High-performance Liquid Chromatography-mass Spectrometry Research Articles

Bio-electrochemical degradation of carbamazepine (CBZ): A comprehensive study on effectiveness, degradation pathway, and toxicological assessment

Recent attention on the detrimental effects of pharmaceutically active compounds (PhACs) in natural water has spurred researchers to develop advanced wastewater treatment methods. Carbamazepine (CBZ), a widely recognized anticonvulsant, has often been a primary focus in numerous studies due to its prevalence and resistance to breaking down. This study aims to explore the effectiveness of a bio-electrochemical system in breaking down CBZ in polluted water and to assess the potential harmful effects of the treated wastewater. The results revealed bio-electro degradation process demonstrated a collaborative effect, achieving the highest CBZ degradation compared to electrodegradation and biodegradation techniques. Notably, a maximum CBZ degradation efficiency of 92.01% was attained using the bio-electrochemical system under specific conditions: Initial CBZ concentration of 60 mg/L, pH level at 7, 0.5% (v/v) inoculum dose, and an applied potential of 10 mV. The degradation pathway established by identifying intermediate products via High-Performance Liquid Chromatography-Mass Spectrometry, revealed the complete breakdown of CBZ without any toxic intermediates or end products. This finding was further validated through in vitro and in vivo toxicity assays, confirming the absence of harmful remnants after the degradation process.

A simple, rapid, and green method for determination of three cholic acids in bio-transformed Jindanfen by HPLC-MS

AbstractA simple, rapid, and green high-performance liquid chromatography-mass spectrometry (HPLC-MS) method was developed for determination of tauroursodeoxycholic acid (TUDCA), taurocholic acid (TCA), and taurochenodeoxycholic acid (TCDCA) in bio-transformed Jindanfen (BTJDF), which is obtained from chicken bile through a bioconversion process. The sample was prepared using water. The HPLC separation was operated on a poroshell 120 EC-C18 column with a 2.0 min gradient elution procedure. Detection was performed on a single quadrupole mass spectrometer in negative mode with selected ion monitoring mode (SIM). This developed HPLC-MS method presented good linearity (r > 0.997) and sensitivity (limit of quantification, 30.0–80.0 pg) for three analytes. The relative standard deviations (RSDs) for precision, repeatability, and stability were all below 3.00%. The matrix effects and average recoveries of three analytes were 91.2–97.9% (RSDs < 1.50%) and 95.4–103% (RSDs < 3.00%), respectively. The average contents of TUDCA, TCA, and TCDCA in ten batches of samples were 33.8, 13.2, and 20.5%, respectively. Finally, the greenness of the developed method was validated by Analytical Eco-Scale and Complex-GAPI. The developed method was proved to be an eco-friendly, effective, and reliable approach for assaying the three cholic acids in BTJDF, which is help to improve the quality evaluation level of the BTJDF industry.

Salivary metabolomic identification of biomarker candidates for oral melanoma and oral squamous cell carcinoma in dogs.

Oral melanoma (OM) and oral squamous cell carcinoma (OSCC) are frequently diagnosed in dogs, presenting a challenge in distinguishing them from benign oral tumors (BN). Salivary metabolomic biomarkers offer a practical solution because of saliva's direct contact with tumors and the noninvasive nature of collection. Assess the diversity and abundance of the salivary metabolome in dogs with BN, OM, and OSCC using amine/phenol submetabolome analysis and high-performance chemical isotope labeling liquid chromatography-mass spectrometry (CIL LC-MS). Study included 11 BN, 24 OM, 10 OSCC, and 20 healthy control dogs. Case-control cross-sectional study was conducted to assess salivary submetabolic profiles in dogs with BN, OM, and OSCC and healthy dogs. Samples were labeled with 12C-dansyl chloride and analyzed using CIL LC-MS targeted to amine- and phenol-containing metabolites for amine/phenol submetabolome analysis. Distinct clusters and significant differences in metabolite concentrations were observed among the oral cancer, BN, and control groups. A total of 154 and 66 metabolites showed significantly altered concentrations, particularly in OM and OSCC, respectively, when compared with BN (Padj < .05). Potential metabolic biomarkers were identified for each cancer, including decreased concentrations of seryl-arginine and sarcosine in OSCC. Moreover, high-confidence putative metabolites were identified, including an increase in tryptophyl-threonine and a decrease in 1,2-dihydroxynapthalene-6-sulfonic acid and hydroxyprolyl-hydroxyproline for OM. We identified high coverage of the amine/phenol submetabolome, including seryl-arginine, and sarcosine, in OSCC. Our findings emphasize the potential of these biomarkers for distinguishing between oral OSCC and BN in dogs.

