Biosensor Based on Graphene Directly Grown by MW-PECVD for Detection of COVID-19 Spike (S) Protein and Its Entry Receptor ACE2.

Biosensors based on graphene field-effect transistors (G-FET) for detecting COVID-19 spike S protein and its receptor ACE2 were reported. The graphene, directly synthesized on SiO2/Si substrate by microwave plasma-enhanced chemical vapor deposition (MW-PECVD), was used for FET biosensor fabrication. The commercial graphene, CVD-grown on a copper substrate and subsequently transferred onto a glass substrate, was applied for comparison purposes. The graphene structure and surface morphology were studied by Raman scattering spectroscopy and atomic force microscope. Graphene surfaces were functionalized by an aromatic molecule PBASE (1-pyrenebutanoic acid succinimidyl ester), and subsequent immobilization of the receptor angiotensin-converting enzyme 2 (ACE2) was performed. A microfluidic system was developed, and transfer curves of liquid-gated FET were measured after each graphene surface modification procedure to investigate ACE2 immobilization by varying its concentration and subsequent spike S protein detection. The directly synthesized graphene FET sensitivity to the receptor ACE2, evaluated in terms of the Dirac voltage shift, exceeded the sensitivity of the transferred commercial graphene-based FET. The concentration of the spike S protein was detected in the range of 10 ag/mL up to 10 µg/mL by using a developed microfluidic system and measuring the transfer characteristics of the liquid-gated G-FETs. It was found that the shift of the Dirac voltage depends on the spike S concentration and was 27 mV with saturation at 10 pg/mL for directly synthesized G-FET biosensor, while for transferred G-FET, the maximal shift of 70 mV was obtained at 10 µg/mL with a tendency of saturation at 10 ng/mL. The detection limit as low as 10 ag/mL was achieved for both G-FETs. The sensitivity of the biosensors at spike S concentration of 10 pg/mL measured as relative current change at a constant gate voltage corresponding to the highest transconductance of the G-FETs was found at 5.6% and 8.8% for directly synthesized and transferred graphene biosensors, respectively. Thus, MW-PECVD-synthesized graphene-based biosensor demonstrating high sensitivity and low detection limit has excellent potential for applications in COVID-19 diagnostics.

Effects of Pulsed Electric Field on the Physicochemical and Structural Properties of Micellar Casein.

Pulsed electric field (PEF) as a green processing technology is drawing greater attention due to its eco-friendliness and potential to promote sustainable development goals. In this study, the effects of different electric field strengths (EFS, 0-30 kV/cm) on the structure and physicochemical features of casein micelles (CSMs) were investigated. It was found that the particle sizes of CSMs increased at low EFS (10 kV/cm) but decreased at high EFS (30 kV/cm). The absolute ζ-potential at 30 kV/cm increased from -26.6 (native CSMs) to -29.5 mV. Moreover, it was noticed that PEF treatment leads to changes in the surface hydrophobicity; it slightly increased at low EFS (10 kV/cm) but decreased at EFS > 10 kV/cm. PEF enhanced the protein solubility from 84.9 (native CSMs) to 87.1% (at 10 kV/cm). PEF at low EFS (10 kV/cm) intensified the emission fluorescence spectrum of CSMs, while higher EFS reduced the fluorescence intensity compared to native CSMs. Moreover, the analysis of the Amide Ι region showed that PEF-treated CSMs reduced the α-helix and increased the ß-sheet content. Raman spectra confirmed that PEF treatment > 10 kV/cm buried tyrosine (Tyr) residues in a hydrophobic environment. It was also found that PEF treatment mainly induced changes in the disulfide linkages. In conclusion, PEF technology can be employed as an eco-friendly technology to change the structure and physiochemical properties of CSMs; this could improve their techno-functional properties.

Magnetoresistance and Magnetic Relaxation of La-Sr-Mn-O Films Grown on Si/SiO2 Substrate by Pulsed Injection MOCVD.

