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.

Multiple drivers and mechanisms of solid-water interfacial interactions in sludge dewatering: Roles of polarity and molecular structure of extracellular polymeric substances.

Water occurrence states in sewage sludge, influenced by sludge physicochemical properties, are crucial for sludge dewaterability and have recently been regarded as a research hotspot. Here, the multifold characteristics of sludge flocs during hydrothermal treatment, including rheological properties, solid-water interfacial interactions, and the polarity distribution and molecular structure of extracellular polymeric substances (EPS), were systematically investigated, and the impact of these characteristics on sludge dewaterability was explored in depth. Hydrothermal treatment at 80 °C and 100 °C induced the conversion of free water into bound water, while an increase in temperature to 180 °C resulted in a significant decrease in bound water content, approximately 4-fold lower than at 100 °C. In addition to the conventional view of decreased sludge surface hydrophilicity at high temperatures, the decline in bound water was associated with the reduction in sludge apparent viscosity. XAD resin fractionation identified the hydrophobic/hydrophilic EPS (HPO-/HPI) ratio as an important factor determining water occurrence states. Especially, hydrolysis of HPI-related hydrophilic proteins and subsequent increase in HPO-related tryptophan-like substances played a dominant role in reducing sludge viscosity and facilitating the release of bound water. Protein conformational analysis revealed that the disruption of α-helix structures and disulfide bonds significantly reduced EPS water-holding capacity, providing strong evidence for the potential of targeting these dense structure units to enhance sludge dewaterability. These findings provide a holistic understanding of multidimensional drivers of water occurrence states in sludge, and guide directions for optimizing sludge treatment efficiency through EPS modification.

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.

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.

Changes in soil water repellency and soil erosion resistance as affected by land uses in karst environments.

Soil water repellency (SWR) exists in various soil ecosystems and can interrupt water infiltration and cause soil erosion. Anthropogenic land-use change can cause shifts in SWR and soil erosion resistance (SER) in sensitive soils. However, the direction and magnitude of these shifts in SWR and SER and their interrelations remain largely unclear. This study examined the changes in SWR, soil erodibility (K), and aggregate fractions in different land uses of a karst trough valley in southwest China. Soil samples were gathered from five land uses: cropland (CL), orchard (OP), secondary forest (SF), grassland (GL), and riverbank (RB), using a 1000 m × 1000 m grid, resulting in 210 sampling sites. Results showed that the water drop penetration time was significantly higher by 86.43%, 68.85%, and 71.47% in the SF, OP, and RB than in the CL, respectively (p < 0.05). The soil organic carbon (SOC) was the greatest in the SF and the lowest in the GL and CL (p < 0.05). The 1000-250 µm aggregate fraction, mean weight diameter (MWD), and geometric mean diameter (GMD) varied markedly among the different land uses (p < 0.05). The silt content, fractal dimension (D), and K were markedly lower in the RB than in the CL, OP, SF and GL (p < 0.05). The SWR had pronouncedly positive correlations with the SOC and 1000-250 µm aggregate fraction (p < 0.05). The K displayed a negative correlation with the GMD but a positive correlation with the D (p < 0.05). The structural equation modeling analysis revealed that the SOC was affected positively by the silt content and the 1000-250 µm aggregate fraction and negatively by the K. These factors directly regulated the SWR. Our results shed light on the mechanisms of land use changes impacting the SWR, SER and other soil properties in karst environments.

Selective extraction of genomic DNA from leopard cat (Prionailurus bengalensis), hairy-crowned deer (Elaphodus cephalophus) and muntjac (Muntiacus reevesi) using hydrophobic magnetic deep eutectic solvents.

