Giant change of MoS2 optical properties along amorphous-crystalline transition: broadband spectroscopic study including the NIR therapeutic window.

This work deals with an ellipsometric study of magnetron sputtered thin MoS2 films. The evolution of the UV-VIS-NIR optical properties of as-deposited and subsequently annealed films is thoughtfully investigated, covering amorphous, amorphous relaxed, partially crystallized, and polycrystallized MoS2 films. The transition from the mixed 1T'@2H local order in the amorphous phase toward the long-range 2H order in the polycrystalline phase is systematically correlated with film optical properties. The early stage of a few-layer 2H ordering toward the 2H bulk-like polycrystalline structure during annealing is evidenced through the energy shift of MoS2 prominent excitonic peaks. A considerable change in optical response between metallic (amorphous) and semiconducting (polycrystalline) MoS2 phases is reported and presented in terms of dielectric permittivity and normal reflectance NIR-VIS-UV spectra. Results of light-heat conversion in the NIR therapeutic window show so far uncovered potential of amorphous MoS2 as an agent for photothermal therapy. Spectroscopic ellipsometry provided sensitive characterization disclosing essential results complementary to other characterization tools. The benefit of these results is expected to be employed in fundamental and application-motivated research, for example, in the field of phase change materials, photothermal cancer therapy, and magneto-optical study of magnetic ordering in metal transition dichalcogenides, among others.

Nanospray-assisted deposition of silver nanoparticles for mapping of a peptide in nanofibrous layers via surface-enhanced Raman spectrometry.

Surface-enhanced Raman spectrometry (SERS) is a universal detection tool identifying molecules via vibrations of their chemical bonds. Its function requires the close localization of metal nanostructures and the analyte. In this work, we present a lab-made instrumentation for the deposition of silver nanoparticles on a strongly hydrophilic nanofibrous composite via a nanospray for SERS mapping of an incorporated peptide. The nanospray-sample distance was revealed as the most crucial parameter since it directly influences the moisture of the deposited colloid. Residual water was recognized as a sensitivity enhancer. Additionally, we continuously introduced a solution of sodium chloride to the colloid increasing its ionic strength, which formed a more homogeneous profile of the deposit. After the deposition process, the treated sample was scanned via a SERS laser and the collected Raman spectra were transformed into a distribution map of the peptide at a concentration of 5 µg/g.

High-quality and easy-to-regenerate personal filter.

Proper respiratory tract protection is the key factor to limiting the rate of COVID-19 spread and providing a safe environment for health care workers. Traditional N95 (FFP2) respirators are not easy to regenerate and thus create certain financial and ecological burdens; moreover, their quality may vary significantly. A solution that would overcome these disadvantages is desirable. In this study a commercially available knit polyester fleece fabric was selected as the filter material, and a total of 25 filters of different areas and thicknesses were prepared. Then, the size-resolved filtration efficiency (40-400 nm) and pressure drop were evaluated at a volumetric flow rate of 95 L/min. We showed the excellent synergistic effect of expanding the filtration area and increasing the number of filtering layers on the filtration efficiency; a filter cartridge with 8 layers of knit polyester fabric with a surface area of 900 cm2 and sized 25 × 14 × 8 cm achieved filtration efficiencies of 98% at 95 L/min and 99.5% at 30 L/min. The assembled filter kit consists of a filter cartridge (14 Pa) carried in a small backpack connected to a half mask with a total pressure drop of 84 Pa at 95 L/min. In addition, it is reusable, and the filter material can be regenerated at least ten times by simple methods, such as boiling. We have demonstrated a novel approach for creating high-quality and easy-to-breathe-through respiratory protective equipment that reduces operating costs and is a green solution because it is easy to regenerate.

3D printed device for epitachophoresis.