The results of magnetoresistance (MR) and resistance relaxation of nanostructured La1-xSrxMnyO3 (LSMO) films with different film thicknesses (60-480 nm) grown on Si/SiO2 substrate by the pulsed-injection MOCVD technique are presented and compared with the reference manganite LSMO/Al2O3 films of the same thickness. The MR was investigated in permanent (up to 0.7 T) and pulsed (up to 10 T) magnetic fields in the temperature range of 80-300 K, and the resistance-relaxation processes were studied after the switch-off of the magnetic pulse with an amplitude of 10 T and a duration of 200 µs. It was found that the high-field MR values were comparable for all investigated films (~-40% at 10 T), whereas the memory effects differed depending on the film thickness and substrate used for the deposition. It was demonstrated that resistance relaxation to the initial state after removal of the magnetic field occurred in two time scales: fast' (~300 µs) and slow (longer than 10 ms). The observed fast relaxation process was analyzed using the Kolmogorov-Avrami-Fatuzzo model, taking into account the reorientation of magnetic domains into their equilibrium state. The smallest remnant resistivity values were found for the LSMO films grown on SiO2/Si substrate in comparison to the LSMO/Al2O3 films. The testing of the LSMO/SiO2/Si-based magnetic sensors in an alternating magnetic field with a half-period of 22 µs demonstrated that these films could be used for the development of fast magnetic sensors operating at room temperature. For operation at cryogenic temperature, the LSMO/SiO2/Si films could be employed only for single-pulse measurements due to magnetic-memory effects.

Engineering of Advanced Materials for High Magnetic Field Sensing: A Review.

Advanced scientific and industrial equipment requires magnetic field sensors with decreased dimensions while keeping high sensitivity in a wide range of magnetic fields and temperatures. However, there is a lack of commercial sensors for measurements of high magnetic fields, from ∼1 T up to megagauss. Therefore, the search for advanced materials and the engineering of nanostructures exhibiting extraordinary properties or new phenomena for high magnetic field sensing applications is of great importance. The main focus of this review is the investigation of thin films, nanostructures and two-dimensional (2D) materials exhibiting non-saturating magnetoresistance up to high magnetic fields. Results of the review showed how tuning of the nanostructure and chemical composition of thin polycrystalline ferromagnetic oxide films (manganites) can result in a remarkable colossal magnetoresistance up to megagauss. Moreover, by introducing some structural disorder in different classes of materials, such as non-stoichiometric silver chalcogenides, narrow band gap semiconductors, and 2D materials such as graphene and transition metal dichalcogenides, the possibility to increase the linear magnetoresistive response range up to very strong magnetic fields (50 T and more) and over a large range of temperatures was demonstrated. Approaches for the tailoring of the magnetoresistive properties of these materials and nanostructures for high magnetic field sensor applications were discussed and future perspectives were outlined.

Measurement System for Short-Pulsed Magnetic Fields.

A measurement system based on the colossal magnetoresistance CMR-B-scalar sensor was developed for the measurement of short-duration high-amplitude magnetic fields. The system consists of a magnetic field sensor made from thin nanostructured manganite film with minimized memory effect, and a magnetic field recording module. The memory effect of the La1-xSrx(Mn1-yCoy)zO3 manganite films doped with different amounts of Co and Mn was investigated by measuring the magnetoresistance (MR) and resistance relaxation in pulsed magnetic fields up to 20 T in the temperature range of 80-365 K. It was found that for low-temperature applications, films doped with Co (LSMCO) are preferable due to the minimized magnetic memory effect at these temperatures, compared with LSMO films without Co. For applications at temperatures higher than room temperature, nanostructured manganite LSMO films with increased Mn content above the stoichiometric level have to be used. These films do not exhibit magnetic memory effects and have higher MR values. To avoid parasitic signal due to electromotive forces appearing in the transmission line of the sensor during measurement of short-pulsed magnetic fields, a bipolar-pulsed voltage supply for the sensor was used. For signal recording, a measurement module consisting of a pulsed voltage generator with a frequency up to 12.5 MHz, a 16-bit ADC with a sampling rate of 25 MHz, and a microprocessor was proposed. The circuit of the measurement module was shielded against low- and high-frequency electromagnetic noise, and the recorded signal was transmitted to a personal computer using a fiber optic link. The system was tested using magnetic field generators, generating magnetic fields with pulse durations ranging from 3 to 20 µs. The developed magnetic field measurement system can be used for the measurement of high-pulsed magnetic fields with pulse durations in the order of microseconds in different fields of science and industry.

