ABSTRACT
Dissolved copper and iron ions are regarded as friendly and economic catalysts for peroxymonosulfate (PMS) activation, however, neither Cu(II) nor Fe(III) shows efficient catalytic performance because of the slow rates of Cu(II)/Cu(I) and Fe(III)/Fe(II) cycles. Innovatively, we observed a significant enhancement on the degradation of organic contaminants when Cu(II) and Fe(III) were coupled to activate PMS in borate (BA) buffer. The degradation efficiency of Rhodamine B (RhB, 20 µmol/L) reached up to 96.3% within 10 min, which was higher than the sum of individual Cu(II)- and Fe(III)- activated PMS process. Sulfate radical, hydroxyl radical and high-valent metal ions (i.e., Cu(III) and Fe(IV)) were identified as the working reactive species for RhB removal in Cu(II)/Fe(III)/PMS/BA system, while the last played a predominated role. The presence of BA dramatically facilitated the reduction of Cu(II) to Cu(I) via chelating with Cu(II) followed by Fe(III) reduction by Cu(I), resulting in enhanced PMS activation by Cu(I) and Fe(II) as well as accelerated generation of reactive species. Additionally, the strong buffering capacity of BA to stabilize the solution pH was satisfying for the pollutants degradation since a slightly alkaline environment favored the PMS activation by coupling Cu(II) and Fe(III). In a word, this work provides a brand-new insight into the outstanding PMS activation by homogeneous bimetals and an expanded application of iron-based advanced oxidation processes in alkaline conditions.
Subject(s)
Copper , Peroxides , Water Pollutants, Chemical , Copper/chemistry , Water Pollutants, Chemical/chemistry , Peroxides/chemistry , Catalysis , Iron/chemistry , Rhodamines/chemistry , Oxidation-ReductionABSTRACT
In this study, non-thermal plasma (NTP) was employed to modify the Cu/TiO2 adsorbent to efficiently purify H2S in low-temperature and micro-oxygen environments. The effects of Cu loading amounts and atmospheres of NTP treatment on the adsorption-oxidation performance of the adsorbents were investigated. The NTP modification successfully boosted the H2S removal capacity to varying degrees, and the optimized adsorbent treated by air plasma (Cu/TiO2-Air) attained the best H2S breakthrough capacity of 113.29 mg H2S/gadsorbent, which was almost 5 times higher than that of the adsorbent without NTP modification. Further studies demonstrated that the superior performance of Cu/TiO2-Air was attributed to increased mesoporous volume, more exposure of active sites (CuO) and functional groups (amino groups and hydroxyl groups), enhanced Ti-O-Cu interaction, and the favorable ratio of active oxygen species. Additionally, the X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results indicated the main reason for the deactivation was the consumption of the active components (CuO) and the agglomeration of reaction products (CuS and SO42-) occupying the active sites on the surface and the inner pores of the adsorbents.
Subject(s)
Copper , Hydrogen Sulfide , Oxidation-Reduction , Titanium , Titanium/chemistry , Adsorption , Copper/chemistry , Hydrogen Sulfide/chemistry , Air Pollutants/chemistry , Plasma Gases/chemistry , Models, ChemicalABSTRACT
Catalytic reduction of nitrate over bimetallic catalysts has emerged as a technology for sustainable treatment of nitrate-containing groundwater. However, the structure of bimetallic has been much less investigated for catalyst optimization. Herein, two main types of Pd-Cu bimetallic nanocrystal structures, heterostructure and intermetallic, were prepared and characterized using high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results show that two individual Pd and Cu nanocrystals with a mixed interface exist in the heterostructure nanocrystals, while Pd and Cu atoms are uniformly distributed across the intermetallic Pd-Cu nanocrystals. The catalytic nitrate reduction experiments were carried out in a semibatch reactor under constant hydrogen flow. The nitrate conversion rate of the heterostructure Pd-Cu nanocrystals supported on α-Al2O3, γ-Al2O3, SBA-15, and XC-72R exhibited 3.82-, 6.76-, 4.28-, 2.44-fold enhancements relative to the intermetallic nanocrystals, and the nitrogen and nitrite were the main products for the heterostructure and intermetallic Pd-Cu nanocrystals, respectively. This indicates that the catalytic nitrate reduction over Pd-Cu catalyst is sensitive to the bimetallic structures of the catalysts, and heterostructure bimetallic nanocrystals exhibit better catalytic performances on both the activity and selectivity, which may provide new insights into the design and optimization of catalysts to improve catalytic activity and selectivity for nitrate reduction in water.
