Bioaccessibility and health risk assessment of hydrophobic organic pollutants in soils from four typical industrial contaminated sites in China.

There have been reports of potential health risks for people from hydrophobic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated hydrocarbons (PCHs), and organophosphate flame retardants (OPFRs). When a contaminated site is used for residential housing or public utility and recreation areas, the soil-bound organic pollutants might pose a threat to human health. In this study, we investigated the contamination profiles and potential risks to human health of 15 PAHs, 6 PCHs, and 12 OPFRs in soils from four contaminated sites in China. We used an in vitro method to determine the oral bioaccessibility of soil pollutants. Total PAHs were found at concentrations ranging from 26.4 ng/g to 987 ng/g. PCHs (0.27‒14.3 ng/g) and OPFRs (6.30‒310 ng/g) were detected, but at low levels compared to earlier reports. The levels of PAHs, PCHs, and OPFRs released from contaminated soils into simulated gastrointestinal fluids ranged from 1.74% to 91.0%, 2.51% to 39.6%, and 1.37% to 96.9%, respectively. Based on both spiked and unspiked samples, we found that the oral bioaccessibility of pollutants was correlated with their logKow and molecular weight, and the total organic carbon content and pH of soils. PAHs in 13 out of 38 contaminated soil samples posed potential high risks to children. When considering oral bioaccessibility, nine soils still posed potential risks, while the risks in the remaining soils became negligible. The contribution of this paper is that it corrects the health risk of soil-bound organic pollutants by detecting bioaccessibility in actual soils from different contaminated sites.

Coconut milk allergenicity: Insight into reducing the affinity of coconut globulin to immunoglobulin E by atmospheric cold plasma.

Atmospheric cold plasma (ACP) presents a promising method for the sterilization of coconut milk and exhibits a modifying effect on coconut globulin (CG), the primary allergen in coconut milk. This study investigated the potential role of ACP treatment in mitigating the allergenic properties of coconut milk by examining changes in protein structure. ACP treatment induced structural alterations in CG, disrupting binding sites with immunoglobulin E (IgE). Consequently, this led to a reduction in the affinity between CG and IgE, evidenced by a decrease in Ka from 2.17 × 104/M to 0.64 × 104/M, thereby diminishing IgE-mediated allergic reactions. The findings from allergenic and cellular models further corroborated that ACP treatment decreased the allergenicity of CG by 55.18%, while inhibiting degranulation and the release of allergic mediators. This study presents an innovative methodology for producing hypoallergenic coconut milk, thereby expanding the applicability of ACP technology within the food industry.

Development of natural product-based targeted protein degraders as anticancer agents.

Targeted protein degradation (TPD) has emerged as a powerful approach for eliminating cancer-causing proteins through an "event-driven" pharmacological mode. Proteolysis-targeting chimeras (PROTACs), molecular glues (MGs), and hydrophobic tagging (HyTing) have evolved into three major classes of TPD technologies. Natural products (NPs) are a primary source of anticancer drugs and have played important roles in the development of TPD technology. NPs potentially expand the toolbox of TPD by providing a variety of E3 ligase ligands, protein of interest (POI) warheads, and hydrophobic tags (HyTs). As a promising direction in the TPD field, NP-based degraders have shown great potential for anticancer therapy. In this review, we summarize recent advances in the development of NP-based degraders (PROTACs, MGs and HyTing) with anticancer applications. Moreover, we put forward the challenges while presenting potential opportunities for the advancement of future targeted protein degraders derived from NPs.

Microbially derived surfactants: an ecofriendly, innovative, and effective approach for managing environmental contaminants.