Enhancement of Room-Temperature Low-Field Magnetoresistance in Nanostructured Lanthanum Manganite Films for Magnetic Sensor Applications.

The results of colossal magnetoresistance (CMR) properties of La1-xSrxMnyO3 (LSMO) films grown by the pulsed injection MOCVD technique onto an Al2O3 substrate are presented. The grown films with different Sr (0.05 ≤ x ≤ 0.3) and Mn excess (y > 1) concentrations were nanostructured with vertically aligned column-shaped crystallites spread perpendicular to the film plane. It was found that microstructure, resistivity, and magnetoresistive properties of the films strongly depend on the strontium and manganese concentration. All films (including low Sr content) exhibit a metal−insulator transition typical for manganites at a certain temperature, Tm. The Tm vs. Sr content dependence for films with a constant Mn amount has maxima that shift to lower Sr values with the increase in Mn excess in the films. Moreover, the higher the Mn excess concentration in the films, the higher the Tm value obtained. The highest Tm values (270 K) were observed for nanostructured LSMO films with x = 0.17−0.18 and y = 1.15, while the highest low-field magnetoresistance (0.8% at 50 mT) at room temperature (290 K) was achieved for x = 0.3 and y = 1.15. The obtained low-field MR values were relatively high in comparison to those published in the literature results for lanthanum manganite films prepared without additional insulating oxide phases. It can be caused by high Curie temperature (383 K), high saturation magnetization at room temperature (870 emu/cm3), and relatively thin grain boundaries. The obtained results allow to fabricate CMR sensors for low magnetic field measurement at room temperature.

Nanostructured Manganite Films Grown by Pulsed Injection MOCVD: Tuning Low- and High-Field Magnetoresistive Properties for Sensors Applications.

The results of colossal magnetoresistance (CMR) properties of La0.83Sr0.17Mn1.21O3 (LSMO) films grown by pulsed injection MOCVD technique onto various substrates are presented. The films with thicknesses of 360 nm and 60 nm grown on AT-cut single crystal quartz, polycrystalline Al2O3, and amorphous Si/SiO2 substrates were nanostructured with column-shaped crystallites spread perpendicular to the film plane. It was found that morphology, microstructure, and magnetoresistive properties of the films strongly depend on the substrate used. The low-field MR at low temperatures (25 K) showed twice higher values (-31% at 0.7 T) for LSMO/quartz in comparison to films grown on the other substrates (-15%). This value is high in comparison to results published in literature for manganite films prepared without additional insulating oxides. The high-field MR measured up to 20 T at 80 K was also the highest for LSMO/quartz films (-56%) and demonstrated the highest sensitivity S = 0.28 V/T at B = 0.25 T (voltage supply 2.5 V), which is promising for magnetic sensor applications. It was demonstrated that Mn excess Mn/(La + Sr) = 1.21 increases the metal-insulator transition temperature of the films up to 285 K, allowing the increase in the operation temperature of magnetic sensors up to 363 K. These results allow us to fabricate CMR sensors with predetermined parameters in a wide range of magnetic fields and temperatures.

The Application of a CMR-B-Scalar Sensor for the Investigation of the Electromagnetic Acceleration of Type II Superconductors.

