Probing the interfacial behaviors of interfacially active and non-active asphaltenes and their impact on emulsion stability.

HYPOTHESIS: Asphaltenes subfractions with distinct interfacial behaviors may play different roles in stabilizing oil-water emulsions. EXPERIMENTS: In this work, whole asphaltenes were separated into interfacially active asphaltenes (IAA) and interfacially non-active asphaltenes (INAA). Employing advanced nanomechanical techniques, we have explored the compositions, morphologies, sizes, adsorption, and interfacial behaviors of IAA and INAA. FINDINGS: IAA exhibits a high and unevenly distributed oxygen content, distinguishing it from INAA. In toluene, the diameters of IAA and INAA are about 60 nm and 6 nm, respectively. When adsorbed irreversibly on mica surfaces, the thickness of the IAA and INAA film was measured at âˆ¼5.5 nm or 1 nm, respectively; while in a toluene solution, the film thickness reached âˆ¼46 nm and 3.1 nm for IAA and INAA, respectively. IAA demonstrates superior interfacial activity, and elastic/viscous moduli compared to INAA at the water-toluene interface. Quantified surface force measurements reveal that IAA stabilizes water droplets in toluene at a concentration of only 10 mg/L, while INAA requires a higher concentration of 100 mg/L. This work provides the first comprehensive investigation into the adsorption and interfacial behaviors of asphaltene subfractions and provides useful insights into the asphaltenes-stabilization mechanism of emulsions.

Dual-Protection Inorganic-Protein Coating on Mg-Based Biomaterials through Tooth-Enamel-Inspired Biomineralization.

Biocompatible magnesium alloys represent revolutionary implantable materials in dentistry and orthopedics but face challenges due to rapid biocorrosion, necessitating protective coatings to mitigate dysfunction. Directly integrating durable protective coatings onto Mg surfaces is challenging because of intrinsic low coating compactness. Herein, inspired by tooth enamel, a novel highly compact dual-protection inorganic-protein (inorganicPro) coating is in situ constructed on Mg surfaces through bovine serum albumin (BSA) protein-boosted reaction between sodium fluoride (NaF) and Mg substrates. The association of Mg ions and BSA establishes a local hydrophobic domain that lowers the formation enthalpy of NaMgF3 nanoparticles. This process generates finer nanoparticles that function as "bricks," facilitating denser packing, consequently reducing voidage inside coatings by over 50% and reinforcing mechanical durability. Moreover, the incorporation of BSA in and on the coatings plays two synergistic roles: 1) acting as "mortar" to seal residual cracks within coatings, thereby promoting coating compactness and tripling anticorrosion performance, and 2) mitigating fouling-accelerated biocorrosion in complex biosystems via tenfold resistance against biofoulant attachments, including biofluids, proteins, and metabolites. This innovative strategy, leveraging proteins to alter inorganic reactions, benefits the future coating design for Mg-based and other metallic materials with tailored anticorrosion and antifouling performances.

Recent advances in fabricating injectable hydrogels via tunable molecular interactions for bio-applications.

Hydrogels with three-dimensional structures have been widely applied in various applications because of their tunable structures, which can be easily tailored with desired functionalities. However, the application of hydrogel materials in bioengineering is still constrained by their limited dosage flexibility and the requirement of invasive surgical procedures. Compared to traditional hydrogels, injectable hydrogels, with shear-thinning and/or in situ formation properties, simplify the implantation process and reduce tissue invasion, which can be directly delivered to target sites using a syringe injection, offering distinct advantages over traditional hydrogels. These injectable hydrogels incorporate physically non-covalent and/or dynamic covalent bonds, granting them self-healing abilities to recover their structural integrity after injection. This review summarizes our recent progress in preparing injectable hydrogels and discusses their performance in various bioengineering applications. Moreover, the underlying molecular interaction mechanisms that govern the injectable and functional properties of hydrogels were characterized by using nanomechanical techniques such as surface forces apparatus (SFA) and atomic force microscopy (AFM). The remaining challenges and future perspectives on the design and application of injectable hydrogels are also discussed. This work provides useful insights and guides future research directions in the field of injectable hydrogels for bioengineering.

Bioinspired engineered proteins enable universal anchoring strategy for surface functionalization.

