Water-in-water (W/W) emulsions have emerged as a promising vehicle for delivering water-soluble compounds within food industry. However, in conventional W/W emulsions, the phase with a lower volume fraction typically serves as the dispersed phase, resulting in limited encapsulation capacity for bioactive substances. In this work, the relationships between the chemistry, wettability of chitosan-based colloidal particles (CS-based CPs), and the type, stability of W/W emulsion were investigated to gain deep insight into the phase inversion mechanism within a dextran-polyethylene glycol (Dex-PEG) aqueous two-phase system (ATPS) at a molecular level. The results demonstrated that the type of W/W emulsions can be tailored through manipulating the chemistry and wettability of CS-based CPs, independent of altering the phase volume ratios. Finally, highly dispersed phase emulsions (HDPEs) with Dex as the dispersed phase in PEG (D/P HDPEs) were fabricated by tuning the chemistry and wettability of CS-based CPs, which were then employed for the encapsulation of riboflavin. The encapsulation capacity significantly improved from 25 % (traditional W/W emulsions) to 66.7 % (D/P HDPEs stabilized by CS-based CPs). The fabrication of D/P HDPEs offers a novel strategy for delivering water-soluble bioactive substances with high encapsulation capacity, showing strong potential for applications in low-fat, low-calorie functional foods.
Hierarchical Pickering foams, which offer multifunctional integration through the synergistic action of multiscale bubbles, have attracted considerable research interest. The controllable fabrication and application-driven development of well-defined hierarchical foams have therefore become a prominent frontier in liquid foam research. Herein, we report a facile high-speed homogenization strategy to construct hierarchical Pickering foams with a unique alveolar sac-like architecture. These foams are stabilized by bubbles coated with hydrophobic random copolymer colloidal particles, while the formation process has turned out to be closely correlated with the hydrophobicity, composition, particle size, and zeta potential of the particles, as well as the surface tension, pH value, and salt concentration of the solution. Such a distinctive alveolar sac-like hierarchical structure comprises interconnected large bubble cavities surrounded by small bubbles, providing a well-defined multiscale platform for exploring interbubble interactions.
Photocatalytic degradation is a promising way for removing industrial pollutants from wastewater. However, selective enrichment and removal of target pollutants especially at ultralow concentrations are extremely challenging. Herein, a highly selective and efficient strategy for photocatalytic degradation of an organic pollutant, p-nitrophenol (PNP), is developed based on photosensitive molecularly imprinted polymer nanoparticles and TiO2 photocatalyst functionalized fiberglass cloth (FGC). The negatively charged p-nitrophenol@photosensitive random copolymer nanoparticles (PNP@PAVE NPs) and the positively charged TiO2 NPs were used as building blocks to successively deposit on the surface of FGC, followed by the removal of the PNP through UV radiation, leading to the formation of PNP-MIP NP and TiO2 NP decorated FGC (TiO2/PNP-MIP NPs/FGC) with high selectivity and photocatalytic activity. As a result, TiO2/PNP-MIP NPs/FGC exhibited a removal rate of 98.7% and excellent selectivity for PNP. This work provides a valuable approach for realizing highly selective degradation of specific pollutants in complex pollutant mixtures in a real environment.
Janus emulsions have particularly drawn researchers' attention due to their asymmetrical morphology and anisotropic characteristics. However, except for Janus emulsions with liquid-liquid structures, other types of Janus emulsions have not been studied yet. Inspired by the occasional discovery that the water film on the foam surface freezes and transforms into a hard solid interface film below freezing point, a Janus emulsion was developed by using the phase change characteristics of solid paraffin wax. In this study, decane or perfluorooctane was used as the oil phase (O), solid paraffin wax as the solid interfacial film (S), and solutions of sodium dodecyl sulfate (SDS) or natural cellulose particles as the water phase (W). By controlling temperature and microgravity, hemispherical (O + S)/W and (S + O)/W type Janus phase change emulsions were successfully prepared. The experimental results show that paraffin wax content, oil phase density and polarity have significant effects on the stability and microstructure of emulsions. By calculating and fitting the solid-liquid interface ratio of Janus emulsions, the quantitative relationship between solid-liquid interface ratio, surfactant concentration and oil phase composition was obtained. This provides a theoretical basis and experimental basis for interface solid-state encapsulation and regulation.