Subject(s)
Copper , Nitrates , Oxidation-Reduction , Palladium , Catalysis , Copper/chemistry , Palladium/chemistry , Nitrates/chemistry , Metal Nanoparticles/chemistry , Nanoparticles/chemistry , Water Pollutants, Chemical/chemistry , Models, ChemicalABSTRACT
Electrocatalytic reduction of nitrate to ammonia has been considered a promising and sustainable pathway for pollutant treatment and ammonia has significant potential as a clean energy. Therefore, the method has received much attention. In this work, Cu/Fe 2D bimetallic metal-organic frameworks were synthesized by a facile method applied as cathode materials without high-temperature carbonization. Bimetallic centers (Cu, Fe) with enhanced intrinsic activity demonstrated higher removal efficiency. Meanwhile, the 2D nanosheet reduced the mass transfer barrier between the catalyst and nitrate and increased the reaction kinetics. Therefore, the catalysts with a 2D structure showed much better removal efficiency than other structures (3D MOFs and Bulk MOFs). Under optimal conditions, Cu/Fe-2D MOF exhibited high nitrate removal efficiency (87.8%) and ammonium selectivity (89.3%) simultaneously. The ammonium yielded up to significantly 907.2 µg/(hr·mgcat) (7793.8 µg/(hr·mgmetal)) with Faradaic efficiency of 62.8% at an initial 100 mg N/L. The catalyst was proved to have good stability and was recycled 15 times with excellent effect. DFT simulations confirm the reduced Gibbs free energy of Cu/Fe-2D MOF. This study demonstrates the promising application of Cu/Fe-2D MOF in nitrate reduction to ammonia and provides new insights for the design of efficient electrode materials.
Subject(s)
Ammonia , Copper , Iron , Metal-Organic Frameworks , Nitrates , Water Pollutants, Chemical , Ammonia/chemistry , Copper/chemistry , Nitrates/chemistry , Metal-Organic Frameworks/chemistry , Iron/chemistry , Water Pollutants, Chemical/chemistry , Catalysis , Models, Chemical , Oxidation-Reduction , KineticsABSTRACT
Herein, three supported catalysts, CuO/Al2O3, CeO2/Al2O3, and CuO-CeO2/Al2O3, were synthesized by the convenient impregnation method to reveal the effect of CeO2 addition on catalytic performance and reaction mechanism for toluene oxidation. Compared with CuO/Al2O3, the T50 and T90 (the temperatures at 50% and 90% toluene conversion, respectively) of CuO-CeO2/Al2O3 were reduced by 33 and 39 °C, respectively. N2 adsorption-desorption experiment, XRD, SEM, EDS mapping, Raman, EPR, H2-TPR, O2-TPD, XPS, NH3-TPD, Toluene-TPD, and in-situ DRIFTS were conducted to characterize these catalysts. The excellent catalytic performance of CuO-CeO2/Al2O3 could be attributed to its strong copper-cerium interaction and high oxygen vacancies concentration. Moreover, in-situ DRIFTS proved that CuO-CeO2/Al2O3 promoted the conversion of toluene to benzoate and accelerated the deep degradation path of toluene. This work provided valuable insights into the development of efficient and economical catalysts for volatile organic compounds.