HYPOTHESIS: Conventional coating strategies and materials for bio-applications with protective, diagnostic, and therapeutic functions are commonly limited by their arduous preparation processes and lack of on-demand functionalities. Herein, inspired by the 'root-leaf' structure of grass, a series of novel polyacrylate-conjugated proteins can be engineered with sticky bovine serum albumin (BSA) protein as a 'root' anchoring layer and a multifunctional polyacrylate as a 'leaf' functional layer for the facile coating procedure and versatile surface functionalities. EXPERIMENTS: The engineered proteins were synthesized based on click chemistry, where the 'root' layer can universally anchor onto both organic and inorganic substrates through a facile dip/spraying method with excellent stability in harsh solution conditions, thanks to its multiple adaptive molecular interactions with substrates that further elucidated by molecular force measurements between the 'root' BSA protein and substrates. The 'leaf' conjugated-polyacrylates imparted coatings with versatile on-demand functionalities, such as resistance to over 99% biofouling in complex biofluids, pH-responsive performance, and robust adhesion with various nanomaterials. FINDINGS: By synergistically leveraging the universal anchoring capabilities of BSA with the versatile physicochemical properties of polyacrylates, this study introduces a promising and facile strategy for imparting novel functionalities to a myriad of surfaces through engineering natural proteins and biomaterials for biotechnical and nanotechnical applications.

Unraveling the hydrophobic interaction mechanisms of hydrocarbon and fluorinated surfaces.

HYPOTHESIS: Numerous hydrocarbon and fluorine-based hydrophobic surfaces have been widely applied in various engineering and bioengineering fields. It is hypothesized that the hydrophobic interactions of hydrocarbon and fluorinated surfaces in aqueous media would show some differences. EXPERIMENTS: The hydrophobic interactions of hydrocarbon and fluorinated surfaces with air bubbles in aqueous solutions have been systematically and quantitatively measured using a bubble probe atomic force microscopy (AFM) technique. Ethanol was introduced to water for modulating the solution polarity. The experimental force profiles were analyzed using a theoretical model combining the Reynolds lubrication theory and augmented Young-Laplace equation by including disjoining pressure arisen from the Derjarguin-Landau-Verwey-Overbeek (DLVO) and non-DLVO interactions (i.e., hydrophobic interactions). FINDINGS: The experiment results show that the hydrophobic interactions were firstly weakened and then strengthened by increasing ethanol content in the aqueous media, mainly due to the variation in interfacial hydrogen bonding network. The fluorinated surface exhibited less sensitivity to ethanol than hydrocarbon surface, which is attributed to the presence of ordered interfacial water layer. Our work reveals the different hydrophobic effects of hydrocarbon and fluorinated surfaces, with useful implications on modulating the interfacial interactions of relevant materials in various engineering and bioengineering applications.

Mussel-inspired polyethylene glycol coating for constructing antifouling membrane for water purification.

HYPOTHESIS: Polyethylene glycol (PEG) holds considerable potential in the fabrication of antifouling surfaces due to its strong hydration property. However, anchoring PEG polymer as a stable surface coating is still challenging because of its weak surface bonding property. Inspired by the mussel adhesion strategy, it is hypothesized that PEG polymer can be robustly attached onto substrates with the assistance of a "bio-glue" layer. EXPERIMENTS: The "bio-glue" layer composited of Levodopa/polyethyleneimine (LP) is firstly deposited onto substrates, followed by covalently anchoring the poly(ethylene glycol) diglycidyl ether (PEGDE) layer via ring-opening reaction. The antifouling property of as-prepared coating was characterized using several techniques including quartz crystal microbalance (QCM) and surface forces apparatus (SFA). Furthermore, the PEGDE/LP coating was applied in membrane functionalization for oil-in-water (O/W) emulsion separation. FINDINGS: PEGDE/LP coating shows outstanding stability and superior antifouling properties towards various potential foulants. In the O/W emulsion separation process, the PEGDE/LP-coated membrane maintains its super-hydrophilic property under harsh solution conditions and achieves high water flux (∼3000 L m-2 h-1 bar-1) and 90% water flux recovery ratio for separation of O/W emulsions containing different bio-foulants. This coating strategy provides a promising approach for fabricating stable coating with outstanding antifouling properties in various environmental engineering applications.

Ecological network analysis for an industrial solid waste metabolism system.

