Regulating the valence and size of the active center of Co/Al2O3 catalyst improved the performance and selectivity of NH3-SCO.

To improve the activity of Co/Al2O3 catalysts in selective catalytic oxidation of ammonia (NH3-SCO), valence state and size of active centers of Al2O3-supported Co catalysts were adjusted by conducting H2 reduction pretreatment. The NH3-SCO activity of the adjusted 2Co/Al2O3 catalyst was substantially improved, outperforming other catalysts with higher Co-loading. Fresh Co/Al2O3 catalysts exhibited multitemperature reduction processes, enabling the control of the valence state of the Co-active centers by adjusting the reduction temperature. Changes in the state of the Co-active centers also led to differences in redox capacity of the catalysts, resulting in different reaction mechanisms for NH3-SCO. However, in situ diffuse reflectance infrared Fourier transform spectra revealed that an excessive O2 activation capacity caused overoxidation of NH3 to NO and NO2. The NH3-SCO activity of the 2Co/Al2O3 catalyst with low redox capacity was successfully increased while controlling and optimizing the N2 selectivity by modulating the active centers via H2 pretreatment, which is a universal method used for enhancing the redox properties of catalysts. Thus, this method has great potential for application in the design of inexpensive and highly active catalysts.

Synthesis of histidine, serine and folic acid-functionalized and boron and iron-doped graphene quantum dot with excellent optical behavior and peroxidase-like activity for colorimetric and fluorescence detection of H2O2 in food.

Low fluorescence under visible light excitation and catalytic activity limit many applications of graphene quantum dots in optical detection, biosensing, catalysis and biomedical. The paper reports design and synthesis of histidine, serine and folic acid-functionalized and boron and iron-doped graphene quantum dot (Fe/B-GQD-HSF). The Fe/B-GQD-HSF shows excellent fluorescence behavior and peroxidase-like activity. Excitation of 330 nm ultraviolet light produces the strongest blue fluorescence and excitation of 480 nm visible light produces the strongest yellow fluorescence. The specific activity reaches 92.67 U g-1, which is higher than that of other graphene quantum dots. The Fe/B-GQD-HSF can catalyze oxidation of 3,3',5,5'-tetramethylbenzidine with H2O2 to form blue compound. Based on this, it was used for colorimetric and fluorescence detection of H2O2. The absorbance at 652 nm linearly increases with the increase of H2O2 concentration between 0.5 and 100 µM with detection limit of 0.43 µM. The fluorescence signal linearly decreases with the increase of H2O2 concentration between 0.05 and 100 µM with detection limit of 0.035 µM. The analytical method has been satisfactorily applied in detection of H2O2 in food. The study also paves one way for design and synthesis of functional graphene quantum dots with ideal fluorescence behavior and catalytic activity.

Mn/S diatomic sites in C3N4 to enhance O2 activation for photocatalytic elimination of emerging pollutants.

Oxygen activation leading to the generation of reactive oxygen species (ROS) is essential for photocatalytic environmental remediation. The limited efficiency of O2 adsorption and reductive activation significantly limits the production of ROS when employing C3N4 for the degradation of emerging pollutants. Doping with metal single atoms may lead to unsatisfactory efficiency, due to the recombination of photogenerated electron-hole pairs. Here, Mn and S single atoms were introduced into C3N4, resulting in the excellent photocatalytic performances. Mn/S-C3N4 achieved 100% removal of bisphenol A, with a rate constant 11 times that of pristine C3N4. According to the experimental results and theoretical simulations, S-atoms restrict holes, facilitating the photo-generated carriers' separation. Single-atom Mn acts as the O2 adsorption site, enhancing the adsorption and activation of O2, resulting the generation of ROS. This study presents a novel approach for developing highly effective photocatalysts that follows a new mechanism to eliminate organic pollutants from water.

A review on recent advances in g-C3N4-MXene nanocomposites for photocatalytic applications.