Subject(s)
Cerium , Copper , Oxidation-Reduction , Toluene , Toluene/chemistry , Catalysis , Copper/chemistry , Cerium/chemistry , Models, Chemical , Air Pollutants/chemistryABSTRACT
Pesticides in environmental samples pose significant risks to ecosystems and human health since they require precise and efficient detection methods. Imidacloprid (IMI), a widely used neonicotinoid insecticide, exemplifies these hazards due to its potential toxicity. This study addresses the urgent need for improved monitoring of such contaminants by introducing a novel fluorometric method for detecting IMI using nitrogen-doped graphite carbon dots (N-GCDs). The sensor operates by quenching fluorescence through the interaction of Cu2+ ions with N-GCDs. Subsequently, IMI binds to the imidazole group, chelates with Cu2+, and restores the fluorescence of N-GCDs. This alternating fluorescence behavior allows for the accurate identification of both Cu2+ and IMI. The sensor exhibits linear detection ranges of 20-100 nM for Cu2+ and 10-140 µg/L for IMI, with detection limits of 18 nM and 1.2 µg/L, respectively. The high sensitivity of this sensor enables the detection of real-world samples, which underscores its potential for practical use in environmental monitoring and agricultural safety.
Subject(s)
Copper , Environmental Monitoring , Fluorometry , Graphite , Neonicotinoids , Nitro Compounds , Nitrogen , Quantum Dots , Neonicotinoids/analysis , Neonicotinoids/chemistry , Nitro Compounds/chemistry , Nitro Compounds/analysis , Copper/chemistry , Copper/analysis , Nitrogen/chemistry , Graphite/chemistry , Quantum Dots/chemistry , Insecticides/analysis , Insecticides/chemistry , Imidazoles/chemistryABSTRACT
The treatment of wound inflammation is intricately linked to the concentration of reactive oxygen species (ROS) in the wound microenvironment. Among these ROS, H2O2 serves as a critical signaling molecule and second messenger, necessitating the urgent need for its rapid real-time quantitative detection, as well as effective clearance, in the pursuit of effective wound inflammation treatment. Here, we exploited a sophisticated 3D Cu2- x Se/GO nanostructure-based nanonzymatic H2O2 electrochemical sensor, which is further decorated with evenly distributed Pt nanoparticles (Pt NPs) through electrodeposition. The obtained Cu2- x Se/GO@Pt/SPCE sensing electrode possesses a remarkable increase in specific surface derived from the three-dimensional surface constructed by GO nanosheets. Moreover, the localized surface plasma effect of the Cu2- x Se nanospheres enhances the separation of photogenerated electron-hole pairs between the interface of the Cu2- x Se NPs and the Pt NPs. This innovation enables near-infrared light-enhanced catalysis, significantly reducing the detection limit of the Cu2- x Se/GO@Pt/SPCE sensing electrode for H2O2 (from 1.45 µM to 0.53µM) under NIR light. Furthermore, this biosensor electrode enables in-situ real-time monitoring of H2O2 released by cells. The NIR-enhanced Cu2- x Se/GO@Pt/SPCE sensing electrode provide a simple-yet-effective method to achieve a detection of ROS (H2O2ã-OH) with high sensitivity and efficiency. This innovation promises to revolutionize the field of wound inflammation treatment by providing clinicians with a powerful tool for accurate and rapid assessment of ROS levels, ultimately leading to improved patient outcomes.
Subject(s)
Copper , Hydrogen Peroxide , Inflammation , Metal Nanoparticles , Platinum , Hydrogen Peroxide/metabolism , Platinum/chemistry , Copper/chemistry , Metal Nanoparticles/chemistry , Inflammation/metabolism , Animals , Mice , Nanostructures/chemistry , Biosensing Techniques/methods , Selenium/chemistry , Humans , Infrared Rays , Reactive Oxygen Species/metabolism , RAW 264.7 CellsABSTRACT
An ultrasensitive photothermal assay was designed for point-of-care testing (POCT) of tumor markers based on a filter membrane. Firstly, Cu2-xSe was successfully encapsulated in liposome spheres with biotin on the surface and connected to carcinoembryonic antigen (CEA) aptamer with 3'end modified biotin by streptavidin. Secondly, the CEA antibody was successfully modified on the surface of the nitrocellulose membrane through simple incubation. Finally, the assay process was completed using a disposable syringe, and the temperature was recorded using a handheld infrared temperature detector. In the range 0-50 ng mL-1, the temperature change of the nitrocellulose membrane has a strong linear relationship with CEA concentration, and the detection limit is 0.097 ng mL-1. It is worth noting that the entire testing process can be easily performed in 10 min, much shorter than traditional clinical methods. In addition, this method was successfully applied to the quantitative determination of CEA levels in human serum samples with a recovery of 96.2-103.3%. This rapid assay can be performed by "one suction and one push" through a disposable syringe, which is simple to operate, and the excellent sensitivity reveals the great potential of the proposed strategy in the POCT of tumor biomarkers.
