Doping Control Research Articles

Tuning leakage current and ferroelectric properties in spin-coated BiFeO3 films through Cr doping and post-annealing atmosphere control

Effective enhancement of ferroelectric properties in BiFe1-xCrxO3 films prepared via the sol-gel method is crucial. Here, by adjusting the Cr content, BiFe1-xCrxO3 films with smooth surfaces and uniform grain structures were successfully synthesized. X-ray photoelectron spectroscopy (XPS) analyses revealed that Cr doping significantly reduces the concentrations of Fe2+ and oxygen vacancies within the BFO films, thereby mitigating leakage currents and enhancing ferroelectricity. Additionally, we investigated the microstructure and electrical characteristics of BiFe0.98Cr0.02O3 thin films subjected to post-annealing in different atmospheres (N2, Air, and O2). Notably, annealing in an O2 atmosphere notably enhanced the crystallinity and grain uniformity of BiFe0.98Cr0.02O3 thin films. This treatment resulted in superior ferroelectric polarization switching behavior, achieving the highest remanent polarization (Pr = 153.1 μC/cm2) due to reduced defect densities. Our findings underscore the critical roles of Cr3+ ions and O2 annealing atmospheres in suppressing leakage currents and boosting ferroelectric properties in BFO films.

Publisher Correction: High-performance p-type field-effect transistors using substitutional doping and thickness control of two-dimensional materials

Publisher Correction: High-performance p-type field-effect transistors using substitutional doping and thickness control of two-dimensional materials

Precise p-type and n-type doping of two-dimensional semiconductors for monolithic integrated circuits

The controllable fabrication of patterned p-type and n-type channels with precise doping control presents a significant challenge, impeding the realization of complementary metal-oxide-semiconductor (CMOS) logic using a single van der Waals material. However, such an achievement could offer substantial benefits by enabling continued transistor scaling and unprecedented interlayer interconnect technologies. In this study, we devise a precise method for two-dimensional (2D) semiconductor substitutional doping, which allows for the production of wafer-scale 2H-MoTe2 thin films with specific p-type or n-type doping. Notably, we extend this approach to the synthesis of spatially selective doped 2H-MoTe2 thin films via a one-step growth method, facilitating the monolithic integration of p-type and n-type semiconductor channels. Leveraging this advancement, we successfully fabricate a chip-sized 2D CMOS inverter array that demonstrates excellent device performance and yield. Collectively, these findings represent a significant stride towards the practical incorporation of 2D semiconductors in very large-scale integration technology.

High-performance p-type field-effect transistors using substitutional doping and thickness control of two-dimensional materials

High-performance p-type field-effect transistors using substitutional doping and thickness control of two-dimensional materials

Tuning Optical and Electrical Properties of Vanadium Oxide with Topochemical Reduction and Substitutional Tin.

Vanadium oxides are widely tunable materials, with many thermodynamically stable phases suitable for applications spanning catalysis to neuromorphic computing. The stability of vanadium in a range of oxidation states enables mixed-valence polymorphs of kinetically accessible metastable materials. Low-temperature synthetic routes to, and the properties of, these metastable materials are poorly understood and may unlock new optoelectronic and magnetic functionalities for expanded applications. In this work, we demonstrate topochemical reduction of α-V2O5 to produce metastable vanadium oxide phases with tunable oxygen vacancies (>6%) and simultaneous substitutional tin incorporation (>3.5%). The chemistry is carried out at low temperature (65 °C) with solution-phase SnCl2, where Sn2+ is oxidized to Sn4+ as V5+ sites are reduced to V4+ during oxygen vacancy formation. Despite high oxygen vacancy and tin concentrations, the transformations are topochemical in that the symmetry of the parent crystal remains intact, although the unit cell expands. Band structure calculations show that these vacancies contribute electrons to the lattice, whereas substitutional tin contributes holes, yielding a compensation doping effect and control over the electronic properties. The SnCl2 redox chemistry is effective on both solution-processed V2O5 nanoparticle inks and mesoporous films cast from untreated inks, enabling versatile routes toward functional films with tunable optical and electronic properties. The electrical conductance rises concomitantly with the SnCl2 concentration and treatment time, indicating a net increase in density of free electrons in the host lattice. This work provides a valuable demonstration of kinetic tailoring of electronic properties of vanadium-oxygen systems through top-down chemical manipulation from known thermodynamic phases.