The natural environment is often contaminated with hydrophobic pollutants such as long-chain hydrocarbons, petrochemicals, oil spills, pesticides, and heavy metals. Hydrophobic pollutants with a toxic nature, slow degradation rates, and low solubility pose serious threats to the environment and human health. Decontamination based on conventional chemical surfactants has been found to be toxic, thereby limiting its application in pharmaceutical and cosmetic industries. In contrast, biosurfactants synthesized by various microbial species have been considered superior to chemical counterparts due to their non-toxic and economical nature. Some biosurfactants can withstand a wide range of fluctuations in temperature and pH. Recently, biosurfactants have emerged as innovative biomolecules not only for solubilization but also for the biodegradation of environmental pollutants such as heavy metals, pesticides, petroleum hydrocarbons, and oil spills. Biosurfactants have been well documented to function as emulsifiers, dispersion stabilizers, and wetting agents. The amphiphilic nature of biosurfactants has the potential to enhance the solubility of hydrophobic pollutants such as petroleum hydrocarbons and oil spills by reducing interfacial surface tension after distribution in two immiscible surfaces. However, the remediation of contaminants using biosurfactants is affected considerably by temperature, pH, media composition, stirring rate, and microorganisms selected for biosurfactant production. The present review has briefly discussed the current advancements in microbially synthesized biosurfactants, factors affecting production, and their application in the remediation of environmental contaminants of a hydrophobic nature. In addition, the latest aspect of the circular bioeconomy is discussed in terms of generating biosurfactants from waste and the global economic aspects of biosurfactant production.

Molecular analysis of changes in DNA binding affinity and bending extent induced by the mutations on the aromatic amino residues in Cren7.

Proteins from Crenarchaeal organisms exhibit remarkable thermal stability. The aromatic amino acids in Cren7, a Crenarchaeal protein, regulate protein stability and further modulate DNA binding and its compaction. Specific aromatic amino acids were mutated, and using spectroscopic and theoretical approaches, we have examined the structure, DNA binding affinity, and DNA bending ability of mutants. and compared with wild-type (WT) Cren7. The reverse titration profiles were analysed by a noncooperativeMcGhee-von Hippel model to estimate affinity constant (Ka) and site size (n) associated with binding to the DNA. Biolayer interferometry (BLI) measurements showed that the binding affinity decreased at higher salt concentrations. For theoretical analysis of extent of DNA bending, radius of gyration and bending angle were compared for WT and mutants. Time evolution of order parameters based on translational and rotational motion of tryptophan residue (W26) was used for qualitative detection of stacking interactions between W26 of Cren7 and DNA nucleobases. It was observed that orientation of W26 in F41A favored formation of a new lone pair-lone pair interaction between DNA and Cren7. Consequently, in thermostable proteins, the aromatic residues at the terminus maintain structural stability, whereas the residues at the core optimize the degree of DNA bending and compaction.

Selective Protein Degradation through Tetrazine Ligation of Genetically Incorporated Unnatural Amino Acids.

Small molecule-responsive tags for targeted protein degradation are valuable tools for fundamental research and drug target validation. Here, we show that genetically incorporated unnatural amino acids bearing a strained alkene or alkyne functionality can act as a minimalist tag for targeted protein degradation. Specifically, we observed the degradation of strained alkene- or alkyne-containing kinases and E2 ubiquitin-conjugating enzymes upon treatment with hydrophobic tetrazine conjugates. The extent of the induced protein degradation depends on the identity of the target protein, unnatural amino acid, and tetrazine conjugate, as well as the site of the unnatural amino acid in the target protein. Mechanistic studies revealed proteins undergo proteasomal degradation after tetrazine tethering, and the identity of tetrazine conjugates influences the dependence of ubiquitination on protein degradation. This work provides an alternative approach for targeted protein degradation and mechanistic insight, facilitating the future development of more effective targeted protein degradation strategies.

Valorization of Protein Materials Through Mechanochemistry and Self-assembly.

The concept of combining mixing of solids by milling (a type of mechanochemistry) with aqueous self-assembly provides interesting possibilities for energy efficient production of advanced nanomaterials. Many proteins are outstanding building blocks for self-assembly, a prominent example being the conversion of proteins into protein nanofibrils (PNFs) - a structure related to amyloid fibrils. PNFs have attractive mechanical properties and have a tendency to form ordered materials. They are accordingly of interest as materials for bioplastics and potentially also for more high-tech applications. In this concept article we highlight our effort on valorization of such proteins with hydrophobic organic compounds such an organic dyes and drug molecules, by developing scalable methodology combining mechanochemistry and self-assembly. Compared to more established methodology, mechanochemical methodology is a valuable complement as it allows potential scalable production of hybrids between e.g. proteins and highly hydrophobic compounds - a class of hybrid material that is difficult to access by other means by conventical means. This may allow for development of sustainable processes for fabrication of advanced protein-based materials derivable from renewable source materials.

