Hybrid Impedimetric Biosensors for Express Protein Markers Detection.

Impedimetric biosensors represent a powerful and promising tool for studying and monitoring biological processes associated with proteins and can contribute to the development of new approaches in the diagnosis and treatment of diseases. The basic principles, analytical methods, and applications of hybrid impedimetric biosensors for express protein detection in biological fluids are described. The advantages of this type of biosensors, such as simplicity and speed of operation, sensitivity and selectivity of analysis, cost-effectiveness, and an ability to be integrated into hybrid microfluidic systems, are demonstrated. Current challenges and development prospects in this area are analyzed. They include (a) the selection of materials for electrodes and formation of nanostructures on their surface; (b) the development of efficient methods for biorecognition elements' deposition on the electrodes' surface, providing the specificity and sensitivity of biosensing; (c) the reducing of nonspecific binding and interference, which could affect specificity; (d) adapting biosensors to real samples and conditions of operation; (e) expanding the range of detected proteins; and, finally, (f) the development of biosensor integration into large microanalytical system technologies. This review could be useful for researchers working in the field of impedimetric biosensors for protein detection, as well as for those interested in the application of this type of biosensor in biomedical diagnostics.

Temperature- and Size-Dependent Photoluminescence of CuInS2 Quantum Dots.

We present the results of a temperature-dependent photoluminescence (PL) spectroscopy study on CuInS2 quantum dots (QDs). In order to elucidate the influence of QD size on PL temperature dependence, size-selective precipitation was used to obtain several nanoparticle fractions. Additionally, the nanoparticles' morphology and chemical composition were studied using transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The obtained QDs showed luminescence in the visible-near infrared range. The PL energy, linewidth, and intensity were studied within an 11-300 K interval. For all fractions, a temperature decrease led to a shift in the emission maximum to higher energies and pronounced growth of the PL intensity down to 75-100 K. It was found that for large particle fractions, the PL intensity started to decrease, with temperature decreasing below 75 K, while the PL intensity of small nanoparticles remained stable.

High-Throughput Screening of 3D-Printed Architected Materials Inspired by Crystal Lattices: Procedure, Challenges, and Mechanical Properties.

The search for load-bearing, impact-resistant, and energy-absorbing cellular materials is of central interest in many fields including aerospace, automotive, civil, sports, packaging, and biomedical. In order to achieve the desired characteristic geometry and/or topology, a perspective approach may be used, such as utilization of atomic models as input data for 3D printing of macroscopic objects. In this paper, we suggest a new approach for the development of advanced cellular materials-crystallomorphic design based on selection of perspective crystal structures and modeling of their electron density distribution and utilization of isoelectronic surfaces as a generatrix for 3D-printed cellular materials. The ATLAS database, containing more than 10 million existing and predicted zeolites, was used as a source of data. Herein, we introduced a high-throughput screening of a data array of crystalline compounds. Several perspective designs were identified, implemented by 3D printing, and showed high characteristics. A linear correlation was found between the strength of the samples and the minimum angle and minimum bond length in the simplified crystal structures. A new cellular geometry with reinforcement struts and increased strength was discovered. This property was found by us independent of the other works, in which the cellular structures were developed by an explicit method. Thus, the developed approach holds perspective for the design of new cellular structures with increased characteristics and for the prediction of their properties.

SnO2-Based Porous Nanomaterials: Sol-Gel Formation and Gas-Sensing Application.

Porous nanocomposites using two (tin dioxide-silica dioxide) and three (tin dioxide-indium oxide-silica dioxide)-component systems for gas sensors were created with the sol-gel method. To understand some of the physical-chemical processes that occurred during the adsorption of gas molecules on the surface of the produced nanostructures, two models-the Langmuir model and the Brunauer-Emmett-Teller theory-were used to carry out calculations. The results of the phase analysis concerning the interaction between the components during the formation of the nanostructures were obtained through the use of X-ray diffraction, thermogravimetric analysis, the Brunauer-Emmett-Teller technique (to determine the surface areas), the method of partial pressure diagrams in a wide range of temperatures and pressures and the results of the measurement of the nanocomposites' sensitivity. The analysis allowed us to find the optimal temperature for annealing nanocomposites. The introduction of a semiconductor additive into a two-component system based on tin and silica dioxides significantly increased the sensitivity of the nanostructured layers to reductional reagent gases.