In Situ Growth of MoN on Nickel Foam for Highly Efficient Hydrogen Evolution in Alkaline Solution.

Highly efficient, stable, and low-cost hydrogen evolution catalysts are urgently required for water electrolysis. Herein, a method for in situ growth of medium-nitrogen nanosheet MoN catalysts with a large electrochemical surface area on nickel foam (NF) is proposed. The results show that the morphology of the as-prepared catalysts greatly depends on the nitrogen sources and nitridation temperature. The MoN/NF catalyst nitride at 700 °C using melamine as a nitrogen source exhibits a spindle-like morphology consisting of stacked nanosheets, which is conducive to exposing more active sites, thereby increasing the catalyst activity. The N atoms in MoN could adjust the chemical environment of the metal by changing the density of the d-band electron state, which further improves the HER performance. Benefiting from the regulation of Mo charge distribution and exposure to more active sites through N doping and morphological control, the MoN/NF catalyst exhibits superior HER performance with an overpotential of 70 mV at a current density of 10 mA·cm-2, a Tafel slope of 44.3 mV dec-1, and an Rct of 1.83 Ω, indicating high HER catalytic activity, fast kinetics, and excellent conductivity. Theoretical calculations reveal that among the (002), (202), and (200) planes of MoN, the (202) plane exhibits the lowest value of |ΔGH*| (0.47 eV), which is close to that of Pt(111) (0.14 eV). More importantly, MoN(202) also has the smallest work function of 3.58 eV, indicating an enhanced capability to offer electrons. This work develops a strategy to design high-performance and low-cost transition-metal nitride HER catalysts.

Long-Term Excretion of Roxadustat in Urine.

Roxadustat (FG-4592), an orally active hypoxia-inducible factor prolyl hydroxylase stabilizer, has been shown to enhance erythropoiesis by increasing endogenous erythropoietin. It is indicated for the treatment of anemia and chronic kidney disease and is approved for clinical use in several countries, including the European Union, Japan and others. Due to its reasonably anticipated performance-enhancing effect in athletes, roxadustat is prohibited for use in sports at all times. A few cases of adverse analytical findings in routine doping controls have been reported worldwide, some of which were claimed to be the result of contaminated dietary supplements. The present study offers new data demonstrating the long-term excretion pattern of roxadustat. Even after a single-dose administration, roxadustat can remain detectable in urine for 8 months, albeit at very low concentrations (<10 pg/mL). Following three times a week treatment with 70 to 100 mg of roxadustat, the drug was still detectable in the urine of anemic patients for between 9 and 18 months after treatment was discontinued. Lastly, an athlete who admitted use of roxadustat for almost a year (50 mg 3 to 5 times a week) has now tested positive multiple times over the course of 15 months (the first test being 12 months after the drug was discontinued), with an estimated concentration of roxadustat between 3 and 8 pg/mL. Altogether, these findings indicate the unusually prolonged terminal excretion kinetics of roxadustat, a property that testing authorities should consider in their results management process.

New Transcriptomic Biomarkers for Detection of the Recombinant Human Erythropoietin (rHuEPO) MirCERA in Horses.

Detection and monitoring of biomarkers related to doping is particularly suitable for the development of analytical strategies dedicated to indirect detection of banned substances. Previous studies in horses have already allowed the investigation of transcriptomic biomarkers in equine blood associated with reGH and rHuEPO administrations. Our most recent developments continue to focus on the discovery and monitoring of transcriptomic biomarkers for the control of ESAs, and a collaborative study with WADA-accredited doping control laboratories has recently been initiated to conduct a pilot study. In humans, three mRNAs (ALAS2, CA1, and SLC4A1) were previously observed to be differentially expressed after blood doping and were associated with immature red blood cells, the so-called circulating reticulocytes. In horses, circulating reticulocytes are rarely observed even after rHuEPO administration. With the improved primers that detect the equine orthologues of the human mRNAs from the ALAS2, CA1, and SLC4A1 genes, we can now report the first evidence of the detection of the three biomarkers in equine blood. In addition, an upregulation of the mRNA levels of the three genes was observed after analysis of blood samples collected from MirCERA-treated animals, with kinetics similar to those previously documented in humans. Our data suggest that ALAS2 and CA1 are promising indirect biomarkers for the detection of recombinant EPO abuse in horses, as observed in humans.