Polyacrylamide or agarose gels are the most frequently used sieving and stabilizing media in slab gel electrophoresis. Recently, we have introduced a new electrophoretic technique for concentration/separation of milliliter sample volumes. In this technique, the gel is used primarily as an anticonvection media eliminating liquid flow during the electromigration. While serving well for the liquid stabilization, the gels can undergo deformation when exposed to a discontinuous electrolyte buffer system used in epitachophoresis. In this work, we have explored 3D printing to form rigid stabilizing manifolds to minimize liquid flow during the epitachophoresis run. The whole device was printed using the stereolithography technique from a low water-absorbing resin. The stabilizing manifold, serving as the gel substitute, was printed as a replaceable composite structure preventing electrolyte mixing during the separation. Different geometries of the 3D printed stabilizing manifolds were tested for use in concentrating ionic sample components without spatial separation. The presented device can focus analytes from 3 or 4 mL of the sample to 150 µL or less, depending on the collection cup size. With the 150 µL collection cup, this represents the enrichment factor from 20 to 27. The time of concentration was from 15 to 25 min, depending on stabilization media and power used.

Electrospray: More than just an ionization source.

Electrospraying (ES) is a potential-driven process of liquid atomization, which is employed in the field of analytical chemistry, particularly as an ionization technique for mass spectrometric analyses of biomolecules. In this review, we demonstrate the extraordinary versatility of the electrospray by overviewing the specifics and advanced applications of ES-based processing of low molecular mass compounds, biomolecules, polymers, nanoparticles, and cells. Thus, under suitable experimental conditions, ES can be used as a powerful tool for highly controlled deposition of homogeneous films or various patterns, which may sometimes even be organized into 3D structures. We also emphasize its capacity to produce composite materials including encapsulation systems and polymeric fibers. Further, we present several other, less common ES-based applications. This review provides an insight into the remarkable potential of ES, which can be very useful in the designing of innovative and unique strategies.

Chiral Templating of Polycarbonate Membranes by Pinene Using the Modified Atomic Layer Deposition Approach.

In this article, chiral templating of a polycarbonate (PC) membrane by (-)-α-pinene using the atomic layer deposition (ALD) approach is investigated. The templating with the enantiomer of (-)-α-pinene, used as a case compound, was performed either on the original commercial PC membrane or on the PC membrane with a beforehand deposited Al2O3 layer. The efficiency of the templating was assessed by a difference in the membrane ability to adsorb/absorb (-)-α-pinene, (+)-α-pinene, and their racemic mixture, using a very sensitive gas sorption analyzer. The results clearly show that the solution-diffusion mechanism rather than the sieving mechanism applied for adsorption/absorption of (-/+)-α-pinene enantiomers, which have the same size of the molecule. The PC membrane with the predeposited Al2O3 before the (-)-α-pinene templating shows significantly higher sorption of (-)-α-pinene compared to (+)-α-pinene and racemate, which clearly demonstrates the presence of a chiral recognition effect.

Atomic Layer Deposition of SnO2-Coated Anodic One-Dimensional TiO2 Nanotube Layers for Low Concentration NO2 Sensing.

The continuous emission of nitrous oxides contributes to the overall air pollution and deterioration of air quality. In particular, an effective NO2 sensor capable of low concentration detection for continuous monitoring is demanded for safety, health, and wellbeing. The sensing performance of a metal oxide-based sensor is predominantly influenced by the availability of surface area for O2 adsorption and desorption, efficient charge transport, and size or thickness of the sensing layer. In this study, we utilized anodic one-dimensional (1D) TiO2 nanotube layers of 5 µm thick which offer large surface area and unidirectional electron transport pathway as a platform to accommodate thin SnO2 coatings as a sensing layer. Conformal and homogeneous SnO2 coatings across the entire inner and outer TiO2 nanotubes were achieved by atomic layer deposition with a controlled thickness of 4, 8, and 16 nm. The SnO2-coated TiO2 nanotube layers attained a higher sensing response than a reference Figaro SnO2 sensor. Specifically, the 8 nm SnO2-coated TiO2 nanotube layer has recorded up to ten-fold enhancement in response as compared to the blank nanotubes for the detection of 1 ppm NO2 at an operating temperature of 300 °C with 0.5 V applied bias. This is attributed to the SnO2/TiO2 heterojunction effect and controlled SnO2 thickness within the range of the Debye length. We demonstrated in this work, a tailored large surface area platform based on 1D nanotubes with thin active coatings as an efficient approach for sensing applications and beyond.