Influencing risk factors of voriconazole-induced liver injury in Uygur pediatric patients undergoing allogeneic hematopoietic stem cell transplantation

PurposeWe aimed to investigated the influencing risk factors of voriconazole-induced liver injury in Uygur pediatric patients undergoing allogeneic hematopoietic stem cell transplantation (HSCT).MethodsThis was a prospective cohort design study. High-performance liquid chromatography-mass spectrometry was employed to monitor voriconazole concentration. First-generation sequencing was performed to detect gene polymorphisms. Indicators of liver function were detected at least once before and after voriconazole therapy.ResultsForty-one patients were included in this study, among which, 15 patients (36.6%) had voriconazole-induced liver injury. The proportion of voriconazole trough concentration > 5.5 μg·mL−1 patients within the DILI group (40.0%) was significantly higher compared to the control group (15.4%) (p < 0.05). After administration of voriconazole, the values of ALT (103.3 ± 80.3 U/L) and AST (79.9 ± 60.6 U/L) in the DILI group were higher than that in the control group (24.3 ± 24.8 and 30.4 ± 8.6 U/L) (p < 0.05). There was no significant difference between the two groups in genotype and allele frequencies of CYP2C19*2, CYP2C19*3, CYP2C19*17, and UGT1A4 (rs2011425) (p > 0.05).ConclusionThere was a significant correlation between voriconazole-induced liver injury and voriconazole trough concentration in high-risk Uygur pediatric patients with allogeneic HSCT.

A phase 1/2 study of disulfiram and copper with concurrent radiation therapy and temozolomide for patients with newly diagnosed glioblastoma

This phase 1/2 study evaluates the safety and preliminary efficacy of combining disulfiram and copper (DSF/Cu) with radiation therapy (RT) and temozolomide (TMZ) in patients with newly diagnosed glioblastoma (GBM). Patients received standard RT and TMZ with DSF (250-375 mg daily) and Cu, followed by adjuvant TMZ plus DSF (500 mg/day) and Cu. Pharmacokinetic analyses determined drug concentrations in plasma and tumors using high-performance liquid chromatography-mass spectrometry. Thirty-three patients, with a median follow-up of 26.0 months, were treated, including 12 IDH-mutant, 9 NF1-mutant, 3 BRAF-mutant, and 9 other IDH-wildtype cases. In the phase-1 arm, 18 patients were treated; dose-limiting toxicity (DLT) probabilities were 10% (95% CI: 3-29%) at 250 mg/day and 21% (95% CI: 7-42%) at 375 mg/day. The phase 2 arm treated 15 additional patients at 250 mg/day. No significant difference in overall survival or progression-free survival were noted between IDH-mutant and NF1-mutant cohorts compared to institutionally counterparts treated without DSF/Cu. However, extended remission occurred in three BRAF-mutant patients. Diethyl-dithiocarbamate-copper, the proposed active metabolite of DSF/Cu, was detected in plasma but not in tumors. The maximum tolerated dose of DSF with RT and TMZ is 375 mg/day. DSF/Cu showed limited clinical efficacy for most patients. However, promising efficacy was observed in BRAF-mutant GBM, warranting further investigation.