Equine Doping Controls of Thymosin 4: A Population Study and Strategy for Misuse Detection.

Thymosin 4 (TB4) is a ubiquitous, highly conserved and abundant peptide among mammals with a critical role in cytoskeleton organization. In spite of its yet non-authorized use as a medicine and being forbidden by the IFHA, the FEI, and the WADA, intelligence and doping control laboratories reported numerous products available online claiming to contain a synthetic acetylated fragment of TB4 or TB4 itself, promoted as a growth factor with regenerative properties. In this article, the first estimation of the endogenous TB4 concentration in racing horses' blood samples was performed through a population study. We reveal that this concentration does not significantly depend on gender, age, nor horse breed. We highlight that the TB4 concentration increases significantly and rapidly in plasma stored at 4°C when not separated from blood cells due to cell lysis. Finally, we also demonstrate that the detection of a non-natural synthesis impurity is possible in equine plasma after a single dose administration of a TB4 containing product to a horse.

Exploring methandienone metabolites generated via homogenized camel liver: Advancements for anti-doping applications through High Resolution-Liquid Chromatography Mass Spectrometry analysis.

Anabolic steroids, also known as anabolic-androgenic steroids (AAS), encompass steroidal androgens such as testosterone, as well as synthetic counterparts with similar structures and effects. The misuse of AAS has increased over the years, leading to ethical and welfare concerns in sports. The World Anti-Doping Agency (WADA) and the International Federation for Equestrian Sports (FEI) have banned AAS in relevant sports. Methandienone is one of the most identified anabolic androgenic steroids in sports drug testing, Therefore, reliable detection methods are crucial for effective doping control and maintaining the integrity of the sports. This study explores the use of homogenized camel liver for detecting methandienone metabolites in camels. The biotransformation pathways of methandienone in homogenized camel liver tissues are analyzed using Liquid Chromatography-High Resolution Mass Spectrometry (LC-HRMS) to identify and characterize the phase I and phase II metabolites. Chromatographic separation was achieved using a Thermo-Hypersil C18 column. The study has identified 11 methandienone metabolites (M1-M11), this includes 10 phase I and one phase II metabolite. A glucuronic acid conjugate of methandienone was observed in this study, but no sulfonic acid conjugations were found. The metabolites and their possible chemical structures, along with their fragmentation patterns are confirmed using MSMS (MS2) experiments in data-independent acquisition (DIA) mode. These findings serve as a vital tool for the rapid detection of methandienone, combating its illicit use in camel racing. Comprehensive screenings covering both the parent drug and its metabolites are recommended to improve detection accuracy and ensure regulatory compliance in sports doping. Future research should explore methandienone's metabolite profile in administered camel samples.

Optimizing dye-sensitized solar cell efficiency through TiO2/CuS doping: effects of internal parameter variations

Dye-sensitized solar cells (DSSC) have attracted significant research interest due to their semi-transparency, ease of fabrication, cost-effectiveness, and environmental friendliness. This research focuses on enhancing dye-sensitized solar cells efficiency by doping titanium dioxide with copper sulfide and varying internal parameters such as concentration, thickness, and temperature. The primary issue addressed is the low electron mobility of titanium dioxide, which limits its performance as a photoanode. Using simulation methods, this study analyzed dye-sensitized solar cells performance under different doping conditions. The results showed that the highest efficiency of 8.18 % was achieved at a TiO2/CuS concentration of 0.3 %. The optimal photoanode thickness was approximately 3 μm, yielding an efficiency of 8.33 %. Temperature variations at room temperature (275 K, 300 K, and 325 K) resulted in efficiency values of 13.94 %, 15.06 %, and 16.18 %, respectively. These findings indicate that targeted doping and precise control of internal parameters can significantly enhance the performance of titanium dioxide-based dye-sensitized solar cells. The improved efficiency is attributed to enhanced electron mobility and better structural and morphological characteristics of the doped titanium dioxide photoanode. This research provides valuable insights into developing more efficient and sustainable dye-sensitized solar cells. The practical implications of these results are significant for advancing dye-sensitized solar cells as a viable alternative to conventional solar cells, contributing to the global effort to address the energy crisis by providing a cost-effective and environmentally friendly energy source.

