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1.
J Environ Sci (China) ; 147: 561-570, 2025 Jan.
Article in English | MEDLINE | ID: mdl-39003071

ABSTRACT

In the present study, we investigated the influence of surface fluorine (F) on TiO2 for the photocatalytic oxidation (PCO) of toluene. TiO2 modified with different F content was prepared and tested. It was found that with the increasing of F content, the toluene conversion rate first increased and then decreased. However, CO2 mineralization efficiency showed the opposite trend. Based on the characterizations, we revealed that F substitutes the surface hydroxyl of TiO2 to form the structure of Ti-F. The presence of the appropriate amount of surface Ti-F on TiO2 greatly enhanced the separation of photogenerated carriers, which facilitated the generation of ·OH and promoted the activity for the PCO of toluene. It was further revealed that the increase of only ·OH promoted the conversion of toluene to ring-containing intermediates, causing the accumulation of intermediates and then conversely inhibited the ·OH generation, which led to the decrease of the CO2 mineralization efficiency. The above results could provide guidance for the rational design of photocatalysts for toluene oxidation.


Subject(s)
Fluorides , Oxidation-Reduction , Titanium , Toluene , Toluene/chemistry , Titanium/chemistry , Catalysis , Fluorides/chemistry , Photochemical Processes , Models, Chemical
2.
Anal Chim Acta ; 1316: 342867, 2024 Aug 08.
Article in English | MEDLINE | ID: mdl-38969430

ABSTRACT

BACKGROUND: Kanamycin (KAN) residues in animal-derived foods continuously enter the human body, which will pose serious threats to human health such as hearing loss, nephrotoxicity and other complications. Therefore, to sensitively detect KAN residues by a reliable technology is extremely urgent in food quality and safety. Compared with traditional methods being limited by cost and complexity, photoelectrochemical (PEC) biosensors benefit from some merits such as rapid response, excellent sensitivity and good stability. In this study, the construction of a highly efficient PEC platform to realize KAN residues detection is discussed. RESULTS: Herein, a novel p-n heterojunction consisting of flower-like BiOI microspheres and graphite carbon nitride (g-C3N4) nanoflakes was developed to establish a PEC aptasensor for KAN detection at 0 V. The prepared g-C3N4/BiOI heterostructure showed not only significantly enhanced PEC activity due to the larger specific surface area but also greatly increased charge separation efficiency owing to the strong internal electric field. Meanwhile, using g-C3N4/BiOI as a highly efficient photoactive material for binding amine-functionalized aptamers to capture KAN, the photocurrent signals showed a 'turn off' mode to achieve the sensitive detection of KAN. The proposed PEC aptasensor exhibited linear response for KAN from 5 × 10-9 to 3 × 10-7 mol L-1 with a low detection limit of 1.31 × 10-9 mol L-1, and satisfactory recoveries (97.44-107.38 %) were obtained in real food samples analysis. SIGNIFICANCE: This work presented a novel p-n heterojunction-based PEC aptasensor with strong selectivity and stability, rendering it allowed to detect KAN in animal-derived foods including milk, honey and pork. Additionally, the detection range satisfied the MRLs for KAN specified by the national standards, demonstrating the potential application for food analysis. The study provides a new insight into the development of efficient and practical biosensors for antibiotic residues detection.


Subject(s)
Aptamers, Nucleotide , Biosensing Techniques , Electrochemical Techniques , Graphite , Kanamycin , Aptamers, Nucleotide/chemistry , Electrochemical Techniques/methods , Graphite/chemistry , Biosensing Techniques/methods , Kanamycin/analysis , Photochemical Processes , Limit of Detection , Food Contamination/analysis , Nitrogen Compounds/chemistry , Animals , Nitriles/chemistry , Anti-Bacterial Agents/analysis , Bismuth
3.
Environ Geochem Health ; 46(8): 302, 2024 Jul 11.
Article in English | MEDLINE | ID: mdl-38990227

ABSTRACT

In this study, a highly efficient CoFe2O4-anchored g-C3N4 nanocomposite with Z-scheme photocatalyst was developed by facile calcination and hydrothermal technique. To evaluate the crystalline structure, sample surface morphology, elemental compositions, and charge conductivity of the as-synthesized catalysts by various characterization techniques. The high interfacial contact of CoFe2O4 nanoparticles (NPs) with g-C3N4 nanosheets reduced the optical bandgap from 2.67 to 2.5 eV, which improved the charge carrier separation and transfer. The photo-degradation of methylene blue (MB) and rhodamine B (Rh B) aqueous pollutant suspension under visible-light influence was used to investigate the photocatalytic degradation activity of the efficient CoFe2O4/g-C3N4 composite catalyst. The heterostructured spinel CoFe2O4 anchored g-C3N4 photocatalysts (PCs) with Z-scheme show better photocatalytic degradation performance for both organic dyes. Meanwhile, the efficiency of aqueous MB and Rh B degradation in 120 and 100 min under visible-light could be up to 91.1% and 73.7%, which is greater than pristine g-C3N4 and CoFe2O4 catalysts. The recycling stability test showed no significant changes in the photo-degradation activity after four repeated cycles. Thus, this work provides an efficient tactic for the construction of highly efficient magnetic PCs for the removal of hazardous pollutants in the aquatic environment.