Degradation and transformation mechanisms of pungent substances in huajiao (Zanthoxylum bungeanum) oil during storage: Induced by ultraviolet irradiation

The pungency of huajiao (scientifically known as Zanthoxylum bungeanum) oil (ZBO), a crucial seasoning oil, is notably influenced by storage conditions, an aspect insufficiently explored in current research. Through the use of high-performance liquid chromatography and liquid chromatography-mass spectrometry, this study systematically investigated the stability of pungent compounds in ZBO under various storage conditions. It also elucidated the degradation and transformation mechanisms of these substances when exposed to ultraviolet (UV) irradiation. The results underscore elevated temperature, light exposure, oxygen, and storage duration as pivotal factors influencing compound degradation, with UV light emerging as the primary driving force. After 48 h of UV exposure, the primary pungent compound, hydroxy-α-sanshool, experienced a significant loss of 85.49%, indicating a pronounced inclination towards isomerization and oxidation. Notably, this study reveals, for the first time, the possible degradation-transformation pattern of hydroxy-γ-sanshool: a mutual conversion with hydroxy-γ-isosanshool and isomerization to (2E,4E,8Z,10E,12Z)-N-(2-hydroxy-2-methylpropyl) tetradeca-2,4,8,10,12-pentaenamide.

Electron transfer mediated photo-Fenton-like synergistic catalysis of Fe,Cu-doped MIL-101 coupled with Ag3PO4: Quantitative evaluation and DFT calculations

Widespread use of tetracycline (TC) results in its persistent residue and bioaccumulation in aquatic environments, posing a high toxicity to non-target organisms. In this study, a bimetal-doped composite material Ag3PO4/MIL-101(Fe,Cu) has been designed for the treatment of TC in aqueous solutions. As the molar ratio of Fe/Cu in composite is 1:1, the obtained material AP/MFe1Cu1 is placed in an aqueous environment under visible light irradiation in the presence of 3 mM peroxydisulfate (PDS), which forms a photo-Fenton-like catalytic system that can completely degrade TC (10 mg/L) within 60 min. Further, the degradation rate constant (0.0668 min−1) is 5.66 and 7.34 times higher than that of AP/MFe and AP/MCu, respectively, demonstrating a significant advantage over single metal-doped catalysts. DFT calculations confirm the strong adsorption capacity and activation advantage of PDS on the composite surface. Therefore, the continuous photogenerated electrons (e−) accelerate the activation of PDS and the production of SO4•−, resulting in the stripping of abundant photogenerated h + for TC oxidation. Meanwhile, the internal circulation of FeⅢ/FeⅡ and CuⅡ/CuⅢ in composite also greatly enhances the photo-Fenton-like catalytic stability. According to the competitive dynamic experiments, SO4•− have the greatest contribution to TC degradation (58.93%), followed by 1O2 (23.80%). The degradation intermediates (products) identified by high-performance liquid chromatography-mass spectrometry (HPLC/MS) technique indicate the involvement of various processes in TC degradation, such as dehydroxylation, deamination, N-demethylation, and ring opening. Furthermore, as the reaction proceeds, the toxicity of the intermediates produced during TC degradation gradually decreases, which can ensure the safety of the aquatic ecosystem. Overall, this work reveals the synergy mechanism of PDS catalysis and photocatalysis, as well as provides technical support for removal of TC-contaminated wastewater.

Rapid analysis of the chemical constituents of traditional Tibetan medicine Sbyor-bzo-ghi-wang using ballpoint electrospray ionization technique.

The chemical constituents of traditional Tibetan medicines (TTM) can be identified using high-performance liquid chromatography and high-resolution mass spectrometry (HPLC-MS/MS) technique. However, the HPLC-MS/MS technique requires the sample to be pretreated and then separated using the specific liquid chromatography method, which is time consuming. This study developed a ballpoint electrospray ionization (BPESI) technique for analyzing the chemical constituents of Sbyor-bzo-ghi-wang. This technique is a simple and inexpensive method for the rapid identification of the chemical constituents of TTMs. After the important parameters of the homemade BPESI device were optimized, the chemical constituents of Sbyor-bzo-ghi-wang were quickly identified without sample pretreatment. The raw data were converted to mzML file using MSConvert and then identified using SIRIUS 5 software. The results showed that 30 compounds were identified from Sbyor-bzo-ghi-wang, namely eight bile acids, six flavonoids, four alkaloids, three amino acids, and nine others. Compared to the ultra-high-performance liquid chromatography-Q/Orbitrap and high-resolution mass spectrometry (UHPLC-Q/Orbitrap HRMS) technique, the BPESI technique identified almost similar types of compounds and also a comparable number of compounds. Compared with the traditional HPLC-MS/MS methods, the BPESI technique does not require complex sample pretreatment and subsequent chromatographic separation steps; also it consumes a small quantity of samples. Therefore, BPESI can be used for the qualitative analysis of the chemical constituents of Sbyor-bzo-ghi-wang.