TiO2 Nanotube Layers Decorated with Al2O3/MoS2/Al2O3 as Anode for Li-ion Microbatteries with Enhanced Cycling Stability.

TiO2 nanotube layers (TNTs) decorated with Al2O3/MoS2/Al2O3 are investigated as a negative electrode for 3D Li-ion microbatteries. Homogenous nanosheets decoration of MoS2, sandwiched between Al2O3 coatings within self-supporting TNTs was carried out using atomic layer deposition (ALD) process. The structure, morphology, and electrochemical performance of the Al2O3/MoS2/Al2O3-decorated TNTs were studied using scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and chronopotentiometry. Al2O3/MoS2/Al2O3-decorated TNTs deliver an areal capacity almost three times higher than that obtained for MoS2-decorated TNTs and as-prepared TNTs after 100 cycles at 1C. Moreover, stable and high discharge capacity (414 µAh cm-2) has been obtained after 200 cycles even at very fast kinetics (3C).

Cyclic Silylselenides: Convenient Selenium Precursors for Atomic Layer Deposition.

Three cyclic silylselenides were prepared in a straightforward manner. Property tuning has been achieved by varying the ring size and the number of embedded selenium atoms. All silylselenides possess improved resistance towards moisture and oxidation as well as high thermal robustness and sufficient volatility with almost zero residues. The six-membered diselenide proved to be particularly superior Se precursors for atomic layer deposition and allowed facile preparation of MoSe2 layers. Their structure and composition have been investigated by Raman and X-ray photoelectron spectroscopy as well as scanning electron microscopy revealing vertically aligned flaky shaped nanosheets.

GaTe-Sb2Te3 thin-films phase change characteristics.

A radio frequency magnetron co-sputtering technique exploiting GaTe and ${\rm Sb}_2 {\rm Te}_3$Sb2Te3 targets was used for the fabrication of Ga-Sb-Te thin films. Prepared layers cover broad region of chemical composition (${\sim}{10.0 {-} 26.3}\,\, {\rm at.}$∼10.0-26.3at. % of Ga, ${\sim}{19.9 {-} 34.4}\,\, {\rm at.}$∼19.9-34.4at. % of Sb) while keeping Te content fairly constant (53.8-55.6 at. % of Te). Upon crystallization induced by annealing, large variations in electrical contrast were found, reaching a sheet resistance ratio of ${{R}_{\rm annealed}}/{{R}_{\rm as - deposited}}\;\sim{2.2} \times {{10}^{ - 8}}$Rannealed/Ras-deposited∼2.2×10-8 for the ${{\rm Ga}_{26.3}}{{\rm Sb}_{19.9}}{{\rm Te}_{53.8}}$Ga26.3Sb19.9Te53.8 layer. Phase transition from the amorphous to crystalline state further leads to huge changes of optical functions demonstrated by optical contrast values up to $|\Delta n| + |\Delta k| = {4.20}$|Δn|+|Δk|=4.20 for ${{\rm Ga}_{26.3}}{{\rm Sb}_{19.9}}{{\rm Te}_{53.8}}$Ga26.3Sb19.9Te53.8 composition.

Thin TiO2 Coatings by ALD Enhance the Cell Growth on TiO2 Nanotubular and Flat Substrates.

The present work exploits Ti sheets and TiO2 nanotube (TNT) layers and their surface modifications for the proliferation of different cells. Ti sheets with a native oxide layer, Ti sheets with a crystalline thermal oxide layer, and two kinds of TNT layers (prepared via electrochemical anodization) with a defined inner diameter of 12 and 15 nm were used as substrates. A part of the Ti sheets and the TNT layers was additionally coated by thin TiO2 coatings using atomic layer deposition (ALD). An increase in cell growth of WI-38 fibroblasts (>50%), MG-63 osteoblasts (>30%), and SH-SY5Y neuroblasts (>30%) was observed for all materials coated by five cycles ALD compared to their uncoated counterparts. The additional ALD TiO2 coatings changed the surface composition of all materials but preserved their original structure and protected them from unwanted crystallization and shape changes. The presented approach of mild surface modification by ALD has a significant effect on the materials' biocompatibility and is promising toward application in implant materials.

