Development of chemometric-assisted supercritical fluid extraction of effective and natural tyrosinase inhibitor from Syzygium aqueum leaves.

Tyrosinase is a key enzyme in enzymatic browning, causing quality losses in food through the oxidation process. Thus, the discovery of an effective and natural tyrosinase inhibitor via green technology is of great interest to the global food market due to food security and climate change issues. In this study, Syzygium aqueum (S. aqueum) leaves, which are known to be rich in phenolic compounds (PC), were chosen as a natural source of tyrosinase inhibitor, and the effect of the sustainable, supercritical fluid extraction (SFE) process was evaluated. Response surface methodology-assisted supercritical fluid extraction (RSM-assisted SFE) was utilized to optimize the PCs extracted from S. aqueum. The highest amount of PC was obtained at the optimum conditions (55 °C, 3350 psi, and 70 min). The IC50 (661.815 µg/mL) of the optimized extract was evaluated, and its antioxidant activity (96.8 %) was determined. Gas chromatography-mass spectrometry (GC-MS) results reveal that 2',6'-dihydroxy-4'-methoxychalcone (2,6-D4MC) (82.65 %) was the major PC in S. aqueum. Chemometric analysis indicated that 2,6-D4MC has similar chemical properties to the tyrosinase inhibitor control (kaempferol). The toxicity and physiochemical properties of the novel 2,6-D4MC from S. aqueum revealed that the 2,6-D4MC is safer than kaempferol as predicted via absorption, distribution, metabolism, and excretion (ADME) evaluation. Enzyme kinetic analysis shows that the type of inhibition of the optimized extract is non-competitive inhibition with Km = 1.55 mM and Vmax = 0.017 µM/s. High-performance liquid chromatography (HPLC) analysis shows the effectiveness of S. aqueum as a tyrosinase inhibitor. The mechanistic insight of the tyrosinase inhibition using 2,6-D4MC was successfully calculated using density functional theory (DFT) and molecular docking approaches. The findings could have a significant impact on food security development by devising a sustainable and effective tyrosinase inhibitor from waste by-products that is aligned with the United Nation's SDG 2, zero hunger.

Electrospun PAN/PEG Nanofibrous Membrane Embedded with a MgO/gC3N4 Nanocomposite for Effective Bone Regeneration.

Developing biomaterial scaffolds using tissue engineering with physical and chemical surface modification processes can improve the bioactivity and biocompatibility of the materials. The appropriate substrate and site for cell attachment are crucial in cell behavior and biological activities. Therefore, the study aims to develop a conventional electrospun nanofibrous biomaterial using reproducible surface topography, which offers beneficial effects on the cell activities of bone cells. The bioactive MgO/gC3N4 was incorporated on PAN/PEG and fabricated into a nanofibrous membrane using electrospinning. The nanocomposite uniformly distributed on the PAN/PEG nanofiber helps to increase the number of induced pores and reduce the hydrophobicity of PAN. The physiochemical characterization of prepared nanoparticles and nanofibers was carried out using FTIR, X-ray diffraction (XRD), thermogravimetry analysis (TGA), X-ray photoelectron spectroscopy (XPS), and water contact angle measurements. SEM and TEM analyses examined the nanofibrous morphology and the structure of MgO/gC3N4. In vitro studies such as on ALP activity demonstrated the membrane's ability to regenerate new bone and healing capacity. Furthermore, alizarin red staining showed the increasing ability of the cell-cell interaction and calcium content for tissue regeneration. The cytotoxicity of the prepared membrane was about 97.09% of live THP-1 cells on the surface of the MgO/gC3N4@PAN/PEG membrane evaluated using MTT dye staining. The soil burial degradation analysis exhibited that the maximum degradation occurs on the 45th day because of microbial activity. In vitro PBS degradation was observed on the 15th day after the bulk hydrolysis mechanism. Hence, on the basis of the study outcomes, we affirm that the MgO/gC3N4@PAN/PEG nanofibrous membrane can act as a potential bone regenerative substrate.

Methyl 4-pyridyl ketone thiosemicarbazone (4-PT) as an effective and safe inhibitor of mushroom tyrosinase and antibrowning agent.