Subject(s)
Aptamers, Nucleotide , Biomarkers, Tumor , Carcinoembryonic Antigen , Copper , Limit of Detection , Humans , Carcinoembryonic Antigen/blood , Copper/chemistry , Aptamers, Nucleotide/chemistry , Biomarkers, Tumor/blood , Liposomes/chemistry , Biosensing Techniques/methods , Point-of-Care Systems , Temperature , Biotin/chemistry , Point-of-Care Testing , Collodion/chemistryABSTRACT
A sequential dual-locked luminescent copper nanoclusters (CuNCs) probe was designed and synthesized for the specific imaging and selective killing of tumor cells. This nanoprobe was prepared by first forming a Fe3+-coupled tannic acid (TA)-stabilized CuNCs (CuNCs-FeIII), which is in quenching state due to the electron transfer between CuNCs and Fe3+, and then coating a protectable layer of hyaluronic acid (HA) on the surface of CuNCs-FeIII to form the final dual-locked nanoprobe (CuNCs-FeIII@HA). When the nanoprobe of CuNCs-FeIII@HA target enter the tumor cells through CD44-HA receptor, HAase will first digest the HA layer of the nanoprobes, and then, GSH over-expressed in tumor cells will reduce Fe3+ to Fe2+, thus restoring the fluorescence emission of CuNCs and at the same time killing the tumor cells with the hydroxyl free radicals (âOH) produced by the Fenton reaction between Fe2+ and H2O2. This sequential dual-locked luminescent nanoprobe of CuNCs-FeIII@HA has been successfully used for the specific imaging and selective killing of tumor cells.
Subject(s)
Copper , Copper/chemistry , Humans , Metal Nanoparticles/chemistry , Hyaluronic Acid/chemistry , Tannins/chemistry , Optical Imaging , Fluorescent Dyes/chemistry , Cell Survival/drug effects , Luminescent Agents/chemistry , Luminescent Agents/chemical synthesis , Cell Line, Tumor , Hydroxyl Radical/chemistry , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Hydrogen Peroxide/chemistryABSTRACT
Cupric ions (Cu2+), pyrophosphate (PPi), and alkaline phosphatase (ALP) are involved in a variety of biochemical processes such as DNA replication, cellular metabolism and play an important role in human growth and development. It is of great significance to establish a method for the sensitive detection of Cu2+, PPi and ALP. In this work, polyethyleneimine-capped silver nanoclusters (PEI-AgNCs) were successfully synthesized by a one-pot method using hydrazine sulfate as reductant, exhibiting a unique strong fluorescence emission in the near-ultraviolet region at â¼339 nm. Since the fluorescence of PEI-AgNCs can be quenched by Cu2+ through inner filtering effect (IFE), then recovered by competitive binding of pyrophosphate and Cu2+, and later weakened again by catalytic hydrolysis of alkaline phosphatase, a sensitive and selective strategy based on the changes of fluorescence "ON" or "OFF" was established to detect Cu2+, PPi and ALP. The LODs of these three analytes were 36 nM, 0.2 µM, and 0.14 U L-1 at a S/N ratio of 3, respectively. A series of logic gate circuits for sensing cupric ions, pyrophosphate, and alkaline phosphatase were successfully constructed. The established methods have the potential for biosensing and environmental analysis and the specific UV-A fluorescence property of PEI-AgNCs may be helpful in photonic and optical areas.