With the rapid science and technology advancement, the oil-water separation in oily wastewater has become an urgent problem, especially the emulsified oil-water mixtures. Hollow carbon spheres (HCSs) have tremendous potential in separating oil-water emulsions due to their rich porous channels and high surface-to-volume ratio. In this work, as-prepared chitosan/poly(γ-glutamic acid) nanoparticles crosslinked by Ni2+ (Ni2+/CS/γ-PGA NPs) were used as carbon precursor to fabricate HCSs. This strategy separated the formation process of the biomolecular microspheres and the carbonization process. Especially, the Ni2+/CS/γ-PGA NPs were fabricated from the self-assembly of chitosan and γ-PGA in aqueous solution and the crosslinking of Ni2+ via the electrostatic interactions, facilitating the formation of biomolecular microspheres and making the usable of biomolecule-based carbon precursors diversity. After lyophilization, Ni2+/CS/γ-PGA NPs powder was obtained, which was then carbonized in a tube furnace under N2 atmosphere. During the carbonization process, the nickel species aggregated together to form the core of nickel@carbon nanoparticles, and carbon formed the shell. At last, nickel nanoparticles were removed from the carbon framework by hydrochloric acid, obtaining HCSs with super-hydrophobicity and lipophilicity. The as-prepared HCSs exhibited excellent separation performance in oil-in-water emulsions.
Hollow carbon spheres (HCSs) have attracted broad attention in aqueous zinc-ion hybrid supercapacitors (ZIHSCs) owing to their distinctive properties. However, traditional methods for fabricating HCSs face limitations, including complex multistep procedures, the use of corrosive chemicals, and stringent reaction conditions. In this work, biomass-based poly(gamma-glutamic acid)/Ni2+/melamine/chitosan 2+ /melamine/chitosan nanoparticles were used as the precursors to fabricate N/O co-doped hollow graphite carbon spheres (HGCSs). Thanks to the appropriate hydrophilic characteristic, specific surface area, pore size distribution, and electrical conductivity, the fabricated HGCSs cathode exhibited superior electrochemical properties. The assembled HGCSs-based ZIHSCs device showed a satisfactory specific capacitance of 133.2 mAh center dot g-- 1 at a current density of 1.0 A center dot g-- 1 , high energy densities of 75.2 Wh center dot kg-- 1 at 10,000 W center dot kg-- 1 and 107.9 Wh center dot kg-- 1 at 1000 W center dot kg-- 1 , respectively. Additionally, the assembled HGCSs-based ZIHSCs device displayed an exceptional cycling stability, enduring up to 10,000 cycles at 0.5 A center dot g-- 1 with a capacity retention rate of 98.1 %. This work provides a facile and novel strategy to prepare superior electrochemical performance biomass-based HGCSs cathode for ZIHSCs.
In recent years, functional foods with lipophilic nutraceutical ingredients are gaining more and more attention because of its potential healthy and commercial value, and developing of various bioderived food-grade particles for use in fabrication of Pickering emulsion has attracted great attentions. Herein, the bio-originated sodium caseinate-lysozyme (Cas-Lyz) complex particles were firstly designed to be used as a novel interfacial emulsifier for Pickering emulsions. Pickering emulsions of various food oils were all successfully stabilized by the Cas-Lyz particles without addition of any synthetic surfactants, while the fluorescence microscopy and SEM characterizations clearly evidenced Cas-Lyz particles were attached on the surface of emulsion droplets. Additionally, the Cas-Lyz particles stabilized emulsion can also be used to encapsulate the β-carotene-loaded soybean oil, suggestion a potential method to carry lipophilic bioactive ingredients in an aqueous formulation for food, cosmetic and medical industry. At last, we present a Pickering emulsion strategy that utilizes biocompatible, edible and body temperature-responsive lard oil as the core material in microcapsules, which can achieve hermetic sealing and physiological temperature-triggered release of model nutraceutical ingredient (β-carotene).
