ABSTRACT
A highly stable flow-injection amperometric sensor for dexamethasone (DEX) was developed using a pencil graphite electrode (PGE) modified with Fe-based metal organic frameworks, MIL-100(Fe) and graphene oxide composite materials (MIL-100(Fe)/GO). Scanning electron microscopy and energy-dispersive X-ray spectroscopy, transmission electron microscopy, powder X-ray diffraction, and Fourier-transform infrared spectroscopy were used to characterize the MIL-100(Fe) composites. The MIL-100(Fe)/GO-modified PGE (denoted MIL-100(Fe)/GO/PGE) was further electrochemically characterized using cyclic voltammetry. As an electrode material, MIL-100(Fe) is a sensing element that undergoes oxidation from Fe(ii)-MOF to Fe(iii)-MOF, and GO possesses high conductivity and a large surface area, which exhibits high absorbability. In the presence of DEX, Fe(iii) is reduced, which accelerates electron transfer at the electrode interface. Therefore, DEX can be quantitatively detected by analyzing the anodic current of MIL-100(Fe). When coupled with amperometric flow injection analysis, excellent performance can be obtained even when a low detection potential is applied (+0.10 V vs. Ag/AgCl). The concentration was linear in the range 0.10-5.0 µM and 0.010-5.0 mM with LOD of 0.030 µM based on 3(sd/slope). The modified electrode also exhibited a remarkably stable response under optimized conditions, and up to 55 injections can be used per electrode. The sensor exhibits high repeatability, reproducibility, and anti-interference properties when used for DEX detection. The effective determination of dexamethasone in real pharmaceutical and cosmetic samples demonstrated the feasibility of the electrochemical sensor, and the results were in good agreement with those obtained from the HPLC-DAD analysis. Acceptable percentage recoveries from the spiked pharmaceutical and cosmetic samples were obtained, ranging from 93-111% for this new method compared with 84-107% for the HPLC-DAD standard method.
ABSTRACT
The wood preservative disodium octaborate tetrahydrate (DOT) migration is studied in clay. Using boron analysis by inductively coupled plasma optical emission spectroscopy (ICP-OES), DOT spatial and temporal dynamics are surveyed to show how DOT permeates into the wood and the clay using concentration profiles as a function of depth, initial wood moisture, and direction of filling. Atomic force microscopy and chemical imaging using photoinduced force microscopy are used to show the morphology of the wood samples and the distribution of DOT on their surface. ICP-OES results show that the average DOT concentration in the wood samples is originally 0.8 and 1.5 wt% in the bulk and at the surface, respectively. Conditioning of the wood to a moisture content of 19% in a climatic chamber reduces DOT concentration by 8% for the fir and 17% for the spruce. After one week of contact with the clays, the results showed a rapid decrease of 25-40% in DOT concentration in wood. On longer periods (5 months), the spruce shows a tendency to reabsorb the DOT from the clay and the DOT migration stabilizes at 20%. These results contribute to defining the dosage of DOT when the wood is exposed to clay.
ABSTRACT
Two new heteroleptic indium aminothiolate compounds [InClSC2H4N(Me)SC2H4]3[1] and [InSC2H4N(Me)SC2H4(C8H5F3NO)] [2] were synthesized by in situ salt metathesis reaction involving indium trichloride, aminothiol, and N,O-ß-heteroarylalkenol ligands. The complexes were subsequently purified and thoroughly characterized by nuclear magnetic resonance (NMR) analysis, elemental studies, mass spectroscopy, and X-ray diffraction single crystal analysis that showed a trigonal bipyramidal coordination of In(III) in both complexes. Thermogravimetric analysis of [1] revealed a multistep decomposition pathway and the formation of In2S3 at 350 °C, which differed from the pattern of [2] due to the lower thermal stability of [1]. Compound [2] exhibited a three-step decomposition process, resulting in the formation of In2S3 at 300 °C. The Chemical Vapor Deposition (CVD) experiment involving compound [2] was conducted on the FTO substrate, resulting in the production of singular-phase In2S3 deposits. A comprehensive characterization of these deposits, including crystal structure analysis via X-ray diffraction (XRD), and surface topography examination through scanning electron microscopy (SEM) has been completed. The presence of In-S units was also supported by the Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and energy dispersive spectroscopy (EDS) of the as-deposited films. Moreover, the electronic structure and thermal properties of compound [2] were investigated through DFT calculations. Electron density localization analysis revealed that the highest occupied molecular orbital (HOMO) exhibited dense concentration at the aminothiolate moiety of the complex, while the lowest unoccupied molecular orbital (LUMO) predominantly resided at the N,O-ß-heteroarylalkenolate ligand. Furthermore, our computational investigation has validated the formation of indium sulfide by elucidating an intermediate state, effectively identified through EI-MS analysis, as one of the plausible pathways for obtaining In2S3. This intermediate state comprises the aminothiolate ligand (LNS) coordinated with indium metal.