The solutions for environmental remediation and renewable energy generation have intensified the exploration of efficient photocatalytic materials. Recently, the composites of g-C3N4 and MXene have gained considerable interest for their potential applications in photocatalysis. In the g-C3N4-MXene composite, the g-C3N4 possesses unique physical, chemical, and optical properties to increase visible light absorption. At the same time, MXene improves conductivity, adsorption of reactant molecules or the active sites, and charge transfer properties. Combining the unique physico-chemical properties of MXene and g-C3N4, the resulting composite exhibits superior photo-responsive behavior and is critical in photocatalytic reactions. Furthermore, the g-C3N4-MXene composite exhibits stability and recyclability, making it a promising candidate for sustainable and scalable photocatalytic material in environmental remediation. This review offers an in-depth analysis of the development and design of g-C3N4-MXene composites through diverse synthesis procedures and a comprehensive analysis of their application in carbon dioxide (CO2) reduction, photocatalytic degradation, water splitting processes, mainly hydrogen (H2) generation, H2O2 production, N2 fixation, and NOx removal. The charge transfer mechanism of g-C3N4-MXene composite for photocatalytic application has also been discussed. This review provides insights into the photocatalytic capabilities of g-C3N4-MXene composites, showing their potential to address current environmental challenges and establish a robust foundation for sustainable energy conversion technologies. .

Harnessing 4f Electron Itinerancy for Integrated Dual-Band Redox Systems Boosts Lithium-Oxygen Batteries Electrocatalysis.

In-depth comprehension and manipulation of band occupation at metal centers are crucial for facilitating effective adsorption and electron transfer in lithium-oxygen battery (LOB) reactions. Rare earth elements play a unique role in band hybridization due to their deep orbitals and strong localization of 4f electrons. Herein, we anchor single Ce atoms onto CoO, constructing a highly active and stable catalyst with d-f a dual-band redox center. It is discovered that the itinerant behavior of 4f electrons introduces an enhanced spin-orbit coupling effect, which facilitates ideal σ/π bonding and flexible adsorption between the Ce/Co active sites and *O. Simultaneously, the injection of localized Ce 4f electrons strengthens the orbital bonding capacity of Co-O, effectively inhibits the dissolution of Co sites and improves the structural stability of the cathode material. Bracingly, the Ce1/CoO-based LOB exhibits an ultra-low charge-discharge polarization (0.46 V) and stable cyclic performance (1088 hours). This work breaks through the traditional limitations in catalyst activity and stability, providing new strategies and theoretical insights for developing high-performance LOBs powered by rare-earth elements.

An Ultrasensitive Bi2O2Se/In2S3 Photodetector with Low Detection Limit and Fast Response toward High-Precision Unmanned Driving.

The machine vision utilized in unmanned driving systems must possess the ability to accurately perceive scenes under low-light illumination conditions. To achieve this, photodetectors with low detection limits and a fast response are essential. Current systems rely on avalanche diodes or lidars, which come with the drawbacks of increased energy consumption and complexity. Here, we present an ultrasensitive photodetector based on a two-dimensional (2D) Bi2O2Se/In2S3 heterostructure, incorporating a homotype unilateral depletion band design. This innovative architecture effectively modulates the transport of both free and photoexcited carriers, suppressing the dark current and facilitating the rapid and efficient separation of photocarriers. Owing to these features, this device exhibits a responsivity of 144 A/W, a specific detectivity of 1.2 × 1014 Jones, and a light on/off ratio of 1.1 × 105. These metrics rank among the top values reported for state-of-the-art 2D devices. Moreover, this device also demonstrates a fast response time of 170/296 µs and a low noise equivalent power of 0.57 fW/Hz1/2, attributes that endow it with ultraweak light imaging capabilities. Furthermore, we have successfully integrated this device into an unmanned driving system, providing a perspective on the design and fabrication of future optoelectronic devices.

Rational Construction of Cyanide-Functionalized D-A-π-D Covalent Organic Framework for Highly Efficient Overall H2O2 Photosynthesis from Air and Water.