Self-Organization Effects of Thin ZnO Layers on the Surface of Porous Silicon by Formation of Energetically Stable Nanostructures.

The formation of complex surface morphology of a multilayer structure, the processes of which are based on quantum phenomena, is a promising domain of the research. A hierarchy of pore of various sizes was determined in the initial sample of porous silicon by the atomic force microscopy. After film deposition by spray pyrolysis, ZnO nanoclusters regularly distributed over the sample surface were formed. Using the electron paramagnetic resonance (EPR) method it was determined that the localization of paramagnetic centers occurs more efficiently as a result of the ZnO deposition. An increase in the number of deposited layers, leads to a decrease in the paramagnetic center relaxation time, which is probably connected with the formation of ZnO nanocrystals with energetically stable properties. The nucleation and formation of nanocrystals is associated with the interaction of particles with an uncompensated charge. There is no single approach to determine the mechanism of this process. By the EPR method supplemented with the signal cyclic saturation, spectral manifestations from individual centers were effectively separated. Based on electron paramagnetic resonance and photoluminescence studies it was revealed that the main transitions between energy levels are due to oxygen vacancies and excitons.

Step-By-Step Modeling and Demetallation Experimental Study on the Porous Structure in Zeolites.

The organization of microporous space in zeolites is discussed. A new step-by-step model is proposed that explains the principles of organizing the hierarchy of microporous space at the stage of assembling zeolites from elements of minimal size: a primary building unit, secondary building units, tertiary building units or building polyhedra, a sodalite cage, and a supercage. To illustrate the stepwise hierarchical porous structure of nanomaterials, the following zeolites with small and large micropores have been selected as the model objects: sodalite (SOD, the maximum diameter of a sphere that can enter the pores is 0.3 nm) and zeolites of type A (LTA, the maximum diameter of a sphere that can enter the pores is 0.41 nm), type X, Y (FAU, the maximum diameter of a sphere that can enter the pores is 0.75 nm), and type BETA (the maximum diameter of a sphere that can enter the pores is 0.67 nm). Two-dimensional and three-dimensional modeling in 3Ds Max software was used. We believe that such an approach will be useful for developing ways to create complex zeolite compositions for specific applications, such as catalysis, where the geometry of the pores determines the size of the molecules entering the voids and computer modeling can play an important predictive role. This work takes a look at specific aspects of using the heat desorption method to study mesoporous materials with a BETA zeolite as an example and presents the results of experimental research into the characteristics of the porous structure of hierarchically structured zeolite materials (specific surface area 180-380 m2/g, external surface area 120-200 m2/g, micropore volume 0.001-0.1 mL/g).

Effect of Carbon Dots Concentration on Electrical and Optical Properties of Their Composites with a Conducting Polymer.

CQD/PEDOT: PSS composites were prepared via the hydrothermal method from glucose carbon quantum dots (CQDs) and an aqueous solution of PEDOT:PSS conducting polymer and their electrical and optical properties were investigated. The morphology and structure of these samples were investigated by AFM, SEM, EDX, and EBSD. It was found that the CQDs and CQD/PEDOT:PSS composites had a globular structure with globule sizes of ~50-300 nm depending on the concentration of PEDOT:PSS in these composites. The temperature dependence of the resistivity was obtained for the CQD/PEDOT:PSS (3%, 5%, 50%) composites, which had a weak activation character. The charge transport mechanism was discussed. The dependence of the resistivity on the storage time of the CQD/PEDOT:PSS (3%, 5%, 50%) composites and pure PEDOT:PSS was obtained. It was noted that mixing CQDs with PEDOT:PSS allowed us to obtain better electrical and optical properties than pure CQDs. CQD/PEDOT: PSS (3%, 5%, 50%) composites are more conductive composites than pure CQDs, and the absorbance spectra of CQD/PEDOT:PSS composites are a synergistic effect of interaction between CQDs and PEDOT:PSS. We also note the better stability of the CQD/PEDOT:PSS (50%) composite than the pure PEDOT:PSS film. CQD/PEDOT: PSS (50%) composite is promising for use as stable hole transport layers in devices of flexible organic electronics.