Subject(s)
Cobalt , Ferric Compounds , Methylene Blue , Nanocomposites , Rhodamines , Water Pollutants, Chemical , Cobalt/chemistry , Ferric Compounds/chemistry , Catalysis , Nanocomposites/chemistry , Rhodamines/chemistry , Water Pollutants, Chemical/chemistry , Methylene Blue/chemistry , Photolysis , Light , Carbon Compounds, Inorganic/chemistry , Nitriles/chemistry , Photochemical Processes , Nitrogen Compounds/chemistry , Graphite
4.
Sci Rep ; 14(1): 15658, 2024 Jul 08.
Article in English | MEDLINE | ID: mdl-38977812

ABSTRACT

Water pollution and antimicrobial resistance (AMR) have become two global threats; 80% of diseases and 50% of child deaths are due to poor water quality. In this study, hydrothermal processing was employed to manufacture manganese oxide nanorods. Silver dopant was deposited on the surface of manganese oxide. XRD diffractogram confirmed the facile synthesis of Ag/Mn2O3 nanocomposite. XPS survey analysis demonstrated silver content of 9.43 atom %. Photocatalytic measurements demonstrated the outstanding efficiency of the Ag-Mn2O3 compared to virgin oxide particles under visible radiation. Degradation efficiencies Mn2O3 and Ag/Mn2O3 on methyl orange (MO) dye was found to be 53% and 85% under visible spectrum. Silver dopant was found to decrease the binding energy of valence electrons; this action could support electron-hole pair generation under visible spectrum and could promote catalytic performance. Ag/Mn2O3 NPs demonstrated most effective performance (95% removal efficiency) at pH 3; this could be ascribed to the electrostatic attraction between positively charged catalyst and the negatively charged MO. Ag/Mn2O3 demonstrated enhanced antibacterial activity against Gram-positive Staphylococcus aureus (S. aureus) (19 mm ZOI), and Gram-negative Escherichia coli (E. coli) (22 mm ZOI) respectively; the developed nanocomposite demonstrated advanced anti-film activity with inhibition percentage of 95.5% against E. coli followed by 89.5% against S. aureus.


Subject(s)
Escherichia coli , Manganese Compounds , Nanocomposites , Oxides , Silver , Staphylococcus aureus , Manganese Compounds/chemistry , Manganese Compounds/pharmacology , Oxides/chemistry , Oxides/pharmacology , Silver/chemistry , Silver/pharmacology , Nanocomposites/chemistry , Catalysis , Escherichia coli/drug effects , Staphylococcus aureus/drug effects , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/chemical synthesis , Light , Azo Compounds/chemistry , Azo Compounds/pharmacology , Microbial Sensitivity Tests , Anti-Infective Agents/pharmacology , Anti-Infective Agents/chemistry , Anti-Infective Agents/chemical synthesis , Photochemical Processes
5.
J Am Chem Soc ; 146(26): 17974-17985, 2024 Jul 03.
Article in English | MEDLINE | ID: mdl-38957136

ABSTRACT

The binding affinity determination of protein-ligand complexes is a cornerstone of drug design. State-of-the-art techniques are limited by lengthy and expensive processes. Building upon our recently introduced novel screening method utilizing photochemically induced dynamic nuclear polarization (photo-CIDNP) NMR, we provide the methodological framework to determine binding affinities within 5-15 min using 0.1 mg of protein. The accuracy of our method is demonstrated for the affinity constants of peptides binding to a PDZ domain and fragment ligands binding to the protein PIN1. The method can also be extended to measure the affinity of nonphoto-CIDNP-polarizable ligands in competition binding experiments. Finally, we demonstrate a strong correlation between the ligand-reduced signals in photo-CIDNP-based NMR fragment screening and the well-established saturation transfer difference (STD) NMR. Thus, our methodology measures protein-ligand affinities in the micro- to millimolar range in only a few minutes and informs on the binding epitope in a single-scan experiment, opening new avenues for early stage drug discovery approaches.