Sacrificial-agent-free overall photosynthesis of H2O2 from water and air represents currently a promising route to reform the industrial anthraquinone production manner, but, still blocks by the requirement of pure O2 feedstock, due to the insufficient oxygen supply from water under air. Herein, we report a rational molecule design on COFs (covalent organic frameworks) equiped with cyanide-functionalized D-A-π-D system for highly efficient overall H2O2 production from air and water through photocatalytic oxygen reduction reactions (ORR) and water oxidation reaction (WOR). Without using any sacrificial agent, the as-synthesized D-A-π-D COF is found to enable a H2O2 production rate as high as 4742 µmol h-1 g-1 from water and air and an O2 utilization and conversion rate up to 88%, exceeding the other D-A-π-A COF by respectively 1.9- and 1.3-fold. Such high performance is attributed to the tuned electronic structure and prolonged charge lifetime facilitated by the unique D-A-π-D structure and cyanide groups. This work highlights a fundamental molecule design on advanced photocatalytic COFs with complicated D-A system for low-cost and massive H2O2 production.

Spermidine Improves Freezing Tolerance by Regulating H2O2 in Brassica napus L.

Low temperature is a common abiotic stress that causes significant damage to crop production. Polyamines (PAs) are a class of aliphatic amine compounds that serve as regulatory molecules involved in plant growth, development, and response to abiotic and biotic stresses. In this study, we found that the exogenous application of two concentrations of spermidine (Spd) significantly enhanced the freezing tolerance of three differently matured rapeseed (Brassica napus L.) varieties, as manifested by higher survival rates, lower freezing injury indexes, and reduced H2O2 content. RNA-seq and qRT-PCR analyses showed that Spd enhanced the freezing tolerance of rapeseed by regulating genes related to the PA metabolic pathway and antioxidant mechanism, and generally inhibited the expression of genes related to the JA signaling pathway. This study provides a reference basis for understanding the functionality and molecular mechanisms of polyamines in the response of rapeseed to freezing stress.

Investigation of the abasic sites induced by hydrogen peroxide and methyl methanesulfonate in calf thymus DNA and BEAS-2B cells.

The primary goals of this study were to investigate the formation of abasic sites (AP sites) induced by methyl methanesulfonate (MMS) and hydrogen peroxide (H2O2), and to characterize specific types of these pro-mutagenic DNA lesions in calf thymus DNA (CT-DNA), and BEAS-2B human lung normal cell line. Furthermore, these profiles were compared with those observed in leukocytes derived from healthy controls (HC), breast cancer patients (BCP) before treatment, and 5-year survivors. Results indicated that both H2O2 and MMS induced the concentration- and time-dependent formation of AP sites in CT-DNA. To characterize the specific types of AP sites induced by H2O2 or MMS, we performed AP site cleavage assay using putrescine, T7 exonuclease (T7 Exo), and exonuclease III (Exo III). Results showed that the AP sites induced by H2O2 in CT-DNA were predominantly 5'-and 3'-nicked AP sites and no intact AP sites were detected. By contrast, the majority of AP sites generated by MMS in CT-DNA are not excisable and are classified as residual and intact AP sites. Similar approaches were performed in human BEAS-2B cells and comparable observations were confirmed in the cell-based model. Further investigation indicated that the profile of the AP sites observed in Taiwanese HC is identical to that of BEAS-2B cells treated with H2O2 whereas the pattern of AP sites detected in BCP is similar to that of CT-DNA exposed to H2O2, suggesting that these AP sites were produced primarily through reactive oxygen species (ROS) generation. More than 70 % of the AP sites in leukocytes derived from BCP were 5'-nicked and residual AP sites. Furthermore, the characteristics of the AP sites detected in 5-year survivors are comparable with the ones in HC by using putrescine cleavage assay. Overall, we speculate that deficiency in the DNA repair cascade may play a role in mediating the formation of specific types of AP sites detected in BCP.

Selective elimination of organic pollutants and analysis of effects and novel mechanisms of aged microplastics on wavelength-dependent UV-LED/H2O2 system.

