Dipole moment as the underlying mechanism for enhancing the immobilization of glucose oxidase by ferrocene-chitosan for superior specificity non-invasive glucose sensing.

Non-invasive methods for sensing glucose levels are highly desirable due to the comfortableness, simplicity, and lack of infection risk. However, the insufficient accuracy and ease of interference limit their practical medical applications. Here, we develop a non-invasive salivary glucose biosensor based on a ferrocene-chitosan (Fc-Chit) modified carbon nanotube (CNT) electrode through a simple drop-casting method. Compared with previous studies that relied mainly on trial and error for evaluation, this is the first time that dipole moment was proposed to optimize the electron-mediated Fc-Chit, demonstrating sturdy immobilization of glucose oxidase (GOx) on the electrode and improving the electron transfer process. Thus, the superior sensing sensitivity of the biosensor can achieve 119.97 µA mM-1 cm-2 in phosphate buffered saline (PBS) solution over a wide sensing range of 20-800 µM. Additionally, the biosensor exhibited high stability (retaining 95.0% after three weeks) and high specificity toward glucose in the presence of various interferents, attributed to the specific sites enabling GOx to be sturdily immobilized on the electrode. The results not only provide a facile solution for accurate and regular screening of blood glucose levels via saliva tests but also pave the way for designing enzymatic biosensors with specific enzyme immobilization through fundamental quantum calculations.

Gamma-Ray Irradiation Induced Ultrahigh Room-Temperature Ferromagnetism in MoS2 Sputtered Few-Layered Thin Films.

Defect engineering is of great interest to the two-dimensional (2D) materials community. If nonmagnetic transition-metal dichalcogenides can possess room-temperature ferromagnetism (RTFM) induced by defects, then they will be ideal for application as spintronic materials and also for studying the relation between electronic and magnetic properties of quantum-confined structures. Thus, in this work, we aimed to study gamma-ray irradiation effects on MoS2, which is diamagnetic in nature. We found that gamma-ray exposure up to 9 kGy on few-layered (3.5 nm) MoS2 films induces an ultrahigh saturation magnetization of around 610 emu/cm3 at RT, whereas no significant changes were observed in the structure and magnetism of bulk MoS2 (40 nm) films even after gamma-ray irradiation. The RTFM in a few-layered gamma-ray irradiated sample is most likely due to the bound magnetic polaron created by the spin interaction of Mo 4d ions with trapped electrons present at sulfur vacancies. In addition, density functional theory (DFT) calculations suggest that the defect containing one Mo and two S vacancies is the dominant defect inducing the RTFM in MoS2. These DFT results are consistent with Raman, X-ray photoelectron spectroscopy, and ESR spectroscopy results, and they confirm the breakage of Mo and S bonds and the existence of vacancies after gamma-ray irradiation. Overall, this study suggests that the occurrence of magnetism in gamma-ray irradiated MoS2 few-layered films could be attributed to the synergistic effects of magnetic moments arising from the existence of both Mo and S vacancies as well as lattice distortion of the MoS2 structure.

Graphene woven fabric-polydimethylsiloxane piezoresistive films for smart multi-stimuli responses.

The outstanding properties of graphene, including its electromechanical property, could be engineered for wearable electronic sensor platforms. The tubular graphene weaved into a mesh or graphene woven fabrics (GWF) has been reported as one of the most sensitive materials for deformation detection, as well as a promising temperature sensor. Herein, we present the performance of our developed flexible, stretchable, and multiple sensitive sensors fabricated from GWF embedded in polydimethylsiloxane (PDMS) film substrate. The GWF/PDMS sensor shows a pressure sensitivity of 0.0142 kPa-1 in a wide linearity range of 0-20 kPa, an outstanding Gauge factor (GF) of 582 at a strain of 6.2 %, and a very high positive sensitivity of 0.0238 °C-1 in the temperature range of 25-80 °C. A practical application as a high sensitivity air pressure sensor able to measure low pressures (in the range of Pa to kPa) was also demonstrated. This sensor platform having desirable performance characteristics is an excellent candidate for wearable devices in the healthcare sector.

A Green Approach for High Oxidation Resistance, Flexible Transparent Conductive Films Based on Reduced Graphene Oxide and Copper Nanowires.