Enzymatic browning is of concern as it can affect food safety and quality. In this study, an effective and safe tyrosinase inhibitor and anti-browning agent, methyl 4-pyridyl ketone thiosemicarbazone (4-PT), was synthesised and characterised using Fourier-transform infrared (FTIR) spectroscopy, CHNS elemental analysis, and proton (1H) and carbon-13 (13C) nuclear magnetic resonance (NMR) spectroscopy. The vibrational frequencies of 4-PT were studied theoretically using vibrational energy distribution analysis (VEDA). Density functional theory (DFT) was applied to elucidate its chemical properties, including the Mulliken atomic charges, molecular electrostatic potential (MEP), quantum theory of atoms in molecules (QTAIM) and reduced density gradient non-covalent interactions (RDG-NCIs). Moreover, 4-PT was compared with kojic acid in terms of its effectiveness as a tyrosinase inhibitor and anti-browning agent. The toxicity and physicochemical properties of 4-PT were predicted via ADME evaluation, which proved that 4-PT is safer than kojic acid. Experimentally, 4-PT (IC50 = 5.82 µM, browning index (10 days) = 0.292 ± 0.002) was proven to be an effective tyrosinase inhibitor and anti-browning agent compared to kojic acid (IC50 = 128.17 µM, browning index (10 days) = 0.332 ± 0.002). Furthermore, kinetic analyses indicated that the type of tyrosinase inhibition is a mixed inhibition, with Km and Vmax values of 0.85 mM and 2.78 E-09 µM/s, respectively. Finally, the mechanism of 4-PT for tyrosinase inhibition was proven by 1D, second derivative and 2D IR spectroscopy, molecular docking and molecular dynamic simulation approaches.

Computer-aided identification of Mycobacterium tuberculosis resuscitation-promoting factor B (RpfB) inhibitors from Gymnema sylvestre natural products.

Tuberculosis (TB), an infectious disease caused by multi-drug resistant Mycobacterium tuberculosis (Mtb), has been a global health concern. Mtb affects over a third of the world's population, causing two million deaths annually due to its dormancy and propensity to spread infection during this period. Resuscitation-promoting factor B (RpfB) plays a pivotal role in the growth of Mtb during dormant periods, making it a critical target for eliminating Mtb and curing TB. Gymnema sylvestre is a famous medicinal plant with several medicinal properties, including antimicrobial activity; however, the therapeutic potential of the various reported metabolites of this plant against Mtb has not yet been explored. The aim of this study was to explore the reported natural products of G. sylvestre against the RpfB of the Mtb. A total of 131 reported secondary metabolites of this plant were collected and virtually screened against the RpfB. We particularly targeted the Glu292 residue of RpfB as it is crucial for the catalysis of this protein. From our in-house library, 114 compounds showed a binding affinity higher than the standard drug. The binding stability of the top three lead compounds was further confirmed through MD simulation analysis. Drug likeness analyses indicated that the ten hits had zero violations of the Lipinski rule of five. In addition, analyses of pharmacokinetics, toxicity, and target prediction revealed that the top compounds are devoid of toxicity and do not affect human proteins. Additionally, they reflect multifaceted approach as anti-TB agents. Our selected hits not only exhibit molecular properties favoring physiological compatibility but also exhibit properties enhancing their potential efficacy as therapeutic candidates. The compounds investigated here are worthy of experimental validation for the discovery of novel treatments against TB. Further, this study also provides a promising avenue for research on the pharmacological potential of G. sylvestre.

Analytic Validation of Optical Genome Mapping in Hematological Malignancies.

Structural variations (SVs) play a key role in the pathogenicity of hematological malignancies. Standard-of-care (SOC) methods such as karyotyping and fluorescence in situ hybridization (FISH), which have been employed globally for the past three decades, have significant limitations in terms of resolution and the number of recurrent aberrations that can be simultaneously assessed, respectively. Next-generation sequencing (NGS)-based technologies are now widely used to detect clinically significant sequence variants but are limited in their ability to accurately detect SVs. Optical genome mapping (OGM) is an emerging technology enabling the genome-wide detection of all classes of SVs at a significantly higher resolution than karyotyping and FISH. OGM requires neither cultured cells nor amplification of DNA, addressing the limitations of culture and amplification biases. This study reports the clinical validation of OGM as a laboratory-developed test (LDT) according to stringent regulatory (CAP/CLIA) guidelines for genome-wide SV detection in different hematological malignancies. In total, 60 cases with hematological malignancies (of various subtypes), 18 controls, and 2 cancer cell lines were used for this study. Ultra-high-molecular-weight DNA was extracted from the samples, fluorescently labeled, and run on the Bionano Saphyr system. A total of 215 datasets, Inc.luding replicates, were generated, and analyzed successfully. Sample data were then analyzed using either disease-specific or pan-cancer-specific BED files to prioritize calls that are known to be diagnostically or prognostically relevant. Sensitivity, specificity, and reproducibility were 100%, 100%, and 96%, respectively. Following the validation, 14 cases and 10 controls were run and analyzed using OGM at three outside laboratories showing reproducibility of 96.4%. OGM found more clinically relevant SVs compared to SOC testing due to its ability to detect all classes of SVs at higher resolution. The results of this validation study demonstrate the superiority of OGM over traditional SOC methods for the detection of SVs for the accurate diagnosis of various hematological malignancies.