Comprehensive Review of Li-Rich Mn-Based Layered Oxide Cathode Materials for Lithium-Ion Batteries: Theories, Challenges, Strategies and Perspectives.

Lithium-rich manganese-based layered oxide cathode materials (LLOs) have always been considered as the most promising cathode materials for achieving high energy density lithium-ion batteries (LIBs). However, in practical applications, LLOs often face some key problems, such as low initial coulombic efficiency, capacity/voltage decay, poor rate performance and poor cycle stability. It seriously shortens the lifespan of lithium-ion batteries and hinder the large-scale commercial application of LLOs. Herein, firstly, the basic theories of LLOs were systematically reviewed, including the structural characteristics, the working mechanism of LLOs, the preparation methods of LLOs (liquid phase co-precipitate method, sol-gel method, hydrothermal synthesis method, solid phase method, low heat solid-phase method, high temperature solid-state method etc.), and electrochemical characteristics of LLOs (first charge discharge characteristics and reversible efficiency, cycling performance, high and low temperature performance and thermal stability etc.). Then, key challenges faced by LLOs were systematically discussed. Finally, the LLOs modification strategies used to address these challenges (element doping, surface modification, defect engineering, structural and morphological control etc.) were elaborated in detail. This important review provides potential insights and directions for further improving the electrochemical performance of LLOs, and provides a necessary theoretical basis for accelerating the large-scale commercial application of LLOs. It possesses important scientific research value and far-reaching social significance.

Molecular dynamics simulation of hybrid structure and mechanical properties of DLC/Ni-DLC thin films

To improve the mechanical properties of the rolling body surface of wind power bearings, extend its service life. In this study, a large-scale molecular/atomic parallel processor LAMMPS was introduced, and then the process of magnetron sputtering technology in the preparation of DLC/Ni-DLC thin films on the 42CrMo substrate material was simulated. The effects of deposition parameters such as sputtering temperature, sputtering voltage, deposition air pressure, and Ni doping on the residual stress, film base bonding, and organizational structure of the thin films were investigated. The simulation results show that for different deposition parameters, the atomic tensile and compressive stresses existed simultaneously in DLC/Ni-DLC films, and the residual stresses were between − 0.504–5.003 Gpa and − 2.11–0.065 Gpa, respectively; the doping of Ni effectively improved the distribution of hybrid structure and the mechanical properties of the DLC films, and the ratio of the sp3 hybrid structure in the film organization was about 2.56 times higher than that of the non-doped films, and the membrane base bonding force was increased by 32.78% and the residual stress is reduced and transitioned from tensile stress to compressive stress. In addition, it was observed that the thickness of the mixed layer of DLC/Ni-DLC films with the substrate was not increased after the thickness of the mixed layer was extended to about 2 nm. Nickel doping and reasonable control of deposition parameters help to reduce the residual stress and improve the bonding strength of the film by changing the organizational structure of the film, which provides an important theoretical and scientific basis for the preparation of low-stress, high-performance and long-life DLC films and the wide application of rolling bodies for wind power bearings under complex working conditions.

Identification of human metabolites of fast skeletal troponin activators Tirasemtiv and Reldesemtiv for doping control purposes.

The fast skeletal troponin activators (FSTAs) Reldesemtiv and Tirasemtiv were developed for patients suffering from neuro-degenerative diseases of the motor nervous system, e.g. amyotrophic lateral sclerosis (ALS). The drug candidates can increase the sensitivity of troponin C to calcium by selectively activating the troponin complex resulting in increased skeletal muscle contraction. Although the development of the drug candidates is currently discontinued because of missed end points in phase III clinical studies with patients with ALS, phase I clinical trials showed an increase in muscle contraction force in healthy humans. This effect could be abused by athletes to enhance performance in sports. As the substances are listed on the 2024 edition of the World Anti-Doping Agency's Prohibited List, the aim of this study was to identify and characterize metabolites of Reldesemtiv and Tirasemtiv to ensure their reliable identification in doping control analyses. The biotransformation of the drug candidates was studied in vitro using pooled human liver microsomes and 3D cultivated human hepatic cells of the cell line HepaRG, yielding a total of 11 metabolites of Reldesemtiv and eight of Tirasemtiv. In addition, a human elimination study was conducted to investigate the metabolism and elimination profile of Tirasemtiv and Reldesemtiv in vivo, suggesting the N-glucuronide of Tirasemtiv and hydroxylated 3-fluoro-2-(3-fluoro-1-methylcyclobutyl)pyridine as well as its glucuronide as suitable target analytes for routine doping controls. Applying a validating HPLC-MS/MS method, optimized to detect Reldesemtiv and Tirasemtiv in human urine, microdosing (50 μg) of each substance was traceable for 24-72 h.

