Oxidative Hydroxylation Research Articles

Arylazopyrazole linked Schiff bases as organocatalysts for the ipso-hydroxylation of arylboronic acids for the synthesis of phenols

A simple metal-free strategy for the synthesis of phenols from aryl and hetero aryl-boronic acids using arylazopyrazole linked o-hydroxyl Schiff base has been illustrated. These sustainable ipso-hydroxylations have very short reaction times, using aqueous H2O2 as the oxidant in aqueous-alcoholic medium. The current protocol has been demonstrated to be effective with a variety of electron-rich and electron-deficient aromatic substrates and provides access to a wide range of phenols. This is the first time that an azoyrazole linked Schiff base has been used to increase the nucleophilicity of H2O2, in oxidative hydroxylation reactions.

Engineering a localized electrostatic environment to enhance hydroxyl activating for electrocatalytic biomass conversion

The 5-hydroxymethylfurfural electrocatalytic oxidation reaction (HMFOR) is a sustainable and efficient route for converting biomass platform molecules into high-value chemicals. The HMFOR process involves the simultaneous oxidation of hydroxyl and aldehyde groups. Optimizing the reaction pathways by modulating the adsorption behavior of 5-Hydroxymethylfurfural molecules toward a higher conversion rate is vital for achieving an efficient HMFOR. In this study, the HMFOR electrocatalytic performance of NiO was enhanced by regulating the surface microenvironment through the decoration of NiO nanosheets with polypyrrole (PPy). Operando Fourier transform infrared spectroscopy, density functional theory calculation, and electrochemical behavior characterizations demonstrated that electropositive PPy can optimize the adsorption behavior of electronegative hydroxyl groups and modulate the reaction pathway toward the formation of 2,5-diformylfuran intermediates. By modulating the local microenvironment, the designed NiO-PPy catalyst showed excellent HMFOR performance with a threefold increase in current density. This study emphasizes the significance of the surface microenvironment in modulating reaction pathways to achieve selective biomass electrocatalytic conversion.

2D layers of interconnected reduced graphene oxide with vanadium disulfide photocatalysts for Rhodamine B degradation

Significant concern has been raised on water remediation processes because of the Fourth Industrial Revolution. Toxic organic chemical compounds generated as industrial waste directly spoil the aquatic environment. Thus, the development of photocatalysis is advancing because of the need to clean refractory organic effluents without causing secondary contamination. This work presents a distinctive method for fabricating a novel, efficient, and low-cost rGO-VS2 hybrid composite for photocatalytic dye degradation. The lattice spacing in rGO-VS2 confirmed the compact structure between rGO (0.33 nm) and VS2 (0.57 nm). The photocatalytic performance of the rGO-VS2 composite was determined by the degradation of Rhodamine B (RhB) dye by various optimization processes involving multiple arrays between rGO and VS2 and the effect of the catalyst dosage. The rVS2-3 photocatalyst shows better performance in degradation of RhB because after the addition of VS2 with rGO, the band gap of VS2 decreases from 1.92 to 0.89 eV. Among various materials, 50 mg of rVS2-3 photocatalyst at pH 6 provides excellent degradation efficiency (84.7%) and the highest reproducibility. The trapping test revealed that the direct oxidation of holes (h+) and hydroxyl radical (OH•) plays significant role while superoxide radical (O2•−) acts as secondary active species. The rVS2-3 provides more significant benefits during the dye degradation process, mainly by boosting hydroxyl radical (OH•) generation, effectively influencing the breakdown of the RhB dye molecules into minor toxic forms and minerals.

