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In the alkaline-surfactant-polymer flooding emulsion, oil droplets with various sizes exhibited different interfacial properties, resulting in different stabilization and destabilization behaviors. In view of this, it is expected to achieve outstanding oil-water separation efficiency by screening targeted demulsifier for oil droplets with different size ranges (0-1, 1-5 and 5-10 µm). Based on the size effect of oil droplets, a series of multibranched polyether-polyquaternium demulsifiers that integrated different charge neutralization and interfacial displacement functionalities were designed by regulating the cationicity and EO:PO ratios. As a result, the most effective polyether-polyquaternium variant for each size range of oil droplet was screened out. By employing these three selected polyether-polyquaternium variants in a sequential batch demulsification test, the maximum demulsification efficiency of 95.1% was obtained, which was much higher than that using a single polyether-polyquaternium variant (82.5%, 80.5% and 83.8%). The adsorption behaviors of polyether-polyquaternium variants on the oil/water interface were investigated by the molecular dynamics simulation. Moreover, the interfacial properties and oil droplet size variations during the demulsification process were monitored, so as explore the demulsification mechanism. This demulsification protocol based on the size effect of oil droplets with its excellent oil-water separation performance offered significant technical promise for the emulsified oil wastewater disposal.
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Emulsiones , Polímeros , Tensoactivos , Tensoactivos/química , Polímeros/química , Emulsiones/química , Aceites/química , Agua/química , Adsorción , Contaminantes Químicos del Agua/química , Tamaño de la Partícula , Simulación de Dinámica MolecularRESUMEN
Lately, emulsions with low-fat and natural stabilizers are predominant. This study extracted the nano cellulose crystals (NCs) from Camellia Oleifera shells, and their gallic acid (GA) conjugates were synthesized by free-radical grafting. Pickering emulsions were prepared using NCs 1â¯%, 1.5â¯%, 2.5â¯%, and gallic acid conjugates NC-GA1, NC-GA2, and NC-GA3 as stabilizers. The obtained nano cellulose crystals exhibited 18-25â¯nm, -40.01⯱â¯2.45 size, and zeta potential, respectively. The contact angle of 83.4° was exhibited by NC-GA3 conjugates. The rheological, interfacial, and microstructural properties and stability of the Pickering emulsion were explored. NC-GA3 displayed the highest absorption content of 79.12â¯%. Interfacial tension was drastically reduced with increasing GA concentration in NC-GA conjugates. Rheological properties suggested that the low-fat NC-GA emulsions showed a viscoelastic behavior, increased viscosity, gel-like structure, and increased antioxidant properties. Moreover, NC-GA3 displayed reduced droplet size and improved emulsion temperature and storage stability (28â¯days) against phase separation. POV and TBARS values were reduced with the NC-GA3 (Pâ¯<â¯0.05). This work confirmed that grafting phenolic compounds on NCs could enhance bioactive properties, which can be used in developing low-fat functional foods. NC-GA conjugates can potentially fulfill the increasing demand for sustainable, healthy, and low-fat foods.
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Antioxidantes , Camellia , Celulosa , Emulsiones , Ácido Gálico , Reología , Camellia/química , Ácido Gálico/química , Celulosa/química , Antioxidantes/química , Viscosidad , Nanopartículas/química , CristalizaciónRESUMEN
Coconut milk is an unstable emulsion system, mainly stabilized by proteins, which limits the development of the food industry. The aim of this study was to investigate mechanisms for increasing emulsion stability through the interaction between coffee polyphenols (CPs) and coconut globulin (CG), the main protein in coconut milk. Caffeic acid (CA), chlorogenic acid (CHA), and ferulic acid (FA) were selected as CP models. The results showed that hydrogen bond interactions mainly occurred between CG and CPs (CG-FA < CG-CA < CG-CHA). CHA containing quinic acid preferentially formed a strong interaction with CG. The interaction changed the lipophilicity of CG and facilitated the formation of a dense and thick interfacial film at the oil-water interface. Furthermore, the emulsion stabilized by CG-CPs showed excellent stability after storage, centrifugation, pH, and salt treatment, especially CG-CHA. This study could provide a theoretical basis for improving the stability of coconut milk products.