Wild animals, as a vital component of our natural world, serve a crucial role in preserving ecological equilibrium and biodiversity. By delving into the genetic constitution of wild animal populations, the evolutionary history, genetic diversity, and adaptation mechanisms could be explored, thereby informing conservation strategies and safeguarding the future of these species. In order to study the genetic information of wild animals, it is necessary to extract high purity and high concentration of wild animal genomic DNA. In this work, a hydrophobic magnetic deep eutectic solvent (HMDES) based vortexed extraction was developed for the extraction of genomic DNA from leopard cat (Prionailurus bengalensis), hairy-crowned deer (Elaphodus cephalophus) and muntjac (Muntiacus reevesi) muscle tissue, respectively. Extraction conditions like the pH value, extraction time, temperature and the amount of HMDES used were optimized by single-factor experiments. Under the optimized condition, genomic DNA could be selectively extracted from the three animal tissues. The limits of detection (LOD) and limits of quantification (LOQ) of the proposed method were 2.86 ng/µL and 8.66 ng/µL, respectively. Meanwhile, the relative standard deviation (RSD) of the method precision and repeatability were 1.64 % and 5.57 % at 20 ng/µL, showing the method has good precision and repeatability. After extraction, the DNA extracted into the HMDES droplets can be quickly recovered and the HMDES can be recycled and reused. The method proposed is a fast, environmental-friendly and high efficient extraction strategy for purification and enrichment of genomic DNA from leopard cat, hairy-crowned deer and muntjac tissues.

Novel three-dimensional live skin-like in vitro composite for bioluminescence reporter gene assay.

We genetically manipulated HaCaT cells, a spontaneously immortalised normal keratinocyte cell line, to stably express two different coloured luciferase reporter genes, driven by interleukin 8 (IL-8) and ubiquitin-C (UBC) promoters, respectively. Subsequently, we generated a three-dimensional (3D) skin-like in vitro composite (SLIC) utilising these cells, with the objective of monitoring bioluminescence emitted from the SLIC. This SLIC was generated on non-woven silica fibre membranes in differentiation medium. Immunohistochemical analyses of skin differentiation markers in the SLIC revealed the expression of keratins 2 and 10, filaggrin, and involucrin, indicating mature skin characteristics. This engineered SLIC was employed for real-time bioluminescence monitoring, allowing the assessment of time- and dose-dependent responses to UV stress, as well as to hydrophilic and hydrophobic chemical loads. Notably, evaluation of responses to hydrophobic substances has been challenging with conventional 2D cell culture methods, suggesting the need for a new approach, which this technology could address. Our observations suggest that engineered SLIC with constitutively expressing reporters driven by selected promoters which are tailored to specific objectives, significantly facilitates assays exploring the physiological functions of skin cells based on genetic response mechanisms. It also highlights new avenues for evaluating the physiological impacts of various compounds designed for topical application to human skin.

Relationship between thermal stability of collagens and the fraction of hydrophobic residues in their molecules.

In this study, a database of the thermal stability of collagens and their synthetic analogues has been compiled taking into account literature sources. In total, our database includes 1200 records. As a result of a comparative theoretical analysis of the collected experimental data, the relationship between the melting temperature (Tm) or denaturation temperature (Td) of collagens and the fraction of hydrophobic residues (f) in their molecules has been established. It is shown that this relationship is linear: the larger the f value, the higher the denaturation or melting temperature of a given collagen.

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.

Utilization of Lead Nitrate to Enhance the Impact of Hydroxamic Acids on the Hydrophobic Aggregation and Flotation Behavior of Cassiterite.

Lead nitrate (LN) is frequently employed as an activator in the flotation of cassiterite using hydroxamic acids as the collectors. This study investigated the effect of LN on the hydrophobic aggregation of cassiterite when benzohydroxamic acid (BHA), hexyl hydroxamate (HHA), and octyl hydroxamate (OHA) were used as the collectors through micro-flotation, focused beam reflectance measurement (FBRM) and a particle video microscope (PVM), zeta potential, and the extended DLVO theory. Micro-flotation tests confirmed that LN activated the flotation of cassiterite using the hydroxamic acids as collectors. Focused beam reflectance measurement (FBRM) and a particle video microscope (PVM) were used to capture in situ data on the changes in size distribution and morphology of cassiterite aggregates during stirring. The FBRM and PVM image results indicated that the addition of LN could promote the formation of hydrophobic aggregates of fine cassiterite, when BHA or HHA was used as the collector, and reduce the dosage of OHA needed to induce the formation of hydrophobic aggregates of cassiterite. The extended DLVO theory interaction energies indicated that the presence of LN could decrease the electrostatic interaction energies (Vedl) and increase the hydrophobic interaction energies (Vhy) between cassiterite particles, resulting in the disappearance of the high energy barriers that existed between the particles in the absence of LN. Thus, cassiterite particles could aggregate in the presence of LN when BHA, HHA, or a low concentration of OHA was used as the collector.

