Neutral pH Conditions Research Articles

Evolution of myoglobin diffusion mechanisms: exploring pore and surface diffusion in a single silica particle.

This study elucidates the mass transfer mechanism of myoglobin (Mb) within a single silica particle with a 50nm pore size at various pH levels (6.0, 6.5, 6.8, and 7.0). Investigation of Mb distribution ratio (R) and distribution kinetics was conducted using absorption microspectroscopy. The highest R was observed at pH 6.8, near the isoelectric point of Mb, as the electrostatic repulsion between Mb molecules on the silica surface decreased. The time-course absorbance of Mb in the silica particle was rigorously analyzed based on a first-order reaction, yielding the intraparticle diffusion coefficient of Mb (Dp). Dp-(1 + R)-1 plots at different pH values were evaluated using the pore and surface diffusion model. Consequently, we found that at pH 6.0, Mb diffused in the silica particle exclusively through surface diffusion, whereas pore diffusion made a more substantial contribution at higher pH. Furthermore, we demonstrated that Mb diffusion was hindered by slow desorption, associated with the electrostatic charge of Mb. This comprehensive analysis provides insights into the diffusion mechanisms of Mb at acidic, neutral, and basic pH conditions.

Garnet geochronology, major and trace element geochemistry of the Huanggangliang Fe-Sn polymetallic deposit, NE China

Cu-Fe (Au), W-Sn (Mo), Pb-Zn (Ag) and other element assemblages are common in many skarn deposits, but examples of Fe and Sn coexistence in nature are relatively rare. The Huanggangliang deposit in the southern Great Xing'an Range is the largest Fe-Sn polymetallic deposit in northern China, and there are five main mining areas (SK Ⅰ–SK Ⅴ) distributed along a SW–NE trend. SK Ⅰ and SK Ⅲ are the two larger mining areas in the Huanggangliang deposit, and their mineral assemblages and wall-rocks are significantly different: cassiterite and metal sulfides are duncommon in SK Ⅰ (andesite), while they are widely distributed in SK Ⅲ (marble). Garnet is widely distributed in SK Ⅰ and SK Ⅲ mining areas, and provides a good opportunity to explore the mechanism of Fe-Sn assemblage differentiation. Three types of garnet are distinguishable (Grt 1, Grt 2 and Grt 3) based on their mineral associations, textures and locations, and they mainly belong to the andradite-grossular solid solution series. The LA–ICP–MS U-Pb ages of the garnets from SK Ⅰ and SK Ⅲ are 136.0 ± 1.2 Ma (n = 25, MSWD = 1.9) and 136.2 ± 2.6 Ma (n = 37, MSWD = 1.8), respectively, suggesting that magmatic-hydrothermal activity in these two mining areas began at the same time. Grt 1 (located deep in SK Ⅰ and SK Ⅲ) and Grt 2 (located shallowly in SK Ⅰ) are mainly andradite, while Grt 3 (located shallowly in SK Ⅲ) is mainly grossular. They are all enriched in high field strength elements (HFSEs) and depleted in large ion lithophile elements (LILEs), and their REE patterns are enriched in light rare earth elements (LREEs) and depleted in heavy rare earth elements (HREEs). However, Grt Ⅰ-1a and 1b (deep garnets in SK Ⅰ) exhibit obvious positive Eu anomalies, while the other garnet types exhibit negative or no obvious Eu anomalies. Additionally, Grt 3 has high contents of V, Sn, U, Th, Zn and Y, and low contents of W and Mo. This pattern implies that the garnets in deep SK Ⅰ may have formed under oxidizing conditions with high temperatures, high oxygen fugacity (fO2) and weak acidity, while the garnets in shallow SK Ⅲ formed under reducing conditions with moderate temperatures, moderate fO2 and near-neutral pH. The garnets in shallow SK Ⅰ and deep SK Ⅲ may have formed under weak oxidation–reduction conditions at moderate to high temperatures, moderate fO2 and weakly acidic to neutral pH conditions. Our newly reported field geological, mineralogical, and geochemical data from garnet suggest that the ore-forming fluids of the Huanggangliang were magmatic-hydrothermal fluids mixed with slightly acidic external fluids, chloride complexes may have been the main transport ligands of REEs. The metallogenic environment may be an important factor leading to the difference of mineral assemblages in the Huanggangliang deposit.