Engineering of molecularly imprinted cavity within 3D covalent organic frameworks: An innovation for enhanced extraction and removal of microcystins

The scarcity of selective adsorbents for efficient extraction and removal of microcystins (MCs) from complex samples greatly limits the precise detection and effective control of MCs. Three-dimensional covalent organic frameworks (3D COFs), characterized by their large specific surface areas and highly ordered rigid structure, are promising candidates, but suffer from lack of specific recognition. Herein, we design to engineer molecularly imprinted cavities within 3D COFs via molecularly imprinted technology, creating a novel adsorbent with exceptional selectivity, kinetics and capacity for the efficient extraction and removal of MCs. As proof-of-concept, a new CC bond-containing 3D COF, designated JNU-7, is designed and prepared for copolymerization with methacrylic acid, the pseudo template L-arginine and ethylene dimethacrylate to yield the JNU-7 based molecularly imprinted polymer (JNU-7-MIP). The JNU-7-MIP exhibits a great adsorption capacity (156 mg g−1) for L-arginine. Subsequently, the JNU-7-MIP based solid-phase extraction coupled with high performance liquid chromatography-mass spectrometry achieves low detection limit of 0.008 ng mL−1, wide linear range of 0.025–100 ng mL−1, high enrichment factor of 186, rapid extraction of 10 min, and good recoveries of 92.4%−106.5% for MC-LR. Moreover, the JNU-7-MIP can rapidly remove the MC-LR from 1 mg L−1 to levels (0.26–0.35 μg L−1) lower than the WHO recommended limit for drinking water (1 μg L−1). This work reveals the considerable potential of 3D COF based MIPs as promising adsorbents for the extraction and removal of contaminants in complex real samples.

Decolorization and degradation of crystal violet dye by electron beam radiation: Performance, degradation pathways, and synergetic effect with peroxymonosulfate

Ionizing radiation (mainly including gamma ray and electron beam) technology provides a more efficient and ecological option for dye-containing wastewater treatment, which is supported by its successful achievements in industrial-scale applications. However, the degradation pathway of triphenylmethane dyes by radiation technology is still unclear. In this study, crystal violet (CV) was selected as representative cationic triphenylmethane dye, the decolorization and degradation performance by electron beam radiation technology was systematically evaluated. The results showed that CV can be efficiently decolorized and mineralized by radiation, and its degradation kinetics followed the first-order kinetic model. The effect of inorganic anions and chelating agents commonly existed in dye-containing wastewater on CV decolorization and total organic carbon (TOC) removal was explored. Quenching experiments, density functional theory (DFT) calculation and high performance liquid chromatography mass spectrometry (HPLC-MS) analysis were employed to reveal CV decolorization and degradation mechanism and pathway, which mainly included N-demethylation, triphenylmethane chromophore cleavage, ring-opening of aromatic products and further oxidation to carboxylic acid, and mineralization to CO2 and H2O. Additionally, electron beam radiation/PMS process was explored to decrease the absorbed dose required for decolorization and degradation, and the synergetic effect of radiation with PMS was elucidated. More importantly, the findings of this study would provide the support for treating actual dyeing wastewater by electron beam radiation technology.

Enrichment and Evaluation of Antitumor Properties of Total Flavonoids from Juglans mandshurica Maxim.

Flavonoids are important secondary metabolites found in Juglans mandshurica Maxim., which is a precious reservoir of bioactive substances in China. To explore the antitumor actions of flavonoids (JMFs) from the waste branches of J. mandshurica, the following optimized purification parameters of JMFs by macroporous resins were first obtained. The loading concentration, flow rate, and loading volume of raw flavonoid extracts were 1.4 mg/mL, 2.4 BV/h, and 5 BV, respectively, and for desorption, 60% ethanol (4 BV) was selected to elute JMFs-loaded AB-8 resin at a flow rate of 2.4 BV/h. This adsorption behavior can be explained by the pseudo-second-order kinetic model and Langmuir isotherm model. Subsequently, JMFs were identified using Fourier transform infrared combined with high-performance liquid chromatography and tandem mass spectrometry, and a total of 156 flavonoids were identified. Furthermore, the inhibitory potential of JMFs on the proliferation, migration, and invasion of HepG2 cells was demonstrated. The results also show that exposure to JMFs induced apoptotic cell death, which might be associated with extrinsic and intrinsic pathways. Additionally, flow cytometry detection found that JMFs exposure triggered S phase arrest and the generation of reactive oxygen species in HepG2 cells. These findings suggest that the JMFs purified in this study represent great potential for the treatment of liver cancer.