Copper nanowires (CuNWs)-based thin film is one of the potential alternatives to tin-doped indium oxide (ITO) in terms of transparent conductive films (TCFs). However, the severe problem of atmospheric oxidation restricts their practical applications. In this work, we develop a simple approach to fabricate highly stable TCFs through the dip-coating method using reduced graphene oxide (rGO) and CuNWs as the primary materials. Compared with previous works using toxic reduction agents, herein, the CuNWs are synthesized via a green aqueous process using glucose and lactic acid as the reductants, and rGO is prepared through the modified Hummers' method followed by a hydrogen-annealing process to form hydrogen-annealing-reduced graphene oxide (h-rGO). In the rGO/CuNWs films, the dip-coated graphene oxide layer can increase the adhesion of the CuNWs on the substrate, and the fabricated h-rGO/CuNWs can exhibit high atmospheric oxidation resistance and excellent flexibility. The sheet resistance of the h-rGO/CuNWs film only increased from 25.1 to 42.2 Ω/sq after exposure to ambient atmosphere for 30 days and remained almost unchanged after the dynamic bending test for 2500 cycles at a constant radius of 5.3 mm. The h-rGO/CuNWs TCF can be not only fabricated via a route with a superior inexpensive and safe method but also possessed competitive optoelectronic properties with high electrical stability and flexibility, demonstrating great opportunities for future optoelectronic applications.

Human Exhalation CO2 Sensor Based on the PEI-PEG/ZnO/NUNCD/Si Heterojunction Electrode.

Gas sensors based on semiconductors have outstanding sensitivity compared with the oxide-based devices; however, the high operation temperature greatly hinders its development in practical applications. Chronic obstructive pulmonary disease (COPD) is one of the leading causes of death worldwide, and the patients with severe COPD with or without exacerbation tend to have airflow obstruction, which results in an increase of CO2 concentration and subsequent hypercapnic respiratory failure. At present, COPD detection relies on professional operation; however, the patients suffer great discomfort during the arterial blood sampling. All these facts reduce patient's willingness to test their physical health. Thus, noninvasive monitoring of CO2 levels is crucial for the early diagnosis of high-risk COPD patients. A nitrogen-incorporated ultrananocrystalline diamond (NUNCD) film exhibits excellent properties in biosensing and polyetherimide-polyethylene glycol (PEI-PEG) polymer possesses a great capability of CO2 capturing. By incorporating NUNCD into PEI-PEG film, this work focuses on ameliorating the sensitivity and selectivity of the present semiconductor CO2 sensor. From the theoretical regression analyses of the experimental results, it is found that the excellent performance of the PEI-PEG/ZnO/NUNCD/Si electrode is contributed by two main reaction layers, the adsorption layer (PEI-PEG) and the electric transfer layer (ZnO/NUNCD). The selectivity is dominated by the PEI-PEG adsorption layer and the sensitivity is directly related to the changes in the work function of the ZnO/NUNCD interface. The high aspect ratio (>10) of the flower-like ZnO structure, growth from ZnO nanoparticles, can provide a more active adsorption area, as a result, extremely enhancing the sensitivity of the CO2 sensor.

Nitrogen-Incorporated Boron-Doped Nanocrystalline Diamond Nanowires for Microplasma Illumination.