2D MoS2 nanosheets on 1D anodic TiO2 nanotube layers: an efficient co-catalyst for liquid and gas phase photocatalysis.

One-dimensional TiO2 nanotube layers with different dimensions were homogeneously decorated with 2D MoS2 nanosheets via atomic layer deposition and employed for liquid and gas phase photocatalysis. The 2D MoS2 nanosheets revealed a high amount of exposed active edge sites and strongly enhanced the photocatalytic performance of TiO2 nanotube layers.

Photon-Upconversion Barcoding with Multiple Barcode Channels: Application for Droplet Microfluidics.

Barcoding facilitates high-throughput analytical methods in complex matrixes with a reduced volume of sample, reagents, time, and cost. Because of orthogonality to fluorescence, photon-upconversion barcodes attracted considerable attention in recent years. We constructed an epiluminescence detector, which, for the first time, demonstrated the reading of photon-upconversion spectra from microdroplets in a microfluidic chip with frequency up to 10 Hz. Non-negative least-squares deconvolution enabled the reading of an unprecedented number of photon-upconversion barcode channels (six) from emission spectra (excitation 980 nm, emission 430-875 nm). The standard deviation of barcode reading from microdroplets was ∼1%. Described barcoding can be, for example, used for multiparameter titrations, multiplexed biological and chemical assays, optimizations on a microfluidic platform, and preparation of barcoded concentration gradients and libraries.

Optimization of background electrolyte composition for simultaneous contactless conductivity and fluorescence detection in capillary electrophoresis of biological samples.

In this article, optimization of BGE for simultaneous separation of inorganic ions, organic acids, and glutathione using dual C4 D-LIF detection in capillary electrophoresis is presented. The optimized BGE consisted of 30 mM 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid, 15 mM 2-amino-2-hydroxymethyl-propane-1,3-diol, and 2 mM 18-crown-6 at pH 7.2 and allowed simultaneous separation of ten inorganic anions and cations, three organic acids and glutathione in 20 min. The samples were injected hydrodynamically from both capillary ends using the double-opposite end injection principle. Sensitive detection of anions, cations, and organic acids with micromolar LODs using C4 D and simultaneously glutathione with nanomolar LODs using LIF was achieved in a single run. The developed BGE may be useful in analyses of biological samples containing analytes with differing concentrations of several orders of magnitude that is not possible with single detection mode.

TiO2 ALD Coating of Amorphous TiO2 Nanotube Layers: Inhibition of the Structural and Morphological Changes Due to Water Annealing.

The present work presents a strategy to stabilize amorphous anodic self-organized TiO2 nanotube layers against morphological changes and crystallization upon extensive water soaking. The growth of needle-like nanoparticles was observed on the outer and inner walls of amorphous nanotube layers after extensive water soakings, in line with the literature on water annealing. In contrary, when TiO2 nanotube layers uniformly coated by thin TiO2 using atomic layer deposition (ALD) were soaked in water, the growth rates of needle-like nanoparticles were substantially reduced. We investigated the soaking effects of ALD TiO2 coatings with different thicknesses and deposition temperatures. Sufficiently thick TiO2 coatings (≈8.4 nm) deposited at different ALD process temperatures efficiently hamper the reactions between water and F- ions, maintain the amorphous state, and preserve the original tubular morphology. This work demonstrates the possibility of having robust amorphous 1D TiO2 nanotube layers that are very stable in water. This is very practical for diverse biomedical applications that are accompanied by extensive contact with an aqueous environment.

Resistive pulse sensing as particle counting and sizing method in microfluidic systems: Designs and applications review.