ABSTRACT
In this study, a one-pot synthesis of a molybdenum diselenide/nitrogen-doped graphene oxide (MoSe2/NGO) composite was demonstrated and used for the fabrication of an electrochemical pH sensor. The MoSe2/NGO composite was characterized using powder X-ray diffraction, infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and Brunauer-Emmett-Teller analysis. The electrochemical behavior at different pH values was determined by recording the open-circuit potential. When applied for pH detection, the MoSe2/NGO modified screen-printed electrode (SPE) showed good linearity with a sensitivity of 61.3 mV pH-1 over a wide pH range of 2-14. In addition, the pH sensor exhibited a remarkably stable response, high reproducibility, and selectivity. The sensor was used to measure the acidity or alkalinity of real food and beverage samples. The results for these samples showed a relative error of less than 10% compared with the results obtained with the commercial pH meter. The portable sensor produced by screen printing electrodes paves the way for the development of simple, cost-effective, real-time, and robust pH sensors for the pH analysis of various sample matrices for clinical diagnostics, biosensing, and cost-effective applications.
ABSTRACT
Cellulose is a biopolymer with numerous advantages that make it an ecological, economical, and high-performing choice for various applications. To fully exploit the potential of cellulose, it is often necessary to dissolve it, which poses a current challenge. The aqueous zinc oxide/sodium hydroxide (ZnO/NaOH/Water) system is a preferred solvent for its rapid dissolution, non-toxicity, low cost, and environmentally friendly nature. In this context, the behavior of cellulose chains in the aqueous solution of ZnO/NaOH and the impact of temperature on the solubility of this polymer were examined through a molecular dynamics simulation. The analysis of the root means square deviation (RMSD), interaction energy, hydrogen bond curves, and radial distribution function revealed that cellulose is insoluble in the ZnO/NaOH solvent at room temperature (T = 298 K). Decreasing the temperature in the range of 273 K to 268 K led to a geometric deformation of cellulose chains, accompanied by a decrease in the number of interchain hydrogen bonds over the simulation time, thus confirming the solubility of cellulose in this system between T = 273 K and T = 268 K.
ABSTRACT
T-cells play a significant role in the development of autoimmune diseases. The CD28-B7 costimulatory pathway is crucial for activating T-cells, and blocking this pathway is essential for treating autoimmune diseases. Therapeutic antibodies and fusion proteins that target costimulatory molecules like CD80, CD86, CTLA-4, and CD28 have been developed to explore the costimulation process and as targeted treatments. To advance our understanding of costimulation in autoimmunity and the inhibition of the costimulatory pathway, it is crucial to have an accurate, precise, and direct method for detecting and quantifying the soluble form of these molecules in body fluids and various biological systems. Herein, we developed a liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for quantifying the four costimulatory proteins depending on the signature peptides derived from the soluble isoform of these proteins in multiple reaction monitoring (MRM) mode. The method was validated using the US FDA guidelines. The LOQ was determined as â¼0.5â¯nM for the four analytes, with quantification extended to 20â¯nM with a correlation coefficient of R2>0.998. The developed MRM method was used to analyze on-bead digested protein mixtures to establish a competitive assay for the CD28-B7 costimulatory pathway using CTLA4-Ig (Abatacept ™) as an FDA-approved drug for rheumatoid arthritis. The IC50 was determined to be 2.99 and 159.8â¯nM for sCD80 and sCD86, respectively. A straightforward MRM-based competitive assay will advance the knowledge about the costimulatory role in autoimmunity and the autoimmune therapeutic drug discovery, with the need for broad application on different in vitro and in vivo models to discover new targeted inhibitors.