Subject(s)
Nuclear Magnetic Resonance, Biomolecular , Ligands , Protein Binding , Photochemical Processes , NIMA-Interacting Peptidylprolyl Isomerase/metabolism , NIMA-Interacting Peptidylprolyl Isomerase/chemistry , Proteins/chemistry , Proteins/metabolism , Peptides/chemistry , Peptides/metabolism , Magnetic Resonance Spectroscopy/methods , Models, Molecular , PDZ Domains
6.
Science ; 385(6706): eadl5763, 2024 Jul 19.
Article in English | MEDLINE | ID: mdl-39024454

ABSTRACT

Proximity labeling proteomics (PLP) strategies are powerful approaches to yield snapshots of protein neighborhoods. Here, we describe a multiscale PLP method with adjustable resolution that uses a commercially available photocatalyst, Eosin Y, which upon visible light illumination activates different photo-probes with a range of labeling radii. We applied this platform to profile neighborhoods of the oncogenic epidermal growth factor receptor and orthogonally validated more than 20 neighbors using immunoassays and AlphaFold-Multimer prediction. We further profiled the protein neighborhoods of cell-cell synapses induced by bispecific T cell engagers and chimeric antigen receptor T cells. This integrated multiscale PLP platform maps local and distal protein networks on and between cell surfaces, which will aid in the systematic construction of the cell surface interactome, revealing horizontal signaling partners and reveal new immunotherapeutic opportunities.


Subject(s)
Eosine Yellowish-(YS) , Fluorescent Dyes , Proteomics , Staining and Labeling , Humans , Catalysis , Cell Membrane/metabolism , Cell Membrane/chemistry , ErbB Receptors/metabolism , Light , Photochemical Processes , Protein Interaction Maps , Proteomics/methods , Receptors, Chimeric Antigen/metabolism , T-Lymphocytes/immunology , Staining and Labeling/methods , Eosine Yellowish-(YS)/chemistry , Fluorescent Dyes/chemistry
7.
Mikrochim Acta ; 191(8): 472, 2024 Jul 19.
Article in English | MEDLINE | ID: mdl-39028442

ABSTRACT

A Ti3C2TxMXene-based biosensor has been developed and the photocatalytic atom transfer radical polymerization (photo ATRP) amplification strategy applied to detect target miRNA-21 (tRNA). Initially, Ti3C2TxMXene nanosheets were synthesized from the Ti3AlC2 MAX precursor via selective aluminum etching. Then, functionalization of Ti3C2TxMXene nanosheets with 3-aminopropyl triethoxysilane (APTES) via silylation reactions to facilitate covalent bonding with hairpin DNA biomolecules specifically designed for tRNA detection. Upon binding with the tRNA, the hairpin DNA liberated the azide (N3) group, initiating a click reaction to affix to the photo ATRP initiator. Through the ATRP photoreaction, facilitated by an organic photoredox catalyst and light, a significant amount of ferrocenyl methyl methacrylate (FMMA) monomer was immobilized on the electrode. Therefore, the electrochemical signal is amplified. The electrochemical efficacy of the biosensor was assessed using square wave voltammetry (SWV). Under optimized conditions, the biosensor demonstrated remarkable sensitivity in detecting tRNA, with a linear detection range from 0.01 fM to 10 pM and a detection limit of 2.81 aM. The findings elucidate that the developed biosensor, in conjunction with the photo ATRP strategy, offers reproducibility, stability, and increased sensitivity, underscoring its potential applications within the experimental medical sector of the biomolecular industry.


Subject(s)
Biosensing Techniques , Electrochemical Techniques , Limit of Detection , MicroRNAs , Titanium , Biosensing Techniques/methods , MicroRNAs/analysis , Electrochemical Techniques/methods , Titanium/chemistry , Catalysis , Photochemical Processes , Humans , Polymerization , Silanes/chemistry
8.
J Org Chem ; 89(14): 9937-9948, 2024 Jul 19.
Article in English | MEDLINE | ID: mdl-38985331

ABSTRACT

Baloxavir marboxil (1; BXM) is a potent drug used for treating influenza infections. The current synthetic route to BXM (1) is based on optical resolution; however, this method results in the loss of nearly 50% of the material. This study aimed to describe an efficient and simpler method for the synthesis of BXM. We achieved a stereoselective synthesis of BXM (1). The tricyclic triazinanone core possessing a chiral center was prepared via diastereoselective cyclization utilizing the readily available amino acid l-serine. The carboxyl moiety derived from l-serine was removed via photoredox decarboxylation under mild conditions to furnish the chiral tricyclic triazinanone core ((R)-14). The synthetic route demonstrated herein provides an efficient and atomically economical method for preparing this potent anti-influenza agent.