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Significant challenges remain in designing sufficient viscoelasticity polysaccharide-based high internal phase Pickering emulsions (HIPPEs) as soft materials for 3D printing. Herein, taking advantage of the interfacial covalent bond interaction between modified alginate (Ugi-OA) dissolved in the aqueous phase and aminated silica nanoparticles (ASNs) dispersed in oil, HIPPEs with printability were obtained. Using multitechniques coupling a conventional rheometer with a quartz crystal microbalance with dissipation monitoring, the correlation between interfacial recognition coassembly on the molecular scale and the stability of whole bulk HIPPEs on the macroscopic scale can be clarified. The results showed that Ugi-OA/ASNs assemblies (NPSs) were strongly retargeted into the oil-water interface due to the specific Schiff base-binding between ASNs and Ugi-OA, further forming thicker and more rigid interfacial films on the microscopic scale compared with that of the Ugi-OA/SNs (bared silica nanoparticles) system. Meanwhile, flexible polysaccharides also formed a 3D network that suppressed the motion of the droplets and particles in the continuous phase, endowing the emulsion with appropriately viscoelasticity to manufacture a sophisticated "snowflake" architecture. In addition, this study opens a novel pathway for the construction of structured all-liquid systems by introducing an interfacial covalent recognition-mediated coassembly strategy, showing promising applications.
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HYPOTHESIS: Cyclodextrin (CD) can spontaneously build up the solid particle membrane with CD-oil inclusion complexes (ICs) by a self-assembly process. Sodium casein (SC) is expected to preferentially adsorb at the interface to transform the type of interfacial film. The high-pressure homogenization can increase interfacial contact opportunities of the components, which promote the phase transition of the interfacial film. EXPERIMENTS: We added SC by sequential and simultaneous orders to mediate the assembly model of the CD-based films, examined the patterns in which the films adopt phase transitions to retard emulsion flocculation, and studied the physic-chemical properties of the emulsions and films from the structural arrest, interface tension, interfacial rheology, linear rheology, and nonlinear viscoelasticities through Fourier transform (FT)-rheology and Lissajous-Bowditch plots. FINDINGS: The interfacial and large amplitude oscillatory shear (LAOS) rheological results showed that the films changed from jammed to unjammed. We divide the unjammed films into two types: one is SC dominated liquid-like film, which is fragile and related to droplet coalescence; the other is cohesive SC-CD film, which helps droplet rearrangement and retards droplet flocculation. Our results highlight the potential of mediating phase transformation of interfacial films to improve emulsion stability.
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Pulmonary surfactant (PS) has been proposed as an efficient drug delivery vehicle for inhaled therapies. Its ability to adsorb and spread interfacially and transport different drugs associated with it has been studied mainly by different surface balance designs, typically interconnecting various compartments by interfacial paper bridges, mimicking in vitro the respiratory air-liquid interface. It has been demonstrated that only a monomolecular surface layer of PS/drug is able to cross this bridge. However, surfactant films are typically organized as multi-layered structures associated with the interface. The aim of this work was to explore the contribution of surface-associated structures to the spreading of PS and the transport of drugs. We have designed a novel vehiculization balance in which donor and recipient compartments are connected by a whole three-dimensional layer of liquid and not only by an interfacial bridge. By combining different surfactant formulations and liposomes with a fluorescent lipid dye and a model hydrophobic drug, budesonide (BUD), we observed that the use of the bridge significantly reduced the transfer of lipids and drug through the air-liquid interface in comparison to what can be spread through a fully open interfacial liquid layer. We conclude that three-dimensional structures connected to the surfactant interfacial film can provide an important additional contribution to interfacial delivery, as they are able to transport significant amounts of lipids and drugs during surfactant spreading.