Cord Blood Adductomics Reveals Oxidative Stress Exposure Pathways of Bronchopulmonary Dysplasia.

Fetal and neonatal exposures to perinatal oxidative stress (OS) are key mediators of bronchopulmonary dysplasia (BPD). To characterize these exposures, adductomics is an exposure science approach that captures electrophilic addition products (adducts) in blood protein. Adducts are bound to the nucleophilic cysteine loci of human serum albumin (HSA), which has a prolonged half-life. We conducted targeted and untargeted adductomics to test the hypothesis that adducts of OS vary with BPD. We studied 205 preterm infants (≤28 weeks) and 51 full-term infants from an ongoing birth cohort. Infant plasma was collected at birth (cord blood), 1-week, 1-month, and 36-weeks postmenstrual age. HSA was isolated from plasma, trypsin digested, and analyzed using high-performance liquid chromatography-mass spectrometry to quantify previously annotated (known) and unknown adducts. We identified 105 adducts in cord and postnatal blood. A total of 51 known adducts (small thiols, direct oxidation products, and reactive aldehydes) were increased with BPD. Postnatally, serial concentrations of several known OS adducts correlated directly with supplemental oxygen exposure. The application of large-scale adductomics elucidated OS-mediated pathways of BPD. This is the first study to investigate the "neonatal-perinatal exposome" and to identify oxidative stress-related exposure biomarkers that may inform antioxidant strategies to protect the health of future generations of infants.

Periodate activation by MnFe2O4 spinel for sulfamethoxazole degradation: Iodate radical dominance, degradation pathway, DFT calculation and toxicity assessment

This study synthesized spinel MnFe2O4 at different temperatures, which was applied to activate periodate (PI) for sulfamethoxazole (SMX) degradation. It was found that the 500-MFO (MnFe2O4 calcined at 500 ℃) demonstrated superior activity in PI activation, with notable sustainability but strong substrate selectivity. Furthermore, a comprehensive analysis, including quenching experiment, electron paramagnetic resonance (EPR) technique, X-ray photoelectron spectroscopy (XPS) analysis, metal ions leaching detection, homogeneous PI activation, and methyl phenyl sulfoxide (PMSO) probe test, revealed that homo- and heterogeneous pathways as well as free and non-free radical routes coexisted in the 500-MFO/PI system. Multiple active species, including iodate radical (IO3•), hydroxyl radical (•OH), superoxide radical (O2•-), singlet oxygen (1O2), and Mn(IV) were identified, with IO3• from heterogeneous activation being the primary species. When PMSO and SMX coexisted, PMSO could react with Mn(IV), promoting the regeneration of Mn reaction sites and the production of IO3•, thereby being beneficial for the degradation of SMX. The degradation pathways of SMX were elucidated through high-performance liquid chromatography-mass spectrometry (HPLC-MS) and density functional theory (DFT) calculation. The acute and chronic toxicity of thirteen by-products to aquatic organisms were predicted using the Ecological Structure Activity Relationships (ECOSAR) software, with the corresponding results revealing that although the toxicity of intermediates fluctuated, the final products were environmentally benign. Therefore, this investigation provides a viable method for SMX degradation in wastewater treatment.

Identification of active compounds in Vernonia anthelmintica (L.) willd by targeted metabolome MRM and kaempferol promotes HaCaT cell proliferation and reduces oxidative stress.