Subject(s)
Dibenzothiepins , Serine , Stereoisomerism , Cyclization , Serine/chemistry , Molecular Structure , Dibenzothiepins/chemistry , Dibenzothiepins/chemical synthesis , Triazines/chemistry , Triazines/chemical synthesis , Oxidation-Reduction , Decarboxylation , Morpholines/chemistry , Morpholines/chemical synthesis , Pyridones/chemistry , Pyridones/chemical synthesis , Photochemical Processes , Antiviral Agents/chemical synthesis , Antiviral Agents/chemistry
9.
Luminescence ; 39(7): e4817, 2024 Jul.
Article in English | MEDLINE | ID: mdl-39019841

ABSTRACT

Alternate antibiotics developed through the involvement of nanomaterials are gaining interest due to their economical and lower toxicity concerns. A newly developed biopolymer-based polyvinylpyrrolidone/zinc oxide (PVP/ZnO) nanocomposite (NCs) was efficiently synthesized by an environment-friendly approach, utilizing onion and garlic peel extract as a bio-surfactant, zinc acetate as the source, PVP as the stabilizing agent, and sodium hydroxide as the precipitant. Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) investigations verified the crystalline properties of ZnO, PVP, and PVP/ZnO-based NCs. The structure of the biopolymer-linked ZnO particles interpolated inside the PVP array was seen to have a layered and flaky structure, as validated by field emission scanning electron microscopy (FE-SEM) analysis, which revealed its occurrence in the nanometer range. The XRD examination verified that the surface topographical image of PVP/ZnO NCs had an average thickness of 21 nm. The PVP/ZnO nanocrystals demonstrated exceptional photocatalytic efficacy, with a breakdown rate of 88% and almost 92% for the methylene blue dye. Therefore, the PVP/ZnO matrix exhibits superior antibacterial activity compared to other extracts, resulting in greater microbial suppression. The results above indicate that the ZnO-intercalated PVP array has a stronger reinforcing effect than other components. Hence, PVP/ZnO nanocrystals exhibit enormous potential as a favorable substance for environmental and biomedical intentions.


Subject(s)
Anti-Bacterial Agents , Nanocomposites , Photochemical Processes , Povidone , Zinc Oxide , Zinc Oxide/chemistry , Zinc Oxide/pharmacology , Povidone/chemistry , Nanocomposites/chemistry , Catalysis , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/chemical synthesis , Microbial Sensitivity Tests , Luminescence , Particle Size , Luminescent Agents/chemistry , Luminescent Agents/chemical synthesis , Methylene Blue/chemistry
10.
Environ Sci Pollut Res Int ; 31(32): 44828-44847, 2024 Jul.
Article in English | MEDLINE | ID: mdl-38955971

ABSTRACT

In the search of novel photocatalysts to increase the effect of visible light in photocatalysis, g-C3N4 (CN) has become a shining star. Rare earth metals have been used as dopant material to reinforce the photocatalytic activity of CN due to their unique electron configuration recently. In this present study, the pure and different amounts of Ho-doped g-C3N4 (HoCN) photocatalysts were successfully synthesized using urea as a precursor by the one-pot method. Morphological, structural, optical, and vibrational properties of the synthesized photocatalysts were characterized by SEM, EDX, XRD, TGA, XPS, FTIR, PL, TRPL, Raman, DRS, and BET analyses. In addition, theoretical calculations using density functional theory (DFT) were meticulously carried out to delve the changes in the structural and electronic structure of CN with holmium doping. According to calculations, the chemical potential, electrophilicity, and chemical softness are higher for HoCN, while HOMO-LUMO gap, dipole moment, and the chemical hardness are lower for the pure one. Thus, holmium doping becomes desirable with low chemical hardness which indicates more effectivity and smaller HOMO-LUMO gap designate high chemical reactivity. To determine the photocatalytic efficiency of the pure and doped CN photocatalysts, the degradation of methylene blue (MB) was monitored under visible light. The results indicate that holmium doping has improved the photocatalytic activities of CN samples. Most strikingly, this improvement is noticeable for the 0.2 mmol doped CN sample that showed two times better photocatalytic activity than the pure one.


Subject(s)
Holmium , Light , Catalysis , Holmium/chemistry , Density Functional Theory , Photochemical Processes
11.
Anal Chem ; 96(28): 11273-11279, 2024 Jul 16.
Article in English | MEDLINE | ID: mdl-38967040

ABSTRACT

Fast Photochemical Oxidation of Proteins (FPOP) is a protein footprinting method utilizing hydroxyl radicals to provide valuable information on the solvent-accessible surface area. The extensive number of oxidative modifications that are created by FPOP is both advantageous, leading to great spatial resolution, and challenging, increasing the complexity of data processing. The precise localization of the modification together with the appropriate reproducibility is crucial to obtain relevant structural information. In this paper, we propose a novel approach combining validated spectral libraries together with utilizing DIA data. First, the DDA data searched by FragPipe are subsequently validated using Skyline software to form a spectral library. This library is then matched against the DIA data to filter out nonrepresentative IDs. In comparison with FPOP data processing using only a search engine followed by generally applied filtration steps, the manually validated spectral library offers higher confidence in identifications and increased spatial resolution. Furthermore, the reproducibility of quantification was compared for DIA, DDA, and MS-only acquisition modes on timsTOF SCP. Comparison of coefficients of variation (CV) showed that the DIA and MS acquisition modes exhibit significantly better reproducibility in quantification (CV medians 0.1233 and 0.1494, respectively) compared to the DDA mode (CV median 0.2104).