The selective removal of organic pollutants and potential impact of aged microplastics (MPs) as emerging pollutants in wavelength-dependent UV-LED/H2O2 system are not fully understood. This study found that cefalexin (CFX) degradation efficiency in UV-LED alone system was highly correlated with its UV molar absorbance (R2=0.994), while in UV-LED/H2O2 system, it was correlated with ·OH yield (R2=0.991) across various wavelengths. Quantitative structure-activity relationship (QSAR) analysis showed selective degradation of six pollutants based on their e--donating capabilities (R2=0.748-0.916). The coexistence of aged MPs, introducing C-O/C=O groups and rearranging their surface e-, potentially affected the elimination efficiency of CFX. Aged polystyrene (PS) decreased the degradation efficiency of CFX by shorting the O-O bond length (lO-O) in H2O2 and capturing e- from H2O2, whereas aged polyethylene (PE), polypropylene (PP) and polyvinyl chloride (PVC) had negligible effects as the lO-O elongation balanced the e--donating effect of H2O2. Additionally, phenol released from aged PS, with strong nucleophilicity, competing with CFX for ·OH, further decreasing CFX degradation efficiency. This study provides valuable insights into organic pollutant selective removal and reveals a novel inhibitory mechanism of aged PS on the performance of UV-LED/H2O2 technology.

Interfacial design of pyrene-based covalent organic framework for overall photocatalytic H2O2 synthesis in water.

Covalent organic frameworks (COFs) have shown great potential in the photocatalytic production of hydrogen peroxide (H2O2) due to their precisely designed and customized ability. Nevertheless, the quest for efficient overall photosynthesis of H2O2 in pure water without sacrificial agents using COF photocatalysts remains a formidable challenge. Herein, three pyrene-based covalent organic frameworks are synthesized using an advanced interfacial design strategy. By incorporating functional groups of F, H, and OH into a COF skeleton, their wettability and charge-separation properties are fine-tuned. These COFs show great performances as photocatalysts for H2O2 production from water and air by utilizing both the oxygen reduction reaction and water oxidation reaction pathways. Compared to PyCOF-F and PyCOF-H, PyCOF-OH demonstrates superior H2O2 production efficiency due to its improved hydrophilicity and enhanced carrier separation, achieving a remarkable rate of 2961 µmol g-1 h-1 from 25 mL pure water and air. Further, the mechanism of H2O2 production over PyCOF-OH is clarified by combining a series of control experiments, in situ characterizations, and theoretical calculations. This study offers valuable insights into the interfacial design of high-performance photocatalysts for H2O2 synthesis.

Stability evaluation from hydrogen peroxide spiking studies.

The ability to detect traces of hydrogen peroxide (H2O2) in water is an important prerequisite to ensure a safe and reliable use of H2O2 for isolator or cleanroom sanitization. While the residual airborne H2O2 concentration can be easily monitored, detection of trace H2O2 residues in aseptically filled drug products is challenging. In an industrial setting, samples must be pulled, handled, stored, and transported before analysis takes place. Therefore, knowledge about the analyte stability in the relevant matrix is crucial to ensure correct results. The objective of this study was to provide stability data for the analyte at low concentrations and in aqueous solutions. For this, H2O2 was spiked into four different aqueous matrices at two different concentrations and stored up to 60 days at four different storage temperatures. The tested matrices included water, buffer, and an exemplary excipient solution with and without additional protein. A developmental quantitative, fluorometric Amplex UltraRed assay was applied for analysis. The results show clearly, that of the four storage temperatures investigated, only -80°C resulted in reasonably good recovery of the spiked H2O2 content within two weeks or even up to two months of storage.

Enantioselectively Generating Imidazolone dIz by the Chiral DNA Intercalating and "Light-switching" Ru(II) Polypyridyl Complex via a Novel Flash-quench Method.