Subject(s)
Autoimmune Diseases , Immunoconjugates , Humans , CD28 Antigens/metabolism , Antigens, CD/metabolism , B7-2 Antigen , Chromatography, Liquid , Liquid Chromatography-Mass Spectrometry , Tandem Mass Spectrometry , B7-1 Antigen/metabolism , AbataceptABSTRACT
Mesalamine, also called 5-ASA (5-aminosalicylic acid), is a largely used anti-inflammatory agent and is a main choice to treat Ulcerative Colitis. This report is aimed to investigate enzymatic processes involved in the oxidation of mesalamine to better understand some of its side-effects. Oxidation with oxygen (catalyzed by ceruloplasmin) or with hydrogen peroxide (catalyzed by peroxidase or hemoglobin) showed that these oxidases, despite their different mechanisms of oxidation, could recognize mesalamine as a substrate and trigger its oxidation to a corresponding quinone-imine. These enzymes were chosen because they may recognize hydroquinone (a p-diphenol) as substrate and oxidize it to p-benzoquinone and that mesalamine, as a p-aminophenol, presents some similarities with hydroquinone. The UV-Vis kinetics, FTIR and 1H NMR supported the hypothesis of oxidizing mesalamine. Furthermore, mass spectrometry suggested the quinone-imine as reaction product. Without enzymes, the oxidation process was very slow (days and weeks), but it was markedly accelerated with the oxidases, particularly with peroxidase. Cyclic voltammetry supported the hypothesis of the oxidative process and allowed a ranking of susceptibility to oxidizing mesalamine in comparison with other oxidizable drug molecules with related structures. The susceptibility to oxidation was higher for mesalamine, in comparison with Tylenol (acetaminophen) and with aspirin (salicylic acid).
Subject(s)
Colitis, Ulcerative , Mesalamine , Humans , Mesalamine/chemistry , Monophenol Monooxygenase , Hydroquinones , Anti-Inflammatory Agents, Non-Steroidal/chemistry , Peroxidase , Colitis, Ulcerative/drug therapy , Oxidation-Reduction , Peroxidases , Quinones/therapeutic use , Catalysis , IminesABSTRACT
Proteinaceous amyloid fibrils are one of the stiffest biopolymers due to their extensive cross-ß-sheet quaternary structure, whereas cellulose nanofibrils (CNFs) exhibit interesting properties associated with their nanoscale size, morphology, large surface area, and biodegradability. Herein, CNFs were supplemented with amyloid fibrils assembled from the Curli-specific gene A (CsgA) protein, the main component of bacterial biofilms. The resulting composites showed superior mechanical properties, up to a 7-fold increase compared to unmodified CNF films. Wettability and thermogravimetric analyses demonstrated high surface hydrophobicity and robust thermal tolerance. Bulk spectroscopic characterization of CNF-CsgA films revealed key insights into the molecular organization within the bionanocomposites. Atomic force microscopy and photoinduced force microscopy revealed the high-resolution location of curli assemblies into the CNF films. This novel sustainable and cost-effective CNF-based bionanocomposites supplemented with intertwined bacterial amyloid fibrils opens novel directions for environmentally friendly applications demanding high mechanical, water-repelling properties, and thermal resistance.
Subject(s)
Cellulose , Nanofibers , Cellulose/chemistry , Amyloid/chemistry , Biopolymers/chemistry , Amyloidogenic Proteins , Microscopy, Atomic Force , Nanofibers/chemistryABSTRACT
Elevating soluble CD80 (sCD80) in human serum is a natural response to autoimmune diseases such as rheumatoid arthritis (RA). The level of sCD80 is associated with RA development and prognosis; therefore, it is potentially used as a biomarker. sCD80 is commonly measured in human serum using immunoassays (e.g., ELISA) with multiple drawbacks, mainly cross-reactivity. Aptamer-based biosensors (aptasensors) development for quantifying and detecting different biological molecules demonstrates applicability in next-generation medicine and biomarker detection. Herein, we selected a specific aptamer for sCD80 by conventional in-vitro selection process (SELEX) with the high-affinity aptamer (Kd = 47.69 nM). A sensitive aptasensor, for the first time, was developed on a screen-printed gold electrode (AuSPE) platform compatible with easy-to-use label-free electrochemical impedance spectroscopy. The immobilization of the aptamer on the gold surface and the presence of sCD80 in a complex with the aptamer were characterized by photo-induced force microscopy, which revealed the uniform assembly of the aptamer monolayer and the distribution of sCD80 on the electrode surface. The developed aptasensor showed a linear performance (0.025-10.0 nM of protein) with a detection limit of 8.0 pM. Furthermore, the aptasensor was tested in a biological matrix, where a linear signal was observed for the increased amount of spiked sCD80 (R2 = 0.9887). The recovery of the spiked amounts ranged from 105 to 125% with coefficient of variation (CV%) <7%, which supported the applicability of this sensor in detecting sCD80 for diagnosis.