Introduction: Vernonia anthelmintica (L.) Willd. is a traditional treatment for vitiligo in Xinjiang. However, its therapeutic mechanism remains unclear owing to its complex composition and limited research on its chemical profile. Methods: We employed a targeted metabolome approach, combining selective reaction monitoring/multiple response monitoring (SRM/MRM) with high-performance liquid chromatography and MRM mass spectrometry to quantitatively analyze the flavonoid constituents of Vernonia anthelmintica. We also used network pharmacology and molecular docking to identify potential vitiligo-linked compounds and targets of V. anthelmintica seeds. Additionally, we assessed HaCaT cell proliferation by AAPH-induced, alongside changes in SOD activity and MDA content, following treatment with V. anthelmintica components. Finally, flow cytometry was used to detect apoptosis and ROS levels. Results and Discussion: We identified 36 flavonoid compounds in V. anthelmintica seeds, with 14 compounds exhibiting druggability. AKT1, VEGFA, ESR1, PTGS2, and IL2 have been identified as key therapeutic target genes, with PI3K/AKT signaling being an important pathway. Notably, kaempferol, one of the identified compounds, exhibited high expression in network pharmacology analysis. Kaempferol exhibited a strong binding affinity to important targets. Further, kaempferol enhanced HaCaT cell viability, inhibited apoptosis, reduced MDA levels, suppressed ROS activity, and upregulated SOD activity, increase the expression of cellular antioxidant genes, including HO-1, GCLC, GCLM, Nrf2, NQO1 and Keap1, providing significant protection against oxidative stress damage in vitro. Here, we present the first comprehensive study integrating SRM/MRM approaches and network analysis to identify active flavonoid compounds within V. anthelmintica (L.) Willd. Moreover, we revealed that its active ingredient, kaempferol, offers protection against AAPH-induced damage in keratinocytes, highlighting its potential as a clinical resource.

Protective effects of sugarcane polyphenol against UV-B-induced photoaging in Balb/c mouse skin: Antioxidant, anti-inflammatory, and anti-glycosylation Effects.

Although the benefits of sugarcane polyphenol (SP) are well documented, its function in preventing photoaging has not yet been investigated. This study aimed to investigate the protective effects of SP in preventing ultraviolet (UV)-B-induced skin photoaging in Balb/c mice, as well as the underlying mechanism. Chlorogenic acid was determined to be the primary component of SP by using high-performance liquid chromatography-mass spectrometry. SP and chlorogenic acid were orally administrated to mice for 56 days, and UV-B radiation exposure was administered 14 days after SP and chlorogenic acid administration and lasted 42 days to cause photoaging. SP and chlorogenic acid administrations significantly alleviated the UV-B-induced mouse skin photoaging, as indicated by the decrease in epidermal thickness, increase in the collagen (COL) volume fraction, and elevation in type 1 and type 3 COL contents. Notably, both SP and chlorogenic acid effectively reversed the overexpression of matrix metalloproteinase induced by UV-B exposure in the mouse skin. Furthermore, SP and chlorogenic acid reduced the expression of receptor for advanced glycosylation end products in the mice; amplified the activities of antioxidant enzymes superoxide dismutase and catalase; reduced malondialdehyde levels; and decreased inflammatory cytokines interleukin 1β, interleukin 6, and tumor necrosis factor α levels. SP could be a prospective dietary supplement for anti-photoaging applications due to its antioxidant, anti-inflammatory, and anti-glycosylation attributes, and chlorogenic acid might play a major role in these effects. PRACTICAL APPLICATION: This study can provide a scientific basis for the practical application of sugarcane polyphenols. We expect that sugarcane polyphenols can be used in food and beverage products to provide flavor while combating skin aging.