Faced with an increasing amount of industrial solid waste (ISW) in the process of rapid industrialization, it is indispensable to carry out ISW metabolism study to realize source and waste reduction. In this study, a new composite waste input-output (WIO) model is developed to examine ISW production and production relationships among different sectors. In particular, the extended methods of network control analysis and network utility analysis are used in the ecological network analysis under two ISW scenarios (i.e. common industrial solid waste (CISW) and hazardous waste (HW) scenarios). Furthermore, comprehensive utilization analysis is first developed to evaluate the ISW utilization level and to guide the planning of sectors with large proportion of ISW production. A case study of Guangdong, China shows that indirect flow analysis can be used to understand the internal ISW metabolism structure. The mining sectors produce a large amount of direct ISW and perform a low level of comprehensive utilization, but they have mutualism relationships with other sectors. The energy transformation (EH) sector in the CISW system has high direct generation intensity and plays as a main controller. The situation of paper manufacturing (MP) sector in HW system is similar to that of EH. Therefore, it is expected that the results of this study will provide scientific foundations for these sectors to formulate future ISW reduction policies.

Reusable Enzymatic Fiber Mats for Neurotoxin Remediation in Water.

Highly effective and reusable organophosphorus hydrolase (OPH)-loaded fiber mats have been fabricated that are capable of degrading toxic organophosphates (OPs) over a broad range of relevant concentrations (from 8 to 8250 ppm). The inherent fragility of enzymes, a major impediment in their incorporation into technologically relevant materials, was overcome while retaining their high catalytic efficiency, selectivity, and sensitivity via a random heteropolymers (RHP) approach. Kinetic analysis guides the design of polycaprolactone matrix morphology from films to fibers, facilitating substrate diffusion in the material. The RHP-OPH fiber mats demonstrate excellent stability and reusability with minimal requirements for storage, retaining over 40% of their initial activity after repeated daily use for three months. Practically, present studies provide valuable guidance toward fabrication of enzyme-based functional materials.

Removal of Tetrabromobisphenol A by adsorption on pinecone-derived activated charcoals: Synchrotron FTIR, kinetics and surface functionality analyses.

This study explored the adsorption of Tetrabromobisphenol A (TBBPA) on pinecone-derived activated charcoal. The interactions between TBBPA and activated-charcoal surface, as well as the corresponding effects of functionality and adsorption capacities, were investigated through synchrotron FTIR, kinetics and surface functionality analyses. It was found that multiple acid functional groups and their interactive effects played important roles. The adsorption on activated charcoal from Yellow pinecone was favored by the surface with high polarity, low aromaticity, and low surface area. In comparison, adsorption on activated charcoal from Scot pinecone was favored by the surface with high aromaticity and high surface area. The adsorption capacity and removal efficiency were significantly dependent upon the contents of acid functional groups on charcoal surface. This study showed that the newly presented evidence of interactions between oxygen-containing functional groups and TBBPA will be helpful for exploring the treatment and transport of such a contaminant in the environment.

Insights into the Toxicity of Triclosan to Green Microalga Chlorococcum sp. Using Synchrotron-Based Fourier Transform Infrared Spectromicroscopy: Biophysiological Analyses and Roles of Environmental Factors.

This study investigated the toxicity of triclosan to the green microalga Chlorococcum sp. under multiple environmental stressors. The interactions between triclosan and environmental stressors were explored through full two-way factorial, synchrotron-based Fourier transform infrared spectromicroscopy and principal component analyses. Phosphorus concentration, pH * phosphorus concentration, and temperature * pH * NaCl concentration were the most statistically significant factors under triclosan exposure. The variation of those factors would have a huge impact on biophysiological performances. It is interesting to find Chlorococcum sp. may become more resistant against triclosan in phosphorus-enriched environment. Besides, particular significant factors from multiple environmental stressors showed the impacts of triclosan on the corresponding response of Chlorococcum sp. owing to the specific structure and performance of biomolecular components. Moreover, two high-order interactions of temperature * pH * NaCl concentration and temperature * pH * NaCl concentration * phosphorus concentration had more contributions than others at the subcellular level, which could be attributed to the interactive complexity of biomolecular components. Due to cellular self-regulation mechanism and short exposure time, the biophysiological changes of Chlorococcum sp. were undramatic. These findings can help reveal the interactive complexity among triclosan and multiple environmental stressors. It is suggested that multiple environmental stressors should be considered during ecological risk assessment and management of emerging pollutants.