ABSTRACT
Ball milling is an environmentally friendly technology for the remediation of petroleum-contaminated soil (PCS), but the cleanup of organic pollutants requires a long time, and the post-remediation soil needs an economically viable disposal/reuse strategy due to its vast volume. The present paper develops a ball milling process under oxygen atmosphere to enhance PCS remediation and reuse the obtained carbonized soil (BCS-O) as wastewater treatment materials. The total petroleum hydrocarbon removal rates by ball milling under vacuum, air, and oxygen atmospheres are 39.83%, 55.21%, and 93.84%, respectively. The Langmuir and pseudo second-order models satisfactorily describe the adsorption capacity and behavior of BCS-O for transition metals. The Cu2+, Ni2+, and Mn2+ adsorbed onto BCS-O were mainly bound to metal carbonates and metal oxides. Furthermore, BCS-O can effectively activate persulfate (PDS) oxidation to degrade aniline, while BCS-O loaded with transition metal (BCS-O-Me) shows better activation efficiency and reusability. BCS-O and BCS-O-Me activated PDS oxidation systems are dominated by 1O2 oxidation and electron transfer. The main active sites are oxygen-containing functional groups, vacancy defects, and graphitized carbon. The oxygen-containing functional groups and vacancy defects primarily activate PDS to generate 1O2 and attack aniline. Graphitized carbon promotes aniline degradation by accelerating electron transfer. The paper develops an innovative strategy to simultaneously realize efficient remediation of PCS and sequential reuse of the post-remediation soil.
Subject(s)
Environmental Restoration and Remediation , Oxygen , Petroleum , Soil Pollutants , Waste Disposal, Fluid , Wastewater , Soil Pollutants/chemistry , Soil Pollutants/analysis , Adsorption , Wastewater/chemistry , Oxygen/chemistry , Oxygen/analysis , Waste Disposal, Fluid/methods , Environmental Restoration and Remediation/methods , Soil/chemistry , CatalysisABSTRACT
The environmental threat posed by stibnite is an important geoenvironmental issue of current concern. To better understand stibnite oxidation pathways, aerobic abiotic batch experiments were conducted in aqueous solution with varying δ18OH2O value at initial neutral pH for different lengths of time (15-300 days). The sulfate oxygen and sulfur isotope compositions as well as concentrations of sulfur and antimony species were determined. The sulfur isotope fractionation factor (Δ34SSO4-stibnite) values decreased from 0.8 to -2.1 during the first 90 days, and increased to 2.6 at the 180 days, indicating the dominated intermediate sulfur species such as S2O32-, S0, and H2S (g) involved in Sb2S3 oxidation processes. The incorporation of O into sulfate derived from O2 (â¼100%) indicated that the dissociated O2 was only directly adsorbed on the stibnite-S sites in the initial stage (0-90 days). The proportion of O incorporation into sulfate from water (27%-52%) increased in the late stage (90-300 days), which suggested the oxidation mechanism changed to hydroxyl attack on stibnite-S sites promoted by nearby adsorbed O2 on stibnite-Sb sites. The exchange of oxygen between sulfite and water may also contributed to the increase of water derived O into SO42-. The new insight of stibnite oxidation pathway contributes to the understanding of sulfide oxidation mechanism and helps to interpret field data.
Subject(s)
Oxidation-Reduction , Oxygen Isotopes , Sulfates , Sulfur Isotopes , Sulfur Isotopes/analysis , Sulfates/chemistry , Oxygen Isotopes/analysis , Antimony/chemistry , Models, Chemical , Aerobiosis , Oxygen/chemistry , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry , OxidesABSTRACT
Plastic particles, particularly micro- and nanoparticles, are emerging pollutants due to the ever-growing amount of plastics produced across a wide variety of sectors. When plastic particles enter a biological medium, they become surrounded by a corona, giving them their biological identity and determining their interactions in the living environment and their biological effects. Here, we studied the interactions of microstructured plastics with hemoglobin (Hb). Virgin polyethylene microparticles (PEMPs) and polypropylene microparticles (PPMPs) as well as heat- or irradiation-aged microparticles (ag-PEMPs and ag-PPMPs) were used to quantify Hb adsorption. Polypropylene filters (PP-filters) were used to measure the oxygenation of adsorbed Hb. Microstructured plastics were characterized using optical microscopy, SAXS, ATR-FTIR, XPS, and Raman spectroscopy. Adsorption isotherms showed that the Hb corona thickness is larger on PPMPs than on PEMPs and Hb has a higher affinity for PPMPs than for PEMPs. Hb had a lower affinity for ag-PEMPs and ag-PPMPs, but they can be adsorbed in larger amounts. The presence of partial charges on the plastic surface and the oxidation rate of microplastics may explain these differences. Tonometry experiments using an original method, the diffuse reflection of light, showed that adsorbed Hb on PP-filters retains its cooperativity, but its affinity for O2 decreases significantly.