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Emulsions are multiscale and thermodynamically unstable systems which will undergo various unstable processes over time. The behavior of emulsifier molecules at the oil-water interface and the properties of the interfacial film are very important to the stability of the emulsion. In this paper, we mainly discussed the instability phenomena and mechanisms of emulsions, the effects of interfacial films on the long-term stability of emulsions and summarized a set of systematic multiscale combined methods for studying emulsion stability, including droplet size and distribution, zeta-potential, the continuous phase viscosity, adsorption mass and thickness of the interfacial film, interfacial dilatational rheology, interfacial shear rheology, particle tracking microrheology, visualization technologies of the interfacial film, molecular dynamics simulation and the quantitative evaluation methods of emulsion stability. This review provides the latest research progress and a set of systematic multiscale combined techniques and methods for researchers who are committed to the study of oil-water interface and emulsion stability. In addition, this review has important guiding significances for designing and customizing interfacial films with different properties, so as to obtain emulsion-based delivery systems with varying stability, oil digestibility and bioactive substance utilization.
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Emulsionantes , Agua , Emulsiones , Adsorción , Viscosidad , ReologíaRESUMEN
Chemical prelithiation is regarded as a crucial method for improving the initial Coulombic efficiency (ICE) of Li-storage anodes. Herein, a substituent-engineered Li-cyanonaphthalene chemical prelithiation system is designed to simultaneously enhance the ICE and construct a multifunctional interfacial film for SiO electrodes. X-ray photoelectron spectroscopy (XPS), electron energy-loss spectroscopy (EELS), nuclear magnetic resonance (NMR) spectroscopy and atomic force microscopy (AFM) prove that the Li-cyanonaphthalene prelithiation reagent facilitates the formation of a rectified solid electrolyte interface (SEI) film in two ways: (1) generation of a gradient SEI film with an organic outer layer (dense N-containing organics, ROCO2Li) and an inorganic LiF-enriched inner layer; (2) homogenization of the horizontal distribution of the composition, mechanical properties and surface potential. As a result, the prelithiated SiO electrode exhibits an ICE above 100%, enhanced CEs during cycling, better cycle stability and inhibition of lithium dendrite formation in the overcharged state. Notably, the prelithiated hard carbon/SiO (9:1)âLiCoO2 cell displays an enhancement in the energy density of 62.3%.
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High internal phase Pickering emulsion (HIPPE) is a type of emulsion stabilized by solid particles irreversibly adsorbed on an interfacial film, and the volume fraction of the dispersed phase (Φ) is larger than the maximum packing volume fraction (Φmax). Proteins, polysaccharides, and their composite particles can be used as good particle stabilizers. The contact angle can most intuitively demonstrate the hydrophilicity and hydrophobicity of the particles and also determines the type of emulsions (O/W or W/O type). Particles' three-phase contact angles can be adjusted to about 90° by compounding or modification, which is more conducive to emulsion stability. As a shear thinning pseudoplastic fluid, HIPPE can be extruded smoothly through 3D printer nozzles, and its high storage modulus can support the structure of printed products. There is huge potential for future applications in 3D printing of food. This work reviewed the biomacromolecules that can be used to stabilize food-grade HIPPE, the stabilization mechanism of the emulsions, and the research progress of food 3D printing to provide a reference for the development of advanced food products based on HIPPE.
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The separation of ultrafine oil droplets from wasted nanoemulsions stabilized with high concentration of surfactants is precondition for oil reuse and the safe discharge of effluent. However, the double barriers of the interfacial film and network structures formed by surfactants in nanoemulsions significantly impede the oil-water separation. To destroy these surfactant protective layers, we proposed a newly-developed polyethyleneimine micelle template approach to achieve simultaneous surface charge manipulation and morphology transformation of magnetic nanospheres to magnetic nanorods. The results revealed that positively charged magnetic nanospheres exhibited limited separation performance of nanoemulsions, with a maximum chemical oxygen demand (COD) removal of 50%, whereas magnetic nanorods achieved more than 95% COD removal in less than 30 s. The magnetic nanorods were also applicable to wasted nanoemulsions from different sources and exhibited excellent resistance to wide pH changes. Owing to their unique one-dimensional structure, the interfacial dispersion of magnetic nanorods was significantly promoted, leading to the efficient capture of surfactants and widespread destruction of both the interfacial film and network structure, which facilitated droplet merging into the oil phase. The easy-to-prepare and easy-to-tune strategy in this study paves a feasible avenue to simultaneously tailor surface charge and morphology of magnetic nanoparticles, and reveals the huge potential of morphology manipulation for producing high-performance nanomaterials to be applied in complex interfacial interaction process. We believe that the newly-developed magnetic-nanorods significantly contribute to hazardous oily waste remediation and advances technology evolution toward problematic oil-pollution control.