Synthesis, Optimization and Molecular Self-Assembly Behavior of Alginate-g-Oleylamine Derivatives Based on Ugi Reaction for Hydrophobic Drug Delivery.

To achieve the optimal alginate-based oral formulation for delivery of hydrophobic drugs, on the basis of previous research, we further optimized the synthesis process parameters of alginate-g-oleylamine derivatives (Ugi-FOlT) and explored the effects of different degrees of substitution (DSs) on the molecular self-assembly properties of Ugi-FOlT, as well as the in vitro cytotoxicity and drug release behavior of Ugi-FOlT. The resultant Ugi-FOlT exhibited good amphiphilic properties with the critical micelle concentration (CMC) ranging from 0.043 mg/mL to 0.091 mg/mL, which decreased with the increase in the DS of Ugi-FOlT. Furthermore, Ugi-FOlT was able to self-assemble into spherical micellar aggregates in aqueous solution, whose sizes and zeta potentials with various DSs measured by dynamic light scattering (DLS) were in the range of 653 ± 25~710 ± 40 nm and -58.2 ± 1.92~-48.9 ± 2.86 mV, respectively. In addition, RAW 264.7 macrophages were used for MTT assay to evaluate the in vitro cytotoxicity of Ugi-FOlT in the range of 100~500 µg/mL, and the results indicated good cytocompatibility for Ugi-FOlT. Ugi-FOlT micellar aggregates with favorable stability also showed a certain sustained and pH-responsive release behavior for the hydrophobic drug ibuprofen (IBU). Meanwhile, it is feasible to control the drug release rate by regulating the DS of Ugi-FOlT. The influence of different DSs on the properties of Ugi-FOlT is helpful to fully understand the relationship between the micromolecular structure of Ugi-FOlT and its macroscopic properties.

Halloysite-based inorganic-organic hybrid coatings for durable flame retardant, hydrophobic and antibacterial properties of cotton fabrics.

Developing durable protective cotton fabrics (CF) against potential environmental dangers such as fire hazards and bacterial growth remains an imperative but tough challenge. In this study, flame retardant, antibacterial and hydrophobic CF were successfully prepared via two-step coating. The inner coating entailed polyelectrolyte complexes consisting of polyethyleneimine and ammonium polyphosphate with the goal of enhancing the flame retardancy of CF. Halloysite nanotubes (HNTs), a kind of tubular silicate mineral, were creatively modified and introduced to multifunctional coatings to improve flame retardant and antibacterial properties of CF. N-halamine modified HNTs (HNTs-EA-Cl) and polydimethylsiloxane were applied as the outer coating to endow CF with antibacterial and hydrophobic properties and further improve the flame retardancy of CF. After halloysite-based inorganic-organic hybrid coatings, the limiting oxygen index of the treated samples (PAHP-CF) was over 28 %, and the release of heat and smoke was significantly inhibited. PAHP-CF could inactivate 100 % E. coli and S. aureus within 2 h. More importantly, PAHP-CF showed excellent hydrophobicity with a water contact angle of 148° and exhibited great prevention of bacterial adhesion. PAHP-CF exhibited excellent washing durability undergoing 5 washing cycles. This study promotes the development of multifunctional coatings and offers a new way to manufacture multifunctional cotton fabrics.

Slip Opacity and Fast Osmotic Transport of Hydrophobes at Aqueous Interfaces with Two-Dimensional Materials.