Subject(s)
Hemoglobins , Oxygen , Plastics , Polypropylenes , Hemoglobins/chemistry , Hemoglobins/metabolism , Adsorption , Oxygen/chemistry , Oxygen/metabolism , Plastics/chemistry , Polypropylenes/chemistry , Polyethylene/chemistry , Microplastics/chemistry , Spectroscopy, Fourier Transform InfraredABSTRACT
Human manganese superoxide dismutase (MnSOD) is a crucial oxidoreductase that maintains the vitality of mitochondria by converting superoxide (O2â-) to molecular oxygen (O2) and hydrogen peroxide (H2O2) with proton-coupled electron transfers (PCETs). Human MnSOD has evolved to be highly product inhibited to limit the formation of H2O2, a freely diffusible oxidant and signaling molecule. The product-inhibited complex is thought to be composed of a peroxide (O22-) or hydroperoxide (HO2-) species bound to Mn ion and formed from an unknown PCET mechanism. PCET mechanisms of proteins are typically not known due to difficulties in detecting the protonation states of specific residues that coincide with the electronic state of the redox center. To shed light on the mechanism, we combine neutron diffraction and X-ray absorption spectroscopy of the product-bound, trivalent, and divalent states of the enzyme to reveal the positions of all the atoms, including hydrogen, and the electronic configuration of the metal ion. The data identifies the product-inhibited complex, and a PCET mechanism of inhibition is constructed.
Subject(s)
Superoxide Dismutase , Humans , Superoxide Dismutase/metabolism , Superoxide Dismutase/chemistry , Hydrogen Peroxide/metabolism , Hydrogen Peroxide/chemistry , Manganese/metabolism , Manganese/chemistry , Electron Transport , Oxidation-Reduction , X-Ray Absorption Spectroscopy , Superoxides/metabolism , Superoxides/chemistry , Protons , Electrons , Models, Molecular , Oxygen/metabolism , Oxygen/chemistryABSTRACT
Enhancing the selectivity of detection methods is essential to distinguish breast cancer biomarker cluster of differentiation 44 (CD44) from other species and reduce false-positive or false-negative results. Here, oxygen vacancy-enriched CoFe2O4 (CoFe2O4-x) was crafted, and its implementation as an electrochemical electrode for the detection of CD44 biomarkers has been scrutinized. This unique electrode material offers significant benefits and novel features that enhance the sensitivity and selectivity of the detection process. The oxygen vacancy density of CoFe2O4-x was tuned by adjusting the mass ratios of iron to cobalt precursors (iron-cobalt ratio) and changing annealing atmospheres. Electrochemical characterization reveals that, when the iron-cobalt ratio is 1:0.54 and the annealing atmosphere is nitrogen, the as-synthesized CoFe2O4-x electrode manifests the best electrochemical activity. The CoFe2O4-x electrode demonstrates high sensitivity (28.22 µA (ng mL)-1 cm-2), low detection limit (0.033 pg mL-1), and robust stability (for 11 days). Oxygen vacancies can not only enhance the conductivities of CoFe2O4 but also provide better adsorption of -NH2, which is beneficial for stability and electrochemical detection performance. The electrochemical detection signal can be amplified using CoFe2O4-x as a signal probe. Additionally, it is promising to know that the CoFe2O4-x electrode has shown good accuracy in real biological samples, including melanoma cell dilutions and breast cancer patient sera. The electrochemical detection results are comparable to ELISA results, which indicates that the CoFe2O4-x electrode can detect CD44 in complex biological samples. The utilization of CoFe2O4-x as the signal probe may expand the application of CoFe2O4-x in biosensing fields.