Frozen reinforced microneedles loaded with NIR-photothermal nanozyme for keratitis treatment

Developing a potential alternative with safe, minimally invasive, and highly effective antimicrobial properties is significant for treating bacterial keratitis. In this paper, we present novel nanozyme-loaded frozen reinforced microneedles (FR-MNs) with the ability to deliver the nanozyme controllably inside the cornea to treat keratitis. The nanozymes constructed by the iron ion, tannic acid (TA), and poly (vinylpyrrolidone; PVP) (FeTAP) are incorporated within the MNs tips. The freezing process could greatly enhance the mechanical strength of the tips. Taking advantage of the pH-dependent peroxidase-mimetic activities of FeTAP, the FeTAP integrated MNs can catalyze hydrogen peroxide (H2O2) to produce much more oxidative hydroxyl (•OH) in acidic condition to kill bacteria. Meanwhile, the excellent photothermal efficiency of FeTAP can further enhance the ability of bacterial killing under near-infrared (NIR) irradiation. In addition, the photothermal action can rapidly increase the temperature of the frozen microneedles and subsequently soften the MNs after penetration, which can result in better adaptation of MNs to soft tissues. Based on the nanozyme-loaded FR-MNs, we have demonstrated that this formulation exhibited superior therapeutic potential in the rat eye infection model compared with conventional eye drops. These features impart the proposed nanozyme-loaded FR-MNs with great scientific value and promising clinical applications.

Kinetics and Products of Heterogeneous Hydroxyl Radical Oxidation of Isoprene Epoxydiol-Derived Secondary Organic Aerosol

Kinetics and Products of Heterogeneous Hydroxyl Radical Oxidation of Isoprene Epoxydiol-Derived Secondary Organic Aerosol

Selective Oxidative Dehydrogenation of Ethane and Propane over Copper‐Containing Mordenite: Insights into Reaction Mechanism and Product Protection

AbstractCopper(II)‐containing mordenite (CuMOR) is capable of activation of C−H bonds in C1‐C3 alkanes, albeit there are remarkable differences between the functionalization of ethane and propane compared to methane. The reaction of ethane and propane with CuMOR results in the formation of ethylene and propylene, while the reaction of methane predominantly yields methanol and dimethyl ether. By combining in situ FTIR and MAS NMR spectroscopies as well as time‐resolved Cu K‐edge X‐ray absorption spectroscopy, the reaction mechanism was derived, which differs significantly for each alkane. The formation of ethylene and propylene proceeds via oxidative dehydrogenation of the corresponding alkanes with selectivity above 95 % for ethane and above 85 % for propane. The formation of stable π‐complexes of olefins with CuI sites, formed upon reduction of CuII‐oxo species, protects olefins from further oxidation and/or oligomerization. This is different from methane, the activation of which proceeds via oxidative hydroxylation leading to the formation of surface methoxy species bonded to the zeolite framework. Our findings constitute one of the major steps in the direct conversion of alkanes to important commodities and open a novel research direction aiming at the selective synthesis of olefins.

Selective Oxidative Dehydrogenation of Ethane and Propane over Copper-Containing Mordenite: Insights into Reaction Mechanism and Product Protection.

Copper(II)-containing mordenite (CuMOR) is capable of activation of C-H bonds in C1 -C3 alkanes, albeit there are remarkable differences between the functionalization of ethane and propane compared to methane. The reaction of ethane and propane with CuMOR results in the formation of ethylene and propylene, while the reaction of methane predominantly yields methanol and dimethyl ether. By combining in situ FTIR and MAS NMR spectroscopies as well as time-resolved Cu K-edge X-ray absorption spectroscopy, the reaction mechanism was derived, which differs significantly for each alkane. The formation of ethylene and propylene proceeds via oxidative dehydrogenation of the corresponding alkanes with selectivity above 95 % for ethane and above 85 % for propane. The formation of stable π-complexes of olefins with CuI sites, formed upon reduction of CuII -oxo species, protects olefins from further oxidation and/or oligomerization. This is different from methane, the activation of which proceeds via oxidative hydroxylation leading to the formation of surface methoxy species bonded to the zeolite framework. Our findings constitute one of the major steps in the direct conversion of alkanes to important commodities and open a novel research direction aiming at the selective synthesis of olefins.