Thermodynamic Analysis and Experimental Study on the Oxidation of PbX (X = S, Se) Nanostructured Layers.

Heat treatment in an oxygen-containing medium is a necessary procedure in the technology of forming photodetectors and emitters based on lead chalcogenides. Lead chalcogenide layers (PbS, PbSe) were prepared via a chemical bath deposition method. Surface oxidation of lead chalcogenide layers was analyzed using X-ray diffraction and Raman spectroscopy methods, and thermodynamic analysis of the oxidation of PbSe and PbS layers was also performed. The calculated phase diagrams from 20 °C to 500 °C showed good agreement with the experimental results. According to the thermodynamic analysis, the oxidation products depend on the initial composition of the layers and temperature of the annealing. In some cases, the formation of a separate metallic phase Pb is possible along with the formation of lead oxide PbO and other oxides. The performed thermodynamic analysis makes it possible to substantiate the two-stage annealing temperature regimes which ensure an increase in the speed of photodetectors.

Polyvinylpyrrolidone as a Stabilizer in Synthesis of AgInS2 Quantum Dots.

A synthesis protocol of polyvinylpyrrolidone-capped AgInS2 quantum dots in aqueous solution is reported. Nanoparticle morphology and chemical composition were studied by means of TEM, XRD, XPS, and FTIR. The obtained quantum dots were luminescent in the visible range. The photoluminescence intensity dependence on the polyvinylpyrrolidone amount was demonstrated. The wavelength of the emission maximum varied with changing the [Ag]:[In] molar ratio. The temperature dependence of the photoluminescence intensity of the polyvinylpyrrolidone-capped AgInS2 quantum dots was investigated within the temperature range of 11-294 K.

Control over the Surface Properties of Zinc Oxide Powders via Combining Mechanical, Electron Beam, and Thermal Processing.

The surface properties of zinc oxide powders prepared using mechanical activation, electron beam irradiation, and vacuum annealing, as well using combinations of these types of treatments, were studied using X-ray photoelectron spectroscopy. The structure of the obtained materials was studied by an X-ray diffraction technique and by scanning electron microscopy. We found that over five hours of grinding in an attritor, the size of nanocrystals decreases from 37 to 21 nm, and microdeformations increase from 0.3% to 0.6%. It was also found that a five-hour grinding treatment promoted formation of vacancies in the zinc sublattice at the surface and diffusion of Zn2+ cations into the bulk of the material. Irradiation of commercial zinc oxide powders with an electron beam with an energy of 0.9 MeV and a dose of 1 MGy induced breaking of Zn-O bonds, diffusion of interstitial zinc ions into the bulk, and oxygen atom escape from regular positions into the gas phase. A combined treatment of five hours of grinding and electron beam irradiation promoted accumulation of interstitial zinc ions at the surface of the material. Annealing of both initial and mechanically activated ZnO powders at temperatures up to 400 °C did not lead to a significant change in the properties of the samples. Upon exceeding the 400 °C annealing temperature the X-ray photoelectron spectra show almost identical atomic composition of the two types of materials, which is related to diffusion of interstitial zinc ions from the bulk of the material to the surface.

Impedance Spectroscopy of Hierarchical Porous Nanomaterials Based on por-Si, por-Si Incorporated by Ni and Metal Oxides for Gas Sensors.

Approaches are being developed to create composite materials with a fractal-percolation structure based on intercalated porous matrices to increase the sensitivity of adsorption gas sensors. Porous silicon, nickel-containing porous silicon, and zinc oxide have been synthesized as materials for such structures. Using the impedance spectroscopy method, it has been shown that the obtained materials demonstrate high sensitivity to organic solvent vapors and can be used in gas sensors. A model is proposed that explains the high sensitivity and inductive nature of the impedance at low frequencies, considering the structural features and fractal-percolation properties of the obtained oxide materials.

Improving the Conductivity of the PEDOT:PSS Layers in Photovoltaic Cells Based on Organometallic Halide Perovskites.