In this paper, we investigated the behavior of a type II superconducting armature when accelerated by a pulsed magnetic field generated by a single-stage pancake coil. While conducting this investigation, we performed a numerical finite element simulation and an experimental study of the magnetic field dynamics at the edge of the pancake coil when the payload was a superconducting disc made from YBa2Cu3O7-x, cooled down to 77 K. The magnetic field measurements were performed using a CMR-B-scalar sensor, which was able to measure the absolute magnitude of the magnetic field and was specifically manufactured in order to increase the sensor's sensitivity up to 500 mT. It was obtained that type II superconducting armatures can outperform normal metals when the launch conditions are tailored to their electromagnetic properties.

Magnetic Field Measurements during Magnetic Pulse Welding Using CMR-B-Scalar Sensors.

The possibility of applying CMR-B-scalar sensors made from thin manganite films exhibiting the colossal magnetoresistance effect as a fast-nondestructive method for the evaluation of the quality of the magnetic pulse welding (MPW) process is investigated in this paper. This method based on magnetic field magnitude measurements in the vicinity of the tools and joining parts was tested during the electromagnetic compression and MPW of an aluminum flyer tube with a steel parent. The testing setup used for the investigation allowed the simultaneous measurement of the flyer displacement, its velocity, and the magnitude of the magnetic field close to the flyer. The experimental results and simulations showed that, during the welding of the aluminum tube with the steel parent, the maximum magnetic field in the gap between the field shaper and the flyer is achieved much earlier than the maximum of the current pulse of the coil and that the first half-wave pulse of the magnetic field has two peaks. It was also found that the time instant of the minimum between these peaks depends on the charging energy of the capacitors and is associated with the collision of the flyer with the parent. Together with the first peak maximum and its time-position, this characteristic could be an indication of the welding quality. These results were confirmed by simultaneous measurements of the flyer displacement and velocity, as well as a numerical simulation of the magnetic field dynamics. The relationship between the peculiarities of the magnetic field pulse and the quality of the welding process is discussed. It was demonstrated that the proposed method of magnetic field measurement during magnetic pulse welding in combination with subsequent peel testing could be used as a nondestructive method for the monitoring of the quality of the welding process.

The link between yeast cell wall porosity and plasma membrane permeability after PEF treatment.

An investigation of the yeast cell resealing process was performed by studying the absorption of the tetraphenylphosphonium (TPP+) ion by the yeast Saccharomyces cerevisiae. It was shown that the main barrier for the uptake of such TPP+ ions is the cell wall. An increased rate of TPP+ absorption after treatment of such cells with a pulsed electric field (PEF) was observed only in intact cells, but not in spheroplasts. The investigation of the uptake of TPP+ in PEF treated cells exposed to TPP+ for different time intervals also showed the dependence of the absorption rate on the PEF strength. The modelling of the TPP+ uptake recovery has also shown that the characteristic decay time of the non-equilibrium (PEF induced) pores was approximately a few tens of seconds and this did not depend on the PEF strength. A further investigation of such cell membrane recovery process using a florescent SYTOX Green nucleic acid stain dye also showed that such membrane resealing takes place over a time that is like that occurring in the cell wall. It was thus concluded that the similar characteristic lifetimes of the non-equilibrium pores in the cell wall and membrane after exposure  to  PEF indicate a strong coupling between these parts of the cell.

Room temperature Co-doped manganite/graphene sensor operating at high pulsed magnetic fields.

The demand to increase the sensitivity to magnetic field in a broad magnetic field ranges has led to the research of novel materials for sensor applications. Therefore, the hybrid system consisting of two different magnetoresistive materials - nanostructured Co-doped manganite La1-xSrx(Mn1-yCoy)zO3 and single- and few-layer graphene - were combined and investigated as potential system for magnetic field sensing. The negative colossal magnetoresistance (CMR) of manganite-cobaltite and positive one of graphene gives the possibility to increase the sensitivity to magnetic field of the hybrid sensor. The performed magnetoresistance (MR) measurements of individual few layer (n = 1-5) graphene structures revealed the highest MR values for three-layer graphene (3LG), whereas additional Co-doping increased the MR values of nanostructured manganite films. The connection of 3LG graphene and Co-doped magnanite film in a voltage divider configuration significantly increased the sensitivity of the hybrid sensor at low and intermediate magnetic fields (1-2 T): 70 mV/VT of hybrid sensor in comparison with 56 mV/VT for 3LG and 12 mV/VT for Co-doped magnanite film, respectively, and broadened the magnetic field operation range (0.1-20) T of the produced sensor prototype.