Rapid Enrichment of a Native Multipass Transmembrane Protein via Cell Membrane Electrophoresis through Buffer pH and Ionic Strength Adjustment.

Supported membrane electrophoresis is a promising technique for collecting membrane proteins in native bilayer environments. However, the slow mobility of typical transmembrane proteins has impeded the technique's advancement. Here, we successfully applied cell membrane electrophoresis to rapidly enrich a 12-transmembrane helix protein, glucose transporter 1 with antibodies (GLUT1 complex), by tuning the buffer pH and ionic strength. The identified conditions allowed the separation of the GLUT1 complex and a lipid probe, Fast-DiO, within a native-like environment in a few minutes. A force model was developed to account for distinct electric and drag forces acting on the transmembrane and aqueous-exposed portion of a transmembrane protein as well as the electroosmotic force. This model not only elucidates the impact of size and charge properties of transmembrane proteins but also highlights the influence of pH and ionic strength on the driving forces and, consequently, electrophoretic mobility. Model predictions align well with experimentally measured electrophoretic mobilities of the GLUT1 complex and Fast-DiO at various pH and ionic strengths as well as with several lipid probes, lipid-anchored proteins, and reconstituted membrane proteins from previous studies. Force analyses revealed the substantial membrane drag of the GLUT1 complex, significantly slowing down electrophoretic mobility. Besides, the counterbalance of similar magnitudes of electroosmotic and electric forces results in a small net driving force and, consequently, reduced mobility under typical neutral pH conditions. Our results further highlight how the size and charge properties of transmembrane proteins influence the suitable range of operating conditions for effective movement, providing potential applications for concentrating and isolating membrane proteins within this platform.

Binary hetero-structured PVDF/TiO2@MXene composite membranes for the removal of antibiotics from wastewater

The presence of pharmaceuticals in hospital wastewaters has generated significant interest among researchers. Current membrane technologies face limitations in effectively removing these emerging contaminants, which has led to continuous advancements in the field. Two-dimensional (2D) nanomaterial-based membranes have proved their ability in providing high water permeability without compromising separation performance. In this study, a binary hetero-structured PVDF/TiO2@MXene composite 2D membrane was prepared and utilized for the rejection of antibiotics, namely tetracycline and meropenem. Vacuum-assisted filtration was employed to fabricate the photocatalytic and highly selective multi-layer TiO2@MXene stacked sheets on hydrophilic PVDF microfilters. The attachment of TiO2 nanoparticles in the MXene structure has significantly improved the wettability and permeation of the PVDF/TiO2@MXene membrane, with a water contact angle of 19.5° and a permeation capacity of 293 L.m−2.h−1.bar−1. In terms of antibiotic rejection, the developed membrane demonstrated a rejection of 87.8% and 60.7% for tetracycline and meropenem solutions, respectively, through interlayer sieving, adsorption, and photocatalysis. The membrane also performed ideally in neutral pH conditions often present in hospital wastewaters, when compared to acidic and alkaline conditions, aiding in the membrane's adsorptive interactions under UV irradiation. When studied in antibiotic mixtures and spiked real hospital wastewater feed solutions, the membrane exhibited a rejection rate of 77.4% and 70.1% for tetracycline, respectively. This research represents a promising approach to addressing the challenges posed by pharmaceuticals in hospital wastewaters through the synergistic utilization of MXene and anatase TiO2.

Spectral changes of light-harvesting complex 2 lacking B800 bacteriochlorophyll a under neutral pH conditions.