A comprehensive gas chromatography electron ionization high resolution mass spectrometry study of a new steroidal selective androgen receptor modulator (SARM) compound S42.

The synthetic 20-keto-steroid S42 (1) demonstrated selective androgen receptor modulator (SARM) properties in preclinical studies and, consequently, received growing attention also in the context of sports drug testing programs. Fundamental understanding of the behavior of S42 (1) and of relevant derivatives in gas chromatography-electron ionization MS experiments at high resolution (GC-EI-HRMS) is indispensable to develop a reliable qualitative and quantitative doping control method for S42 (1) and its metabolites in body fluid matrices. We present important fundamental mechanistic data on the EI fragmentation behavior of S42 (1) and of silyl ether derivatives as well as of stable isotope-labelled reference material.

Switching of magnetoelectric states in the Y-type hexaferrite Ba0.5Sr1.5CoMgFe11AlO22

The multiferroic Y-type hexaferrites BaxSr2−xMe2Fe12−yAlyO22 (Me = Zn2+, Co2+, Mg2+, etc.) have attracted much attention due to their giant magnetoelectric (ME) effect up to room temperature and low modulated magnetic field by the chemical doping control of the complex magnetic phases. However, the research of substitution between the Me ions is rare. As doping at the Me ion site can combine the advantages of both, e.g., higher magnetic ordering temperature in Co2 and stronger ME coefficient in Mg2 Y-type hexaferrites, herein, we report the stability and switching of magnetoelectric states in the Y-type hexaferrites Ba0.5Sr1.5CoMgFe11AlO22 single crystals. Our results demonstrate that substituting half of the Mg2+ with Co2+ enhances the transition temperature of the alternating longitudinal conical phase to proper screw spin order up to room temperature compared to those Mg2 Y-type hexaferrites. Simultaneous occurrence of in-plane and out-of-plane ferroelectric polarization is observed, alongside comparable spontaneous magnetization. It was found that the in-plane spin-driven polarization can be reversible below 50 K with a substantial ME coefficient α = −8000 ps/m but becomes irreversible at 100 K. This reversal in the sign of the ME coefficient signifies the transition between two distinct ME states at high temperature. The reversibility and irreversibility of spin-induced polarization are discussed within the framework of free energy based on the ferroelectric phase, which prevail in numerous Y-type hexaferrites. Our results provide insights into understanding the role of the Me ions in the magnetoelectric coupling in Y-type hexaferrites.

Enhance Ethanol Sensing Performance of Fe-Doped Tetragonal SnO2 Films on Glass Substrate with a Proposed Mathematical Model for Diffusion in Porous Media.

This research enhances ethanol sensing with Fe-doped tetragonal SnO2 films on glass, improving gas sensor reliability and sensitivity. The primary objective was to improve the sensitivity and operational efficiency of SnO2 sensors through Fe doping. The SnO2 sensors were synthesized using a flexible and adaptable method that allows for precise doping control, with energy-dispersive X-ray spectroscopy (EDX) confirming homogeneous Fe distribution within the SnO2 matrix. A morphological analysis showed a surface structure ideal for gas sensing. The results demonstrated significant improvement in ethanol response (1 to 20 ppm) and lower temperatures compared to undoped SnO2 sensors. The Fe-doped sensors exhibited higher sensitivity, enabling the detection of low ethanol concentrations and showing rapid response and recovery times. These findings suggest that Fe doping enhances the interaction between ethanol molecules and the sensor surface, improving performance. A mathematical model based on diffusion in porous media was employed to further analyze and optimize sensor performance. The model considers the diffusion of ethanol molecules through the porous SnO2 matrix, considering factors such as surface morphology and doping concentration. Additionally, the choice of electrode material plays a crucial role in extending the sensor's lifespan, highlighting the importance of material selection in sensor design.