Subject(s)
Alkaline Phosphatase , Copper , Diphosphates , Metal Nanoparticles , Polyethyleneimine , Silver , Spectrometry, Fluorescence , Silver/chemistry , Polyethyleneimine/chemistry , Copper/chemistry , Metal Nanoparticles/chemistry , Alkaline Phosphatase/analysis , Alkaline Phosphatase/metabolism , Diphosphates/analysis , Diphosphates/chemistry , Spectrometry, Fluorescence/methods , Limit of Detection , Humans , Fluorescence , Ultraviolet RaysABSTRACT
A binary system of uridine-5'-diphosphoglucuronic acid with copper (II) ions was studied. Potentiometric studies in aqueous solutions using computer data analysis were carried out. The pH of dominance, the overall stability constants (logß), and the equilibrium constants of the formation reaction (logKe) were determined for each complex compound formed in the studied system. Spectroscopic studies were carried out to determine the mode of coordination in the compounds studied. Cytotoxicity and metabolic activity tests of the compounds obtained showed an increase in the biological activity of the complexes tested against the free ligand. The current research may contribute to the knowledge of complex compounds of biomolecules found in the human body and may also contribute to the characterization of a group of complex compounds with potential anticancer properties.
Subject(s)
Coordination Complexes , Copper , Thermodynamics , Copper/chemistry , Humans , Coordination Complexes/chemistry , Hydrogen-Ion Concentration , Potentiometry , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Cell Line, TumorABSTRACT
Amyotrophic lateral sclerosis (ALS) is characterized by degeneration of motor neurons in the central nervous system (CNS). Mutations in the metalloenzyme SOD1 are associated with inherited forms of ALS and cause a toxic gain of function thought to be mediated by dimer destabilization and misfolding. SOD1 binds two Cu and two Zn ions in its homodimeric form. We have applied native ambient mass spectrometry imaging to visualize the spatial distributions of intact metal-bound SOD1G93A complexes in SOD1G93A transgenic mouse spinal cord and brain sections and evaluated them against disease pathology. The molecular specificity of our approach reveals that metal-deficient SOD1G93A species are abundant in CNS structures correlating with ALS pathology whereas fully metalated SOD1G93A species are homogenously distributed. Monomer abundance did not correlate with pathology. We also show that the dimer-destabilizing post-translational modification, glutathionylation, has limited influence on the spatial distribution of SOD1 dimers.
Subject(s)
Amyotrophic Lateral Sclerosis , Brain , Mass Spectrometry , Mice, Transgenic , Spinal Cord , Superoxide Dismutase-1 , Animals , Superoxide Dismutase-1/genetics , Superoxide Dismutase-1/metabolism , Superoxide Dismutase-1/chemistry , Amyotrophic Lateral Sclerosis/genetics , Amyotrophic Lateral Sclerosis/metabolism , Amyotrophic Lateral Sclerosis/pathology , Mice , Spinal Cord/metabolism , Spinal Cord/pathology , Mass Spectrometry/methods , Brain/metabolism , Brain/diagnostic imaging , Brain/pathology , Copper/metabolism , Zinc/metabolism , Humans , Superoxide Dismutase/metabolism , Superoxide Dismutase/genetics , Superoxide Dismutase/chemistry , Mutation , Protein Processing, Post-Translational , Protein Multimerization , Disease Models, Animal , MaleABSTRACT
Copper is a trace element whose electronic configuration provides it with essential structural and catalytic functions. However, in excess, both its high protein affinity and redox-catalyzing properties can lead to hazardous consequences. In addition to promoting oxidative stress, copper is gaining interest for its effects on neurotransmission through modulation of GABAergic and glutamatergic receptors and interaction with the dopamine reuptake transporter. The aim of the present study was to investigate the effects of copper overexposure on the levels of dopamine, noradrenaline, and serotonin, or their main metabolites in rat's striatum extracellular fluid. Copper was injected intraperitoneally using our previously developed model, which ensured striatal overconcentration (2 mg CuCl2/kg for 30 days). Subsequently, extracellular fluid was collected by microdialysis on days 0, 15, and 30. Dopamine (DA), 3,4-dihydroxyphenylacetic acid (DOPAC), homovanillic acid (HVA), 5-hydroxyindoleacetic acid (5-HIAA), and noradrenaline (NA) levels were then determined by HPLC coupled with electrochemical detection. We observed a significant increase in the basal levels of DA and HVA after 15 days of treatment (310% and 351%), which was maintained after 30 days (358% and 402%), with no significant changes in the concentrations of 5-HIAA, DOPAC, and NA. Copper overload led to a marked increase in synaptic DA concentration, which could contribute to the psychoneurological alterations and the increased oxidative toxicity observed in Wilson's disease and other copper dysregulation states.