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Nanotubos , Tensoactivos , Emulsiones/química , Fenómenos Magnéticos , Tensoactivos/química , Agua/químicaRESUMEN
HYPOTHESIS: Amphiphilic Janus nanosheets are plate-shaped, with one hydrophilic and one hydrophobic side; they are expected to assemble at oil-water interfaces. The assembled Janus nanosheets layers at the oil-water interface will exhibit a unique mechanical response under the vertical pressure of a probe. EXPERIMENTS: The interfacial behaviors of amphiphilic Janus nanosheets and the morphology of the assembled particle film at an oil-water interface were observed. The dynamic morphologies and force-displacement curves of the oil-water interface covered with amphiphilic Janus nanosheets were investigated during the insertion of a cylindrical probe. FINDINGS: Amphiphilic Janus nanosheets spontaneously aggregated at the oil-water interface. The morphology of the assembled particle film was controlled by the interfacial nanosheets concentration and can be divided into three regimes: unsaturated, monolayer, and collapsed. The wettability of the probe and the density of nanosheets at the interface played critical roles in the deformation and mechanical response of the oil-water interface under vertical pressure. The presence of amphiphilic Janus nanosheets reduced the stiffness and enhanced the flexibility and deformability of the oil-water interface. The oil-water interface covered with amphiphilic Janus nanosheets could produce larger deformation under a smaller vertical stress. This work not only improves the understanding of the interfacial properties of amphiphilic Janus nanosheets but also provides a method for characterizing nanoparticle layers at oil-water interfaces.
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The development of lithium-ion battery (LIB) has gone through nearly 40 year of research. The solid electrolyte interface film in LIBs is one of most vital research topics, its behavior affects the cycle life and safety of LIBs significantly. Progress in understanding the interfacial layer on the negative and positive electrodes in LIBs has been the focus of considerable research in the past few decades, but there remains a number of problem to be understood at the fundamental level, and there is still a great deal of controversy regarding the composition and formation mechanism of the interfacial film. In this article, we summarize recent research conducted on the interfacial film in LIBs, including the film formation mechanism, the composition, and stability of the interfacial film on the positive electrodes (in both diluted and high-concentration electrolytes). And the methodologies and advanced techniques implemented for the characterization of the interfacial film. Finally, we put forward some of the future development direction for the interfacial film and urgent problems that need to be solved.
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The chemical stability of the lipophilic bioactives encapsulated in emulsions can be influenced by emulsion droplet interfacial characteristics as well as by the ability of antioxidants incorporated in emulsion to prevent the degradation of the encapsulated compounds. Therefore, this study evaluated the effects of the interfacial characteristics of emulsions and the polarity of antioxidants on the storage stability of lycopene in emulsions. Emulsions with 5% (w/w) oil containing lycopene (30 µmol/kg emulsion) were prepared using a series of polyethylene glycol acyl ether-type emulsifiers through microfluidization. Change in lycopene content in emulsions was monitored by high performance liquid chromatography. Our findings show that the hydrophilic group size (or length) of emulsifiers and the emulsifier concentration at the interfacial film play a role, albeit minor, in controlling the storage stability of lycopene encapsulated in emulsions. Lipophilic (tert-butylhydroquinone (TBHQ)) and amphiphilic (lauryl gallate) antioxidants similarly improved the storage stability of lycopene in emulsions from acid- and radical-mediated degradation, independent of the characteristics of interfacial films of emulsions. However, TBHQ inhibited the degradation of lycopene in emulsions more effectively than lauryl gallate under conditions intended to accelerate the acid-mediated degradation of lycopene. Therefore, our findings can provide helpful information about what type of emulsifiers and antioxidants can be chosen for preparing food emulsions capable of maximizing the stability of lycopene encapsulated therein.