Exchange of B800 bacteriochlorophyll (BChl) a in light-harvesting complex 2 (LH2) is promising for a better understanding of the mechanism on intracomplex excitation energy transfer of this protein. Structural and spectroscopic properties of LH2 lacking B800 BChl a (B800-depleted LH2), which is an important intermediate protein in the B800 exchange, will be useful to tackle the energy transfer mechanism in LH2 by the B800 exchange strategy. In this study, we report a unique spectral change of B800-depleted LH2, in which the Qy absorption band of B800 BChl a is automatically recovered under neutral pH conditions. This spectral change was facilitated by factors for destabilization of LH2, namely, a detergent, lauryl dimethylamine N-oxide, and an increase in temperature. Spectral analyses in the preparation of an LH2 variant denoted as B800-recovered LH2 indicated that most BChl a that was released by decomposition of part of B800-depleted LH2 was a source of the production of B800-recovered LH2. Characterization of purified B800-recovered LH2 demonstrated that its spectroscopic and structural features was quite similar to those of native LH2. The current results indicate that the recovery of the B800 Qy band of B800-depleted LH2 originates from the combination of decomposition of part of B800-depleted LH2 and in situ reconstitution of BChl a into the B800 binding pockets of residual B800-depleted LH2, resulting in the formation of stable B800-recovered LH2.

Overcoming Fe0/Cr(VI) redox-induced low electron transfer efficiency under neutral pH by iron-based dual active sites-mediated hydrogen atom activation

Efficiently removing hexavalent chromium (Cr(VI)) using iron-based adsorbents under neutral pH conditions continues to pose a challenge. In this study, we constructed nano zero-valent iron (nZVI) supported by carboxylated multi-walled carbon nanotubes (OCNT) composites with iron-based dual active sites through the nitrilotriacetic acid modification (FOC-NA). The acid dissolution experiment, high-resolution transmission electron microscopy (HRTEM), thermogravimetric analyzer (TGA), X-ray photoelectron spectroscopy (XPS), and Raman analysis proved these active sites consisted of iron-carboxylate complex (−COOFe(II)) and OCNT-confined nZVI (Fe0-in-OCNT). The existence of iron-based dual active sites enhanced electron transfer efficiency in Cr(VI) removal under neutral pH conditions. This leaded to a superior adsorption capacity for Cr(VI), as evidenced by a maximum adsorption capacity of 141.29 mg·g−1 at a pH of 6.5. Meanwhile, the formation of a Cr-containing product (−COOFe-O-Cr) on the surface of FOC-NA substantially hindered the re-release of chromium into the environment. Furthermore, this study proposed the significant involvement of active hydrogen atoms (H*) in the reduction of Cr(VI), as confirmed by quenching experiments and analyses using electron spin resonance (EPR), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The formation pathway and energy barrier of H* and the −COOFe-O-Cr complex were analyzed by density functional theory (DFT) calculations. This study provided insights for the rational design of iron-based adsorbents with dual active sites to facilitate the activation of H* for Cr(VI) reduction under neutral pH conditions

Fe2W18Fe4@MOF-Ni-100 nanocomposite: Insights into synthesis and application as a promising material towards the electrocatalytic water oxidation

In this research, a new nanocomposite was synthesized via the sol–gel method by encapsulation of tetranuclear sandwich-type hetropolyanion (Na9K[(FeW9O34)2Fe4(H2O)2].32H2O, abbreviated as Fe2W18Fe4, on the surface of MOF-Ni-100 for the first time. The as-prepared nanocomposite (Fe2W18Fe4@MOF-Ni-100) was examined using different microscopy and spectroscopy techniques, including FT-IR, UV–vis, XRD, SEM, EDX, and BET techniques. The assembled Fe2W18Fe4@MOF-Ni-100 nanocomposite served as a potential heterogeneous catalyst in the water oxidation process for the purpose of oxygen evolution reaction (OER) at neutral pH conditions (N2-saturated 0.1 M Na2SO4). The electrochemical characteristics of the Fe2W18Fe4@MOF-Ni-100 nanocomposite was assessed through cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) methods. The desired nanocatalyst displayed a low onset potential of 1.1 V vs. NHE and low overpotential of 269 mV at a current density (j) of 10 mAĊcm−2 with a Tafel slope of 73 mV.dec−1 (pH = 7). Furthermore, the Fe2W18Fe4@MOF-Ni-100 nanocomposite exhibited remarkable stability and retained its catalytic activity even after 200 catalytic cycles.