Subject(s)
Aptamers, Nucleotide , Biosensing Techniques , Humans , Biosensing Techniques/methods , Limit of Detection , Electrochemical Techniques/methods , Aptamers, Nucleotide/chemistry , Cell Adhesion Molecules , Gold/chemistry , Biomarkers , ElectrodesABSTRACT
BACKGROUND AND AIMS: Rheumatoid arthritis (RA) is a chronic autoimmune disease. RA-induced immunological responses are coordinated by T-cell stimulation. The costimulatory signal CD28-B7 is essential for T-cell activation by interacting CD28 with CD80 and CD86 costimulatory proteins. CTLA4 is another costimulatory protein that binds to CD80 and CD86 to inhibit T-cell activity. The soluble costimulatory proteins: sCD80, sCD86, sCD28, and sCTLA-4 were detected and quantified in human plasma and correlated with RA development. As potential diagnostic biomarkers for RA, developing a sensitive, specific, and reproducible method for quantifying these costimulatory molecules in human plasma and establishing quantitative ranges for each protein in healthy and RA patients' plasma is essential for advancing the clinical diagnostic and health outcomes. MATERIALS AND METHODS: A novel quantitative liquid chromatography-tandem spectrometry (LC-MS/MS) technique using multiple reaction monitoring (MRM) modes was developed and validated to measure soluble costimulatory molecules sCTLA4, sCD28, sCD80, and sCD86 in human plasma samples. Furthermore, the method was applied to determine sCTLA4, sCD28, sCD80, and sCD86 levels in plasma samples from RA patients (n = 23) and healthy controls (n = 21). RESULTS: The method was successfully developed and validated according to international inter- and intra-assay precision and accuracy guidelines. The linearity of the method was achieved between 0.5 nM and 100 nM for each protein with a correlation coefficient of > 0.998. The plasma level of sCTLA4, sCD80, and sCD86 in RA patients was significantly elevated compared to controls. RA patients had 63.32 ± 17.63 nM sCTLA4 and controls 36.05 ± 18.83 nM; p < 0.0001. The performance of the four proteins was determined using ROC curves, where sCTLA4 showed the highest diagnostic and clinical performance compared to the others. CONCLUSIONS: This study reports the first use of LC-MS/MS in MRM mode to accurately quantify soluble costimulatory molecules in plasma samples as potential RA diagnostic biomarkers. Determination of the reference range for each protein with high selectivity and sensitivity increases the potential for utilizing this method as a clinical diagnostic.
Subject(s)
Arthritis, Rheumatoid , CD28 Antigens , Humans , Antigens, CD , B7-2 Antigen , Chromatography, Liquid , Tandem Mass Spectrometry , B7-1 Antigen/metabolism , Transcription Factors , Arthritis, Rheumatoid/diagnosis , BiomarkersABSTRACT
Core-shell magnetic covalent organic framework (COF) materials were prepared, followed by shell material functionalization with different organic ligands, including thiosemicarbazide, through a postsynthetic modification approach. The structures of the prepared samples were characterized with various techniques, including powder X-ray diffraction (PXRD), Brunauer-Emmett-Teller (BET) method, thermogravimetric analysis (TGA), photoinduced force microscopy (PiFM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and solid 13C NMR. PXRD and BET studies revealed that the crystalline and porous nature of the functionalized COFs was well maintained after three steps of postsynthetic modification. On the other hand, solid 13C NMR, TGA, and PiFM analyses confirmed the successful functionalization of COF materials with good covalent linkage connectivity. The use of the resulting functionalized magnetic COF for selective and ultrafast adsorption of Hg(II) has been investigated. The observations displayed rapid kinetics with adsorption dynamics conforming to the quasi-second-order kinetic model and the Langmuir adsorption model. Furthermore, this prepared crystalline magnetic material demonstrated a high Langmuir Hg(II) uptake capacity, reaching equilibrium in only 5 min. Thermodynamic calculations proved that the adsorption process is endothermic and spontaneous.