Subject(s)
Biomarkers, Tumor , Breast Neoplasms , Cobalt , Electrochemical Techniques , Electrodes , Ferric Compounds , Hyaluronan Receptors , Cobalt/chemistry , Humans , Breast Neoplasms/blood , Hyaluronan Receptors/analysis , Hyaluronan Receptors/chemistry , Electrochemical Techniques/methods , Biomarkers, Tumor/blood , Biomarkers, Tumor/analysis , Ferric Compounds/chemistry , Oxygen/chemistry , Female , Limit of DetectionABSTRACT
Films for coffee-pod packaging usually contain aluminium as an impermeable foil that is not recyclable and has to be discharged as waste. In this study, a recyclable polypropylene multilayer film is proposed as an alternative. The performance on the chemical composition of coffee was evaluated and compared to that of film containing aluminium (standard). The oxygen in the headspace, moisture, lipidic oxidation, and volatile organic compounds were studied in coffee pods during storage for 12 months at 25 and 40 °C. In addition, the acidity and acceptability of extracted coffee were evaluated. In the polypropylene-packaged pods, the percentage of oxygen during storage at 25 °C was lower than that in the standard. Moisture was not affected by the type of packaging materials. No differences were found between the peroxide values, except in pods stored for 3, 10, and 11 months at 25 °C, where they were even lower than the standard. Furans and pyrazines were the main volatile organic compounds detected. No differences were found in the pH and titratable acidity of the coffee brew either. All samples were well accepted by consumers without any perceived difference related to the packaging film. The polypropylene multilayer film is a sustainable recyclable material with high performance, in particular, against oxygen permeation.
Subject(s)
Coffee , Food Packaging , Odorants , Polypropylenes , Volatile Organic Compounds , Polypropylenes/chemistry , Coffee/chemistry , Volatile Organic Compounds/analysis , Volatile Organic Compounds/chemistry , Odorants/analysis , Food Storage/methods , Oxygen/analysis , Oxygen/chemistry , RecyclingABSTRACT
[FeFe]-hydrogenase is nature's most efficient proton reducing and H2-oxidizing enzyme. However, biotechnological applications are hampered by the O2 sensitivity of this metalloenzyme, and the mechanism of aerobic deactivation is not well understood. Here, we explore the oxygen sensitivity of four mimics of the organometallic active site cofactor of [FeFe]-hydrogenase, [Fe2(adt)(CO)6-x(CN)x]x- and [Fe2(pdt)(CO)6-x(CN)x]x- (x = 1, 2) as well as the corresponding cofactor variants of the enzyme by means of infrared, Mössbauer, and NMR spectroscopy. Additionally, we describe a straightforward synthetic recipe for the active site precursor complex Fe2(adt)(CO)6. Our data indicate that the aminodithiolate (adt) complex, which is the synthetic precursor of the natural active site cofactor, is most oxygen sensitive. This observation highlights the significance of proton transfer in aerobic deactivation, and supported by DFT calculations facilitates an identification of the responsible reactive oxygen species (ROS). Moreover, we show that the ligand environment of the iron ions critically influences the reactivity with O2 and ROS like superoxide and H2O2 as the oxygen sensitivity increases with the exchange of ligands from CO to CN-. The trends in aerobic deactivation observed for the model complexes are in line with the respective enzyme variants. Based on experimental and computational data, a model for the initial reaction of [FeFe]-hydrogenase with O2 is developed. Our study underscores the relevance of model systems in understanding biocatalysis and validates their potential as important tools for elucidating the chemistry of oxygen-induced deactivation of [FeFe]-hydrogenase.
Subject(s)
Catalytic Domain , Hydrogenase , Iron-Sulfur Proteins , Oxygen , Hydrogenase/chemistry , Hydrogenase/metabolism , Oxygen/chemistry , Oxygen/metabolism , Iron-Sulfur Proteins/chemistry , Iron-Sulfur Proteins/metabolism , Density Functional TheoryABSTRACT
Herein, we, for the first time, synthesize silver nanoparticles (Ag NPs) within the nanochannels of amino group-functionalized vertically ordered mesoporous silica films (NH2-VMSF) and investigate their coreaction accelerator role in the luminol-dissolved oxygen (O2) electrochemical stripping chemiluminescence (ESCL) system. The synthesized Ag NPs are capable of electrocatalytic reduction of O2 to superoxide radicals, and meanwhile, sliver ions (Ag+) electrochemically stripped from Ag NPs can promote the amount of luminol anion radicals, generating the boosted ECL intensity of the luminol-dissolved O2 system. This proposed Ag NPs@NH2-VMSF on the indium tin oxide electrode was applied to construct the ESCL aptasensor for quantitative determination of prostate-specific antigen (PSA), yielding a low detection limit [0.19 pg/mL (S/N = 3)] and a broad linear dynamic range (1 pg/mL to 100 ng/mL). Furthermore, good analytical performance of PSA in serum with satisfactory recoveries and low relative standard deviation values is achieved by our developed ESCL aptasensor, rendering it a convenient and sensitive method for PSA determination in clinical applications and further broadening the strategy of ESCL techniques.