The 2-aminoimidazolone is a major and ubiquitous in vitro product of guanine oxidation. The flash-quench method, combining spectroscopy and product analysis, offers a novel and tunable approach to study guanine oxidation on double helical DNA. Herein we found that imidazolone dIz (2-amino-5-[(2-deoxy-ß-D-erythro-pentofuranosyl)amino]-4H-imidazol-4-one) and dZ (2,2-diamino-5-[2-deoxy-ß-D-erythro-pentofuranosyl)amino]-5(2H)-oxazolone) were the major oxidation products of double-strand DNA from the visible-light irradiation of the well-known DNA intercalating and light-switching Ru(OP)2dppz2+ (OP = 1,10-phenanthroline, dppz = dipyrido[3,2-a:2',3'-c]phenazine) in the presence of a typical quencher methyl viologen (MV2+). Using ESR spin-trapping method, the radical intermediate MV•+ with typical hyperfine pattern was detected which indicated the successful formation of the corresponding Ru3+ intercalated oxidant. The formation of dIz and dZ decreased markedly with the addition of nitrotetrazolium blue chloride (NBT), a typical O2•- reactant. With a more specific and highly sensitive O2•- probe CT02-H, its ESR signal decayed rapidly in the presence of Ru(OP)2dppz2+ and MV2+, suggesting that O2•- was indeed produced. More interestingly, enantio-selective generation of oxidation products from dsDNA was observed with the two chiral forms of Ru(OP)2dppz2+. This represents the first report that the flash-quench technique with MV2+ as the quencher can oxidize dsDNA effectively to form dIz and dZ via the Ru3+/O2•- mediated mechanism. Our new findings provide a novel method to generate two radicals simultaneously, G(-H)• and O2•-, in close proximity to one another in dsDNA.

Electron Donor-Acceptor Complex-Assisted Photochemical Conversion of O-2-Nitrobenzyl Protected Hydroxamates to Amides.

The hydroxamic acid functionality is present in various medicinal agents and has attracted special interest for synthetic transformations in both organic and medicinal chemistry. The N-O bond cleavage of hydroxamic acid derivatives provides an interesting transformation for the generation of various products. We demonstrate, herein, that O-benzyl-type protected hydroxamic acids may undergo photochemical N-O bond cleavage, in the presence or absence of a catalyst, leading to amides. Although some O-benzyl protected aromatic hydroxamates may be photochemically converted to amides in the presence of a base and anthracene as the catalyst, employing O-2-nitrobenzyl group allowed the smooth conversion of both aliphatic and aromatic hydroxamates to primary or secondary amides in good to excellent yields in the presence of an amine, bypassing the need of a catalyst. DFT and UV-Vis studies supported the effective generation of an electron donor-acceptor (EDA) complex between O-2-nitrobenzyl hydroxamates and amines, which enabled the successful product formation under these photochemical conditions. An extensive substrate scope was demonstrated, showcasing that both aliphatic or aromatic hydroxamates are compatible with this protocol, affording a wide variety of primary and secondary amides.

Tunable Luminescent Properties and Multifunctional Imaging Applications of (Gd1-xRx)2O2S:Tb3+ (R = Y, La) Phosphor Screens.

Gd2O2S:Tb3+ phosphor screens are widely used in image intensifiers, computed tomography, and neutron imaging. To improve the luminescent properties and thermal stability, (Gd1-xRx)2O2S:yTb3+ (R = Y, La) (x = 0, 0.05, 0.15, 0.25, and 0.35; y = 0.02, 0.04, 0.06, 0.08, and 0.10) phosphors were successfully prepared by the carbothermal reduction method. The luminescent spectra showed that the optimum concentrations of Tb3+ ions were 6 and 4 mol % when excited by 292 nm UV light and cathode ray, respectively. The emission wavelengths mainly peaked at 489 and 544 nm. It was found that the introduction of Y3+ ions could improve the luminescent intensity, and the luminescent intensity of (Gd1-xYx)2O2S:0.06Tb3+ was the highest at x = 0.25, while La3+ ions played the opposite role. Then, the thermal stability also improved, and the emission intensities of Gd2O2S:0.06Tb3+, (Gd0.75Y0.25)2O2S:0.06Tb3+, and (Gd0.75La0.25)2O2S:0.06Tb3+ phosphors at 423 K decreased to 66.22%, 68.23%, and 76.10% of the emission intensities at 303 K, respectively. Finally, the (Gd0.75Y0.25)2O2S:0.06Tb3+ phosphor screen was successfully prepared by the gravity deposition method and could be well imaged under UV light and cathode ray excitation with a CMOS camera. In summary, this study demonstrates that (Gd1-xRx)2O2S:Tb3+ (R = Y, La) is a phosphor with excellent luminescent and thermal stability properties and has great potential for application in the field of low-level-light night vision, nondestructive testing, and medical imaging.