Subject(s)
Copper , Corpus Striatum , Dopamine , Extracellular Fluid , Homovanillic Acid , Animals , Dopamine/metabolism , Copper/metabolism , Homovanillic Acid/metabolism , Rats , Male , Extracellular Fluid/metabolism , Corpus Striatum/metabolism , 3,4-Dihydroxyphenylacetic Acid/metabolism , Rats, Wistar , Serotonin/metabolism , Norepinephrine/metabolismABSTRACT
The negative environmental and social impacts of food waste accumulation can be mitigated by utilizing bio-refineries' approach where food waste is revalorized into high-value products, such as prodigiosin (PG), using microbial bioprocesses. The diverse biological activities of PG position it as a promising compound, but its high production cost and promiscuous bioactivity hinder its wide application. Metal ions can modulate the electronic properties of organic molecules, leading to novel mechanisms of action and increased target potency, while metal complex formation can improve the stability, solubility and bioavailability of the parent compound. The objectives of this study were optimizing PG production through bacterial fermentation using food waste, allowing good quantities of the pure natural product for further synthesizing and evaluating copper(II) and zinc(II) complexes with it. Their antimicrobial and anticancer activities were assessed, and their binding affinity toward biologically important molecules, bovine serum albumin (BSA) and DNA was investigated by fluorescence emission spectroscopy and molecular docking. The yield of 83.1 mg/L of pure PG was obtained when processed meat waste at 18 g/L was utilized as the sole fermentation substrate. The obtained complexes CuPG and ZnPG showed high binding affinity towards target site III of BSA, and molecular docking simulations highlighted the affinity of the compounds for DNA minor grooves.
Subject(s)
Coordination Complexes , Copper , DNA , Molecular Docking Simulation , Prodigiosin , Serum Albumin, Bovine , Zinc , Prodigiosin/chemistry , Prodigiosin/metabolism , Prodigiosin/pharmacology , Copper/chemistry , Copper/metabolism , Zinc/metabolism , Zinc/chemistry , Serum Albumin, Bovine/chemistry , Serum Albumin, Bovine/metabolism , DNA/metabolism , DNA/chemistry , Animals , Coordination Complexes/chemistry , Coordination Complexes/pharmacology , Humans , Cattle , Antineoplastic Agents/pharmacology , Antineoplastic Agents/chemistry , Binding SitesABSTRACT
Copper (Cu2+) is a metal chemical element closely related to human life and is widely used in many fields. However, with the discharge of copper wastewater, the water quality will be seriously affected, leading to excessive intake of Cu2+ and a variety of diseases. Hence, there is a pressing need for an effective detection method for Cu2+ in aqueous environments. Leveraging the remarkable attributes of GFP chromophores and indenone derivatives, we have created a novel colorimetric fluorescent probe P-Cu2+, tailored for efficient copper ion detection. The addition of Cu2+ causes the solution to visibly change from colorless to a pronounced yellow, enabling naked-eye detection and offering promise for real sample analysis.
Subject(s)
Colorimetry , Copper , Fluorescent Dyes , Copper/chemistry , Copper/analysis , Fluorescent Dyes/chemistry , Fluorescent Dyes/chemical synthesis , Molecular Structure , Water Pollutants, Chemical/analysis , Water/chemistry , Indans/chemistry , Indans/analysis , Ions/analysis , Ions/chemistry , Spectrometry, FluorescenceABSTRACT
A novel signal amplification strategy was developed by combining near-infrared light with MoS2/CuO/Au nanocomposite for building a colorimetric immunoassay. First, MoS2/CuO/Au nanocomposite was synthesized by precipitation and photoreduction methods and characterized by scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). MoS2/CuO/Au nanocomposite has oxidase-like activity and can oxidize TMB to form a blue product (TMBox). Further, the catalytic oxidation of TMB was accelerated under near-infrared (NIR) laser radiation. The sandwich-type colorimetric immunoassay was constructed using MoS2/CuO/Au nanocomposite. Under the enhancement of near-infrared light, carcinoembryonic antigen (CEA) was sensitively detected in the range 0.1 to 40 ng/mL with the limit of detection of 0.03 ng/mL. Moreover, the immunosensor has excellent selectivity and anti-interference, good repeatability, and stability.