Development of a Janus tissue adhesive hemostatic patch based on hydrophobically-modified Alaska pollock gelatin.

Uncontrollable hemorrhage from trauma and open surgery leads to a high percentage of death. Even though some patch-type hemostatic materials have been used in the clinic, sufficient tissue adhesion property and the management of tissue adhesion and anti-adhesion have been the challenges. In this report, we designed Janus tissue adhesive hemostatic patch, consisting of Alaska pollock gelatin (Org-ApGltn) as a support layer and decanoyl group-modified ApGltn (C10-ApGltn) with pentaerythritol poly(ethylene glycol) ether tetrasuccinimidyl glutarate (4S-PEG) as an adhesive layer, named as the C10-ApGltn patch. The C10-ApGltn patch adhered onto blood vessel surface by the activation 4S-PEG and hydrophobic groups in C10-ApGltn through the covalent bond formation and physical interaction. The burst strength of the C10-ApGltn patch was optimized in terms of the degree of substitution, the molecular weight of 4S-PEG, the concentration of C10-ApGltn, and the NHS/NH2 ratio. The optimized C10-ApGltn patch showed significantly higher burst strength with commercially available TachoSil®. The C10-ApGltn patch showed enzymatic degradability in a buffer solution with collagenase. In a rat liver hemorrhage model, the C10-ApGltn patch acted as a sealant on the hemorrhage site and exhibited competitive hemostatic property to TachoSil®.

Starch/ionic liquid/hydrophobic association hydrogel with high stretchability, fatigue resistance, self-recovery and conductivity for sensitive wireless wearable sensors.

Conductive hydrogels have been widely used in wearable electronics due to their flexible, conductive and adjustable properties. With ever-growing demand for sustainable and biocompatible sensing materials, biopolymer-based hydrogels have drawn significant attention. Among them, starch-based hydrogels have a great potential for wearable electronics. However, it remains challenging to develop multifunctional starch-based hydrogels with high stretchability, good conductivity, excellent durability and high sensitivity. Herein, amylopectin and ionic liquid were introduced into a hydrophobic association hydrogel to endow it with versatility. Benefiting from the synergistic effect of amylopectin and ionic liquid, the hydrogel exhibited excellent mechanical properties (the elongation of 2540 % with a Young's modulus of 12.0 kPa and a toughness of 1.3 MJ·m-3), self-recovery, good electrical properties (a conductivity of 1.8 S·m-1 and electrical self-healing), high sensitivity (gauge factor up to 26.85) and excellent durability (5850 cycles). The above properties of the hydrogel were closely correlated to its internal structure from hydrophobic association, H-bonding and electrostatic interaction, and can be regulated by changing the component contents. A wireless wearable sensor based on the hydrogel realized accurate and stable monitoring of joint motions and expression changes. This work demonstrates a kind of promising biopolymer-based materials as candidates for high-performance flexible wearable sensors.

Tanomastat exerts multi-targeted inhibitory effects on viral capsid dissociation and RNA replication in human enteroviruses.

BACKGROUND: Global cyclical outbreaks of human enterovirus infections has positioned human enterovirus A71 (EV-A71) as a neurotropic virus of clinical importance. However, there remains a scarcity of internationally approved antivirals and vaccines. METHODS: In pursuit of repurposing drugs for combating human enteroviruses, we employed a comprehensive pharmacophore- and molecular docking-based virtual screen targeting EV-A71 capsid protein VP1-4, 3C protease, and 3D polymerase proteins. Among 15 shortlisted ligand candidates, we dissected the inhibitory mechanism of Tanomastat in cell-based studies and evaluated its in vivo efficacy in an EV-A71-infected murine model. FINDINGS: We demonstrated that Tanomastat exerts dose-dependent inhibition on EV-A71 replication, with comparable efficacy profiles in enterovirus species A, B, C, and D in vitro. Time-course studies suggested that Tanomastat predominantly disrupts early process(es) of the EV-A71 replication cycle. Mechanistically, live virus particle tracking and docking predictions revealed that Tanomastat specifically impedes viral capsid dissociation, potentially via VP1 hydrophobic pocket binding. Bypassing its inhibition on entry stages, we utilized EV-A71 replication-competent, 3Dpol replication-defective, and bicistronic IRES reporter replicons to show that Tanomastat also inhibits viral RNA replication, but not viral IRES translation. We further showed that orally administered Tanomastat achieved 85% protective therapeutic effect and alleviated clinical symptoms in EV-A71-infected neonatal mice. INTERPRETATION: Our study establishes Tanomastat as a broad-spectrum anti-enterovirus candidate with promising pre-clinical efficacy, warranting further testing for potential therapeutic application. FUNDING: MOE Tier 2 grants (MOE-T2EP30221-0005, R571-000-068-592, R571-000-076-515, R571-000-074-733) and A∗STARBiomedical Research Council (BMRC).