Investigating the Effects of Chelidonic Acid on Oxidative Stress-Induced Premature Cellular Senescence in Human Skin Fibroblast Cells.

This study investigated the effects of chelidonic acid (CA) on hydrogen peroxide (H2O2) induced cellular senescence in human skin fibroblast cells (BJ). Cellular senescence is a critical mechanism that is linked to age-related diseases and chronic conditions. CA, a γ-pyrone compound known for its broad pharmacological activity, was assessed for its potential to mitigate oxidative stress and alter senescence markers. A stress-induced premature senescence (SIPS) model was designed in BJ fibroblast cells using the oxidative stress agent H2O2. After this treatment, cells were treated with CA, and the potential effect of CA on senescence was evaluated using senescence-related ß-galactosidase, 4',6-diamino-2-phenylindole (DAPI), acridine-orange staining (AO), comet assay, molecular docking assays, gene expression, and protein analysis. These results demonstrate that CA effectively reduces senescence markers, including senescence-associated ß-galactosidase activity, DNA damage, lysosomal activity, and oxidative stress indicators such as malondialdehyde. Molecular docking revealed CA's potential interactions with critical proteins involved in senescence signalling pathways, suggesting mechanisms by which CA may exert its effects. Gene expression and protein analyses corroborated the observed anti-senescent effects, with CA modulating p16, p21, and pRB1 expressions and reducing oxidative stress markers. In conclusion, CA appeared to have senolytic and senomorphic potential in vitro, which could mitigate and reverse SIPS markers in BJ fibroblasts.

Effects of Melatonin and 3,5,3'-Triiodothyronine on the Development of Rat Granulosa Cells.

Melatonin, as an endocrine neurotransmitter, can promote the development of the ovary. Meanwhile, it also has protective effect on the ovary as an antioxidant. Thyroid hormone (TH) is essential for normal human reproductive function. Many studies have shown that 3,5,3'-triiodothyronine (T3) regulates the development of ovarian granulosa cells. However, little is known about the specific mechanisms by which melatonin combines with T3 to regulate granulosa cell development. The aim of present study was to investigate the effects and the possible mechanisms of melatonin and T3 on ovarian granulosa cell development. In the present study, cell development and apoptosis were detected by CCK8, EdU and TUNEL, respectively. The levels of related proteins were analyzed by Western blotting. The results showed that oxidative stress (OS) and reactive oxygen species (ROS) were induced by H2O2 in granulosa cells, and cell apoptosis was also increased accompanied with the decreased cellular proliferation and viability. Melatonin protects granulosa cells from H2O2-induced apoptosis and OS by downregulating ROS levels, especially in the presence of T3. Co-treatment of cell with melatonin and T3 also promotes the expression of GRP78 and AMH, while inhibiting CHOP, Caspase-3, and P16. It was demonstrated that melatonin alone or in combination with T3 had positive effect on the development of granulosa cells. In addition, the AMPK/SIRT1 signaling pathway is involved in the process of melatonin/T3 promoting granulosa cell development.

Effect of H2O2/ascorbic acid degradation and gradient ethanol precipitation on the physicochemical properties and biological activities of pectin polysaccharides from Satsuma Mandarin.

In this work, three degraded polysaccharides (DMPP-40, DMPP-60, DMPP-80) were successfully obtained by H2O2/ascorbic acid degradation and gradient ethanol precipitation from Satsuma mandarin peel pectin (MPP), and their physicochemical properties, antioxidant and prebiotic activities were investigated. The molecular weight of MPP, DMPP-40, DMPP-60, DMPP-80 were determined to be 336.83 ± 10.57, 18.93 ± 0.54, 26.07 ± 0.83 and 8.71 ± 0.27 kDa, respectively. The ethanol concentration significantly affected the physicochemical properties of DMPPs. DMPP-60 showed the highest yield (69.07 %) and uronic acid content (64.85 %), DMPP-80 showed the lowest molecular weight (8.71 kDa), and the composition and proportion of monosaccharides of DMPPs were significantly different. Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance spectroscopy (1H NMR) confirmed that DMPPs exhibited similar functional groups, while X-ray diffraction (XRD) indicated that DMPP-40 possessed some crystallographic sequences. Scanning electron microscopy (SEM) images directly verified the fragmented structure and reduced surface area of DMPPs. Besides, the H2O2/ascorbic acid treatment could obviously reduce the apparent viscosity and thermal stability of MPP. Meanwhile, the results of bioactivity assay showed that DMPPs possessed better antioxidant activity and probiotics pro-proliferative effects compared with MPP. DMPP-80 could significantly inhibit lipopolysaccharides (LPS)-stimulated production of inflammatory factors (including nitric oxide (NO), interleukin (IL)-6, tumor necrosis factor (TNF)-α and interleukin (IL)-1ß) in RAW264.7 cells. Results suggest that the H2O2/ascorbic acid combined with gradient ethanol precipitation has potential applications in degradation and separation of MPP to improve its biological activities.