Resistive pulse sensing is a well-known and established method for counting and sizing particles in ionic solutions. Throughout its development the technique has been expanded from detection of biological cells to counting nanoparticles and viruses, and even registering individual molecules, e.g., nucleotides in nucleic acids. This technique combined with microfluidic or nanofluidic systems shows great potential for various bioanalytical applications, which were hardly possible before microfabrication gained the present broad adoption. In this review, we provide a comprehensive overview of microfluidic designs along with electrode arrangements with emphasis on applications focusing on bioanalysis and analysis of single cells that were reported within the past five years.

Spaced TiO2 Nanotubes Enable Optimized Pt Atomic Layer Deposition for Efficient Photocatalytic H2 Generation.

In the present work, we report the use of TiO2 nanotube (NT) layers with a regular intertube spacing that are decorated by Pt nanoparticles through the atomic layer deposition (ALD) of Pt. These Pt-decorated spaced (SP) TiO2 NTs are subsequently explored for photocatalytic H2 evolution and are compared to classical close-packed (CP) TiO2 NTs that are also decorated with various amounts of Pt by using ALD. On both tube types, by varying the number of ALD cycles, Pt nanoparticles of different sizes and areal densities are formed, uniformly decorating the inner and outer walls from tube top to tube bottom. The photocatalytic activity for H2 evolution strongly depends on the size and density of Pt nanoparticles, driven by the number of ALD cycles. We show that, for SP NTs, a much higher photocatalytic performance can be achieved with significantly smaller Pt nanoparticles (i.e. for fewer ALD cycles) compared to CP NTs.

Ideally Hexagonally Ordered TiO2 Nanotube Arrays.

Ideally hexagonally ordered TiO2 nanotube layers were produced through the optimized anodization of Ti substrates. The Ti substrates were firstly covered with a TiN protecting layer prepared through atomic layer deposition (ALD). Pre-texturing of the TiN-protected Ti substrate on an area of 20×20 µm2 was carried out by focused ion beam (FIB) milling, yielding uniform nanoholes with a hexagonal arrangement throughout the TiN layer with three different interpore distances. The subsequent anodic nanotube growth using ethylene-glycol-based electrolyte followed the pre-textured nanoholes, resulting in perfectly ordered nanotube layers (resembling honeycomb porous anodic alumina) without any point defects and with a thickness of approximately 2 µm over the whole area of the pattern.

ALD Al2O3-Coated TiO2 Nanotube Layers as Anodes for Lithium-Ion Batteries.

The utilization of the anodic TiO2 nanotube layers, with uniform Al2O3 coatings of different thicknesses (prepared by atomic layer deposition, ALD), as the new electrode material for lithium-ion batteries (LIBs), is reported herein. Electrodes with very thin Al2O3 coatings (∼1 nm) show a superior electrochemical performance for use in LIBs compared to that of the uncoated TiO2 nanotube layers. A more than 2 times higher areal capacity is received on these coated TiO2 nanotube layers (∼75 vs 200 µAh/cm2) as well as higher rate capability and coulombic efficiency of the charging and discharging reactions. Reasons for this can be attributed to an increased mechanical stability of the TiO2 nanotube layers upon Al2O3 coating, as well as to an enhanced diffusion of the Li+ ions within the coated nanotube layers. In contrast, thicker ALD Al2O3 coatings result in a blocking of the electrode surface and therefore an areal capacity decrease.

Recent strategies toward microfluidic-based surface-enhanced Raman spectroscopy.

Surface-enhanced Raman spectroscopy (SERS) is an extremely powerful analytical tool, which not only yields information about the molecular structure of the analyte in the form of characteristic vibrational spectrum but also gives sensitivities approaching those in fluorescence spectroscopy. The SERS measurement on the microfluidic platform provides possibility to manufacture the device with design perfectly fulfilling the needs of the application with minimal sample consumption. This review aims at describing basic strategies for SERS measurement in microfluidic devices published in the last decade and covers current trends in microfluidics with SERS detection in the field of bioanalysis and approaches toward on-line coupling of liquid-based separation techniques with SERS detection.