Application of biochar in electro-Fenton process: Advantages and recent advancements

The electro-Fenton (EF) process is a well-known electrochemical advanced oxidation process that produces highly active hydroxyl radicals via the externally added catalytic amount of iron catalyst and in-situ generated hydrogen peroxide. The performance of the EF process depends on the choice of catalyst and the cathode. Biochar, an economically viable carbon-rich material derived from locally available biomass, presents a promising option for both catalyst support and cathode materials. The heterogeneous EF process using biochar-based catalyst has several advantages over the conventional EF process, including enhanced efficiency, declined iron leaching, surface-predominated radical generation, and pollutant degradation even in neutral pH conditions. Moreover, biochar demonstrates the capacity to generate a significant amount of hydrogen peroxide and regenerate ferrous ions rapidly. Additionally, biochar has a high adsorption capacity for many organic pollutants and ensures the contaminants' proximity and generated reactive species when applied as supports, catalysts, or electrodes in EF and related processes. The novelty of this work lies in its comprehensive review of the significant advancements and advantages of the applications of biochar in the EF process, emphasizing its potential to revolutionize wastewater treatment methodologies.

Magnetite-driven Bio-Fenton degradation of chloroacetanilide herbicides by a newly isolated hydrogen peroxide producing bacterium Desemzia sp. strain C1

The efficiency of the Fenton reaction is markedly contingent upon the operational pH related to iron solubility. Therefore, a heterogeneous Fenton reaction has been developed to function at neutral pH. In the present study, the Bio-Fenton reaction was carried out using magnetite (Fe(II)Fe(III)2O4) and H2O2 generated by a newly isolated H2O2-producing bacterium, Desemzia sp. strain C1 at pH 6.8 to degrade chloroacetanilide herbicides. The optimal conditions for an efficient Bio-Fenton reaction were 10 mM of lactate, 0.5% (w/v) of magnetite, and resting-cells (O.D.600 = 1) of strain C1. During the Bio-Fenton reaction, 1.8–2.0 mM of H2O2 was generated by strain C1 and promptly consumed by the Fenton reaction with magnetite, maintaining stable pH conditions. Approximately, 40–50% of the herbicides underwent oxidation through non-specific reactions of •OH, leading to dealkylation, dechlorination, and hydroxylation via hydrogen atom abstraction. These findings will contribute to advancing the Bio-Fenton system for non-specific oxidative degradation of diverse organic pollutants under in-situ environmental conditions with bacteria producing high amount of H2O2 and magnetite under a neutral pH condition.

Physicochemical assessment of ammonium adsorption using a palm shell-based adsorbent activated with acetic acid: experimental and theoretical studies.

The adsorption of ammonium from water was studied on an activated carbon obtained using raw oil palm shell and activated with acetic acid. The performance of this adsorbent was tested at different operating conditions including the solution pH, adsorbent dosage, and initial ammonium concentration. Kinetic and equilibrium studies were carried out, and their results were analyzed with different models. For the adsorption kinetics, the pseudo-first order equation was the best model to correlate this system. Calculated adsorption rate constants ranged from 0.071 to 0.074 g/mg min. The ammonium removal was 70-80% at pH 6-8, and it was significantly affected by electrostatic interaction forces. Ammonium removal (%) increased with the adsorbent dosage, and neutral pH condition favored the adsorption of this pollutant. The best ammonium adsorption conditions were identified with a response surface methodology model where the maximum removal was 91.49% with 2.27 g/L of adsorbent at pH 8.11 for an initial ammonium concentration of 36.90 mg/L. The application of a physical monolayer model developed by statistical physics theory indicated that the removal mechanism of ammonium was multi-ionic and involved physical interactions with adsorption energy of 29 kJ/mol. This activated carbon treated with acetic acid is promising to depollute aqueous solutions containing ammonium.