We investigate the interfacial transport of water and hydrophobic solutes on van der Waals bilayers and heterostructures formed by stacking graphene, hBN, and MoS2 using extensive ab initio molecular dynamics simulations. We compute water slippage and the diffusio-osmotic transport coefficient of hydrophobic particles at the interface by combining hydrodynamics and the theory of the hydrophobic effect. We find that slippage is dominated by the layer that is in direct contact with water and only marginally altered by the second layer, leading to a so-called "slip opacity". The screening of the lateral forces, where the liquid does not feel the forces coming from the second nearest layer, is one of the factors leading to the "slip opacity" in our systems. The diffusio-osmotic transport of small hydrophobes (with a radius below 2.5 Å) is also affected by the slip opacity, being dramatically enhanced by slippage. Furthermore, the direction of diffusio-osmotic flow is controlled by the solute size, with the flow in the opposite direction of the concentration gradient for smaller hydrophobes, and vice versa for larger ones. We connect our findings to the wetting properties of two-dimensional materials, and we propose that slippage and wetting can be controlled separately: whereas the slippage is mostly determined by the layer in closer proximity to water, wetting can be finely tuned by stacking different two-dimensional materials. Our study advances the computational design of two-dimensional materials and van der Waals heterostructures, enabling precise control over wetting and slippage properties for applications in coatings and water purification membranes.

Sulfur fractionation using high-resolution continuum source molecular absorption spectrometry with calcium and hydrophobic palladium nanoparticles as chemical modifiers.

The unprecedented use of high-resolution continuum source molecular absorption spectrometry (HR-CS MAS) for the fractionation of organic and inorganic sulfur (S) species through monitoring the CS molecule is presented here. Two separate methods for determining organic (CSorg) and inorganic (CSino) sulfur were developed to work sequentially. The optimized temperature program for both methodologies has two pyrolysis steps and one vaporization step (1st Tpyr: 1800 and 2ndTpyr: 800 °C, and Tvap: 2500 °C). The fractionation was achieved by implementing hydrophobic Pd NPs and Ca as chemical modifiers for the CSorg and CSino methods. Method development was performed by applying different statistical models, allowing the definition of optimal conditions for the chemical modifier mass, and minimizing the S species interconversion, i.e., Doehlert design, and central composite design. The limits of detection (LoD) for CSorg and CSino were 2.4 and 2.1 mg L-1, respectively. Recovery tests evaluated the method's specificity and accuracy; over 92 % recovery was found for both CSorg and CSino. Thus, the proposed methods offer a reliable alternative for fractionating organic and inorganic S by using HR-CS MAS.

An overview of cellulose aerogels and foams for oil sorption: Preparation, modification, and potential of 3D printing.

Sorption is one of the most efficient methods to remediate the increasing oil spill incidents, but the currently available absorbents are inadequate to tackle such a global threat. Recently, numerous researchers have attempted to develop sustainable oil sorbents. Cellulose aerogels and foams, a type of lightweight porous material with excellent sorption performance, are one of the most promising candidates. Significant progress has been made in the past decade towards the development of cellulose porous materials as effective oil sorbents, with improvements in their oil sorption capacity, reusability, and enhanced multifunctionality, indicating their potential for oil spill remediation. This article reviews recent reports and provides a comprehensive overview of the preparation and modification strategies for cellulose porous materials, with a specific emphasis on their oil sorption performance and structure control. We also focus on the burgeoning 3D printing technology within this field, summarizing the latest advances with a discussion of the potential for using 3D printing to customize and optimize the structure of cellulose porous materials. Lastly, this review addresses current limitations and outlines future directions for development.

Small hydrophobic (SH) proteins of Pneumoviridae and Paramyxoviridae: small but mighty.

Small hydrophobic (SH) proteins are a class of viral accessory proteins expressed by many members of the negative-stranded RNA viral families Paramyxoviridae and Pneumoviridae. Identified SH proteins are type I or II transmembrane (TM) proteins with a single-pass TM domain. Little is known about the functions of SH proteins; however, several possess viroporin activity, enhancing membrane permeability of infected cells or those expressing SH protein. Moreover, several SH proteins inhibit apoptosis and immune signaling pathways within infected cells, including TNF and interferon signaling, or activate inflammasomes. SH proteins are generally nonessential for viral replication in vitro, but loss of SH is often associated with reduced replication in vivo, suggesting a role in enhancing viral replication or evading host immunity. Analogous proteins are expressed by a variety of pathogens of public health importance; thus, understanding the functional importance and mechanisms of SH proteins provides insight into the pathogenesis and replication of negative-sense RNA viruses.