ABSTRACT
Highly cross-linked inorganic and organic hybrid cyclomatrix-polyphosphazenes microspheres (C-PPZs) have been successfully synthesized by a one-pot polymerization technique between hexachlorocyclotriphosphazene and p-phenylenediamine in the presence of triethylamine (TEA), and they were used for enhancing the flame retardancy of epoxy resins (EPs). A thermoset EP was prepared by incorporating different percentages (2, 5, and 10%) of C-PPZs into diglycidyl ether of bisphenol A (DGEBA). The results reveal that the size and morphology of the microspheres can be tuned by varying the synthesis temperature. The average size of C-CPPZs gradually increased from 3.1, 4.9, to 7.8 µm as the temperature was increased from 100, 120, to 200 °C, respectively. The thermogravimetric analysis showed that the C-CPPZ microspheres have good thermal stability up to 900 °C with about â¼10 wt % mass loss for C-CPPZs formed at 200 °C compared to â¼30 wt % mass loss for those obtained at 100 and 120 °C. The 10% loss at 900 °C is much lower than the previous research concerning the thermal stability of cyclophosphazene, in which more weight losses were observed at lower temperatures. The resulting C-CPPZ microspheres were characterized by spectroscopic and imaging techniques including Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, elemental mapping, and X-ray photoelectron spectroscopy.
ABSTRACT
This paper presents a novel cheminformatics approach for the design and synthesis of hydroxyapatite/collagen nanocomposites, which have potential biomedical applications in tissue engineering, drug delivery, and orthopedic and dental implants. The nanocomposites are synthesized by the co-precipitation method with different ratios of hydroxyapatite and collagen. Their mechanical, biological, and degradation properties are analyzed using various experimental and computational techniques. Attenuated total reflection-Fourier-transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction unveil the low crystallinity and nanoscale particle size of hydroxyapatite (22.62 nm) and hydroxyapatite/collagen composites (14.81 nm). These findings are substantiated by scanning electron microscopy with energy-dispersive X-ray spectroscopy, confirming the Ca/P ratio between 1.65 and 1.53 and attesting to the formation of non-stoichiometric apatites in all samples, further validated by molecular simulation. The antimicrobial activity of the nanocomposites is evaluated in vitro against several bacterial and fungal strains, demonstrating their medical potential. Additionally, in silico analyses are performed to predict the absorption, distribution, metabolism, and excretion properties and the bioavailability of the collagen samples. This study paves the way for the development of novel biomaterials using chemoinformatics tools and methods, facilitating the optimization of design and synthesis parameters, as well as the prediction of biological outcomes. Future research directions should encompass the investigation of in vivo biocompatibility and bioactivity of the nanocomposites, while exploring further applications and functionalities of these innovative materials.
ABSTRACT
Water purification from toxic metals was the main objective of this work. A composite in film form was prepared from the biomaterials hydroxyapatite, chitosan and glycerol using the dissolution/recrystallization method. A nanoparticle-based film with a homogenous and smooth surface was produced. The results of total reflectance infrared spectroscopy (ATR-FTIR) and thermal gravimetric analysis (TGA/DTA) demonstrated the presence of a substantial physical force between composite components. The composite was tested for its ability to absorb Cd2+ and Zn2+ ions from aqueous solutions. Cd2+ and Zn2+ adsorption mechanisms are fit using the Langmuir model and the pseudo-second-order model. Thermodynamic parameters indicated that Cd2+ and Zn2+ ion adsorption onto the composite surface is spontaneous and preferred at neutral pH and temperatures somewhat higher than room temperature. The adsorption studies showed that the maximum adsorption capacity of the HAp/CTs bio-composite membrane for Cd2+ and Zn2+ ions was in the order of cadmium (120 mg/g) > Zinc (90 mg/g) at an equilibrium time of 20 min and a temperature of 25 °C. The results obtained on the physico-chemical properties of nanocomposite membranes and their sorption capacities offer promising potential for industrial and biological activities.