Structural informatics approach for designing an epitope-based vaccine against the brain-eating Naegleria fowleri.

Primary Amoebic Meningoencephalitis (PAM), a severe lethal brain disease, is caused by a parasite, Naegleria fowleri, also known as the "brain-eating amoeba". The chances of a patient's recovery after being affected by this parasite are very low. Only 5% of people are known to survive this life-threatening infection. Despite the fact that N. fowleri causes a severe, fatal infection, there is no proper treatment available to prevent or cure it. In this context, it is necessary to formulate a potential vaccine that could be able to combat N. fowleri infection. The current study aimed at developing a multi-epitope subunit vaccine against N. fowleri by utilizing immunoinformatics techniques and reverse vaccinology approaches. The T- and B-cell epitopes were predicted by various tools. In order to choose epitopes with the ability to trigger both T- and B-cell-mediated immune responses, the epitopes were put through a screening pipeline including toxicity, antigenicity, cytokine-inductivity, and allergenicity analysis. Three vaccine constructs were designed from the generated epitopes linked with linkers and adjuvants. The modeled vaccines were docked with the immune receptors, where vaccine-1 showed the highest binding affinity. Binding affinity and stability of the docked complex were confirmed through normal mode analysis and molecular dynamic simulations. Immune simulations developed the immune profile, and in silico cloning affirmed the expression probability of the vaccine construct in Escherichia coli (E. coli) strain K12. This study demonstrates an innovative preventative strategy for the brain-eating amoeba by developing a potential vaccine through immunoinformatics and reverse vaccinology approaches. This study has great preventive potential for Primary Amoebic Meningoencephalitis, and further research is required to assess the efficacy of the designed vaccine.

Structural and Functional Characterization of Novel Phosphotyrosine Phosphatase Protein from Drosophila melanogaster (Pupal Retina).

A novel pair of protein tyrosine phosphatases in Drosophila melanogaster (pupal retina) has been identified. Phosphotyrosyl protein phosphatases (PTPs) are structurally diverse enzymes increasingly recognized as having a fundamental role in cellular processes including effects on metabolism, cell proliferation, and differentiation. This study presents identification of novel sequences of PTPs and their comparative homology modeling from Drosophila melanogaster (Dr-PTPs) and complexation with the potent inhibitor HEPES. The 3D structure was predicted based on sequence homology with bovine heart low molecular weight PTPs (Bh-PTPs). The sequence homologies are approximately 50% identical to each other and to low molecular weight protein tyrosine phosphatases (PTPs) in other species. Comparison of the 3D structures of Bh-PTPs and Dr-PTPs (primo-2) reveals a remarkable similarity having a four stranded central parallel ß sheet with flanking α helices on both sides, showing two right handed ß-α-ß motifs. The inhibitor shows similar binding features as seen in other PTPs. The study also highlights the key catalytic residues important for target recognition and PTPs' activation. The structure guided studies of both proteins clearly reveal a common mechanism of action and inhibitor binding at the active site and will be expected to contribute toward the basic understanding of functional association of this enzyme with other molecules.

Palladium Nanoparticles on Chitosan-Coated Superparamagnetic Manganese Ferrite: A Biocompatible Heterogeneous Catalyst for Nitroarene Reduction and Allyl Carbamate Deprotection.