Capability lignin from Acacia crassicarpa black liquor as an environmentally benign antibacterial agent to produce antibacterial and hydrophobic textiles.

Recently, the growing health awareness of society on the utilization of fabrics has led to an increasing demand for natural-based antibacterial textiles. Lignin, a generous polyphenol compound in nature, is capable of preventing bacterial growth; in particular, it dwells bacteria closely together on human skin, such as Staphylococcus epidermidis, Bacillus subtilis, Propionibacterium acnes, and Staphylococcus aureus. However, the antibacterial properties of lignin are limited by factors such as the lignin concentration, source, and type of bacteria. This study aimed to evaluate the potency of lignin as an antibacterial agent for textiles. Moreover, the thermal properties and wettability of the textile after lignin coating were also investigated. This study showed that lignin isolation methods significantly contributed to the inhibition of bacterial growth in the clear zone diameter. In addition, the lignin structure, lignin concentration, and type of bacteria had notably different antibacterial effects. SEM images showed that lignin was successfully coated on the fiber, and the antibacterial textile was successfully fabricated with clear zones in the range of 0.1-0.5 cm against four different bacteria. Lignin did not significantly improve the thermal stability of the textile, as proven by the TGA results. After the HDTMS coating by dispersion method, the wettability of the lignin-textile improved to that of the hydrophobic material, with a contact angle greater than 119.05° with excellent antibacterial properties (clear zone of 0.1-0.43 cm).

Long-lasting anti-corrosion direct-to-metal polyurethane NP-GLIDE coatings based on the coordination effect and dual cross-linking of polyphenol.

Aluminum and its alloys have been widely used in our lives. However, Aluminum and its alloys is prone to corrosion, especially in harsh environment. In recent years, hydrophobic coatings were used in the corrosion protection of metal. But, the low surface tension of resins made them have a worse wettability on metal which had high surface tension, resulting in a worse adhesion of these coatings. Herein, we developed a long-lasting anti-corrosion direct-to-metal polyurethane NP-Glide coating based on the coordination effect of polyphenol and dual cross-linking. In comparative evaluation, the corrosion protection and anti-contamination performances of direct-to-metal polyurethane NP-Glide coating are significantly improved by the introduction of functional monomer dopamine methacrylamide (DMA) and TEMAc-8. The PU coatings with 10 wt% TEMAc-8 possesses high impedance value (|Z|0.01Hz > 109 Ω•cm2) after 40 days of immersion in 3.5 wt% NaCl solution, exhibiting a great pull-off adhesion both in dry and wet coating, and a long-term anti-corrosion performance for aluminum alloy protection.

Clinical evaluation of hydrophilic and hydrophobic resin-based sealants in uncooperative children: a randomized controlled clinical trial.

This clinical trial aimed to evaluate and compare the retention and cariostatic effects of hydrophilic and hydrophobic resin-based sealants (RBSs) for sealing pits and fissures in the permanent molars of uncooperative children. A split-mouth and double-blind randomized clinical trial (RCT) was conducted among 6- to 9-year-old uncooperative children. One hundred and four sound mandibular and maxillary first permanent molars were randomly allocated to be sealed with group I (UltraSeal XT® hydro™) or group II (Helioseal-F) in 34 uncooperative children. Clinical evaluation was performed by two investigators using the Color, Coverage and Caries system to assess sealant retention and cariostatic effect at 3-, 6- and 12-month intervals. Data analysis was performed using Friedman's and Mann-Whitney U tests. The final analysis included 31 children with 49 pairs of teeth. No significant differences were observed between the retention and cariostatic effects of hydrophilic and hydrophobic RBSs at the 3-, 6- and 12-month intervals (p = 0.23, p = 0.638, and p = 0.706, respectively) (p = 0.175, p = 0.065, and p = 0.171, respectively). After 12 months of follow-up, the hydrophilic RBSs showed an outcome equivalent to that of conventional hydrophobic RBSs in terms of retention and cariostatic effects. Therefore, hydrophilic RBSs could be considered as the sealing material of choice when isolation is difficult, particularly in uncooperative children.