Hybrid graphene-manganite thin film structure for magnetoresistive sensor application.

An increasing demand of magnetic field sensors with high sensitivity at room temperatures and spatial resolution at micro-nanoscales has resulted in numerous investigations of physical phenomena in advanced materials, and fabrication of novel magnetoresistive devices. In this study the novel magnetic field sensor based on combination of a single layer graphene (SLG) and thin nanostructured manganite La0.8Sr0.2MnO3 (LSMO) film-hybrid graphene-manganite (GM) structure, is proposed and fabricated. The hybrid GM structure employs the properties of two materials-SLG and LSMO-on the nanoscale level and results in the enhanced sensitivity to magnetic field of the hybrid sensor on the macroscopic level. Such result is achieved by designing the hybrid GM sensor in a Wheatstone half-bridge which enables to employ in the device operation two effects of nanomaterials-large Lorentz force induced positive magnetoresistance of graphene and colossal negative magnetoresistance of nanostructured manganite film, and significantly increase the sensitivity S of the hybrid GM sensor in comparison with the individual SLG and LSMO sensors: S = 5.5 mV T-1 for SLG, 14.5 mV T-1 for LSMO and 20 mV T-1 for hybrid GM at 0.5 T, when supply voltage was 1.249 V. The hybrid GM sensor operates in the range of (0.1-2.3) T and has lower sensitivity to temperature variations in comparison to the manganite sensor. Moreover, it can be applied for position sensing. The ability to control sensor's characteristics by changing technological conditions of the fabrication of hybrid structure and tuning the nanostructure properties of manganite film is discussed.

Relation between thickness, crystallite size and magnetoresistance of nanostructured La1- x Sr x Mn y O3±Î´ films for magnetic field sensors.

In the present study the advantageous pulsed-injection metal organic chemical vapour deposition (PI-MOCVD) technique was used for the growth of nanostructured La1- x Sr x Mn y O3±Î´ (LSMO) films on ceramic Al2O3 substrates. The compositional, structural and magnetoresistive properties of the nanostructured manganite were changed by variation of the processing conditions: precursor solution concentration, supply frequency and number of supply sources during the PI-MOCVD growth process. The results showed that the thick (≈400 nm) nanostructured LSMO films, grown using an additional supply source of precursor solution in an exponentially decreasing manner, exhibit the highest magnetoresistance and the lowest magnetoresistance anisotropy. The possibility to use these films for the development of magnetic field sensors operating at room temperature is discussed.

Electric field-induced effects on yeast cell wall permeabilization.

The permeability of the yeast cells (Saccharomyces cerevisiae) to lipophilic tetraphenylphosphonium cations (TPP(+) ) after their treatment with single square-shaped strong electric field pulses was analyzed. Pulsed electric fields (PEF) with durations from 5 to 150 µs and strengths from 0 to 10 kV/cm were applied to a standard electroporation cuvette filled with the appropriate buffer. The TPP(+) absorption process was analyzed using an ion selective microelectrode (ISE) and the plasma membrane permeability was determined by measurements obtained using a calcein blue dye release assay. The viability of the yeast and the inactivation of the cells were determined using the optical absorbance method. The experimental data taken after yeasts were treated with PEF and incubated for 3 min showed an increased uptake of TPP(+) by the yeast. This process can be controlled by setting the amplitude and pulse duration of the applied PEF. The kinetics of the TPP(+) absorption process is described using the second order absolute rate equation. It was concluded that the changes of the charge on the yeast cell wall, which is the main barrier for TPP(+) , is due to the poration of the plasma membrane. The applicability of the TPP(+) absorption measurements for the analysis of yeast cells electroporation process is also discussed.