Natural Phenolic‐Metal Framework Strengthened Mesona Chinensis Polysaccharides Microgels for Improved Viability of Probiotics to Alleviate the Liver Injury and Gut Microbiota Dysbiosis

AbstractOral probiotics meet challenges during processing, storage, and gastrointestinal harsh conditions. Polysaccharide‐based hydrogels delivery system is promising in probiotic protection, but its semi‐solid and weak strength, and often requires additional cross‐links to solidify its structure. Herein a ferric ion co‐crosslinked microgel of Mesona chinensis polysaccharides and mechanically strengthened by phenolic‐metal frameworks of naturally bound brown bioactives is designed. These microgels has an intact structure in acidic condition and ruptured only at pH neutral conditions which can responsively release highly viable probiotics with high mucoadhesion and colonization. Brown bioactives are naturally bound to polysaccharides (MCPC) by hydrophobic interactions and hydrogen bonding, and they exhibited outstanding anti‐inflammatory and antioxidant properties. Moreover, these brown bioactives are the precise prebiotics which can specifically improve the abundance of Akkermansia genus in gut in vivo. Then, the probiotics Akkermansia muciniphila (AKK) are loaded into brown bioactives frameworks strengthened microgels. There is a more synergistic healthy benefit between MCPC components and loaded AKK compared with free and pasteurized AKK. MCPC microgels can deliver high viable AKK specifically to gut consequently modulating the microbiota balance, and protecting the intestinal barriers. MCPC microgels also delivered the antioxidant brown bioactives specifically into liver to alleviate the hepatic oxidative stress and inflammation.

Dual templated-based synthesis of smart zeolites and its self-healing anticorrosion coatings

The process for the synthesis of smart zeolite is complex. The porous zeolite was synthesized by a hydrothermal route. Aluminium powder and tetraethyl orthosilicate (TEOS) are used as alumina and silica sources. The presence of tetrapropylammonium hydroxide (TPAH) and sodium dodecyl benzene sulphonic acid (SDBS) acts as a structural directing agent and soft templates. The chemical growth mechanism of porous zeolite to form needle structures with the help of templates is discussed. The porous zeolite was prepared using optimum crystallization conditions (temperature and duration) and Si/Al component ratios. Following calcination, the porous zeolite was loaded with mercaptobezothaizole (MBT) and layer by layer (LBL) covered with both cationic and anionic polyelectrolytes. This is the first time a study has been conducted that embraces the porous zeolite pre-loaded with a corrosion inhibitor (MBT). Here, the MBT is released in high pH conditions to prevent corrosion, simultaneously increasing the life of the smart zeolite coatings in a corrosive environment. The smart zeolite-based coatings prevent corrosion by the pH activity of smart zeolite above the neutral pH condition.

Effect of benzoic acid-based and cinnamic acid-based polyphenols on foaming properties of ovalbumin at acidic, neutral and alkaline pH conditions

To broaden the application of ovalbumin (OVA) in food formulations, it is meaningful to improve its foaming characteristics. This study aimed to investigate the effect of benzoic acid-based (3,4-dihydroxybenzoic acid, DA) and cinnamic acid-based polyphenols (trans-2-hydroxycinnamic acid, T2A) on the foaming properties of OVA at acidic (pH 3.0), neutral (pH 7.4) and alkaline (pH 9.0) pH conditions. Both the addition of polyphenols and acid treatment enhanced the foaming properties of OVA. Surface hydrophobicity, circular dichroism, free sulfhydryl groups, and Fourier transform infrared spectroscopy results indicated that after acidic workup, the presence of stronger hydrophobic interactions in OVA-polyphenol aggregates induced more disordered protein conformation and conversion or breakage of disulfide bonds. Particle size and zeta potential indicated that acidic treatment neutralized protein surface charges, further inducing self-aggregation and swelling of OVA, ultimately enhancing foaming properties. Comparatively, T2A exhibited better foam-inducing capacity due to its stronger interaction with OVA, leading to the unfolding of the OVA structure and the exposure of more hydrophobic groups. The intrinsic and 3-D fluorescence spectra experiments also confirmed that OVA-T2A aggregates at pH 3.0 had greater altered non-covalent interaction forces and protein secondary and tertiary structures compared to other complexes. This study provides a theoretical basis for designing protein formulations with excellent foaming properties.