Although metallic nanocatalysts such as palladium nanoparticles (Pd NPs) are known to possess higher catalytic activity due to their large surface-to-volume ratio, however, in nanosize greatly reducing their activity due to aggregation. To overcome this challenge, superparamagnetic chitosan-coated manganese ferrite was successfully prepared and used as a support for the immobilization of palladium nanoparticles to overcome the above-mentioned challenge. The Pd-Chit@MnFe2O4 catalyst exhibited high catalytic activity in 4-nitrophenol and 4-nitroaniline reductions, with respective turnover frequencies of 357.1 min-1 and 571.4 min-1, respectively. The catalyst can also be recovered easily by magnetic separation after each reaction. Additionally, the Pd-Chit@MnFe2O4 catalyst performed well in the reductive deprotection of allyl carbamate. Coating the catalyst with chitosan reduced the Pd leaching and its cytotoxicity. Therefore, the catalytic activity of Pd-Chit@MnFe2O4 was proven to be unrestricted in biology conditions.

Corrigendum: Structural informatics approach for designing an epitope-based vaccine against the brain-eating Naegleria fowleri.

[This corrects the article DOI: 10.3389/fimmu.2023.1284621.].

Ecotoxicological Assessment of Heavy Metal and Its Biochemical Effect in Fishes.

Level of toxic heavy metal concentration like lead (Pb), chromium (Cr), cadmium (Cd), iron (Fe), copper (Cu), zinc (Zn), and nickel (Ni) in thirty-six soft and hard organs and their impact on lipid profile of Hypophthalmichthys molitrix and Catla catla fish species inhibiting in Tanda Dam reservoir were investigated. The heavy metal concentrations in water, sediment, and fish of the different regions in the reservoir were determined with atomic absorption spectrophotometer. Lipid profile was carried out by AOAC official methods. The results showed that Pb was dominant among all the heavy metals in six organs, and its maximum concentration of Pb (22.5 mg kg-1 and 32.9 mg kg-1) was observed in scales in Hypophthalmichthys molitrix and tail of Catla catla, respectively. The maximum concentrations of Cd were observed in the head, scales, fins, and gills of Catla catla. The bioaccumulation of heavy metals was significantly different at (p ≤ 0.01) within the organs and between the fish species. The lipid concentration was minimum in those organs where the concentrations of heavy metals were maximum. It is clear from the findings that heavy metal accumulation reduces the lipid content of fish. It is inevitable to monitor the Tanda Dam reservoir to safeguard human health.

Identification, kinetics and thermodynamic analysis of novel ß-galactosidase from Convolvulus arvensis seeds: An efficient agent for delactosed milk activity.

The ß-galactosidase was extracted and purified from 100 g of C. arvensis seeds using a variety of protein purification procedures such as ammonium sulphate fractionation, gel filtration, and finally chromatography on a cationic ion exchanger. The effects of metal ions, kinetics parameters, and glycoprotein nature were determined, as well as the optimal pH and temperature of the purified enzyme. With a high specific activity (72 units/mg), ß-galactosidase was isolated to a 24-fold apparent electrophoretic homogeneity. The molecular mass of ß-galactosidase was determined as monomeric, which was further confirmed by SDS-PAGE and MALDI-TOF/MS analysis, with a 45 kDa molecular weight. The enzyme has a Km of 0.33 mM and a Vmax of 42 µmol/min Lactose in milk was reduced by 38.5 and 70 % after 4 h of incubation with ß-galactosidase from C. arvensis. The ß-galactosidase thermal inactivation kinetic parameters ΔH°, ΔS°, and ΔG° were calculated, indicating that the enzyme undergoes significant unfolding events during denaturation. Using ß-galactosidase from C. arvensis seeds, lactose hydrolysis in milk up to approx. 50 % was observed. The findings indicate the potential use of C. arvensis seeds for the production of low/delactosed milk for lactose-intolerant population.

Deciphering the Path of S-nitrosation of Human Thioredoxin: Evidence of an Internal NO Transfer and Implication for the Cellular Responses to NO.

Nitric oxide (NO) is a free radical with a signaling capacity. Its cellular functions are achieved mainly through S-nitrosation where thioredoxin (hTrx) is pivotal in the S-transnitrosation to specific cellular targets. In this study, we use NMR spectroscopy and mass spectrometry to follow the mechanism of S-(trans)nitrosation of hTrx. We describe a site-specific path for S-nitrosation by measuring the reactivity of each of the 5 cysteines of hTrx using cysteine mutants. We showed the interdependence of the three cysteines in the nitrosative site. C73 is the most reactive and is responsible for all S-transnitrosation to other cellular targets. We observed NO internal transfers leading to C62 S-nitrosation, which serves as a storage site for NO. C69-SNO only forms under nitrosative stress, leading to hTrx nuclear translocation.