Triangulenium Ions: Versatile Organic Photoredox Catalysts for Green-Light-Mediated Reactions

AbstractThe development of tunable organic photoredox catalysts remains important in the field of photoredox catalysis. A highly modular and tunable family of trianguleniums (azadioxatriangulenium, diazaoxatriangulenium, and triazatriangulenium), and the related [4]helicene quinacridinium have been used as organic photoredox catalysts for photoreductions and photooxidations under visible light irradiation (λ = 518–640 nm). A highlight of this family of photoredox catalysts is their readily tunable redox properties, leading to different reactivities. We report their use as photocatalysts for the aerobic oxidative hydroxylation of arylboronic acids and the aerobic cross-dehydrogenative coupling reaction of N-phenyl-1,2,3,5-tetrahydroisoquinoline with nitromethane through reductive quenching. Furthermore, their potential as photoreduction catalysts has been demonstrated through the catalysis of an intermolecular atom-transfer radical addition via oxidative quenching. These transformations serve as benchmarks to highlight that the easily synthesized trianguleniums, congeners of the acridiniums, are versatile organic photoredox catalysts with applications in both photooxidations and photoreductions.

Sunlight-driven photocatalytic degradation of Norfloxacin antibiotic in wastewater by ZnSe microsphere functionalized RGO composite

The release of hazardous pollutants into the water, such as dyes, phenolic compounds, pesticides, different heavy metals, and antibiotics is the primary cause of environmental pollution. The solar energy-based photocatalysis technique has the potential to eliminate pollutants from the aquatic environment. ZnSe is a significant and commendable II-VI group photocatalyst having 2.82 eV direct band gap energy. Its performance towards degrading antibiotics in the presence of light was improved by anchoring it on the Reduced graphene oxide (RGO) matrix. Solution-processable RGO-ZnSe composites were characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Several spectroscopic studies like Raman spectroscopy, ultraviolet-visible spectroscopy, and photoluminescence spectroscopy were employed to illustrate the optical properties of the composites. The findings demonstrate that the ZnSe microsphere was supported effectively onto the two-dimensional RGO matrix. The performance of as-synthesized RGO-ZnSe composites was assessed based on the photocatalytic degradation of the antibiotic Norfloxacin in the presence of simulated solar light. An optimized RGO-ZnSe composite degrades approximately 83.5% of Norfloxacin in 40 min, while controlled-ZnSe photocatalysis only yields 33% in an identical experimental condition. The optimized RGO-ZnSe achieves the highest degradation reaction rate constant (k) of Norfloxacin (k = 0.057 min−1), and the k value is 4.38 times greater compared to the controlled-ZnSe microsphere. The light-dependent catalytic degradation mechanism was examined by employing scavenger experiments which gave away the responsible reactive radicals. Our results establish that the photo-generated hole has the leading role in the degradation of Norfloxacin in our system. In addition to that, the oxide radical and hydroxyl radical has also an important role in the degradation of Norfloxacin under our experimental condition. The finding suggests that the addition of RGO has enhanced photocatalytic performance and cyclic stability by preventing photo-generated electron-hole pair recombination. The photocatalytic oxidative deactivation mechanism of the Norfloxacin antibiotic was proposed. Our study offers new perceptiveness for the design of efficient solution-processable solar light-responsible photocatalysts for environmental pollution remediation.

Hydroxyquinolinate diarylboron complexes for photocatalytic activity

In this paper, readily obtainable hydroxyquinolinate diarylboron complexes were characterized by UV–vis measurements, computational calculations and they were tested as photocatalysts in perfluoroalkylation of unsaturated bonds through a photocatalytic ATRA process. Amongst the studied compounds the respective diphenyl derivative was selected as the most economic photocatalyst. It was next utilized in a visible-light driven aerobic oxidative hydroxylation of arylboronic acids using air as the oxygen source.

Peroxides on the Surface of Organic Aerosol Particles Using Matrix-Assisted Ionization in Vacuum (MAIV) Mass Spectrometry.