Among conductive polymers, PEDOT films find the widest application in electronics. For photovoltaic applications, studies of their optical properties, stability, and electrical conductivity are of greatest interest. However, the PEDOT:PSS transport layers, when used in photovoltaic cells, have a high electrical resistance, which prevents solar cells from increasing their efficiency. One of the promising ways to improve their electrical properties is the use of composite materials based on them, in which the conductivity can be increased by introducing various additives. In this work, conductive polymer films PEDOT:PSS (poly (3,4-ethylenedioxythiophene):polystyrene sulfonate acid) doped with a number of amines (Pentylamine, Octylamine, Diethylamine, Aniline with carbon nanotubes) were obtained and studied. It is shown that, depending on the concentration of dopants, the electrical conductivity of PEDOT:PSS films can be significantly improved. In this case, the light transmission of the films practically does not change. The process of improving the conductivity by treating the surface of the finished film with amines, followed by heat treatment, was studied. It is assumed that the improvement in conductivity is the result of the self-assembly of monolayers of organic molecules on the surface of the PEDOT:PSS film leading to its p-doping due to intermolecular interaction.

Fractal-Percolation Structure Architectonics in Sol-Gel Synthesis.

It was developed a new technique to assess micro- and mesopores with sizes below a few nanometers. The porous materials with hierarchical fractal-percolation structure were obtained with the sol-gel method. The tetraethoxysilane hydrolysis and polycondensation reactions were performed in the presence of salts as the sources of metal oxides. The porous materials were obtained under spinodal decomposition conditions during application of the polymer sol to the substrate surface and thermal treatment of the structures. The model is based on an enhanced Kepler net of the 4612 type with hexagonal cells filled with a quasi-two-dimensional projection of the Jullien fractal after the 2nd iteration. The materials obtained with the sol-gel method were studied using the atomic force microscopy, electron microscopy, thermal desorption, as well as an AutoCAD 2022 computer simulation of the percolation transition in a two-component system using the proposed multimodal model. Based on the results obtained, a new method was suggested to assess micro- and mesopores with sizes below a few nanometrs, which cannot be analyzed using the atomic force microscopy and electron microscopy.

Low-Frequency Dielectric Relaxation in Structures Based on Macroporous Silicon with Meso-Macroporous Skin-Layer.

The spectra of dielectric relaxation of macroporous silicon with a mesoporous skin layer in the frequency range 1-106 Hz during cooling (up to 293-173 K) and heating (293-333 K) are presented. Macroporous silicon (pore diameter ≈ 2.2-2.7 µm) with a meso-macroporous skin layer was obtained by the method of electrochemical anodic dissolution of monocrystalline silicon in a Unno-Imai cell. A mesoporous skin layer with a thickness of about 100-200 nm in the form of cone-shaped nanostructures with pore diameters near 13-25 nm and sizes of skeletal part about 35-40 nm by ion-electron microscopy was observed. The temperature dependence of the relaxation of the most probable relaxation time is characterized by two linear sections with different slope values; the change in the slope character is observed at T ≈ 250 K. The features of the distribution of relaxation times in meso-macroporous silicon at temperatures of 223, 273, and 293 K are revealed. The Havriliak-Negami approach was used for approximation of the relaxation curves ε″ = f(ν). The existence of a symmetric distribution of relaxers for all temperatures was found (Cole-Cole model). A discussion of results is provided, taking into account the structure of the studied object.

The Multisensor Array Based on Grown-On-Chip Zinc Oxide Nanorod Network for Selective Discrimination of Alcohol Vapors at Sub-ppm Range.

We discuss the fabrication of gas-analytical multisensor arrays based on ZnO nanorods grown via a hydrothermal route directly on a multielectrode chip. The protocol to deposit the nanorods over the chip includes the primary formation of ZnO nano-clusters over the surface and secondly the oxide hydrothermal growth in a solution that facilitates the appearance of ZnO nanorods in the high aspect ratio which comprise a network. We have tested the proof-of-concept prototype of the ZnO nanorod network-based chip heated up to 400 °C versus three alcohol vapors, ethanol, isopropanol and butanol, at approx. 0.2-5 ppm concentrations when mixed with dry air. The results indicate that the developed chip is highly sensitive to these analytes with a detection limit down to the sub-ppm range. Due to the pristine differences in ZnO nanorod network density the chip yields a vector signal which enables the discrimination of various alcohols at a reasonable degree via processing by linear discriminant analysis even at a sub-ppm concentration range suitable for practical applications.