1,3,5-Thiadiazinane thione derivatives as significant urease inhibitors.

We report the promising urease inhibitory activity of four sets of tetrahydro thiadiazine thiones (THTT) namely 3,5-disubstituted tetrahydro-2H-1,3,5-thiadiazine thiones: THTT 5-8 (set A) having alkyl/aryl substituents at N-3 and N-5 positions; THTT 9-12 (set B) and THTT 13-14 (set C) with 3-carboxylic acid derivatives and tetrahydro-2H-1,3,5-thiadiazine-6-thione esters 15-16 (set D). Gratifyingly, all four sets of THTT were recognized as promising inhibitors of urease enzyme. Among 12 tested compounds; THTT 6, 8, 10, 14 and 15 from each set respectively, demonstrated significant urease inhibitory activity with IC50 values between 11.2-29.8µM which is mostly found higher than that for thiourea, a standard urease inhibitor with IC50 value of 22.4µM. Furthermore, compound 7 showed almost the same level of inhibition (IC50 = 22.5µM) as of standard. In addition, molecular docking study supported the phenomenon that thiadiazinane ring itself is an active pharmacophore that binds through CH2 groups and S atom via carbon-hydrogen/π-sulfur interactions respectively to the active site of the urease enzyme. The optimistic results from this study suggest the use of thiadiazinane skeleton as a guided template for the advancement of new urease inhibitors in drug discovery.

A Patient with SIADH, Urinary Retention, Constipation, and Bell's Palsy following a Tick Bite.

Introduction. Lyme disease is the most common vector borne disease in the USA caused by the bacterium Borrelia burgdorferi. If untreated, Lyme disease can cause a variety of secondary symptoms often difficult to interpret. Some of the rare manifestations of Lyme disease include SIADH-like syndrome, enteroparesis, and urinary retention. Case Report. A 69-year-old male presented with anorexia and constipation and was found to have hyponatremia. Several days after admission, Bell's palsy developed and he experienced urinary retention requiring catheterization. Lyme disease was confirmed on serology, and he recalled a rash on his elbow four weeks prior. Ceftriaxone was started and the patient improved; he had multiple bowel movements after receiving laxatives and the Foley catheter was removed; serum sodium normalized with fluid restriction. He was discharged home and was well with symptoms completely resolved at three-month follow-up. Discussion. There should be a high alert of atypical presentation of this common tick bite associated infection. Review of the literature revealed ten similar cases, but only three of these patients were reported to have a combination of SIADH, urinary retention, and enteroparesis.

First-principal investigations of electronic, structural, elastic and optical properties of the fluoroperovskite TlLF3 (L = Ca, Cd) compounds for optoelectronic applications.

In this research work, the Tl-based fluoroperovskite compounds TlLF3 (L = Ca, Cd) were investigated computationally using density functional theory (DFT) to comprehend their structural, elastic, optical, and electronic properties. Computation of the tolerance factor and Birch-Murnaghan curve indicated that the compounds are cubic and structurally stable. The structurally optimized lattice constants and the optimum volume corresponding to the optimum energy were measured. Elastic properties were predicted using the IRelast package, and the results showed that the compounds of interest are mechanically stable, ductile, and anisotropic in nature. The electronic properties (band structures and density of states) show that TlCaF3 and TlCdF3 possess a wide direct bandgap from (X-X) symmetry points of 5.7 eV and 5.6 eV, respectively. The contributions of different elemental states to the valence and conduction bands are evaluated from the total and partial density of states (TDOS & PDOS). Analysis of the optical properties showed that these compounds possess a high refractive index, absorption coefficient, and reflectivity at high energy ranges. The values of the direct bandgap indicated that these compounds are expected to be semiconducting in nature, and their use is primarily considered to be in the semiconductor industries and optoelectronic devices. These compounds are new and have been investigated for the first time using the computational approach, which provides comprehensive insight into their different properties; based on the results, they are recommended as industrial candidates.

Insight into the photodegradation mechanism of bisphenol-A by oxygen doped mesoporous carbon nitride under visible light irradiation and DFT calculations.