Organic peroxides are key intermediates in the atmosphere but are challenging to detect, especially in the particle phase, due to their instability, which has led to substantial gaps in the understanding of their environmental effects. We demonstrate that matrix-assisted ionization in vacuum (MAIV) mass spectrometry (MS), which does not require an ionization source, enables in situ characterization of peroxides and other products in the surface layers of organic particles. Hydroxyl radical oxidation of glutaric acid particles yields hydroperoxides and organic peroxides, which were detected with signals of the same order of magnitude as the major, more stable products. Product identification is supported by MS/MS analysis, peroxide standards, and offline high-resolution MS. The peroxide signals relative to the stable carbonyl and alcohol products are significantly larger using MAIV compared to those in the offline bulk analysis. This is also the case for analysis using fast, online easy ambient sonic-spray ionization mass spectrometry. These studies demonstrate the advantage of MAIV for the real-time characterization of labile peroxides in the surface layers of solid particles. The presence of peroxides on the surface may be important for surface oxidation processes as well as for the toxicity of inhaled particles.

Effects of photochlorination on the physicochemical transformation of polystyrene nanoplastics: Mechanism and environmental fate.

With the increasingly severe plastic pollution, the environmental behavior and effects of nanoplastics (NPs) have attracted much attention. The transformation of NPs in natural and engineered environments (e.g., photooxidation, disinfection) can significantly alter the physicochemical properties and thus affect the fate and toxicity of NPs. However, how solar irradiation with free chlorine, an inevitable process once NPs enter the environment from wastewater treatment plants, affects the physicochemical properties of NPs is still unclear. In this study, the behavior and mechanism of polystyrene (PS) NPs transformation in the solar/chlorine process were evaluated. The results demonstrated that solar irradiation significantly enhanced the physicochemical transformation of PS NPs during chlorination, including chain scission, surface oxidation, and organic release. In addition, two-dimensional correlation spectroscopy analysis using Fourier transform infrared spectroscopy and reactive species quenching experiments showed that chain scission and surface oxidation of PS NPs were primarily caused by direct oxidation of hydroxyl radicals and ozone, while reactive chlorine species played an indirect role. Moreover, photochlorination-induced changes in the properties of PS NPs enhanced the colloidal stability in synthetic wastewater solution and toxicity to Caenorhabditis elegans. These findings reveal an important transformation behavior of nanoplastics in the environment and emphasize the importance of accounting for photochlorination to accurately assess the ecological risk of nanoplastics.

Solar-Driven Reforming of Methane and Nitrogen to Methanol and Ammonium on Iron-Modified Zeolite under Ambient Conditions in Water.

Artificial photosynthesis from selective methane oxidation or nitrogen reduction to value-added chemicals provides a promising pathway for the sustainable chemical industry, while still remaining a great challenge due to the extreme difficulty in C-H and N≡N bond cleavage under ambient conditions. Catalysts that can cocatalyze these two reactions simultaneously are rarely reported. Here, Fe-ZSM-5 with highly dispersed extra-framework Fe-oxo species enables efficient and selective photocatalytic conversion of methane and nitrogen to coproduce methanol and ammonia using H2O as the redox reagent under ambient conditions. The optimized Fe-ZSM-5 photocatalyst achieves up to 0.88 mol/molFe·h of methanol products with 97% selectivity. Meanwhile, the productivity of ammonia is 0.61 mol/molFe·h. In situ EPR and DRIFT studies disclose that water serves as a redox reagent to provide hydroxyl radicals for methane oxidation and protons for nitrogen hydrogenation. Quantum chemical calculations revealed that Fe-oxo species play a significant role in the coactivation of methane and nitrogen molecules, which lowers the energy barriers of rate-determining steps for methanol and ammonia generation.

Photocatalytic Oxidative Hydroxylation of Arylboronic Acids to Phenols by a CdS-TiO2 Nanohybrid

Photocatalytic Oxidative Hydroxylation of Arylboronic Acids to Phenols by a CdS-TiO2 Nanohybrid

Sodium Hydroxide (NaOH)‐Mediated Oxidative Hydroxylation of Arylboronic Acids and Its Applications in C‐O Bond Formation

AbstractWe have developed a straightforward methodology for converting arylboronic acids into phenols using NaOH‐mediated air oxidation. This reaction offers several advantages, including simple operation, excellent tolerance towards various functional groups, and scalability. The transmetalation of the resulting borate ester with NaOH occurs readily, enabling convenient derivatization of the borate ester into aryl ethers and esters using alkyl and acyl halides.