The origin of nitrogen-incorporated boron-doped nanocrystalline diamond (NB-NCD) nanowires as a function of substrate temperature (Ts) in H2/CH4/B2H6/N2 reactant gases is systematically addressed. Because of Ts, there is a drastic modification in the dimensional structure and microstructure and hence in the several properties of the NB-NCD films. The NB-NCD films grown at low Ts (400 °C) contain faceted diamond grains. The morphology changes to nanosized diamond grains for NB-NCD films grown at 550 °C (or 700 °C). Interestingly, the NB-NCD films grown at 850 °C possess one-dimensional nanowire-like morphological grains. These nanowire-like NB-NCD films possess the co-existence of the sp3-diamond phase and the sp2-graphitic phase, where diamond nanowires are surrounded by sp2-graphitic phases at grain boundaries. The optical emission spectroscopy studies stated that the CN, BH, and C2 species in the plasma are the main factors for the origin of nanowire-like conducting diamond grains and the materialization of graphitic phases at the grain boundaries. Moreover, conductive atomic force microscopy studies reveal that the NB-NCD films grown at 850 °C show a large number of emission sites from the grains and the grain boundaries. While boron doping improved the electrical conductivity of the NCD grains, the nitrogen incorporation eased the generation of graphitic phases at the grain boundaries that afford conducting channels for the electrons, thus achieving a high electrical conductivity for the NB-NCD films grown at 850 °C. The microplasma devices using these nanowire-like NB-NCD films as cathodes display superior plasma illumination properties with a threshold field of 3300 V/µm and plasma current density of 1.04 mA/cm2 with a supplied voltage of 520 V and a lifetime stability of 520 min. The outstanding plasma illumination characteristics of these conducting nanowire-like NB-NCD films make them appropriate as cathodes and pave the way for the utilization of these materials in various microplasma device applications.

Correction: Consequences of gamma-ray irradiation on structural and electronic properties of PEDOT:PSS polymer in air and vacuum environments.

[This corrects the article DOI: 10.1039/D1RA03463D.].

Consequences of gamma-ray irradiation on structural and electronic properties of PEDOT:PSS polymer in air and vacuum environments.

In this work, the effects of gamma-ray irradiation (up to 3 kGy) on the structural and electronic properties of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), irradiated in air and vacuum environments are systematically investigated. Raman spectroscopy indicates that there is no significant change in structural conformation of PEDOT:PSS film after gamma-ray irradiation. However, the conductivity of the film decreases as a function of dose in both air and vacuum environments, which can be deduced as a result of defects created in the structure. Hall effect measurements showed higher carrier concentration when the samples are irradiated under vacuum in comparison to the air environment, whereas mobility decreases as a function of dose irrespective of the environment. Furthermore, the electron spin resonance spectra provided evidence of the evolution of polaron population after gamma-ray exposure of 3 kGy, due to the decrease in charge delocalization and molecular ordering of the molecules. This decrease in conductivity and mobility of the PEDOT:PSS films irradiated in air and vacuum environments can be mainly ascribed to the defects and radical formation after gamma-ray exposure, favoring chain scission or cross-linking of the polymers.

Enhancing the Efficiency of a Forward Osmosis Membrane with a Polydopamine/Graphene Oxide Layer Prepared Via the Modified Molecular Layer-by-Layer Method.

Water scarcity is one of the most critical problems that humans have to face. Working toward solving this problem, we have developed a thin-film composite (TFC) membrane using the modified molecular layer-by-layer (modified mLBL) method to fabricate polyamide (PA) active layers on different substrates. Besides, it has been found that graphene oxide (GO) contains abundant functional groups such as hydroxyl and epoxide groups, which are able to improve both the physical and chemical properties of the forward osmosis (FO) membrane. Thus, we have employed graphene oxide (GO) as the substrate and used the modified mLBL method to prepare active polydopamine/graphene oxide (PDA/GO) layers to enhance the water flux of the forward osmosis (FO) membrane. PDA/GO-coated layers could enhance the hydrophilic nature of the substrate and lower its surface roughness, which would facilitate the formation of the PA layer. Moreover, the PDA/GO coating can be applied to all substrates because of the high degree of adhesion of PDA to different substrates. In this study, the highly hydrophilic poly(vinylidene fluoride) membrane is superior in FO properties, with a water flux of 17.32 LMH and a reverse solute flux of 4.34 gMH. In addition, an excellent performance of 60.15 LMH and 14.88 gMH can be achieved when the pressure-retarded osmosis (PRO) test mode with a draw solution concentration of 2.0 M is used in the test. It shows that the membrane prepared using the novel method showed excellent FO performance, which has high potential in industrial applications such as desalination.

Gamma Ray Irradiation Enhances the Linkage of Cotton Fabrics Coated with ZnO Nanoparticles.