Oxygen doped mesoporous carbon nitride (O-MCN) was successfully synthesized through one-step thermal polymerization of urea and glucose utilizing nanodisc silica (NDS) from rice husk ash as a hard template. The CO2 gas, NH3 and water vapor produced during the thermal process reshaped the morphology and textural properties of the of O-MCN compared to pristine mesoporous carbon nitride (MCN). Highest bisphenol A (BPA) removal achieved under visible light irradiation was 97%, with 60% mineralization ([BPA] = 10 mg L-1: catalyst dosage = 40 mg L-1; pH = 10; 180 min). In addition to mesoporosity, the sub-gap impurity states created from the oxygen doping reduced recombination rate of photogenerated carriers. Holes (h+) and superoxide (O2˙-) were identified as the predominant active species responsible for the photodegradation process. The photodegradation route was proposed based on the intermediates detected by LC-time-of-flight/mass spectrometry (LC/TOF-MS). The Density of States (DOS) showed that oxygen doping resulted in a higher photoactivity due to the stronger localization and delocalization of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). The adsorption pathway of the BPA on the O-MCN and MCN was successfully predicted using the DFT calculations, namely molecular electrostatic potential (MEP), global and local descriptors.

Health Risk Assessment and Multivariate Statistical Analysis of Heavy Metals in Vegetables of Khyber Pakhtunkhwa Region, Pakistan.

The level of heavy metals in vegetables grown in soil irrigated with various sources of water and the health risks associated with the consumption of these vegetables were assessed in this study. Samples of water, soil, and vegetables were collected from farmer fields. After digestion in acidic solution, analytical measurements were made using an atomic absorption spectrophotometer. The mean concentration of Pb, Cr, Cd, Cu, Zn, Ni, Fe, and Mn in the soil of two sampling area were in the range from 60.00 to 84.00 mg kg-1, 68.00 to 98.00 mg kg-1, 1.60 to 2.60 mg kg-1, 26.10 to 33.20 mg kg-1, 22.60 to 30.80 mg kg-1, 50.10 to 78.30 mg kg-1, 420.00 to 471.00 mg kg-1, and 270.20 to 340.50 mg kg-1, respectively. Heavy metals in soil varied significantly at (P ≤ 0.001) among sampling area. The nine heavy metals were divided into two clusters for wastewater and soil, according to cluster analysis. The number of variables was reduced using principal component analysis, which yielded three latent factors, one for wastewater and one for soil. Pb, Cr, Cd, Cu, Zn, Ni, Fe, and Mn concentrations were significantly higher at P ≤ 0.001 in nine vegetables grown on soil irrigated with untreated wastewater than in vegetables grown on fresh-tube well-water-irrigated soil. The health risks associated with metal intake were assessed using the estimated daily intake of metals (EDIM), hazard quotients (HQs), and hazard index (HI). The rates of metal transfer to vegetables have been determined. Except for Pb and Cd, all of the elements' EDMI values were found to be lower than their RfD values. The corresponding HRI values of metals in the various vegetables were found to be below 1, implying that vegetable consumption in the studied region poses no carcinogenic risk. Constant determination of heavy metals in all fruits and vegetables is essential for the assessment of health risks associated with dietary metal exposure. The study has provided valuable information to the general public about the use of wastewater for irrigation of vegetables.

Ionic-Liquid-Stabilized TiO2 Nanostructures: A Platform for Detection of Hydrogen Peroxide.

Hydrogen peroxide (H2O2) acts as a signaling molecule to direct different biological processes. However, its excess amount results in oxidative stress, which causes the onset of different types of cancers. TiO2 nanostructure was synthesized by a facile hydrothermal method. The prepared material was characterized by FTIR spectroscopy, XRD, SEM, EDX, TGA, and Raman spectroscopy, which confirmed the formation of nanostructured material. Subsequently, the prepared nanoparticles (NPs) were capped with 1-H-3-methylimidazolium acetate ionic liquid (IL) to achieve its deagglomeration and functionalization. A new colorimetric sensing probe was prepared for the detection of H2O2 based on ionic liquid-capped TiO2 nanoparticles (TiO2/IL) and 3,3',5,5'-tetramethylbenzidine (TMB) dye, which acts as an oxidative chromogenic substrate. H2O2 reacts with TMB, in the presence of ionic liquid-coated TiO2 NPs, to form a blue-green product. The color was visualized with the naked eye, and the colorimetric change was confirmed by a UV-vis spectrophotometer. To obtain the best response of the synthesized sensor, different parameters (time, pH, concentrations, loading of nanomaterials) were optimized. It showed a low limit of detection 8.61 × 10-8 M, a high sensitivity of 2.86 × 10-7 M, and a wide linear range of 1 × 10-9-3.6 × 10-7 M, with a regression coefficient (R 2) value of 0.999. The proposed sensor showed a short incubation time of 4 min. The sensing probe did not show any interference from the coexisting species. The TiO2/IL sensor was effectively used for finding H2O2 in the urine samples of cancer patients.