Subject(s)
Oxidation-Reduction , Photochemical Processes , Proteins , Proteins/chemistry , Proteins/analysis , Hydroxyl Radical/chemistry , Hydroxyl Radical/analysis , Software
12.
Anal Methods ; 16(28): 4691-4699, 2024 Jul 18.
Article in English | MEDLINE | ID: mdl-38973362

ABSTRACT

Herein, a new dual-model photoelectrochemical (PEC)/electrochemical (EC) sensor based on Z-scheme titanium dioxide (TiO2) disk/methylene blue (MB) sensibilization for the detection of kanamycin (Kana) was developed. Metal-organic framework-derived porous TiO2 disks were synthesized and exhibited excellent anodic photocurrent under visible light excitation. Subsequently, amino-labeled double-stranded DNA (dsDNA) was introduced into the modified electrode. Photocurrent was enhanced with MB embedded in dsDNA to form Z-scheme TiO2/MB sensibilization. When the target, Kana, was present, it specifically bound to the aptamer in the dsDNA, leading to the disruption of the dsDNA structure and the release of MB. This release of MB and the increase in target spatial resistance resulted in a significant weakening of PEC signal and a decreased oxidation peak current of MB. The PEC sensor successfully detected Kana in the range of 2-1000 pM with an LOD of 0.17 pM. Meanwhile, the EC sensor for Kana detection showed a linear range of 5-500 pM with an LOD of 1.8 pM. Additionally, the sensor exhibited excellent selectivity, reproducibility, stability, and good recoveries when applied to milk and honey samples. As a result, this method has the potential for application in ensuring food safety through the rapid determination of antibiotics in food.


Subject(s)
Electrochemical Techniques , Kanamycin , Methylene Blue , Milk , Titanium , Titanium/chemistry , Kanamycin/analysis , Kanamycin/chemistry , Methylene Blue/chemistry , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Milk/chemistry , Animals , Limit of Detection , Biosensing Techniques/methods , Honey/analysis , Anti-Bacterial Agents/analysis , Anti-Bacterial Agents/chemistry , Photochemical Processes , Reproducibility of Results , Electrodes
13.
Anal Chim Acta ; 1317: 342911, 2024 Aug 15.
Article in English | MEDLINE | ID: mdl-39030011

ABSTRACT

Natural products-based screening of active ingredients and their interactions with target proteins is an important ways to discover new drugs. Assessing the binding capacity of target proteins, particularly when multiple components are involved, presents a significant challenge for sensors. As far as we know, there is currently no sensor that can accomplish high-throughput quantitative analysis of natural product-target protein binding capacity based on Raman spectroscopy. In this study, a novel sensor model has been developed for the quantitative analysis of binding capacity based on Surface-Enhanced Raman Spectroscopy (SERS) and Photocrosslinked Molecular Probe (PCMP) technology. This sensor, named SERS-PCMP, leverages the high throughput of molecular probe technology to investigate the active ingredients in natural products, along with the application of SERS labelling technology for target proteins. Thus it significantly improves the efficiency and accuracy of target protein identification. Based on the novel strategy, quantitative analysis of the binding capacity of 20 components from Shenqi Jiangtang Granules (SJG) to α-Glucosidase were completed. Ultimately, the binding capacity of these active ingredients was ranked based on the detected Raman Intensity. The compounds with higher binding capacity were Astragaloside IV (Intensity, 138.17), Ginsenoside Rh2 (Intensity, 87.46), Ginsenoside Rg3 (Intensity, 73.92) and Ginsenoside Rh1 (Intensity, 64.37), which all exceeded the binding capacity of the positive drug Acarbose (Intensity, 28.75). Furthermore, this strategy also performed a high detection sensitivity. The limit of detection for the enzyme using 0.1 mg of molecular probe magnetic nanoparticles (MP MNPs) was determined to be no less than 0.375 µg/mL. SERS-PCMP sensor integrating SERS labeling and photocrosslinked molecular probes which offers a fresh perspective for future drug discovery studies. Such as high-throughput drug screening and the exploration of small molecule-target protein interactions in vitro.