ABSTRACT
Pompe, Gaucher and Krabbe disease are lysosomal storage disorders (LSDs) which are a group of genetic diseases that causes the accumulation of lipids in tissues and cells. Pompe, Gaucher and Krabbe are characterized by the deficiency of acid α-glucosidase (GAA), ß-Glucocerebrosidase (GBA) and galactocerebrosidase (GALC), and treatable if detected in their early stages. Here, we present the fabrication of an electrochemical immunosensor for the multiplexed quantification and simultaneous detection of GAA, GBA and GALC. The sensor was developed by electrodepositing gold nanoparticles (AuNPs) on an array of carbon electrodes, followed by the immobilization of GAA, GBA and GALC specific antibodies via functionalization with cysteamine and glutaraldehyde. The multiplexed immunosensor was able to successfully detect GAA, GBA and GALC at the femtomolar level with respective low detection limits of 0.12 pg/ml, 0.31 pg/ml and 0.18 pg/ml. The immunosensor showed good selectivity, sensitivity and good recovery when spiked in human serum, which confirms its possible applicability in point-of-care testing for the early diagnosis of LSDs.
Subject(s)
Biosensing Techniques , Lysosomal Storage Diseases , Metal Nanoparticles , Early Diagnosis , Electrochemical Techniques , Galactosylceramidase , Gold/chemistry , Humans , Immunoassay , Limit of Detection , Lysosomal Storage Diseases/diagnosis , Lysosomes , Metal Nanoparticles/chemistryABSTRACT
The aim of this study is to develop a new, efficient, and inexpensive natural-based adsorbent with high efficacy for the cationic dye methylene blue (MB). A natural-based nanocomposite based on hydroxyapatite (HAp) and hydroxypropyl methylcellulose (HPMC) was selected for this purpose. It was synthesized by the dissolution/reprecipitation method. A film with a homogeneous and smooth surface composed of nanoparticles was prepared from the nanocomposite. HPMC and HAp biopolymers were selected due to their compatibility, biodegradability, and non-toxicity. Total reflectance infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), and calorimetric/thermal gravimetric (DSC/TGA) analysis results revealed the existence of strong physical interaction between the composite components. Scanning electron microscopy (SEM) observations show a composite sheet with a homogenous and smooth surface, indicating excellent compatibility between HPMC and HAp in the composite. The nanocomposite was evaluated as an adsorbent for organic dyes in an aqueous solution. The effects of solution pH, initial MB concentration, composite concentration, and adsorption time on the adsorption efficiency were evaluated. The highest adsorption rate was seen as 52.0 mg of MB/g composite. The adsorption rate reached equilibrium in about 20 min. Fitting of the adsorption data to the Langmuir and Freundlich adsorption models was investigated. Results showed that the adsorption process follows the Langmuir isotherm model. The kinetic study results revealed that the adsorption process was pseudo-second-order. The herein composite is an excellent alternative for use as contemporary industrial-scale adsorbents.
ABSTRACT
Sufficient sunlight absorption and exciton generation are critical for developing efficient nonfullerene organic solar cells (OSCs). In this work, polyelectrolyte polystyrenesulfonate (PSS)-coated plasmonic gold nanorods (GNRs@PSS) were incorporated, for the first time, into the inverted nonfullerene OSCs as rear interfacial modifiers to improve sunlight absorption and charge generation via the near-field plasmonic and backscattering effects. The plasmonic GNRs effectively improved the sunlight absorption and enhanced the charge generation. Meanwhile, the negatively charged PSS shell ensured the uniform dispersion of the GNRs on the surface of the photoactive layer, optimized the interfacial contact, and further promoted the hole transport to the electrode. These concerted synergistic effects augmented the efficiency (10.11%) by nearly 20% relative to the control device (8.47%). Remarkably, the ultrathin (â¼2.2 nm) organic layer on the surface of GNRs was closely examined by acquiring the carbon contrast image through energy-filtered transmission electron microscopy (EF-TEM), which clearly confirmed the coating uniformity from the side to end-cap of GNRs. The surface plasmon resonance (SPR) effect of the GNRs@PSS on the surface of the photoactive layer was unprecedentedly mapped by photoinduced force microscopy (PiFM) under the illumination of a tunable wavelength supercontinuum laser mimicking sunlight. Furthermore, investigations into the effect of size, surface coverage, and incorporation location of GNRs@PSS on the performance of OSCs revealed that the appropriate design and incorporation of the plasmonic nanostructures are crucial, otherwise the performance can be decreased, as evidenced in the case of front interface integration.