Ag improves the performance of the oxygen evolution reaction by lowering the D-band center of the active site Ni

The development of high activity catalysts with excellent durability is a great challenge to realize the industrialization of electrolytic water oxygen evolution. In this work, Ag nanoparticles modified cross column nickel-iron hydroxyl oxide system (NiFeAg) nanocomposites were synthesized by a two-step strategy. Through XPS spectrum, Tafel slope, and EIS electrochemical impedance spectroscopy, it was found that Ag mainly plays a conductive role, accelerates charge transfer, and adjusts the surface electronic structure, to improve the activity of the catalyst. Impressive is the overall hydrolysis performance, with a current density of 10 mA cm−2 achieved at an overpotential of 211 mV, which shows better performance than other catalysts reported in the literature. Finally, through the theoretical calculation of the determination steps of adsorption energy and rate of oxygen-containing intermediates, it is determined that the active center of the catalyst is mainly Ni site. According to the theory of D-band center, Ag can effectively adjust the D-band center, thereby adjusting the adsorption strength of Ni sites on the surface of NiFe catalyst to adsorbent, and finally improving the OER performance of the catalyst.

Cyclic amplification of intracellular ROS boosts enzymatic prodrug activation for enhanced chemo-immunotherapy.

Tumor-associated enzyme activated prodrug is a potential strategy to overcome the limitations of chemotherapeutic agents. However, the efficiency of enzymatic prodrug activation is limited by the inability to reach adequate enzyme levels in vivo. Herein, we report an intelligent nanoplatform with cyclic amplification of intracellular reactive oxygen species (ROS) that significantly up-regulates the expression of tumor-associated enzyme, NAD(P)H:quinone oxidoreductase 1 (NQO1), to efficiently activate the prodrug of doxorubicin (DOX) for enhanced chemo-immunotherapy. The nanoplatform termed as CF@NDOX was fabricated by self-assembly of the amphiphilic cinnamaldehyde (CA) containing poly(thioacetal) conjugated with ferrocene (Fc) and poly(ethylene glycol) (PEG) (TK-CA-Fc-PEG), which further encapsulated the NQO1 responsive prodrug of DOX (NDOX). After CF@NDOX accumulates in tumors, the TK-CA-Fc-PEG with ROS responsive thioacetal group responds to endogenous ROS in tumor to release CA, Fc or NDOX. CA induces mitochondria dysfunction and elevates the intracellular hydrogen peroxide (H2O2) levels, which react with Fc to generate highly oxidative hydroxyl radical (•OH) through Fenton reaction. The •OH not only promotes ROS cyclic amplification but also increase the expression of NQO1 through Keap1-Nrf2 pathway regulation, which further boost the prodrug activation of NDOX for enhanced chemo-immunotherapy. Overall, our well-designed intelligent nanoplatform provides a tactic to enhance the antitumor efficacy of tumor-associated enzyme activated prodrug. STATEMENT OF SIGNIFICANCE: In this work, a smart nanoplatform CF@NDOX with intracellular ROS cyclic amplification for continuous upregulation of NQO1 enzyme expression was innovatively designed. It could utilize Fenton reaction of Fc to increase the level of NQO1 enzyme and CA to increase the level of intracellular H2O2, thereby facilitating the continuous Fenton reaction. This design allowed for a sustained elevation of the NQO1 enzyme, and a more complete activation of the NQO1 enzyme in response to the prodrug NDOX. This smart nanoplatform can achieve a desirable anti-tumor effect with the combined therapy of chemotherapy and ICD effects.