Subject(s)
Biological Products , Molecular Probes , Spectrum Analysis, Raman , Spectrum Analysis, Raman/methods , Biological Products/chemistry , Biological Products/analysis , Molecular Probes/chemistry , alpha-Glucosidases/metabolism , alpha-Glucosidases/chemistry , Protein Binding , Photochemical Processes , Cross-Linking Reagents/chemistry , Silver/chemistry
14.
Anal Chim Acta ; 1317: 342910, 2024 Aug 15.
Article in English | MEDLINE | ID: mdl-39030010

ABSTRACT

Highly sensitive and rapid detection of ethylene, the smallest alkene of great significance in human physiological metabolism remains a great challenge. In this study, we developed a new photoionization-induced substitution reaction chemical ionization time-of-flight mass spectrometry (PSCI-TOFMS) for trace exhaled ethylene detection. An intriguing ionization phenomenon involving a substitution reaction between the CH2Br2+ reactant ion and ethylene molecule was discovered and studied for the first time. The formation of readily identifiable [CH2Br·C2H4]+ product ion greatly enhanced the ionization efficiency of ethylene, which led to approximately 800-fold improvement of signal intensity over that in single photon ionization mode. The CH2Br2+ reactant ion intensity and ion-molecule reaction time were optimized, and a Nafion tube was employed to eliminate the influence of humidity on the ionization of ethylene. Consequently, a limit of detection (LOD) as low as 0.1 ppbv for ethylene was attained within 30 s at 100 % relative humidity. The application of PSCI-TOFMS on the rapid detection of trace amounts of exhaled ethylene from healthy smoker and non-smoker volunteers demonstrated the satisfactory performance and potential of this system for trace ethylene measurement in clinical diagnosis, atmospheric measurement, and process monitoring.


Subject(s)
Ethylenes , Ethylenes/chemistry , Ethylenes/analysis , Humans , Limit of Detection , Breath Tests/methods , Photochemical Processes , Exhalation , Mass Spectrometry/methods
15.
Anal Chim Acta ; 1317: 342920, 2024 Aug 15.
Article in English | MEDLINE | ID: mdl-39030014

ABSTRACT

BACKGROUND: As a broad-spectrum tetracycline antibiotic, Oxytetracycline (OTC) was widely used in a variety of applications. But, the overuse of OTC had led to the detection of it in food, water and soil, which could present significance risk to human health and cause damage to ecosystem. It was of great significance to develop sensitive detection methods for OTC. Herein, an environmentally friendly photoelectrochemical (PEC) aptasensor was constructed for the sensitive detection of OTC based on CuO-induced BiOBr/Ag2S/PDA (Polydopamine) photocurrent polarity reversal. RESULTS: BiOBr/Ag2S/PDA composites modified electrode not only produced stable initial anodic photocurrent but also provided attachment sites for the aptamer S1 of OTC by the strong adhesion of PDA. On the other hand, CuO loaded OTC aptamer S2 (Cu-S2) was got through Cu-S bonds. After the target OTC was identified on the electrode surface, CuO was introduced to the surface of ITO/BiOBr/Ag2S/PDA through the specific binding of OTC to S2. This identification process formed dual Z-type heterojunctions and resulted in a remarkable reversal of photocurrent polarity from anodic to cathodic. Under optimization conditions, the PEC aptasensor showed a wide linear range (50 fM âˆ¼ 100 nM), low detection limit (1.9 fM), excellent selectivity, stability and reproducibility for the detection of OTC. Moreover, it was successfully used for the analysis of OTC in real samples of tap water, milk and honey, and had the potential for practical application. SIGNIFICANCE: This work developed an environmentally friendly photocurrent-polarity-switching PEC aptasensor with excellent selectivity, reproducibility, stability, low LOD and wide linear range for OTC detection. This sensitive system, which was including BiOBr, Ag2S, PDA and CuO were low toxicity, not only reduced the risk of traditional toxic semiconductors to operators and the environment, but can also be used for the detection of real samples, broadening the wider range of applications for BiOBr, Ag2S, PDA and CuO.


Subject(s)
Aptamers, Nucleotide , Biosensing Techniques , Bismuth , Copper , Electrochemical Techniques , Oxytetracycline , Oxytetracycline/analysis , Copper/chemistry , Aptamers, Nucleotide/chemistry , Electrochemical Techniques/methods , Bismuth/chemistry , Photochemical Processes , Silver Compounds/chemistry , Polymers/chemistry , Electrodes , Animals , Limit of Detection , Indoles/chemistry , Anti-Bacterial Agents/analysis , Anti-Bacterial Agents/chemistry
16.
Luminescence ; 39(7): e4818, 2024 Jul.
Article in English | MEDLINE | ID: mdl-39004769

ABSTRACT

Fexofenadine (FEX) is a non-sedating antihistamine commonly used for the treatment of allergic conditions such as seasonal rhinitis and chronic idiopathic urticaria. This study describes the tuning "ON" the intrinsic fluorescence of FEX by switching "OFF" its intramolecular photoinduced electron transfer (PET) through the protonation of the piperidinyl nitrogen atom using sulfuric acid. The resulting fluorescence was utilized as a basis for the development of a highly sensitive microwell spectrofluorimetric assay (MW-SFA) for the one-step determination of FEX in pharmaceutical tablets and plasma. The linear range of the assay was 10-500 ng ml-1, and its limit of quantitation was 25.9 ng ml-1. The proposed MW-SFA was successfully applied to analyze FEX in pharmaceutical tablets and plasma samples, demonstrating good accuracy and precision. The greenness of the assay was confirmed using three metric assessment tools. In conclusion, the MW-SFA is a straightforward, single-step analysis that requires no experimental adjustments. It offers high sensitivity, efficient sample processing, and environmental sustainability. This assay is highly recommended for pharmaceutical quality control and clinical lab use, particularly for measuring FEX levels.