ABSTRACT
It is highly desired to develop advanced characterization techniques to explore the 3D nanoscale morphology of the complicated blend film of ternary organic solar cells (OSCs). Here, ternary OSCs are constructed by incorporating the nonfullerene acceptor perylenediimide (PDI)-diketopyrrolopyrrole (DPP)-PDI and their morphology is characterized in depth to understand the performance variation. In particular, photoinduced force microscopy (PiFM) coupled with infrared laser spectroscopy is conducted to qualitatively study the distribution of donor and acceptors in the blend film by chemical identification and to quantitatively probe the segmentation of domains and the domain size distribution after PDI-DPP-PDI acceptor incorporation by PiFM imaging and data processing. In addition, the energy-filtered transmission electron microscopy with energy loss spectra is utilized to visualize the nanoscale morphology of ultrathin cross-sections in the configuration of the real ternary device for the first time in the field of photovoltaics. These measurements allow to "view" the surface and cross-sectional morphology and provide strong evidence that the PDI-DPP-PDI acceptor can suppress the aggregation of the fullerene molecules and generate the homogenous morphology with a higher-level of the molecularly mixed phase, which can prevent the charge recombination and stabilize the morphology of photoactive layer.
ABSTRACT
Rapid, mass diagnosis of the coronavirus disease 2019 (COVID-19) is critical to stop the ongoing infection spread. The two standard screening methods to confirm the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) are polymerase chain reaction (PCR), through the RNA of the virus, and serology by detecting antibodies produced as a response to the viral infection. However, given the detection complexity, cost and relatively long analysis times of these techniques, novel technologies are urgently needed. Here, we report an aptamer-based biosensor developed on a screen-printed carbon electrode platform for rapid, sensitive, and user-friendly detection of SARS-CoV-2. The aptasensor relies on an aptamer targeting the receptor-binding domain (RBD) in the spike protein (S-protein) of the SARS-CoV-2. The aptamer immobilization on gold nanoparticles, and the presence of S-protein in the aptamer-target complex, investigated for the first time by photo-induced force microscopy mapping between 770 and 1910 cm-1 of the electromagnetic spectrum, revealed abundant S-protein homogeneously distributed on the sensing probe. The detection of SARS-CoV-2 S-protein was achieved by electrochemical impedance spectroscopy after 40 min incubation with several analyte concentrations, yielding a limit of detection of 1.30 pM (66 pg/mL). Moreover, the aptasensor was successfully applied for the detection of a SARS-CoV-2 pseudovirus, thus suggesting it is a promising tool for the diagnosis of COVID-19.
Subject(s)
Biosensing Techniques , COVID-19 , Metal Nanoparticles , Electrodes , Gold , Humans , Microscopy, Atomic Force , SARS-CoV-2ABSTRACT
Photoelectrochemical (PEC) hydrogen evolution has been acknowledged as a promising "green" technique to convert solar energy into clean chemical fuel. Photoanodes play a key role in determining the performance of PEC systems, spurring numerous efforts to develop advanced materials as well as structures to improve the photoconversion efficiency. In this work, we report the rational design of a plasmonic hierarchical nanorod array, composed of oriented one-dimensional (1D) CdS nanorods decorated with a uniformly wrapped graphite-like carbon (CPDA) layer and Au nanoparticles (Au NPs), as highly efficient photoanode materials. An interfacial in situ reduction-graphitization method has been conducted to prepare the CdS/CPDA/Au nanoarchitecture, where polydopamine (PDA) coating was used as a C source and a reductant. The CdS/CPDA/Au nanoarray photoanode demonstrates superior photoconversion efficiency with a photocurrent density of 8.74 mA/cm2 and an IPCE value (480 nm) of 30.2% (at 1.23 V vs RHE), under simulated sunlight irradiation, which are 12.7 and 13.5 times higher than pristine CdS. The significant enhancement of PEC performance is mainly benefited from the increase of the entire quantum yield and efficiency due to the formation of a Schottky rectifier, localized surface plasmon resonance (LSPR)-enhanced light absorption, and promoted hot-electron injection from interlayered graphene-like carbon. More importantly, thanks to the inhibited charge carrier recombination process and transferred oxidation reaction sites, the fabricated CdS/CPDA/Au photoelectrode exhibits lengthened electron lifetimes and better photostability, illustrating its wonderful potential for future PEC application.