Evaluation of the complexation behaviour among functionalized diphenyl viologens and cucurbit[7] and [8]urils

The complexation behaviour of Diphenyl viologens (DPVs) with Cucurbit[n]urils (CB[n]) was evaluated in detail and the results were reported. In this work, we present the synthesis of various DPVs functionalised with electron withdrawing and electron donating groups (EWGs & EDGs) and investigate their complexation behaviour with CB[7] and CB [8]. Carboxylic acid functionalized DPV’s (DPV-COOH) complexation with CB[8] gives additional insights, i.e., indicates hydrogen bonding plays an effective role in the complexation. The formation of a 2:2 quaternary complex of DPV-COOH/CB[8] under neutral pH conditions was supported by various analytical techniques. The complexation of DPVs with CB[7] specifies that irrespective of the functional group attached, they all form a 1:2 ternary complex, but the findings elaborate that the pattern followed in the complexation depends on the EW or EDG attached to the DPVs. The competition experiments conducted between functionalized DPVs and CB[7], CB[8] shows that they have more affinity towards CB[8] than CB[7] because of the better macrocyclic confinement effect of CB[8], as confirmed using UV–Vis spectroscopy. The binding affinity among EWG and EDG functionalised DPVs with CB[8] concludes EDG functionalised DPVs show better affinity towards CB[8], because they can form a charge transfer complex inside the CB[8] cavity. Exploring these host–guest interactions in more complex biological or environmental settings and studying their impact on the functionality of DPVs could be an exciting avenue for future research.

Mechanism and degradation pathways of photo-Fenton system using Fe(III)-EDDS for Microcystis aeruginosa and microcystin-LR removal

Harmful algal blooms is a global problem of water pollution causing great economic losses to countries. Microcystis aeruginosa, as a dominant algal species in cyanobacterial blooms, has attracted extensive attention. However, most of the current studies on the treatment of alga-containing waters focus on the removal of algal cells or microcystins, lacking the exploration of the degradation pathways and analyses of the toxicity of the products. In this paper, we constructed a photo-Fenton system using Fe(III)-EDDS (EDDS: Ethylenediamine-N,N’-disuccinic acid) complex as an iron source for the simultaneous removal of Microcystis aeruginosa as well as microcystin-LR (MC-LR). The results showed that adding 0.1 mM of Fe(III)-EDDS complex and 1.0 mM of H2O2 achieved 83.3% algal cell removal in 240 min under neutral pH conditions and also degraded 72.5% of MC-LR. Moreover, the degradation products of MC-LR and EDDS were analyzed by LC-MS, which showed that the toxicity of the MC-LR molecule was greatly reduced by benzene ring removal and decarboxylation of partial amino acids, while its degradation resulted from the destruction of amino acids in the MC-LR molecule. The toxicity analyses provide a basis for the practical application of the system, hence consideration can be given to combining or improving it with the existing UV disinfection technologies in water supply plants for potential algal bloom outbreaks. This study was the first time to apply the Fe(III)-EDDS system to the field of microalgae removal and MC-LR detoxication, aiming to provide new development ideas for water purification and photochemical algae removal technology.

Enhancement of cellulase production by cellulolytic bacteria SB125 in submerged fermentation medium and biochemical characterization of the enzyme