Subject(s)
Aptamers, Nucleotide , Electrochemical Techniques , Luminescent Measurements , Luminol , Metal Nanoparticles , Oxygen , Silicon Dioxide , Silver , Silicon Dioxide/chemistry , Luminol/chemistry , Silver/chemistry , Metal Nanoparticles/chemistry , Aptamers, Nucleotide/chemistry , Oxygen/chemistry , Humans , Biosensing Techniques , Prostate-Specific Antigen/blood , Prostate-Specific Antigen/analysis , Limit of Detection , Electrodes , LuminescenceABSTRACT
Current treatment strategies for infection of chronic wounds often result in compromised healing and necrosis due to antibiotic toxicity, and underlying biomarkers affected by treatments are not fully known. Here, a multifunctional dressing was developed leveraging the unique wound-healing properties of chitosan, a natural polysaccharide known for its numerous benefits in wound care. The dressing consists of an oxygenating perfluorocarbon functionalized methacrylic chitosan (MACF) hydrogel incorporated with antibacterial polyhexamethylene biguanide (PHMB). A non-healing diabetic infected wound model with emerging metabolomics tools was used to explore the anti-infective and wound healing properties of the resultant multifunctional dressing. Direct bacterial bioburden assessment demonstrated superior antibacterial properties of hydrogels over a commercial dressing. However, wound tissue quality analyses confirmed that sustained PHMB for 21 days resulted in tissue necrosis and disturbed healing. Therefore, a follow-up comparative study investigated the best treatment course for antiseptic application ranging from 7 to 21 days, followed by the oxygenating chitosan-based MACF treatment for the remainder of the 21 days. Bacterial counts, tissue assessments, and lipidomics studies showed that 14 days of application of MACF-PHMB dressings followed by 7 days of MACF dressings provides a promising treatment for managing infected non-healing diabetic skin ulcers.
Subject(s)
Anti-Bacterial Agents , Bandages , Chitosan , Hydrogels , Wound Healing , Chitosan/chemistry , Chitosan/pharmacology , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/administration & dosage , Hydrogels/chemistry , Hydrogels/pharmacology , Hydrogels/administration & dosage , Wound Healing/drug effects , Animals , Biguanides/chemistry , Biguanides/pharmacology , Biguanides/administration & dosage , Wound Infection/drug therapy , Wound Infection/microbiology , Male , Oxygen/chemistry , Chronic Disease , Fluorocarbons/chemistry , Fluorocarbons/pharmacology , Fluorocarbons/administration & dosageABSTRACT
The burgeoning field of continuous glucose monitoring (CGM) for diabetes management faces significant challenges, particularly in achieving precise and stable biosensor performance under changing environmental conditions such as varying glucose concentrations and O2 levels. To address this, we present a novel biosensor based on the electroless coupling of glucose oxidation catalyzed by flavin-dependent glucose dehydrogenase (FAD-GDH) and O2 reduction catalyzed by bilirubin oxidase (BOD) via a redox polymer, dimethylferrocene-modified linear poly(ethylenimine), FcMe2-LPEI. Initial cyclic voltammetry tests confirm the colocalization of both enzymatic reactions within the potential range of the polymer, indicating an effective electron shuttle mechanism. As a result, we created a hybrid biosensor that operates at open-circuit potential (OCP). It can detect glucose concentrations of up to 100 mM under various O2 conditions, including ambient air. This resulted from optimizing the enzyme ratio to 120 ± 10 mUBOD·UFAD-GDH-1·atmO2-1. This biosensor is highly sensitive, a crucial feature for CGM applications. This distinguishes it from FAD-GDH traditional biosensors, which require a potential to be applied to measure glucose concentrations up to 30 mM. In addition, this biosensor demonstrates the ability to function as a noninvasive, external device that can adapt to changing glucose levels, paving the way for its use in diabetes care and, potentially, personalized healthcare devices. Furthermore, by leveraging the altered metabolic pathways in tumor cells, this system architecture opened up new avenues for targeted glucose scavenging and O2 reduction in cancer therapy.