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Dendrons consisting of two phosphonate functions and three oligo(ethylene glycol) (OEG) chains grafted on a central phenoxyethylcarbamoylphenoxy group were synthesized and investigated as Langmuir monolayers at the surface of water. The OEG chain in the para position was grafted with a t-Bu end-group, a hydrocarbon chain, or a partially fluorinated chain. These dendrons are models of structurally related OEG dendrons that were found to significantly improve the stability of aqueous dispersions of iron oxide nanoparticles when grafted on their surface. Compression isotherms showed that all OEG dendrons formed liquid-expanded Langmuir monolayers at large molecular areas. Further compression led to a transition ascribed to the solubilization of the OEG chains in the aqueous phase. Brewster angle microscopy (BAM) provided evidence that the dendrons fitted with hydrocarbon chains formed liquid-expanded monolayers throughout compression, whilst those fitted with fluorinated end-groups formed crystalline-like domains, even at large molecular areas. Dimyristoylphosphatidylcholine and dendron molecules were partially miscible in monolayers. The deviations to ideality were larger for the dendrons fitted with a fluorocarbon end-group chain than for those fitted with a hydrocarbon chain. Brewster angle microscopy and atomic force microscopy supported the view that the dendrons were ejected from the phospholipid monolayer during the OEG conformational transition and formed crystalline domains on the surface of the monolayer.
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Dendrímeros/química , Glicol de Etileno/química , Fosfolípidos/química , Agua/química , Aire , Microscopía de Fuerza Atómica , Propiedades de SuperficieRESUMEN
HYPOTHESIS: Understanding and monitoring the film formation of interfacially formed layered films allows for the design of conductive nanocomposite films suitable for strain sensing. EXPERIMENTS: To understand the mechanism of interfacial film formation, the hexane/water interface was monitored during the evaporation process via confocal laser scanning microscopy. Scanning electron microscopy and atomic force microscopy were utilized to investigate final film morphology. Tensile testing was used to determine their mechanical properties under uniaxial strain. FINDINGS: Conductive nanocomposite films were formed at the hexane/water interface. Due to their low colloidal stability in hexane, the Vulcan carbon (VC) nanoparticles settled to the hexane/water interface prior to the onset of paraffin wax precipitation. Consequently, after the evaporation of hexane a two-layer structured film was formed. The bottom (water-facing, VC-rich) layer was conductive due to the existence of a percolated network of nanoparticle aggregates, while the top (hexane facing, paraffin-rich) layer was not conductive. The films showed high sensitivity for strains between 1% and 10%. We propose that the mechanism of strain sensing is similar to that of layer-structured sensors fabricated through embedding conductive nanofillers onto flexible polymeric substrates. The advantage of the films derived by the method proposed here is their ease of fabrication as well as their low cost.
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The presence of liquid-air interfaces in protein pharmaceuticals is known to negatively impact product stability. Nevertheless, the mechanisms behind interface-related protein aggregation are not yet fully understood. Little is known about the physical-chemical behavior of proteins adsorbed to the interface. Therefore, the combinatorial use of appropriate surface-sensitive analytical methods such as Langmuir trough experiments, Infrared Reflection-Absorption Spectroscopy (IRRAS), Brewster Angle Microscopy (BAM), and Atomic Force Microscopy (AFM) is highly expedient to uncover structures and events at the liquid-air interface directly. Concentration-dependent adsorption of a human immunoglobulin G (IgG) and characteristic surface-pressure/area isotherms substantiated the amphiphilic nature of the protein molecules as well as the formation of a compressible protein film at the liquid-air interface. Upon compression, the IgG molecules do not readily desorb but form a highly compressible interfacial film. IRRA spectra proved not only the presence of the protein at the interface, but also showed that the secondary structure does not change considerably during adsorption or compression. IRRAS experiments at different angles of incidence indicated that the film thickness and/or packing density increases upon compression. Furthermore, BAM images exposed the presence of a coherent but heterogeneous distribution of the protein at the interface. Topographical differences within the protein film after adsorption, compression and decompression were revealed using underwater AFM. The combinatorial use of physical-chemical, spectroscopic and microscopic methods provided useful insights into the liquid-air interfacial protein behavior and revealed the formation of a continuous but inhomogeneous film of native-like protein molecules whose topographical appearance is affected by compressive forces.