Аминокислотный профиль при сниженном овариальном резерве

Diminished ovarian reserve (DOR) represents a relevant issue of reproductive medicine that is often associated with infertility and reduced efficacy of IVF programs. The changes in amino acid metabolism can play a role in the DOR pathogenesis as manifestations of the folliculogenesis and oogenesis epigenetic alterations. The study was aimed to assess alterations of amino acid metabolic pathways in blood plasma and follicular fluid and estimate their clinical significance in DOR. A total of 115 infertile women aged 25–42 years were included in the study. Groups were formed based on the ovarian reserve and age. Amino acid levels in blood plasma and follicular fluid were assessed by high performance liquid chromatography–mass spectrometry (HPLC-MS); bioinformatics analysis of amino acid metabolic pathways was performed. We revealed significant changes in the phenylalanine, tyrosine and tryptophan biosynthesis (effect = 0.5; p = 0.026), alanine, aspartate and glutamate metabolism (effect = 0.114; p = 0.013), and arginine biosynthesis (effect = 0.289; p &lt; 0.001) pathways playing a role in folliculogenesis, oogenesis, and embryogenesis. The detected differences in the amino acid levels in various body fluids made it possible to construct the logistic regression models confirming DOR with the 88% probability based on the amino acid levels in follicular fluid (sensitivity 88%, specificity 84%) and 82% probability based on plasma levels (sensitivity 65%, specificity 91%). The findings can be used for further research focused on the pathogenesis of infertility associated with DOR and for selection of the most optimal diagnostic and treatment tactics.

Synthesis of green-engineered silver nanoparticles using Cymbopogon citratus (lemongrass) and its antibacterial activity against clinical Pseudomonas aeruginosa

Background and Aim: The use of bioengineered nanocomposites as antimicrobials has increased in recent years, but very few investigations have been conducted to test their effectiveness against Pseudomonas aeruginosa, a pathogen presenting public health risks that can impact both humans and animals. The aim of this study was to assess the antimicrobial potential of phytofabricated silver nanoparticles synthesized using lemongrass extract against clinical isolates of P. aeruginosa. Materials and Methods: The extraction of active compounds from the leaves of Cymbopogon citratus was performed using ethanol (80%) as a solvent, high-performance liquid chromatography-mass spectrometry was used to analyze the chemical composition of the extract, the synthesis of silver nanoparticles (AgNPs) was done using silver nitrate (AgNO3) as a precursor, and the antimicrobial and antibiofilm activity of the extract and the AgNPs phytofabricated was assessed against 10 clinical strains of P. aeruginosa. Results: Lemongrass extract was found to consist of the following main compounds: Caffeic acid (445.21 ± 32.77 μg/g), p-coumaric acid (393.32 ± 39.56 μg/g), chlorogenic acid (377.65 ± 4.26 μg/g), quinic acid (161.52 ± 17.62 μg/g), and quercetin-3-glucoside (151.35 ± 11.34 μg/g). AgNPs were successfully phytofabricated using 2.5 mM AgNO3. The ultraviolet (UV)-visible absorption spectra of the AgNPs showed a localized surface plasmon resonance at 464 nm with an absorbance of 0.32 A. The 50x hydrodynamic diameter was 50.29 nm with a surface area value of 120.10 m2/ cm3, and the volume mean diameter and Sauter mean diameter were 50.63 nm and 49.96 nm, respectively. Despite the compound found in lemongrass extract, no antimicrobial activity was observed with the extract, while AgNPs exhibited noteworthy dose-dependent antimicrobial activity with inhibition diameters up to 24 mm and minimum inhibitory concentration (MIC) and minimum bactericidal concentration ranging from 2 to 16 and 4–64 µg/mL, respectively. AgNPs also demonstrated significant antibiofilm activity by inhibiting biofilms up to 99% between MIC/2 and 2MIC. Conclusion: The present study suggests that lemongrass is a good candidate for the synthesis of AgNPs with good physicochemical characteristics and having a strong anti-pseudomonas activity. Further research is needed to assess the stability and safety of these AgNPs. Keywords: antibiofilm capacity, antimicrobial activity, green synthesis, lemongrass, Pseudomonas aeruginosa, silver nanoparticles.

Targeted Discovery of Glycosylated Natural Products by Tailoring Enzyme-Guided Genome Mining and MS-Based Metabolome Analysis.