Cardioprotective effect of 2-methoxy phenol derivatives against oxidative stress-induced vascular complications: An integrated in vitro, in silico, and in vivo investigation

BackgroundOxidative stress and inflammation play crucial roles in macro/microvascular complications. Phenolic compounds and their derivatives show promise as therapeutic agents for diseases like cancer, metabolic disorders, and cardiovascular diseases. With their antioxidant and anti-inflammatory properties, these compounds hold potential for mitigating vascular complications and improving overall health. MethodologyThis study aimed to assess the therapeutic potential of five 2-methoxy phenol derivatives (T2, T5, T6, T7, and T8) as antioxidants, anti-inflammatory agents, and vasorelaxants using in vitro, in silico, and in vivo approaches. ResultsAmong all, T2 exhibited substantial antioxidant potential against 2, 2-diphenyl-1-picrylhydrazyl (DPPH) radicals with IC50 (27.97 µg/mL), nitric oxide (NO) radicals (IC50 = 34.36 µg/mL), hydroxyl (OH) radicals (IC50 = 34.83 µg/mL) and Iron chelation (IC50 = 24.32 µg/mL). Molecular docking analysis confirms that all derivatives, particularly T2, exhibit favorable binding energies with the target proteins, ACE (−7.7 Kcal/mol), ECE-1 (−7.9 Kcal/mol), and COX-1 (−7.8 Kcal/mol). All of the compounds demonstrated satisfactory physicochemical and pharmacokinetic characteristics, and showed minimal to no toxicity during in silico, in vitro, and in vivo assessments. In isolated aortic rings from Sprague Dawley rats, pre-contracted with high K+ (80 mM), T2 induced vasorelaxation in dose dependent manner and shifted calcium response curves to the right as compared to verapamil. T2 also showed substantial platelet aggregation inhibition in a dose dependent manner with IC50 21.29 µM. All derivatives except T7 exhibited significant conservation of endogenous antioxidants i.e. catalase (CAT), peroxidase (POD), superoxide dismutase (SOD) and reduced glutathione (GSH) and significantly suppressed serum levels of inflammatory markers i.e. nitric oxide (NO), peroxides (TBARS), interleukin-6 (IL-6) and cyclooxygenase-2 (COX-2). ConclusionThe study concludes that T2 has significant antioxidant potential and vasorelaxant effects with adequate pharmacokinetics, making it a promising lead compound for further molecular investigation in cardiovascular disorders.

Oxidation of Cathepsin D by Hydroxy Radical: Its Effect on Enzyme Structure and Activity against Myofibrillar Proteins Extracted from Coregonus peled.

In this study, cathepsin D was oxidized in vitro with different concentrations of H2O2, and the activity, structure, and extent of myofibrillar protein degradation by oxidized cathepsin D were evaluated. The sulfhydryl content of cathepsin D decreased to 9.20% after oxidation, while the carbonyl content increased to 100.06%. The β-sheet in the secondary structure altered due to oxidation as well. The changes in the intrinsic fluorescence and UV absorption spectra indicated that oxidation could cause swelling and aggregation of cathepsin D molecules. The structure of cathepsin D could change its activity, and the activity was highest under 1 mM H2O2. Cathepsin D could degrade myofibrillar proteins in different treatment groups, and the degree of degradation is various. Therefore, this study could provide a scientific basis for the mechanism of interaction among hydroxyl radical oxidation, cathepsin D, and MP degradation.

Low environmental impact remediation of microplastics: Visible-light photocatalytic degradation of PET microplastics using bio-inspired C,N-TiO2/SiO2 photocatalysts

Microplastics (MPs) are plastic particles with sizes between 1 μm and 5 mm with a ubiquitous presence in aquatic ecosystems. MPs harm marine life and can cause severe health problems for humans. Advanced oxidation processes (AOPs) that involve the in-situ generation of highly oxidant hydroxyl radicals can be an alternative to fight MPs pollution. Of all the AOPs, photocatalysis has been proven a clean technology to overcome microplastic pollution. This work proposes novel C,N-TiO2/SiO2 photocatalysts with proper visible-active properties to degrade polyethylene terephthalate (PET) MPs. Photocatalysis was performed in an aqueous medium and at room temperature, evaluating the influence of two pH values (pH 6 and 8). The results demonstrated that the degradation of the PET MPs by C,N-TiO2/SiO2 semiconductors is possible, achieving mass losses between 9.35 and 16.22 %.