. The spectral reflectance and transmittance of dielectric films made of titanium dioxide (TiO2) and aluminum oxide (Al2O3) with thicknesses from 30 to 220 nm have been evaluated numerically and compared. TiO2 films were found to be the most promising candidates for the tuning of FPI reflectivity. In order to verify and illustrate the results of modelling, TiO2 films with the thickness of 80 nm have been deposited on the tip of a single-mode optical fiber by atomic layer deposition (ALD). The thickness, the structure, and the chemical properties of the films have been determined. The ability of the selected TiO2 films to modify the reflectivity of the Fabry-Pérot cavity, to provide protection of the fibers from aggressive environments, and to create multi-cavity interferometric sensors in FPI has then been studied. The presented sensor exhibits an ability to measure refractive index in the range close to that of silica glass fiber, where sensors without reflective films do not work, as was demonstrated by the measurement of the refractive index of benzene. This opens up the prospects of applying the investigated sensor in biosensing, which we confirmed by measuring the refractive index of hemoglobin and glucose.

Influence of Adsorption on Proteins and Amyloid Detection by Silicon Nitride Nanopore.

For the past 2 decades, emerging single-nanopore technologies have opened the route to multiple sensing applications. Besides DNA sensing, the identification of proteins and amyloids is a promising field for early diagnosis. However, the influence of the interactions between the nanopore surface and proteins should be taken into account. In this work, we have selected three proteins (avidin, lysozyme, and IgG) that exhibit different affinities with the SiNx surface, and we have also examined lysozyme amyloid. Our results show that the piranha treatment of SiNx significantly decreases protein adsorption. Moreover, we have successfully detected all proteins (pore diameter 17 nm) and shown the possibility of discriminating between denatured lysozyme and its amyloid. For all proteins, the capture rates are lower than expected, and we evidence that they are correlated with the affinity of proteins to the surface. Our result confirms that proteins interacting only with the nanopore surface wall stay long enough to be detected. For lysozyme amyloid, we show that the use of the nanopore is suitable for determining the number of monomer units even if only the proteins interacting with the nanopore are detected.

Biomimetic solution against dewetting in a highly hydrophobic nanopore.

A water molecule is the foundation of life and is the primary compound in every living system. While many of its properties are understood in a bulk solvent, its behavior in a small hydrophobic nanopore still raises fundamental questions. For instance, a wetting/dewetting transition in a hydrophobic solid-state or a polymer nanopore occurs stochastically and can only be prevented by external physical stimuli. Controlling these transitions would be a primary requirement to improve many applications. Some biological channels, such as gramicidin A (gA) proteins, show a high rate of water and ion diffusion in their central subnanochannel while their external surface is highly hydrophobic. The diameter of this channel is significantly smaller than the inner size of the lowest artificial nanopore in which water drying occurs (i.e. 1.4 nm). In this paper, we propose an innovative idea to generate nanopore wetting as a result of which the application of an external field is no longer required. In a nanopore, the drying or wetting of the inner walls occurs randomly (in experiments and in simulations). However, we have shown how the confinement of gA, in a dried hydrophobic nanopore, rapidly generates a stable wetting of the latter. We believe that this simple idea, based on biomimetism, could represent a real breakthrough that could help to improve and develop new nanoscale applications.

Influence of nanopore surface charge and magnesium ion on polyadenosine translocation.

We investigate the influence of a nanopore surface state and the addition of Mg(2+) on poly-adenosine translocation. To do so, two kinds of nanopores with a low aspect ratio (diameter ∼3-5 nm, length 30 nm) were tailored: the first one with a negative charge surface and the second one uncharged. It was shown that the velocity and the energy barrier strongly depend on the nanopore surface. Typically if the nanopore and polyA exhibit a similar charge, the macromolecule velocity increases and its global energy barrier of entrance in the nanopore decreases, as opposed to the non-charged nanopore. Moreover, the addition of a divalent chelating cation induces an increase of energy barrier of entrance, as expected. However, for a negative nanopore, this effect is counterbalanced by the inversion of the surface charge induced by the adsorption of divalent cations.

Tuning of ZnO 1D nanostructures by atomic layer deposition and electrospinning for optical gas sensor applications.

We explored for the first time the ability of a three-dimensional polyacrylonitrile/ZnO material-prepared by a combination of electrospinning and atomic layer deposition (ALD) as a new material with a large surface area-to enhance the performance of optical sensors for volatile organic compound (VOC) detection. The photoluminescence (PL) peak intensity of these one-dimensional nanostructures has been enhanced by a factor of 2000 compared to a flat Si substrate. In addition, a phase transition of the ZnO ALD coating from amorphous to crystalline has been observed due to the properties of a polyacrylonitrile nanofiber template: surface strain, roughness, and an increased number of nucleation sites in comparison with a flat Si substrate. The greatly improved PL performance of these nanostructured surfaces could produce exciting materials for implantation in VOC optical sensor applications.