Two-Dimensional Infrared Correlation Spectroscopy, Conductor-like Screening Model for Real Solvents, and Density Functional Theory Study on the Adsorption Mechanism of Polyvinylpolypyrrolidone for Effective Phenol Removal in an Aqueous Medium.

The discharge of industrial effluents, such as phenol, into aquatic and soil environments is a global problem due to its serious negative impacts on human health and aquatic ecosystems. In this study, the ability of polyvinylpolypyrrolidone (PVPP) to remove phenol from an aqueous medium was investigated. The results showed that a significant proportion of phenol (up to 74.91%) was removed using PVPP at pH 6.5. Isotherm adsorption experiments of phenol on PVPP indicated that the best-fit adsorption was obtained using Langmuir models. The response peaks of the hydroxyl groups of phenol (OH) and the carboxyl groups (i.e., C=O) of PVPP were altered, indicating the formation of a hydrogen bond between the PVPP and phenol during phenol removal, as characterized using 1D and 2D IR spectroscopy. The resulting complexes were successfully characterized based on their thermodynamic properties, Mulliken charge, and electronic transition using the DFT approach. To clarify the types of interactions taking place in the complex systems, quantum theory of atoms in molecules (QTAIM) analysis, reduced density gradient noncovalent interaction (RDG-NCI) approach, and conductor-like screening model for real solvents (COSMO-RS) approach were also successfully calculated. The results showed that the interactions that occurred in the process of removing phenol by PVPP were through hydrogen bonding (based on RDG-NCI and COSMO-RS), which was identified as an intermediate type (∇2ρ(r) > 0 and H < 0, QTAIM). To gain a deeper understanding of how these interactions occurred, further characterization was performed based on adsorption mechanisms using molecular electrostatic potential, global reactivity, and local reactivity descriptors. The results showed that during hydrogen bond formation, PVPP acts as a nucleophile, whereas phenol acts as an electrophile and the O9 atom (i.e., donor electron) reacts with the H22 atom (i.e., acceptor electron).

Comparison of the Surface Properties of Hydrothermally Synthesised Fe3O4@C Nanocomposites at Variable Reaction Times.

The influence of variable reaction time (tr) on surface/textural properties (surface area, total pore volume, and pore diameter) of carbon-encapsulated magnetite (Fe3O4@C) nanocomposites fabricated by a hydrothermal process at 190 °C for 3, 4, and 5 h was studied. The properties were calculated using the Brunauer-Emmett-Teller (BET) isotherms data. The nanocomposites were characterised using Fourier transform infrared spectroscopy, X-ray diffraction analysis, thermogravimetry, and scanning and transmission electron microscopies. Analysis of variance shows tr has the largest effect on pore volume (F value = 1117.6, p value < 0.0001), followed by the surface area (F value = 54.8, p value < 0.0001) and pore diameter (F value = 10.4, p value < 0.001) with R2-adjusted values of 99.5%, 88.5% and 63.1%, respectively. Tukey and Fisher tests confirmed tr rise to have caused increased variations in mean particle sizes (11-91 nm), crystallite sizes (5-21 nm), pore diameters (9-16 nm), pore volume (0.017-0.089 cm3 g-1) and surface area (7.6-22.4 m2 g-1) of the nanocomposites with individual and simultaneous confidence limits of 97.9 and 84.4 (p-adj < 0.05). The nanocomposites' retained Fe-O vibrations at octahedral (436 cm-1) and tetrahedral (570 cm-1) cubic ferrite sites, modest thermal stability (37-60 % weight loss), and large volume-specific surface area with potential for catalytic application in advanced oxidation processes.