Incorrectly Focused Neodymium:Yttrium-Aluminum-Garnet (Nd:YAG) Laser Beam Leads to Massive Destructive Effects in Small-Aperture (Pinhole) Intraocular Lenses.

INTRODUCTION: Pinhole intraocular lenses (IOLs) were developed to improve reading by compensating for loss of accommodative function. The IC-8® Apthera™ is a small-aperture presbyopia-correcting IOL that combines the proven principle of small-aperture optics with an aspheric monofocal lens to deliver a continuous range of vision for patients with cataracts from distance to near vision. Posterior capsule opacification is the most common sequela after cataract surgery. It is effectively treated by laser capsulotomy. However, if the laser beam is incorrectly focused, the IOL can be permanently damaged (pits/shots). METHODS: In this experimental study, yttrium-aluminum-garnet (YAG) pits were purposefully created. Defects were analyzed and compared between the periphery of the ring in the clear area of the hydrophobic acrylic lens and at the carbon black (CB)-polyvinylidene fluoride (PVDF) filtering component (FilterRing™) of the pinhole lens. All defects were made using identical settings/energy levels (2.6 mJ). The damage induced to the IC-8® Apthera™ IOL was examined by low-magnification images, light microscopy, scanning electron microscopy, and micro-computed tomography (micro-CT). RESULTS: YAG defects in the carbon black filter ring were much more severe than those in the clear zone due to the high absorption of the carbon black. Massive defects and destruction of the lens with tearing out of fragments and particles were observed. The missing volume calculated from the micro-CT reconstruction was 0.266 mm3, which is 1.6% of the entire IOL volume, or more than 1000 times the volume damaged in the largest shot in the periphery. CONCLUSION: Based on the results, we highly recommend using the lowest possible energy levels, posterior offset setting, and circular pattern for maximum safety when performing laser capsulotomy with pinhole implants. Care should be taken to avoid creating irreversible iatrogenic defects that may affect overall quality. The safest area for performing capsulotomy seems to be the periphery of the ring segment. Video available for this article.

Separation of iodate, bromide, nitrite, nitrate, and iodide in seawater by ion chromatography using 1-aminoundecyl group chemically bonded silica columns.

The separation and detection of six common inorganic anions (iodate (IO3-), bromate (BrO3-), bromide (Br-), nitrite (NO2-), nitrate (NO3-), and iodide (I-)) in pure water and 35 ‰ artificial seawater were examined by ion chromatography (IC). As packing materials of separation columns, 1-aminoundecyl group chemically bonded silica (AUS) gels were prepared. Separation of the anions in pure water was achieved using separation columns (150 mm × 4.6 mm i.d.) packed with the AUS gels, 0.1 M NaCl + 5 mM phosphate buffer (pH 4.5) as eluent, and a UV detector (wavelength 225 nm). The anions in artificial seawater were separated and detected with a 300 mm-long column without interferences by matrix anions such as chloride (Cl-) and sulfate (SO42-). The stationary phases have high-capacity anion-exchange/hydrophilic/hydrophobic interaction mixed-modes. The IC system was applied to five inorganic anions, IO3-, Br-, NO2-, NO3-, and I- in seawater of the Seto-Inland Sea, Japan. The detection limits (DLs, S/N = 3) were 11 µg L-1 (IO3-), 93 (Br-), 1.3 (NO2-), 1.4 (NO3-), and 1.1 (I-) for a 100-µL sample injection.

Photophysical Response of Propranolol in Biomimetic Micellar Media of Alkyltrimethylammonium Bromide Surfactants: Effect of pH and Alkyl Chain Length.