Subject(s)
Biomarkers, Tumor , Carcinoembryonic Antigen , Colorimetry , Copper , Disulfides , Gold , Infrared Rays , Limit of Detection , Molybdenum , Nanocomposites , Molybdenum/chemistry , Nanocomposites/chemistry , Copper/chemistry , Disulfides/chemistry , Colorimetry/methods , Gold/chemistry , Humans , Carcinoembryonic Antigen/blood , Carcinoembryonic Antigen/analysis , Biomarkers, Tumor/blood , Biomarkers, Tumor/analysis , Immunoassay/methods , Biosensing Techniques/methods , Antibodies, Immobilized/immunologyABSTRACT
A simple, selective, and affordable dual fluorescence-colorimetric indicator for hydrogen sulfide was developed based on a complex of copper nanoparticles and N-doped carbon quantum dots (CuNPs/NCQDs). Real-time and visual freshness tracking of fish was done using a colorimetric indicator by incorporating CuNPs/NCQDs into agar hydrogel (AH-CuNPs/NCQDs). The fluorescence response of the CuNPs/NCQDs solution is quenched upon exposure to H2S. The field-emission scanning electron microscopy image of the AH-CuNPs/NCQDs film revealed a unified structure. The prepared indicator exhibited a good and irreversible response to H2S, with a LOD of 91.36 and a LOQ of 276.86 µM, based on the localized surface plasmon resonance (LSPR) mechanism. The X-ray photoelectron spectrometer and Fourier transform infrared spectrometer results confirmed the formation of a CuS bond in the colorimetric indicator exposed to fish spoilage. The prepared indicator demonstrated good stability and remained unaffected by pH or other volatile compounds. Notably, there was a strong correlation between ΔΕ and fish freshness parameters (pH, TV-BN, and TVC). Light green, pale yellow, and dark yellow colors, respectively, indicated freshness, semi-freshness, and spoilage of fish during storage in the refrigerator. Overall, the prepared indicator can be effectively used for detecting spoilage in meat products as a highly sensitive freshness indicator.
Subject(s)
Agar , Colorimetry , Copper , Fishes , Hydrogels , Hydrogen Sulfide , Quantum Dots , Quantum Dots/chemistry , Animals , Colorimetry/methods , Copper/chemistry , Hydrogels/chemistry , Agar/chemistry , Hydrogen Sulfide/analysis , Hydrogen Sulfide/chemistry , Metal Nanoparticles/chemistry , Carbon/chemistry , Seafood/analysis , Limit of DetectionABSTRACT
Copper (Cu) is an essential micronutrient for humans, but excessive Cu in rice grains causes health risks. Currently, the mechanisms underlying Cu accumulation in rice are unclear. Here, we identified a novel member of the high-affinity copper transporter (Ctr)-like (COPT) protein family in rice, OsCOPT7, which controls Cu accumulation in rice grains. Mutation in the coding sequence of OsCOPT7 (mutant lc1) leads to inhibition of Cu transport through the xylem, contributing to lower Cu concentrations in the grain of lc1. Knockout or modulation of the expression of OsCOPT7 significantly impacts Cu transportation in the xylem and its accumulation in rice grains. OsCOPT7 localizes at the multi-pass membrane in the cell and the gene is expressed in the exodermis and stele cells, facilitating Cu loading into the xylem. OsCOPT7 expression is upregulated under Cu deficiency and in various organs, implying its contribution to Cu distribution within the rice plant. The variable expression pattern of OsCOPT7 suggests that OsCOPT7 expression responds to Cu stress in rice. Moreover, assays reveal that OsCOPT7 expression level is suppressed by the SQUAMOSA promoter-binding protein-like 9 (OsSPL9) and that OsCOPT7 interacts with Antioxidant Protein1 (OsATX1). This study elucidates the involvement of OsCOPT7 in Cu loading into the xylem, its subsequent distribution within the rice plant, and the potential of this protein in reducing the risk of high Cu concentrations in rice grain grown on Cu-contaminated soil.