In this work, we aim to study zinc oxide (ZnO)-based functional materials over cotton fabrics and their effects after gamma ray exposure of 9 kGy. We found that the binding of the nanoparticles with cotton fabrics can be enhanced after irradiation. This could be due to the oxygen deficiency or defects created in the interface between ZnO and cotton fabrics after irradiation. Near-edge X-ray absorption fine structure and X-ray photoelectron spectroscopy (XPS) were used to detect the oxygen inadequacies generated in the interior and at the surface of the ZnO nanoparticles after gamma ray exposure. XPS results showed that the binding energy of Zn shifts by 2 eV at 1.5 kGy and by 4 eV at 9 kGy. This huge shift of about 4 eV is completely different from other works due to the reaction that takes place on the interface between ZnO nanostructures and cotton fabrics after gamma ray irradiation. Overall, this work suggests that after gamma ray irradiation, there is an enhanced level of binding between the coated functional nanoparticles and cotton fabrics, which can be advantageous for the textile industries.

Flexible Supercapacitors Prepared Using the Peanut-Shell-Based Carbon.

In this work, we report the fabrication and performance of supercapacitors made from carbonized peanut shells, which are renewable materials with a huge annual yield and are usually discarded directly by people. With proper treatment, peanut shells could be used for many applications. Herein, we demonstrate that the peanut shells treated with carbonization and activation processes not only possess an extremely high surface area but also provide a hierarchical structure for energy storage. The performance of the electrode can be further improved by nitrogen doping and adding graphene oxide to the electrode. The electrode shows a specific capacitance of 289.4 F/g, which can be maintained at an acceptable level even at a high scanning rate. In addition, a good capacitance retention of 92.8% after 5000 test cycles demonstrates that the electrode possesses an excellent electrochemical property.

Green Treatment of Phosphate from Wastewater Using a Porous Bio-Templated Graphene Oxide/MgMn-Layered Double Hydroxide Composite.

Excessive phosphorus in water is the primary culprit for eutrophication, which causes approximately $2.2 billion annual economic loss in the United States. This study demonstrates a phosphate-selective sustainable method by adopting Garcinia subelliptica leaves as a natural bio-template, where MgMn-layered double hydroxide (MgMn-LDH) and graphene oxide (GO) can be grown in situ to obtain L-GO/MgMn-LDH. After calcination, the composite shows a hierarchical porous structure and selective recognition of phosphate, which achieves significantly high and recyclable selective phosphate adsorption capacity and desorption rate of 244.08 mg-P g-1 and 85.8%, respectively. The detail variation of LDHs during calcination has been observed via in situ transmission electron microscope (TEM). Moreover, the roles in facilitating phosphate adsorption and antimicrobial ability of chemical constituents in Garcinia subelliptica leaves, biflavonoids, and triterpenoids have been investigated. These results indicate the proposed bio-templated adsorbent is practical and eco-friendly for phosphorus sustainability in commercial wastewater treatment.

Influence of gamma-ray irradiation and post-annealing studies on pentacene films: the anisotropic effects on structural and electronic properties.

In this work, γ-ray irradiation effects on pentacene thin films are investigated in terms of the change in the crystallinity, and electronic structure as well as chemical states of the film. The pentacene films are γ-irradiated up to 3 kGy and then characterized using synchrotron X-ray diffraction, near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy. We found that γ-ray irradiation creates defects, resulting in a decrease of X-ray diffraction intensity both in the plane normal and in-plane directions. From angle dependent NEXAFS; the transition of C 1s to π* orbital for irradiated samples increases; suggesting that the unoccupied π* states enhance due to defects or radical formation in pentacene thin films. Additionally, the in-plane resistivity shows a decreasing trend of resistance after irradiation. This trend of increase in conductivity is also consistent with C 1s to π transition, which manifests the increase in carrier concentration. Hall effect measurements further confirmed the increase in carrier concentration as a function of dose; however, the mobility of the sample decreases as the dose rate increases due to the defects created. By post-irradiation annealing, the thin film phase diffraction intensity can be recovered. Altogether, the anisotropic studies on pentacene films disclosed that the irradiation leads to defect formation along in-plane and plane normal directions. Overall, these results suggest that pentacene is one of the robust organic electronic materials; whose structure remains mostly intact even after irradiation up to a dose of 3 kGy.

Origin of Conductive Nanocrystalline Diamond Nanoneedles for Optoelectronic Applications.