Subject(s)
Biosensing Techniques , Glucose 1-Dehydrogenase , Glucose , Oxidation-Reduction , Oxidoreductases Acting on CH-CH Group Donors , Oxygen , Biosensing Techniques/methods , Oxygen/chemistry , Oxygen/metabolism , Glucose/analysis , Glucose/metabolism , Humans , Oxidoreductases Acting on CH-CH Group Donors/metabolism , Oxidoreductases Acting on CH-CH Group Donors/chemistry , Glucose 1-Dehydrogenase/chemistry , Glucose 1-Dehydrogenase/metabolism , Polymers/chemistry , Ferrous Compounds/chemistry , Polyethyleneimine/chemistry , Enzymes, Immobilized/chemistry , Enzymes, Immobilized/metabolismABSTRACT
A new type of carbonized polymer dot was prepared by the one-step hydrothermal method of triethoxylsilane (TEOS) and citric acid (CA). The sensor made from carbonized polymer dots (CPDs) showed superior gas sensing performance toward ammonia at room temperature. The Si, O-codoped CPDs exhibited superior ammonia sensing performance at room temperature, including a low practical limit of detection (pLOD) of 1 ppm (Ra/Rg: 1.10, 1 ppm), short response/recovery time (30/36 s, 1 ppm), high humidity resistance (less than 5% undulation when changing relative humidity to 80 from 30%), high stability (less than 5% initial response undulation after 120 days), reliable repeatability, and high selectivity against other interferential gases. The gas sensing mechanism was investigated through control experiments and in situ FTIR, indicating that Si, O-codoping essentially improves the electron transfer capability of CPDs and synergistically dominates the superior ammonia sensing properties of the CPDs. This work presents a facile strategy for constructing novel high-performance, single-component carbonized polymer dots for gas sensing.
Subject(s)
Ammonia , Polymers , Temperature , Ammonia/analysis , Polymers/chemistry , Carbon/chemistry , Gases/analysis , Gases/chemistry , Silicon/chemistry , Limit of Detection , Quantum Dots/chemistry , Oxygen/chemistryABSTRACT
Oxygen homeostasis is maintained in plants and animals by O2-sensing enzymes initiating adaptive responses to low O2 (hypoxia). Recently, the O2-sensitive enzyme ADO was shown to initiate degradation of target proteins RGS4/5 and IL32 via the Cysteine/Arginine N-degron pathway. ADO functions by catalysing oxidation of N-terminal cysteine residues, but despite multiple proteins in the human proteome having an N-terminal cysteine, other endogenous ADO substrates have not yet been identified. This could be because alternative modifications of N-terminal cysteine residues, including acetylation, prevent ADO-catalysed oxidation. Here we investigate the relationship between ADO-catalysed oxidation and NatA-catalysed acetylation of a broad range of protein sequences with N-terminal cysteines. We present evidence that human NatA catalyses N-terminal cysteine acetylation in vitro and in vivo. We then show that sequences downstream of the N-terminal cysteine dictate whether this residue is oxidised or acetylated, with ADO preferring basic and aromatic amino acids and NatA preferring acidic or polar residues. In vitro, the two modifications appear to be mutually exclusive, suggesting that distinct pools of N-terminal cysteine proteins may be acetylated or oxidised. These results reveal the sequence determinants that contribute to N-terminal cysteine protein modifications, with implications for O2-dependent protein stability and the hypoxic response.