Subject(s)
Copper , Oryza , Plant Proteins , Xylem , Copper/metabolism , Xylem/metabolism , Oryza/metabolism , Oryza/genetics , Plant Proteins/metabolism , Plant Proteins/genetics , Gene Expression Regulation, Plant , Biological TransportABSTRACT
The copper chaperone for Sod1 (Ccs) is a metallochaperone that plays a multifaceted role in the maturation of Cu,Zn superoxide dismutase (Sod1). The Ccs mutation R163W was identified in an infant with fatal neurological abnormalities. Based on a comprehensive structural and functional analysis, we developed the first data-driven model for R163W-related pathogenic phenotypes. The work here confirms previous findings that the substitution of arginine with tryptophan at this site, which is located adjacent to a conserved Zn binding site, creates an unstable Zn-deficient protein that loses its ability to efficiently activate Sod1. Intriguingly, R163W Ccs can reduce copper (i.e., Cu(II) â Cu(I)) bound in its Sod1-like domain (D2), and this novel redox event is accompanied by disulfide bond formation. The loss of Zn binding, along with the unusual ability to bind copper in D2, diverts R163W Ccs toward aggregation. The remarkably high affinity of D2 Cu(I) binding converts R163W from a Cu chaperone to a Cu scavenger that accelerates Sod1 deactivation (i.e., an Anti-chaperone). Overall, these findings present a first-of-its-kind molecular mechanism for Ccs dysfunction that leads to pathogenesis in humans.
Subject(s)
Copper , Molecular Chaperones , Superoxide Dismutase-1 , Humans , Molecular Chaperones/metabolism , Molecular Chaperones/genetics , Superoxide Dismutase-1/metabolism , Superoxide Dismutase-1/genetics , Superoxide Dismutase-1/chemistry , Copper/metabolism , Zinc/metabolism , Models, Molecular , Amino Acid Substitution , Binding Sites , Oxidation-ReductionABSTRACT
The excellent versatility of 5-axis computer numerical control (CNC) micromilling has led to its application for prototyping NMR microcoils tailored to mass-limited samples (reducing development time and cost). However, vibrations during 5-axis milling can hinder the creation of complex 3D volume microcoils (i.e., solenoids and saddle coils). To address these limitations, a high-resolution NSCNC ELARA 4-axis milling machine was developed with the extra precision required for making complex 3D volume microcoils. Upon investigating the performance of resonators made with various copper-coated dielectrics, resonators with poly(methyl methacrylate) (PMMA) provided the best SNR/line shape. Thus, complex 1.7 mm microcoil designs were machined from Cu-coated PMMA. A milled 6.4 mm solenoid also provided 6.6× the total carbon signal for a 13C-labeled broccoli seed compared to a commercial inverse 5 mm NMR probe (demonstrating potential for larger coil designs). However, the manufacture of coils <1.7 mm with copper-coated PMMA rods was challenging as â¼0.5 mm of remaining PMMA was needed to retain their structural integrity. To manufacture smaller microcoils, both a solenoid and saddle coil (both with 1 mm O.D., 0.1 mm thick walls) were etched from Cu-coated glass capillaries using a UV picosecond laser that was mounted onto an NSCNC 5-axis MiRA7L. Both resonators showed excellent signal and identified a wide range of metabolites in a 13C-labeled algae extract, while the solenoid was further tested on two copepod egg sacs (â¼4 µg of total sample). In summary, the flexibility to prototype complex microcoils in-house allows laboratories to tailor microcoils to specific mass-limited samples while avoiding the costs of cleanrooms.