Glycosides make up a biomedically important class of secondary metabolites. Most naturally occurring glycosides were isolated from plants and bacteria; however, the chemical diversity of glycosylated natural products in fungi remains largely unexplored. Herein, we present a paradigm to specifically discover diverse and bioactive glycosylated natural products from fungi by combining tailoring enzyme-guided genome mining with mass spectrometry (MS)-based metabolome analysis. Through in vivo genes deletion and heterologous expression, the first fungal C-glycosyltransferase AuCGT involved in the biosynthesis of stromemycin was identified from Aspergillus ustus. Subsequent homology-based genome mining for fungal glycosyltransferases by using AuCGT as a probe revealed a variety of biosynthetic gene clusters (BGCs) containing its homologues in diverse fungi, of which the glycoside-producing capability was corroborated by high-performance liquid chromatography-mass spectrometry (HPLC-MS) analysis. Consequently, 28 fungal aromatic polyketide C/O-glycosides, including 20 new compounds, were efficiently discovered and isolated from the three selected fungi. Moreover, several novel fungal C/O-glycosyltransferases, especially three novel α-pyrone C-glycosyltransferases, were functionally characterized and verified in the biosynthesis of these glycosides. In addition, a proof of principle for combinatorial biosynthesis was applied to design the production of unnatural glycosides in Aspergillus nidulans. Notably, the newly discovered glycosides exhibited significant antiviral, antibacterial, and antidiabetic activities. Our work demonstrates the promise of tailoring enzyme-guided genome-mining approach for the targeted discovery of fungal glycosides and promotes the exploration of a broader chemical space for natural products with a target structural motif in microbial genomes.

Photocatalytic adsorption/degradation of tetracycline by S-scheme BiOI/BiOIO3 p-n heterojunction from dissociation of BiOIO3in-situ solvothermal process

The pollution of tetracycline (TC) had attracted more and more attention due to its unprecedented use and potential hazards. The S-scheme BiOI/BiOIO3 p-n heterojunction was successfully fabricated by in-situ solvothermal treatment of BiOIO3, and was used for the removal of TC from aqueous solutions. The results demonstrated that the construction of S-scheme p-n heterojunction could significantly improve the removal of TC by photocatalytic adsorption/degradation synergism. The removal rate of TC was significantly enhanced after solvothermal modification. The three main reasons for the enhanced removal efficiency were as follows: first, the light absorption range of the BiOIO3 was enhanced by solvothermal treatment; secondly, the construction of the heterojunction was beneficial to the valid separation and migration of the photo-generated carriers; finally, the adsorption of TC enhanced the speed of TC reaching the semiconductor interface and reacting with active species. Trapping tests were conducted to reveal that •O2− and 1O2 are the main reactive species for TC degradation. The nine degradation products were identified by the high performance liquid chromatography-mass spectrometry (HPLC-MS), and the three reaction pathways were deduced. A possible S-scheme p-n heterojunction photocatalytic mechanism was presented on the basis of band structures and active species capturing experiment.

Direct recycle waste silicon wafer as the charge transfer bridge to assemble a Z-scheme heterojunction for enhanced photocatalytic performance

The retirement wave of photovoltaic (PV) panels is expected to result in a significant number of discarded panels in the near future. Recycling PV silicon in a rational manner will not only help reduce the environmental impact but also lead to substantial economic gains. In this study, aaste solar silicon wafers were ball-milled to obtain recycled silicon (r-Si) powder. The TiO2/r-Si carrier was prepared through a simple hydrothermal process, followed by the creation of a novel Ag3PO4/TiO2/r-Si (APO/TIO/r-Si) ternary heterojunction composite using a co-precipitation method. The photocatalytic properties of the materials doped with different concentrations of Ag3PO4 were examined using Rhodamine B (RhB) degradation rate as a performance metric. Among them, 40 %APO/TIO/r-Si heterojunction exhibits excellent photodegradation activity under visible light irradiation. The photocatalytic degradation efficiency reached 93.0 % in 30 min, with a removal rate of 82.8 % after 5 cycles. It was found that superoxide radicals and hydroxyl radicals are the main drivers of RhB photodecomposition. The decomposition pathways of RhB dye were identified using high performance liquid chromatography mass spectroscopy (HPLC-MS), revealing N-de-ethylated intermediates as the main intermediate. The photoreaction mechanism and RhB degradation pathway over APO/TIO/r-Si were elucidated, showing a direct Z-Scheme heterojunction electron transfer pathway with r-Si acting as charge transfer center. The formation of the heterojunction not only minimizes interfacial resistance effectively but also enhances disintegration and preservation of photo-carriers, leading to improved photo-redox ability and increased photoactivity. This study presents a win–win approach for recycling waste silicon wafers from retired PV panels as potential heterojunction photocatalysts for efficient photocatalytic oxidation of dye contamination.