The photophysical behavior of a ß-blocker drug propranolol (PPL) in micellar environments, formed by alkyltrimethylammonium bromide surfactants viz.; Cetyltrimethylammonium bromide (CTAB), Tetradecyltrimethylammonium bromide (TTAB), and Dodecyltrimethylammonium bromide (DTAB), has been investigated through fluorescence and UV-visible spectroscopic techniques at pH levels of 3.5, 7.4, and 10.4. The impact of pH on the critical micelle concentration (cmc) and micropolarity of micelles were assessed using pyrene as a photophysical probe. The cmc values were found to be lower at pH 10.4 compared to pH 7.4 and pH 3.5. Fluorescence emission intensities of PPL at 323 nm, 338 nm, and 352 nm were significantly influenced by pH, hydrophobic alkyl chain length of surfactants, and their concentrations. Quenching experiments with Cetylpyridinium chloride (CpCl) indicated the localization of charged and uncharged forms of PPL within micelles, with quenching constant (Ksv) values dependent on alkyl chain length and pH. At pH < pKa, PPL is positioned near the Stern layer, whereas at pH 10.4, its naphthalene moiety resides near the hydrophobic micellar core. UV spectroscopy showed that the charged form of PPL interacted with micelles only above cmc, while the neutral form interacted even below the cmc. Density Functional Theory (DFT) reveals the HOMO of the surfactants to be localized on the hydrocarbon chains, and the LUMO localized around the quaternary ammonium unit. Upon complexation with PPL, both HOMO and LUMO shifted to the drug, thereby decreasing energy levels. The findings are explained based on weak noncovalent interactions, further supported and analyzed through Reduced Density Gradient (RDG) and Noncovalent Interaction (NCI) methods, confirming synergistic non-covalent interactions in surfactant-PPL complexes.

Surface Characteristics and Artificial Weathering Resistance of Oil-Based Coatings on the Chemically and Thermally Modified Short-Rotation Teak Wood.

Improving the durability of short-rotation wood can be achieved through chemical and thermal modification. Chemical and thermal modification can have an impact on the physicochemical properties of wood, which can affect wood's surface characteristics and its resistance to weathering. The purpose of this study was to investigate the surface characteristics and artificial weathering resistance of chemically and thermally modified short-rotation teak wood coated with linseed oil (LO)-, tung oil (TO)-, and commercial oil-based coatings consisting of a mixture of linseed oil and tung oil (LT) and commercial oil-based polyurethane resin (LB) coatings. The short-rotation teak woods were prepared in untreated and treated with furfuryl alcohol (FA), thermal treatment (HT) at 150 and 220 °C, and combination of glycerol-maleic anhydride (GMA) impregnation with thermal treatment at 150 and 220 °C. The surface characteristics measured were surface free energy, wettability, Persoz hardness, bonding quality, and color changes before and after artificial weathering exposure. The results showed that chemical and thermal modifications treatment tended to reduce total surface free energy (SFE), hardness, wettability, and bonding quality. FA and GMA at 220 °C treatments provided homogenization effect on surface characteristics, especially in total SFE and wettability. The total SFE of untreated wood ranged from 45.00 to 51.13 mN/m, and treated wood ranged from 40.58 to 50.79 mN/m. The wettability of oil-based coating according to K-value ranged from 0.20 to 0.54. TO presented better photostability than LO. Short-rotation teak wood coated with oil-based commercial coatings presented better weathering resistance compared to pure natural drying oil. Commercial oil-based coatings provided better weathering protection for the chemically and thermally modified teak wood. The application of oil-based coatings on chemically and thermally modified short-rotation teak is being considered for the development of a better wood-protection system.

A Novel DLLME Method Involving a Solidifying Hydrophobic Deep Eutectic Solvent Using Hydrophilic Deep Eutectic Solvent as the Dispersant for the Determination of Polychlorinated Biphenyls in Water Samples.