Subject(s)
Cysteine , Oxidation-Reduction , Protein Stability , Cysteine/metabolism , Cysteine/chemistry , Acetylation , Humans , Oxygen/metabolism , Oxygen/chemistry , Protein Processing, Post-Translational , Amino Acid Sequence , HEK293 CellsABSTRACT
Implant infections are severe complications in clinical treatment, which often accompany the formation of bacterial biofilms with high antibiotic resistance. Sonodynamic therapy (SDT) is an antibiotic-free method that can generate reactive oxygen species (ROS) to kill bacteria under ultrasound (US) treatment. However, the extracellular polymeric substances (EPS) barrier of bacterial biofilms and the hypoxic microenvironment significantly limit the antibiofilm activity of SDT. In this study, lipid-shelled perfluoropentane (PFP) nanodroplets loaded with gallium protoporphyrin IX (GaPPIX) and oxygen (O2) (LPGO NDs) were developed for the treatment of implant infections. Under US stimulation, LPGO NDs undergo the cavitation effect and disrupt the biofilm structure like bombs due to liquid-gas phase transition. Meanwhile, the LPGO NDs release O2 and GaPPIX upon US stimulation. The released O2 can alleviate the hypoxic microenvironment in the biofilm and enhance the ROS formation by GaPPIX for enhanced bacterial killing. In vivo experimental results demonstrate that the LPGO NDs can efficiently treat implant infections of methicillin-resistant Staphylococcus aureus (MRSA) in a mouse model by disrupting the biofilm structure, alleviating hypoxia, and enhancing bacterial killing by SDT. Therefore, this work provides a new multifunctional sonosensitizer to overcome the limitations of SDT for treating implant infections.
Subject(s)
Biofilms , Fluorocarbons , Gallium , Methicillin-Resistant Staphylococcus aureus , Oxygen , Protoporphyrins , Staphylococcal Infections , Ultrasonic Therapy , Animals , Fluorocarbons/chemistry , Fluorocarbons/pharmacology , Mice , Gallium/chemistry , Gallium/pharmacology , Protoporphyrins/chemistry , Protoporphyrins/pharmacology , Methicillin-Resistant Staphylococcus aureus/drug effects , Biofilms/drug effects , Oxygen/chemistry , Staphylococcal Infections/drug therapy , Reactive Oxygen Species/metabolism , Nanoparticles/chemistry , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/chemistry , Mice, Inbred BALB C , Female , PentanesABSTRACT
Antibiotics and organic residues from Tetracycline (TC) and other pharmaceuticals administered to aquatic living organism have negative impacts on aquatic environment by killing-off non-target living organisms and developing antibiotic-resistant bacteria. In this study, Micro-Nano Bubble (MNB) system was used to remove TC residues. MNB system demonstrated good level of degradation efficiency, as resulted in experiment where in time of 100 min, the TC degraded at rate of 82.66% from its initial concentration of TC when the initial concentration was 1 mg/L. When the initial concentration was increased to 10 mg/L, MNB system degraded TC at 64.35% of their initial, this means MNB system demonstrated good level of efficiency for TC removal and indicated that it is more efficient in TC degradation under the conditions of low initial TC concentration and high availability of dissolved oxygen (DO). In the system as the temperature increased there was a significant decrease in DO saturation which was related to the TC complex structure that contain multiple function groups such as amino groups, hydroxyl and carboxyl which possess high strong affinity with oxygen that leads to their adsorption onto bubble surface. This study provides significant insights into the application of MNB system for the removal of organic residues within aquatic ecosystem and underscores the need for further exploration of MNB technology for environmental remediation.
Subject(s)
Tetracycline , Tetracycline/chemistry , Tetracycline/analysis , Water Pollutants, Chemical/chemistry , Adsorption , Oxygen/chemistry , Anti-Bacterial Agents/chemistryABSTRACT
Defect engineering is regarded as an effective strategy to boost the photo-activity of photocatalysts for organic contaminants removal. In this work, abundant surface oxygen vacancies (Ov) are created on AgIO3 microsheets (AgIO3-OV) by a facile and controllable hydrogen chemical reduction approach. The introduction of surface Ov on AgIO3 broadens the photo-absorption region from ultraviolet to visible light, accelerates the photoinduced charges separation and migration, and also activates the formation of superoxide radicals (â¢O2-). The AgIO3-OV possesses an outstanding degradation rate constant of 0.035 min-1, for photocatalytic degrading methyl orange (MO) under illumination of natural sunlight with a light intensity is 50 mW/cm2, which is 7 and 3.5 times that of the pristine AgIO3 and C-AgIO3 (AgIO3 is calcined in air without generating Ov). In addition, the AgIO3-OV also exhibit considerable photoactivity for degrading other diverse organic contaminants, including azo dye (rhodamine B (RhB)), antibiotics (sulflsoxazole (SOX), norfloxacin (NOR), chlortetracycline hydrochloride (CTC), tetracycline hydrochloride (TC) and ofloxacin (OFX)), and even the mixture of organic contaminants (MO-RhB and CTC-OFX). After natural sunlight illumination for 50 min, 41.4% of total organic carbon (TOC) for MO-RhB mixed solution can be decreased over AgIO3-OV. In a broad range of solution pH from 3 to 11 or diverse water bodies of MO solution, AgIO3-OV exhibits attractive activity for decomposing MO. The MO photo-degradation process and mechanism over AgIO3-OV under natural sunlight irradiation has been systemically investigated and proposed. The toxicities of MO and its degradation intermediates over AgIO3-OV are compared using Toxicity Estimation Software (T.E.S.T.). Moreover, the non-toxicity of both AgIO3-OV catalyst and treated antibiotic solution (CTC-OFX mixture) are confirmed by E. coli DH5a cultivation test, supporting the feasibility of AgIO3-OV catalyst to treat organic contaminants in real water under natural sunlight illumination.