Microbial diversity from indigenous cultures has the potential to accelerate lignocellulose degradation through enzymes and make composting economically feasible. Therefore, this study is designed to boost cellulase output from a bacterial strain obtained from soil using a one-variable-at-a-time approach and response surface methodology. The bacteria recognized as Bacillus tequilensis (ON754229) produced the maximum cellulase at a temperature of 37 °C, pH -7.0, and incubation time of 72 h. A major contribution was anticipated by glucose (17 %) and ammonium sulfate (11 %) with cellulase activity of 0.56 U/mL in the optimized medium. The enzyme possessed activity of CMCase, FPase, and amylase of 0.589 μmol/min, 1.22 μmol/min, and 0.92 μmol/min respectively. SDS-PAGE showed a 65 kDa molecular weight of the enzyme capable of degrading cellulose, as confirmed by zymogram analysis. The enzyme showed relatively moderate thermo-stability towards neutral pH conditions possessing optimum conditions at pH 6.5 and temperature of 50 °C. The Km and Vmax values were 11.44 mM and 0.643 μmol/min respectively. The presence of MgSO4, ZnSO4, and Triton X- 100 increased the enzymatic reaction however AgNO3, EDTA, and HgCl2 altered the activation process. These results showed cellulase from B. tequilensis SB125 would be suitable for conventional industrial processes that convert biomass into biofuels.

Application of Fe-ethylene diamine tetraacetic acid complex to enhance the electrocatalytic activation of peroxymonosulfate under neutral pH condition for removal of refractory naphthenic acids

In this work, ethylene diamine tetraacetic acid (EDTA) was applied as a chelating agent to stabilize Fe(III)/Fe(II) cycle to effectively activate peroxymonosulfate (PMS) in an electrochemical (EC) co-catalytic system for elimination of naphthenic acids (NAs) under neutral pH condition. 1-Adamantanecarboxylic acid (ACA) was applied as the model compound for NAs that are persistent contaminants in petroleum industrial wastewater. In the PMS/EC/Fe(III)-EDTA system, complete removal of ACA has been achieved in 20-min reaction under neutral pH condition. Degradation mechanisms were investigated via electron paramagnetic resonance (EPR) analysis, probe experiments and quenching experiments to reveal the reactive species •OH, SO4•− and 1O2 for ACA removal, the production of which have been significantly facilitated by the introduction of EDTA complex. A new pathway has been found for the production of 1O2 via several intermediates including hydrogen peroxide and superoxide radicals. Density functional theory (DFT) calculations and mass spectrometry analysis were applied to predict ACA degradation pathways and byproducts. Decarboxylation, hydroxyl substitution and carbonyl substitution byproducts of ACA were detected. The PMS/EC/Fe(III)-EDTA system suffered nonimportant influence at the presence of humic acid, H2PO4-, HCO3–, NO3– and Cl- for ACA removal. Overall results demonstrate the effectiveness and reliability of the PMS/EC/Fe(III)-EDTA system for efficient removal of NAs in petroleum wastewater in natural environment under neutral pH condition.

PH-sensitive dual-preventive siRNA-based nanomicrobicide reactivates autophagy and inhibits HIV infection in vaginal CD4+ cells

Women are more susceptible to HIV transmission through unprotected heterosexual intercourse due to biological and social vulnerabilities. Intravaginal delivery of siRNAs targeting viral genes, host genes, or in combination has shown promising outcomes against HSV, HPV and HIV. Therefore, in this study, we designed, developed and evaluated a pH-sensitive RNAi-based combination nanomicrobide for the prevention/reduction of vaginal transmission of HIV. The nanomicrobide was composed of siRNA-PEI encapsulated PLGA-PEG nanoparticles (siRNA NP) loaded in a HEC gel dosage form with siRNA targeting host gene CCR5 and the viral gene Nef as a dual preventive strategy. Knocking down CCR5, a co-receptor for HIV could prevent HIV from attaching to and entering host cells and knocking down Nef could reactivate autophagy that was inhibited by Nef to improve the elimination of intracellular virus that escaped the first line of defense. The siRNA NP showed a desirable particle size and zeta potential for intravaginal delivery and a pH-dependent release profile whereby low amounts of siRNA was released under acidic vaginal conditions (vaginal fluid simulant; VFS, pH 4.2) (6.0 ± 0.4% released over 15 days) but significantly higher amounts of siRNA was released under neutral pH conditions (phosphate buffered saline; PBS, pH 7.4) (22.9 ± 0.4% released over 15 days). The CCR5-Nef-specific siRNA NP efficiently knocked down CCR5 and Nef protein expression by 43% and 63%, respectively, reactivated Nef-blocked autophagy and inhibited the replication of HIV in vitro (71.8% reduction in p24 expression). After being formulated into a gel dosage form, siRNA NP could be readily released from the gel, penetrate the vaginal epithelial layer, get taken up into the target cells and knockdown Nef and CCR5 without causing cytotoxicity in a vaginal mucosal co-culture model. Functionalization of siRNA NP with anti-CD4 antibody and loaded into a 0.5% HEC gel improved vaginal distribution and uptake of siRNA in a mouse model with distribution of siRNA restricted to the reproductive tract without any unwanted systemic uptake. The 0.5% HEC gel loaded with siRNA NP-(m)CD4 significantly downregulated approximately 40% of CCR5 protein in the lower vagina and 36% of CCR5 protein in the upper vaginal and cervical region. In contrast, 0.5% HEC gel loaded with siRNA NP-IgG did not result in significant gene knockdown.