This paper presents a novel dispersive liquid-liquid microextraction (DLLME) method that employs solidified hydrophobic deep eutectic solvent (DES) with hydrophilic DES acting as the dispersant. The aim is to enrich polychlorinated biphenyls (PCBs) from water samples for subsequent determination by gas chromatography-mass spectrometry. The effects of both the hydrophobic DES as the extractant and the hydrophilic DES as the dispersant were thoroughly investigated. Optimization of the key factors influencing extraction efficiency was performed, and the method was subsequently validated. Specifically, a hydrophobic DES called DES2, prepared by combining thymol and decanoic acid in a molar ratio of 3:2, was selected as the extraction solvent. Meanwhile, a hydrophilic DES named DES6, prepared from choline chloride and acetic acid in a molar ratio of 1:2, was chosen as a dispersant. Under the optimal extraction conditions, the developed method exhibited excellent linearity over the concentration range of 0.01-5.0 µg/L, low limits of detection ranging from 3.0 to 5.1 ng/L, relative standard deviations less than 4.1%, and enrichment factors between 182 and 204 for PCBs. Finally, the effectiveness of the developed method was successfully demonstrated through residue determination of PCBs in water samples.

Study on the Pyrolysis and Fire Extinguishing Performance of High-Temperature-Resistant Ultrafine Dry Powder Fire Extinguishing Agents for Aviation Applications.

Ultrafine KAl(OH)2CO3 dry powder (UDWP), as a novel high-temperature-resistant ultrafine dry powder fire extinguishing agent, has garnered significant attention in the field of aviation fire protection. However, its development has been hindered by its hydrophilicity, which leads to hygroscopicity, and its tendency for re-ignition due to oil deposition. Therefore, this study employs perfluorodecyltrimethoxysilane (PFDTMS) to modify the surface of UDWP, resulting in hydrophobic and oleophobic M-UDWP. The thermal stability and hydrophobicity of M-UDWP ensure its long-term stable storage in aircraft equipment compartments, thereby reducing aircraft maintenance costs. Additionally, its oleophobicity provides excellent anti-re-ignition performance, protecting aircraft power compartments from secondary fire damage. Energy-dispersive X-ray spectroscopy (EDS), Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) analyses indicate that the PFDTMS modifier was successfully grafted onto KAl(OH)2CO3. Furthermore, M-UDWP exhibits a three-stage thermal decomposition process. The first-stage decomposition can be regarded as a single-step reaction, and the calculated kinetic parameters provide accurate predictions. Thermogravimetric analysis-Fourier transform infrared spectroscopy-mass spectrometry (TG-FTIR-MS) results reveal that M-UDWP significantly produces H2O and CO2 during thermal decomposition, which is one of its core fire extinguishing mechanisms. For the combustion of #RP-3 and #RP-5 aviation kerosene, commonly found in aircraft engine nacelles, the extinguishing times required by M-UDWP are 243 ms and 224 ms, respectively, with minimum extinguishing concentrations (MEC) of 25.9 g/m3 and 23.4 g/m3, respectively. The study of M-UDWP's thermal stability aids in understanding its storage stability under high-temperature conditions and its fire extinguishing mechanisms in fire zones. Moreover, the research findings suggest that M-UDWP has the potential to replace Halon 1301 in aircraft engine nacelles.

Combining the Fragment Molecular Orbital and GRID Approaches for the Prediction of Ligand-Metalloenzyme Binding Affinity: The Case Study of hCA II Inhibitors.

Polarization and charge-transfer interactions play an important role in ligand-receptor complexes containing metals, and only quantum mechanics methods can adequately describe their contribution to the binding energy. In this work, we selected a set of benzenesulfonamide ligands of human Carbonic Anhydrase II (hCA II)-an important druggable target containing a Zn2+ ion in the active site-as a case study to predict the binding free energy in metalloprotein-ligand complexes and designed specialized computational methods that combine the ab initio fragment molecular orbital (FMO) method and GRID approach. To reproduce the experimental binding free energy in these systems, we adopted a machine-learning approach, here named formula generator (FG), considering different FMO energy terms, the hydrophobic interaction energy (computed by GRID) and logP. The main advantage of the FG approach is that it can find nonlinear relations between the energy terms used to predict the binding free energy, explicitly showing their mathematical relation. This work showed the effectiveness of the FG approach, and therefore, it might represent an important tool for the development of new scoring functions. Indeed, our scoring function showed a high correlation with the experimental binding free energy (R2 = 0.76-0.95, RMSE = 0.34-0.18), revealing a nonlinear relation between energy terms and highlighting the relevant role played by hydrophobic contacts. These results, along with the FMO characterization of ligand-receptor interactions, represent important information to support the design of new and potent hCA II inhibitors.