Subject(s)
Photolysis , Sunlight , Oxygen/chemistry , Water Pollutants, Chemical/chemistry , Azo Compounds/chemistry , Catalysis , Rhodamines/chemistryABSTRACT
Understanding how water ligands regulate the conformational changes and functionality of the oxygen-evolving complex (OEC) in photosystem II (PSII) throughout the catalytic cycle of oxygen evolution remains a highly intriguing and unresolved challenge. In this study, we investigate the effect of water insertion (WI) on the redox state of the OEC by using the molecular dynamics (MD) and quantum mechanics/molecular mechanics (QM/MM) hybrid methods. We find that water binding significantly reduces the free energy change for proton-coupled electron transfer (PCET) from Mn to YZâ¢, underscoring the important regulatory role of water binding, which is essential for enabling the OEC redox-leveling mechanism along the catalytic cycle. We propose a water binding mechanism in which WI is thermodynamically favored by the closed-cubane form of the OEC, with water delivery mediated by Ca2+ ligand exchange. Isomerization from the closed- to open-cubane conformation at three post-WI states highlights the importance of the location of the MnIII center in the OEC and the orientation of its Jahn-Teller axis to conformational changes of the OEC, which might be critical for the formation of the O-O bond. These findings reveal a complex interplay between conformational changes in the OEC and the ligand environment during the activation of the OEC by YZâ¢. Analogous regulatory effects due to water ligand binding are expected to be important for a wide range of catalysts activated by redox state transitions in aqueous environments.
Subject(s)
Oxidation-Reduction , Oxygen , Photosystem II Protein Complex , Water , Photosystem II Protein Complex/chemistry , Photosystem II Protein Complex/metabolism , Water/chemistry , Ligands , Oxygen/chemistry , Oxygen/metabolism , Molecular Dynamics Simulation , Thermodynamics , Quantum TheoryABSTRACT
The review presents the results of the blood substitute development based on perfluororganic compounds (PFC). The limitations of PFC due to which their further development was suspended are described. The presented data allows us to imagine a possible way to create optimal drugs based on PFC. Chemically inactive perfluorocomponents should be used - perfluorinated hydrocarbons and tertiary perfluorinated amines. However, in order to emulsify and stabilize the emulsion, other types of effective and chemically indifferent surfactants that do not interact with oxygen and other components of the drug are needed.
Subject(s)
Blood Substitutes , Fluorocarbons , Fluorocarbons/chemistry , Humans , Surface-Active Agents/chemistry , Surface-Active Agents/pharmacology , Emulsions/chemistry , Oxygen/chemistry , AnimalsABSTRACT
Zn-air batteries are a highly promising clean energy sustainable conversion technology, and the design of dual-function electrocatalysts with excellent activity and stability is crucial for their development. In this work, FeCo alloy loaded biomass-based N and S co-doped carbon aerogels (FeCo@NS-LCA) were fabricated from chitosan and lignosulfonate-metal chelates via liquid nitrogen pre-frozen synergistic high-temperature carbonization with application in electrocatalytic reactions. The abundant oxygen-containing functional groups on lignosulfonates have a chelating effect on metal ions, which can avoid the aggregation of metal nanoparticles during carbonation and catalysis, facilitating the construction of a nanoconfinement catalytic system with biomass carbon as the domain-limiting body and FeCo nanoparticles as the active sites. FeCo@NS-LCA exhibited catalytic activity (E1/2 = 0.87 V, JL = 5.7 mA cm-2) comparable to the commercial Pt/C in the oxygen reduction reaction (ORR), excellent resistance to methanol toxicity and stability. Meanwhile, the overpotential of oxygen evolution reaction (OER) was 324 mV, close to that of commercial RuO2 catalysts (351 mV). This study utilizes the coordination action of lignosulfonate to provide a novel and environmentally friendly method for the preparation of confined nano-catalysts and provides a new perspective for the high-value utilization of biomass resources.