Microstructural evolution of nanocrystalline diamond (NCD) nanoneedles owing to the addition of methane and nitrogen in the reactant gases is systematically addressed. It has been determined that varying the concentration of CH4 in the CH4/H2/N2 plasma is significant to tailor the morphology and microstructure of NCD films. While NCD films grown with 1% CH4 in a CH4/H2/N2 (3%) plasma contain large diamond grains, the microstructure changed considerably for NCD films grown using 5% (or 10%) CH4, ensuing in nanosized diamond grains. For 15% CH4-grown NCD films, a well-defined nanoneedle structure evolves. These NCD nanoneedle films contain sp3 phase diamond, sheathed with sp2-bonded graphitic phases, achieving a low resistivity of 90 Ω cm and enhanced field electron emission (FEE) properties, namely, a low turn-on field of 4.3 V/µm with a high FEE current density of 3.3 mA/cm2 (at an applied field of 8.6 V/µm) and a significant field enhancement factor of 3865. Furthermore, a microplasma device utilizing NCD nanoneedle films as cathodes can trigger a gas breakdown at a low threshold field of 3600 V/cm attaining a high plasma illumination current density of 1.14 mA/cm2 at an applied voltage of 500 V, and a high plasma lifetime stability of 881 min is evidenced. The optical emission spectroscopy studies suggest that the C2, CN, and CH species in the growing plasma are the major causes for the observed microstructural evolution in the NCD films. However, the increase in substrate temperature to ∼780 °C due to the incorporation of 15% CH4 in the CH4/H2/N2 plasma is the key driver resulting in the origin of nanoneedles in NCD films. The outstanding optoelectronic characteristics of these nanoneedle films make them suitable as cathodes in high-brightness display panels.

Nanoscale measurement of giant saturation magnetization in α″-Fe16N2 by electron energy-loss magnetic chiral dichroism.

Metastable α″-Fe16N2 thin films were reported to have a giant saturation magnetization of above 2200 emu/cm3 in 1972 and have been considered as candidates for next-generation rare-earth-free permanent magnetic materials. However, their magnetic properties have not been confirmed unequivocally. As a result of the limited spatial resolution of most magnetic characterization techniques, it is challenging to measure the saturation magnetization of the α″-Fe16N2 phase, as it is often mixed with the parent α'-Fe8N phase in thin films. Here, we use electron energy-loss magnetic chiral dichroism (EMCD), aberration-corrected transmission electron microscopy, X-ray diffraction and macroscopic magnetic measurements to study α″-Fe16N2 (containing ordered N atoms) and α'-Fe8N (containing disordered N atoms). The ratio of saturation magnetization in α″-Fe16N2 to that in α'-Fe8N is determined to be 1.31 ± 0.10 from quantitative EMCD measurements and dynamical diffraction calculations, confirming the giant saturation magnetization of α″-Fe16N2. Crystallographic information is also obtained about the two phases, which are mixed on the nanoscale.

Layered composites composed of multi-walled carbon nanotubes/manganese dioxide/carbon fiber cloth for microwave absorption in the X-band.

In this paper, multi-layered composites are fabricated for their application in electromagnetic interference (EMI) shielding. Composites of multi-walled carbon nanotubes/manganese dioxide (MnO2)/epoxy are used as a microwave absorption layer, and a commercial carbon fiber cloth is used as a reflection layer. When the electromagnetic (EM) waves impinge on such layered composites, the absorption layer can absorb most of the EM waves, and the transmitted EM waves from the absorption layer will be reflected back by the reflection layer and absorbed by the absorption layer. Based on the rational design, the composites with four absorption layers and one reflection layer (with a total thickness of 2.85 mm) show a high EMI shielding effectiveness of 41.24 dB, while the average reflection loss of 13.62 dB can be attained in the X-band (8.2-12.4 GHz). Moreover, the layered composites can absorb nearly 95% of the EM waves at the operating frequency, and provide an absorption dominant EMI shielding which are favorable for commercial and military applications.

Effect of Oxygen Interstitial Ordering on Multiple Order Parameters in Rare Earth Ferrite.