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Inmunoglobulina G/química , Adsorción/efectos de los fármacos , Aire , Humanos , Microscopía de Fuerza Atómica/métodos , Presión , Estructura Secundaria de Proteína , Espectrofotometría Infrarroja , Propiedades de Superficie , Agua/químicaRESUMEN
An oil-in-water emulsion stabilized by saponified epoxidized soybean oil-grafted hydroxyethyl cellulose (H-ESO-HEC) was investigated. By using an ultrasonic method, oil-in-water emulsions were prepared by blending 50 wt % soybean oil and 50 wt % H-ESO-HEC aqueous suspensions. The influence of H-ESO-HEC concentrations on the properties of oil-in-water emulsions was examined. The H-ESO-HEC concentrations in the aqueous phase varied from 0.02 to 0.40 wt %. When the H-ESO-HEC concentration was 0.4 wt %, the emulsion remained stable for >80 days. The mean droplet sizes of the emulsions decreased by increasing the H-ESO-HEC concentration and extending the ultrasonic time. The adsorption amounts of H-ESO-HEC at the oil-water interface increased when the H-ESO-HEC concentrations in the aqueous phase increased. The rheological property revealed that the apparent viscosity of the H-ESO-HEC-stabilized oil-in-water emulsions increased when the H-ESO-HEC concentrations increased. Steady flow curves indicated an interfacial film formation in the emulsions. The evolution of G', Gâ³, and tan η indicated the predominantly elastic behaviors of all the emulsions.
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Celulosa/análogos & derivados , Aceite de Soja/química , Agua/química , Celulosa/química , Emulsiones/química , Reología , ViscosidadRESUMEN
The current simple nanofluid flooding method for tertiary or enhanced oil recovery is inefficient, especially when used with low nanoparticle concentration. We have designed and produced a nanofluid of graphene-based amphiphilic nanosheets that is very effective at low concentration. Our nanosheets spontaneously approached the oil-water interface and reduced the interfacial tension in a saline environment (4 wt % NaCl and 1 wt % CaCl2), regardless of the solid surface wettability. A climbing film appeared and grew at moderate hydrodynamic condition to encapsulate the oil phase. With strong hydrodynamic power input, a solid-like interfacial film formed and was able to return to its original form even after being seriously disturbed. The film rapidly separated oil and water phases for slug-like oil displacement. The unique behavior of our nanosheet nanofluid tripled the best performance of conventional nanofluid flooding methods under similar conditions.
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The elemental characteristics of the fluorine atom tell us that replacing an alkyl chain by a perfluoroalkyl or polyfluorinated chain in a molecule or polymer is consequential. A brief reminder about perfluoroalkyl chains, fluorocarbons and fluorosurfactants is provided. The outstanding, otherwise unattainable physicochemical properties and combinations thereof of poly and perfluoroalkyl substances (PFASs) are outlined, including extreme hydrophobic and lipophobic character; thermal and chemical stability in extreme conditions; remarkable aptitude to self-assemble into sturdy thin repellent protecting films; unique spreading, dispersing, emulsifying, anti-adhesive and levelling, dielectric, piezoelectric and optical properties, leading to numerous industrial and technical uses and consumer products. It was eventually discovered, however, that PFASs with seven or more carbon-long perfluoroalkyl chains had disseminated in air, water, soil and biota worldwide, are persistent in the environment and bioaccumulative in animals and humans, raising serious health and environmental concerns. Further use of long-chain PFASs is environmentally not sustainable. Most leading manufacturers have turned to shorter four to six carbon perfluoroalkyl chain products that are not considered bioaccumulative. However, many of the key performances of PFASs decrease sharply when fluorinated chains become shorter. Fluorosurfactants become less effective and less efficient, provide lesser barrier film stability, etc. On the other hand, they remain as persistent in the environment as their longer chain homologues. Surprisingly little data (with considerable discrepancies) is accessible on the physicochemical properties of the PFASs under examination, a situation that requires consideration and rectification. Such data are needed for understanding the environmental and in vivo behaviour of PFASs. They should help determine which, for which uses, and to what extent, PFASs are environmentally sustainable.