Subject(s)
Alloys , Carbon , Electric Power Supplies , Lignin , Nitrogen , Oxygen , Zinc , Lignin/chemistry , Lignin/analogs & derivatives , Alloys/chemistry , Carbon/chemistry , Oxygen/chemistry , Catalysis , Zinc/chemistry , Porosity , Nitrogen/chemistry , Gels/chemistry , Oxidation-Reduction , Sulfur/chemistry , Cobalt/chemistry , BiomassABSTRACT
Bacteria use the second messenger cyclic dimeric guanosine monophosphate (c-di-GMP) to control biofilm formation and other key phenotypes in response to environmental signals. Changes in oxygen levels can alter c-di-GMP signaling through a family of proteins termed globin coupled sensors (GCS) that contain diguanylate cyclase domains. Previous studies have found that GCS diguanylate cyclase activity is controlled by ligand binding to the heme within the globin domain, with oxygen binding resulting in the greatest increase in catalytic activity. Herein, we present evidence that heme-edge residues control O2-dependent signaling in PccGCS, a GCS protein from Pectobacterium carotovorum, by modulating heme distortion. Using enzyme kinetics, resonance Raman spectroscopy, small angle X-ray scattering, and multi-wavelength analytical ultracentrifugation, we have developed an integrated model of the full-length PccGCS tetramer and have identified conformational changes associated with ligand binding, heme conformation, and cyclase activity. Taken together, these studies provide new insights into the mechanism by which O2 binding modulates activity of diguanylate cyclase-containing GCS proteins.
Subject(s)
Bacterial Proteins , Heme , Pectobacterium carotovorum , Phosphorus-Oxygen Lyases , Phosphorus-Oxygen Lyases/metabolism , Phosphorus-Oxygen Lyases/chemistry , Heme/chemistry , Heme/metabolism , Bacterial Proteins/chemistry , Bacterial Proteins/metabolism , Pectobacterium carotovorum/enzymology , Protein Conformation , Oxygen/chemistry , Oxygen/metabolism , Cyclic GMP/metabolism , Cyclic GMP/analogs & derivatives , Cyclic GMP/chemistry , Escherichia coli ProteinsABSTRACT
Among various non-covalent interactions, selenium-centered chalcogen bonds (SeChBs) have garnered considerable attention in recent years as a result of their important contributions to crystal engineering, organocatalysis, molecular recognition, materials science, and biological systems. Herein, we systematically investigated π-hole-type SeâââO/S ChBs in the binary complexes of SeO2 with a series of O-/S-containing Lewis bases by means of high-level ab initio computations. The results demonstrate that there exists an attractive interaction between the Se atom of SeO2 and the O/S atom of Lewis bases. The interaction energies computed at the MP2/aug-cc-pVTZ level range from -4.68 kcal/mol to -10.83 kcal/mol for the SeâââO chalcogen-bonded complexes and vary between -3.53 kcal/mol and -13.77 kcal/mol for the SeâââS chalcogen-bonded complexes. The SeâââO/S ChBs exhibit a relatively short binding distance in comparison to the sum of the van der Waals radii of two chalcogen atoms. The SeâââO/S ChBs in all of the studied complexes show significant strength and a closed-shell nature, with a partially covalent character in most cases. Furthermore, the strength of these SeâââO/S ChBs generally surpasses that of the C/O-HâââO hydrogen bonds within the same complex. It should be noted that additional C/O-HâââO interactions have a large effect on the geometric structures and strength of SeâââO/S ChBs. Two subunits are connected together mainly via the orbital interaction between the lone pair of O/S atoms in the Lewis bases and the BD*(OSe) anti-bonding orbital of SeO2, except for the SeO2âââHCSOH complex. The electrostatic component emerges as the largest attractive contributor for stabilizing the examined complexes, with significant contributions from induction and dispersion components as well.