Oxygen interstitials and vacancies play a key role in modulating the microstructure and properties of nonstoichiometric oxide systems, such as those used for superconductors and multiferroics. Key to understanding the tuning mechanisms resulting from oxygen doping is a knowledge of the precise positions of these lattice defects, and of the interaction both between these defects and with many order parameters. Here, we report how such information can, for the first time, be obtained from a sample of LuFe_{2}O_{4.22} using a range of techniques including advanced electron microscopy, atomic-resolution spectroscopy, and density functional theory calculations. The results provide quantitative atomic details of the crystal unit cell, together with a description of the ferroelastic, ferroelectric, and ferromagnetic order parameters. We elucidate also the interaction between these order parameters and the positions of the oxygen interstitials in the oxygen-enriched sample. The comprehensive analysis of oxygen interstitial ordering provides insights into understanding the coupling among different degrees of freedom in rare earth ferrites and demonstrates that oxygen content regulation is a powerful tool for tuning the microstructure and properties for this class of quantum material.

Low Temperature Synthesis of Lithium-Doped Nanocrystalline Diamond Films with Enhanced Field Electron Emission Properties.

Low temperature (350 °C) grown conductive nanocrystalline diamond (NCD) films were realized by lithium diffusion from Cr-coated lithium niobate substrates (Cr/LNO). The NCD/Cr/LNO films showed a low resistivity of 0.01 Ω·cm and excellent field electron emission characteristics, viz. a low turn-on field of 2.3 V/µm, a high-current density of 11.0 mA/cm² (at 4.9 V/m), a large field enhancement factor of 1670, and a life-time stability of 445 min (at 3.0 mA/cm²). The low temperature deposition process combined with the excellent electrical characteristics offers a new prospective for applications based on temperature sensitive materials.

Effect of cation ratio and order on magnetic circular dichroism in the double perovskite Sr2Fe1+xRe1-xO6.

Superexchange-based magnetic coupling of the two B-site cations in rock-salt-ordered double perovskite oxides is extremely sensitive to the cation ratio and degree of order. However, as a result of the limited spatial resolution of most magnetic characterization techniques, it is challenging to establish a direct relationship between magnetic properties and structure in these materials, including the effects of elemental segregation and cation disorder. Here, we use electron energy-loss magnetic chiral dichroism together with aberration-corrected electron microscopy and spectroscopy to record magnetic circular dichroism (MCD) spectra at the nm scale, in combination with structural and chemical information at the atomic scale from the very same region. We study nanoscale phases in ordered Sr2[Fe][Re]O6, ordered Sr2[Fe][Fe1/5Re4/5]O6 and disordered Sr[Fe4/5Re1/5]O3 individually, in order to understand the role of cation ratio and order on local magnetic coupling. When compared with ordered Sr2[Fe][Re]O6, we find that antiferromagnetic Fe3+-O2--Fe3+superexchange interactions arising from an excess of Fe suppress the MCD signal from Fe cations in ordered Sr2[Fe][Fe1/5Re4/5]O6, while dominant Fe3+-O2--Fe3+antiferromagnetic coupling in disordered Sr[Fe4/5Re1/5]O3 leads to a decrease in MCD signal down to the noise level. Our work demonstrates a protocol that can be used to correlate crystallographic, electronic and magnetic information in materials such as Sr2Fe1+xRe1-xO6, in order to provide insight into structure-property relationships in double perovskite oxides at the atomic scale.

Nitrogen-Incorporated Ultrananocrystalline Diamond Electrodes for Dopamine Determination.

In this paper, nitrogen incorporated ultrananocrystalline diamond (NUNCD) films were fabricated for use as electrodes to detect dopamine. The NUNCD electrodes achieved high sensitivity, great selectivity, and excellent detection limits for dopamine sensing. The NUNCD electrode, fabricated as a potential sensitive biosensor for dopamine without any catalyst or mediators, demonstrated good activity for the direct detection of dopamine by simply putting the bare NUNCD electrode into a dopamine solution. Furthermore, the marked selectivity of the NUNCD electrode is very favorable for the determination of dopamine (DA) concentration (0.32 µM) in the presence of ascorbic acid (AA) and uric acid (UA). Considering dopamine detection in real biological fluid samples, the NUNCD electrode performed excellently with a detection limit of 0.39 µM and a high recovery ranging from 90-120%, revealing that NUNCD electrodes have promising use in the sensing of dopamine.