Detection of the GH analog somatrogon in sports drug testing: Immunological approaches and LC-HRMS/MS.

Due to the presumed lipolytic and anabolic properties, the misuse of human growth hormone (hGH) and its synthetic analogs in sports is prohibited both in- and out-of-competition. Within this research project, the detectability of somatrogon, a recombinant fusion glycoprotein of 22 kDa hGH and the C-terminal peptide (CTP) of the human chorionic gonadotropin (hCG) β-subunit, with current WADA-approved doping control assays for hGH and hCG was investigated. For that purpose, cross-reactivity tests and a somatrogon administration study were conducted, and only "Kit 2" of the GH isoform differential immunoassays proved applicable to the detection of somatrogon administration in serum. In urine, the immunoassay specific for total hCG yielded presumptively positive findings for several post-administration samples, which can probably be attributed to the presence of an immunoreactive fragment of the hCG β-subunit. As the detectability of somatrogon with these approaches was found to be limited, a highly specific detection assay (LOD: 10ng/mL) for the drug in serum samples was developed by using affinity purification with GH receptor (GHR)-conjugated magnetic beads, proteolytic digestion, and liquid chromatography high-resolution tandem mass spectrometry (LC-HRMS/MS). Following optimization, the approach was comprehensively characterized, and authentic post-administration serum samples were successfully analyzed as proof-of-concept, indicating a detection window of at least 96 h. Consequently, the presented method can be employed to confirm the presence of somatrogon in serum samples, where only "Kit 2" of the currently used immunoassay kits yielded an abnormally high Rec/Pit ratio.

Detection of transgenes in equine dried blood spots using digital PCR and qPCR for gene doping control.

Due to the ease of collection, transport and storage, the use of dried blood spots (DBS) offers an attractive alternative matrix for detection of the abuse of gene therapy, otherwise known as gene doping. This study evaluated the recovery, extraction efficiency and resulting detection capability of DNA from DBS by evaluating different target types, DNA extraction kits, the number of punches and blood tube preservatives. The long-term storage stability of low-copy-number transgene targets in DBS was not assessed in this study but would be noteworthy to investigate further. DNA was quantified using two detection methods: qPCR and digital PCR (dPCR). Using six punches with the Qiagen Investigator kit gave the best overall DNA yield compared with other extraction methods. Including three punches, however, gave better DNA extraction efficiency. Reference material could be detected using qPCR and dPCR in DBS spiked with 5000 copies/mL of blood (approximately 15 copies per 3 mm of punch). The optimal DNA extraction protocol was used on DBS samples from a custom recombinant adeno-associated virus administration study and showed successful detection of vector targets in DBS samples.

Detection of the selective androgen receptor modulator S-23 and its metabolites in equine urine and plasma following oral administration.

S-23 is an arylpropionamide selective androgen receptor modulator that has been investigated in animal models for use as a male hormonal contraceptive but is not yet available therapeutically. S-23 is available alongside other selective androgen receptor modulators (SARMs) to purchase online via uncontrolled sites, sold as supplement products. It has been detected in several human doping cases, highlighting the importance of identifying the best analytical targets for equine doping control. The purpose of this study was to investigate the detection of S-23 and its phase I metabolites in equine urine and plasma following a multiple dose oral administration to two Thoroughbred racehorses. Liquid chromatography-high resolution mass spectrometry was used for metabolite identification, and liquid chromatography-tandem mass spectrometry was used for full sample analysis and generation of urine and plasma profiles. S-23 and seven phase I metabolites were observed in urine following enzyme hydrolysis and solvolysis. The most abundant analyte detected was the hydroxylated 4-amino-2-(trifluoromethyl)benzonitrile metabolite, which also allowed the longest duration of detection in urine from both horses, for up to 360 h following administration. The data suggest that this metabolite was likely to be highly conjugated with both sulphate and glucuronide moieties. In plasma, S-23 and two phase I metabolites were observed. S-23 was the most abundant analyte detected for both horses, allowing detection for up to 143 h post-administration. To the best of the authors' knowledge, this is the first report of S-23 and metabolites in equine urine and plasma samples.