Hidden diversity of Pestalotiopsis and Neopestalotiopsis (Amphisphaeriales, Sporocadaceae) species allied with the stromata of entomopathogenic fungi in Taiwan

Pestalotiopsissensu lato, commonly referred to as pestalotiopsis-like fungi, exhibit a broad distribution and are frequently found as endophytes, saprobes and pathogens across various plant hosts. The taxa within pestalotiopsis-like fungi are classified into three genera viz. Pestalotiopsis, Pseudopestalotiopsis and Neopestalotiopsis, based on the conidial colour of their median cells and multi-locus molecular phylogenies. In the course of a biodiversity investigation focusing on pestalotiopsis-like fungi, a total of 12 fungal strains were identified. These strains were found to be associated with stromata of Beauveria, Ophiocordyceps and Tolypocladium in various regions of Taiwan from 2018 to 2021. These strains were evaluated morphologically and multi-locus phylogenetic analyses of the ITS (internal transcribed spacer), tef1-α (translation elongation factor 1-α) and tub2 (beta-tubulin) gene regions were conducted for genotyping. The results revealed seven well-classified taxa and one tentative clade in Pestalotiopsis and Neopestalotiopsis. One novel species, Pestalotiopsis manyueyuanani and four new records, N. camelliae-oleiferae, N. haikouensis, P. chamaeropis and P. hispanica, were reported for the first time in Taiwan. In addition, P. formosana and an unclassified strain of Neopestalotiopsis were identified, based on similarities of phylogeny and morphology. However, the data obtained in the present study suggest that the currently recommended loci for species delimitation of pestalotiopsis-like fungi do not deliver reliable or adequate resolution of tree topologies. The in-vitro mycelial growth rates of selected strains from these taxa had an optimum temperature of 25 °C, but growth ceased at 5 °C and 35 °C, while all the strains grew faster under alkaline than acidic or neutral pH conditions. This study provides the first assessment of pestalotiopsis-like fungi, associated with entomopathogenic taxa.

Electrochemical Redox Conversion of Formate to CO via Coupling Fe-Co Layered Double Hydroxides and Au Catalysts.

Formate has been considered an inactive molecule and thus cannot be further reduced under CO2 reduction conditions, which limits its widespread application as feedstock. Here we present an electrochemical redox conversion of formate to CO through the potential-dependent generation of carbon dioxide radical anions (CO2 ⋅- ) on Fe-Co layered double hydroxides (Fe-Co LDHs) and the subsequent reduction of CO2 ⋅- to CO on Au catalysts. We present an electrodeposition protocol for the synthesis of Fe-Co LDHs with precise composition control and find that Fe1 Co4 exhibits a promising potential window for CO2 ⋅- formation between 1.14 and 1.4 V and an optimized potential at 1.24 V at a neutral pH condition. We further determined the formation of CO2 ⋅- at 1.24 V via electron paramagnetic resonance and CO2 at >1.4 V through differential electrochemical mass spectrometry. This work provides a redox chemistry route for converting formate into CO through a coupled slit parallel-plate electrode system.