Subject(s)
Spectrometry, Fluorescence , Tablets , Terfenadine , Terfenadine/analogs & derivatives , Terfenadine/blood , Terfenadine/analysis , Terfenadine/chemistry , Electron Transport , Humans , Fluorescence , Photochemical Processes , High-Throughput Screening Assays , Molecular Structure
17.
Environ Sci Technol ; 58(28): 12554-12562, 2024 Jul 16.
Article in English | MEDLINE | ID: mdl-38959497

ABSTRACT

Dissecting the photochemical reactivity of metal ions is a significant contribution to understanding secondary pollutant formation, as they have a role to be reckoned with atmospheric chemistry. However, their photochemical reactivity has received limited attention within the active nitrogen cycle, particularly at the gas-solid interface. In this study, we delve into the contribution of magnesium ion (Mg2+) and ferric ion (Fe3+) to nitrate decomposition on the surface of photoactive mineral dust. Under simulated sunlight irradiation, the observed NOX production rate differs by an order of magnitude in the presence of Mg2+ (6.02 × 10-10 mol s-1) and Fe3+ (2.07 × 10-11 mol s-1). The markedly decreased fluorescence lifetime induced by Mg2+ and the change in the valence of Fe3+ revealed that Mg2+ and Fe3+ significantly affect the concentration of nitrate decomposition products by distinct photochemical reactivity with photogenerated electrons. Mg2+ promotes NOX production by accelerating charge transfer, while Fe3+ hinders nitrate decomposition by engaging in a redox cyclic reaction with Fe2+ to consume photogenerated carriers continuously. Furthermore, when Fe3+ coexists with other metal ions (e.g., Mg2+, Ca2+, Na+, and K+) and surpasses a proportion of approximately 12%, the photochemical reactivity of Fe3+ tends to be dominant in depleting photogenerated electrons and suppressing nitrate decomposition. Conversely, below this threshold, the released NOX concentration increases sharply as the proportion of Fe3+ decreases. This research offers valuable insights into the role of metal ions in nitrate transformation and the generation of reactive nitrogen species, contributing to a deep understanding of atmospheric photochemical reactions.


Subject(s)
Metals , Nitrates , Nitrates/chemistry , Metals/chemistry , Minerals/chemistry , Dust , Atmosphere/chemistry , Ions , Photochemical Processes
18.
Anal Chem ; 96(28): 11525-11532, 2024 Jul 16.
Article in English | MEDLINE | ID: mdl-38966896

ABSTRACT

The urgent need for field detection of uranium in seawater is 2-fold: to provide prompt guidance for uranium extraction and to prevent human exposure to nuclear radiation. However, current methods for this purpose are largely hindered by bulky instrumentation, high costs of developed materials, and severe matrix interferences, which limit their further application in the field. Herein, we demonstrated a portable and label-free strategy for the field detection of uranyl in seawater based on the efficient photocleavage of DNA. Further experiments confirmed the generation of ultraviolet (UV) light-induced reactive oxygen species (ROS), such as O2•- and •OH, which fragmented oligomeric DNA in the presence of uranyl and UV light. Detailed studies showed that DNA significantly enhances uranyl absorption in the UV-visible region, leading to the generation of more ROS. A fluorescence system for the selective detection of uranyl in seawater was established by immobilizing two complementary oligonucleotides with the fluorescent dye SYBR Green I. The strategy of UV-induced photocleavage offers high selectivity, excellent interference immunity, and high sensitivity for uranyl, with a detection limit of 6.8 nM. Additionally, the fluorescence can be visually detected using a 3D-printed miniaturized device integrated with a smartphone. This method has been successfully applied to the on-site detection of uranyl in seawater in 18 Chinese coastal cities and along the coast of Hainan Island within 3 min for a single sample. The sample testing and field analysis results indicate that this strategy has promising potential for real-time monitoring of trace uranyl in China's coastal waters. It is expected to be utilized for the rapid assessment of nuclear contamination and nuclear engineering construction.