Kinetic modelling of UVC and UVC/H2O2 oxidation of an aqueous mixture of antibiotics in a completely mixed batch photoreactor.

The removal kinetics of an aqueous mixture of thirteen antibiotics (i.e., ampicillin, cefuroxime, ciprofloxacin, flumequine, metronidazole, ofloxacin, oxytetracycline, sulfadimethoxine, sulfamethoxazole, sulfamethazine, tetracycline, trimethoprim and tylosin) by batch UVC and UVC/H2O2 processes has been modeled in this work. First, molar absorption coefficients (ε), direct quantum yields (Φ) and the rate constants of the reaction of antibiotics with hydroxyl radical (kHO•) (model inputs) were determined for each antibiotic and compared with literature data. The values of these parameters range from 0.3 to 21.8 mM-1 cm-1 for ε, < 0.01 to 67.8 mmol·E-1 for Φ and 3.8 × 109 to 1.7 × 1010 M-1 s-1 for kHO•. Second, a regression model was developed to compute the rate constants of the reactions of the antibiotics with singlet oxygen (k1O2) from experimental data obtained in batch UVC experiments treating a mixture of the antibiotics. k1O2 values in the 1-50 × 106 M-1 s-1 range were obtained for the antibiotics studied. Finally, a semi-empirical kinetic model comprising a set of ordinary differential equations was solved to simulate the evolution of the residual concentration of antibiotics and hydrogen peroxide (model outputs) in a completely mixed batch photoreactor. Model predictions were reasonably consistent with the experimental data. The kinetic model developed might be combined with computational fluid dynamics to predict process performance and energy consumption in UVC and UVC/H2O2 applications at full scale.

Impact of Negative Pressure Wound Therapy on Perfusion Dynamics in Free Latissimus Dorsi Muscle Flaps.

Background: Free muscle flaps can develop significant postoperative edema and wound exudation, thereby increasing interstitial pressure and potentially compromising microcirculation. While concerns exist regarding negative pressure wound therapy (NPWT) to compress free flaps and hinder monitoring, recent studies have indicated a reduction in edema and an increase in blood flow. Objective: To compare microcirculation in free latissimus dorsi muscle (LDM) flaps dressed with and without NPWT. Methods: This retrospective cohort study analyzed prospectively collected data of patients who received free LDM flap reconstruction. Patients were separated into two groups according to management with or without NPWT. Microcirculation was evaluated continuously for up to 72 h utilizing laser doppler flowmetry and tissue spectrometry. Results: In total, n = 61 patients (26 females, 35 males) with an average age of 56.90 (17.4) years were included. NPWT was applied in 12 patients, while a regular cotton dressing was used in 49 patients. Overall, no significant differences in the number of minor and major complications were observed between groups. Both groups showed an increase in microvascular flow over the investigated time period. The flow showed higher absolute values in the NPWT group, reaching statistical significance at 12 h post-anastomosis, p = 0.038. There was a tendency for lower rHb values in the NPWT group, without reaching statistical significance. Conclusions: The presented study confirms the increase in microvascular flow after NPWT application. Whilst ensuring continuous free flap monitoring utilizing laser doppler flowmetry and spectrometry, the data further support the safety of NPWT application without risking vascular compromise due to external compression.