Subject(s)
DNA , Seawater , Ultraviolet Rays , Uranium , Seawater/analysis , Seawater/chemistry , DNA/analysis , China , Uranium/analysis , Fluorescent Dyes/chemistry , Reactive Oxygen Species/analysis , Limit of Detection , Photochemical Processes , Diamines , Benzothiazoles/chemistry , Organic Chemicals/analysis , Organic Chemicals/chemistry , Quinolines
19.
Int J Mol Sci ; 25(13)2024 Jun 22.
Article in English | MEDLINE | ID: mdl-38999979

ABSTRACT

This study presents a pioneering synthesis of a direct Z-scheme Y2TmSbO7/GdYBiNbO7 heterojunction photocatalyst (YGHP) using an ultrasound-assisted hydrothermal synthesis technique. Additionally, novel photocatalytic nanomaterials, namely Y2TmSbO7 and GdYBiNbO7, were fabricated via the hydrothermal fabrication technique. A comprehensive range of characterization techniques, including X-ray diffractometry, Fourier-transform infrared spectroscopy, Raman spectroscopy, UV-visible spectrophotometry, X-ray photoelectron spectroscopy, transmission electron microscopy, X-ray energy-dispersive spectroscopy, fluorescence spectroscopy, photocurrent testing, electrochemical impedance spectroscopy, ultraviolet photoelectron spectroscopy, and electron paramagnetic resonance, was employed to thoroughly investigate the morphological features, composition, chemical, optical, and photoelectric properties of the fabricated samples. The photocatalytic performance of YGHP was assessed in the degradation of the pesticide acetochlor (AC) and the mineralization of total organic carbon (TOC) under visible light exposure, demonstrating eximious removal efficiencies. Specifically, AC and TOC exhibited removal rates of 99.75% and 97.90%, respectively. Comparative analysis revealed that YGHP showcased significantly higher removal efficiencies for AC compared to the Y2TmSbO7, GdYBiNbO7, or N-doped TiO2 photocatalyst, with removal rates being 1.12 times, 1.21 times, or 3.07 times higher, respectively. Similarly, YGHP demonstrated substantially higher removal efficiencies for TOC than the aforementioned photocatalysts, with removal rates 1.15 times, 1.28 times, or 3.51 times higher, respectively. These improvements could be attributed to the Z-scheme charge transfer configuration, which preserved the preferable redox capacities of Y2TmSbO7 and GdYBiNbO7. Furthermore, the stability and durability of YGHP were confirmed, affirming its potential for practical applications. Trapping experiments and electron spin resonance analyses identified active species generated by YGHP, namely •OH, •O2-, and h+, allowing for comprehensive analysis of the degradation mechanisms and pathways of AC. Overall, this investigation advances the development of efficient Z-scheme heterostructural materials and provides valuable insights into formulating sustainable remediation strategies for combatting AC contamination.


Subject(s)
Light , Toluidines , Catalysis , Toluidines/chemistry , Photolysis , Water Pollutants, Chemical/chemistry , Photochemical Processes , Photoelectron Spectroscopy , Gadolinium/chemistry
20.
ACS Appl Bio Mater ; 7(7): 4580-4592, 2024 Jul 15.
Article in English | MEDLINE | ID: mdl-38958462

ABSTRACT

Nanomaterial-mediated antibacterial photodynamic therapy (aPDT) emerges as a promising treatment against antibiotic-resistant bacterial biofilms. Specifically, titanium dioxide nanoparticles (TiO2 NPs) are being investigated as photosensitizers in aPDT to address biofilm related diseases. To enhance their photocatalytic performance in the visible spectral range for biomedical applications, various strategies have been adopted, including reduction of TiO2 NPs. However, despite improvements in visible-light photoactivity, reduced TiO2 NPs have yet to reach their expected performance primarily due to the instability of oxygen vacancies and their tendency to reoxidize easily. To address this, we present a two-step approach to fabricate highly visible-light active and stable TiO2 NP photocatalysts, involving nitrogen doping followed by a magnesium-assisted reductive annealing process. X-ray photoelectron spectroscopy analysis of the synthesized reduced nitrogen-doped TiO2 NPs (H:Mg-N-TiO2 NPs) reveals that the presence of nitrogen stabilizes oxygen vacancies and reduced Ti species, leading to increased production of reactive oxygen species under visible-light excitation. The improved aPDT efficiency translates to a 3-fold enhancement in the antibiofilm activity of nitrogen-doped compared to undoped reduced TiO2 NPs against both Gram-positive (Streptococcus mutans) and Gram-negative (Porphyromonas gingivalis, Fusobacterium nucleatum) oral pathogens. These results underscore the potential of H:Mg-N-TiO2 NPs in aPDT for combating bacterial biofilms effectively.


Subject(s)
Anti-Bacterial Agents , Biofilms , Materials Testing , Nitrogen , Particle Size , Titanium , Titanium/chemistry , Titanium/pharmacology , Biofilms/drug effects , Nitrogen/chemistry , Nitrogen/pharmacology , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/chemical synthesis , Catalysis , Nanoparticles/chemistry , Microbial Sensitivity Tests , Light , Biocompatible Materials/chemistry , Biocompatible Materials/pharmacology , Photochemical Processes
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