Bio-macromolecules alginic acid (ALG), lysozyme (Lys) and calcium ion can self-assemble to prepare ALG/Ca2+/Lys colloidal particles by electrostatic interaction. The size and morphology of the colloidal particles were characterized by BI-90PIus Zeta potentiometer and scanning electron microscope. The results showed that the formed colloidal particles have a spherical structure with a particle size of 480 nm. The colloidal particles can be reassembled at the oil (containing fat-soluble vitamin D-3)-water interface to stabilize oil-in-water functional Pickering emulsions. The effects of pH values and salt concentrations on the properties and emulsifying properties of colloidal particles were investigated in detail. The sustained release properties of the emulsion to Ca2+ and vitamin D-3 functional factors were studied. The results show that the emulsion has better sustained release performance for both Ca2+ and vitamin D-3. Using zinc ion (Zn2+) instead of Ca2+ and bio-macromolecule hyaluronic acid (HA) instead of ALG, the colloidal particles ALG/Zn2+/Lys and HA/Zn2+/Lys were prepared. The Pickering emulsion prepared with colloidal particles still has good sustained release performance for functional factors. The prepared functional emulsion has potential applications in the fields of food, medicine and cosmetics.
A new strategy was developed to prepare nanoscale porous carbon spheres (PCSs) using cross-linked chitosan/poly(gamma-glutamic acid) colloidal particles as precursor. The fabricated cross-linked chitosan/poly(gamma-glutamic acid) colloidal particles (Ca2+/CS/gamma-PGA CPs) were prepared from the self-assembly of negatively charged poly(gamma-glutamic acid) and positively charged chitosan, and the cross-linking of Ca2+ in aqueous solution, via the electrostatic interaction. After lyophilization, the Ca2+/CS/gamma-PGA CPs power was obtained, followed by carbonization in a tube furnace under N-2 atmosphere. Finally, the products were washed by hydrochloric acid, obtaining PCSs with hierarchical pore structure and super-hydrophobicity. The prepared PCSs exhibited excellent separation performance for oil-in-water emulsions.
为建设创新培养模式,有机融合理论学习和实践过程,并深度思考从"基本理论"到"应用拓展"的外延措施,我们将化工原理课程知识体系与工程思维相结合,将工科流程化的思维逻辑与课程知识结构相关联,实现创新培养方式、提升理论深度,最终达到弥补传统陈述式培养模式的不足.而且,为进一步培养学生的工程化思维模式、实践和创新能力,基于"化工原理"课程公式繁多,计算过程交叉、内容关联复杂等特点,借助"思维导图"的构建,实现课程知识结构的"流程化",帮助学生理清学习思路和构建知识脉络,进而提升学生的学习效率和逻辑系统.
With the improvement of the medical level and the need for pathological research, loading multiple drugs and controlling the burst release and differential release of multiple drugs has become a current research hotspot. In this work, a spherical VB12/Lys/CMC colloidal particle of approximately 400 nm was prepared from sodium carboxymethylcellulose (CMC), lysozyme (Lys) and hydrophilic drug (VB12) by macromolecular self-assembly technique. Subsequently, an oil-in-water emulsion was obtained by using VB12/Lys/CMC colloidal particles as emulsifiers, gelatin as spinning aid, and corn oil containing hydrophobic drug (VD3) as oil phase. Dual drugloaded core-shell nanofibers were further obtained by emulsion electrospinning. The sustained release effect of drugs in nanofibers was investigated. The results indicate that nanofibers have good sustained release effects on VB12 and VD3 over a long period of time, and the sustained release effect is controllable. The kinetic data of sustained release indicate that the main mechanism of sustained release is Fick diffusion. In vitro cytotoxicity test showed that the prepared nanofibers had good biocompatibility. In this work, a new method for preparing dualloaded core-shell nanofibers is presented, which has potential application in the field of combined therapy for complex diseases.
Dextran (Dex) and poly(ethylene glycol) (PEG)-based aqueous emulsions were stabilized using the self-assembled chitosan colloidal particles (CS CPs). Besides, the effects of pH, CS CPs concentration, polymer concentration, volume ratio of PEG solution to Dex solution, temperature, homogenizing speed and homogenizing time on the property of the W/W emulsions were investigated, respectively. In order to enhance the stability of the PEG-Dex emulsion, sodium tripolyphosphate was used to cross-link the CS CPs at the interface of emulsion droplets, which resulted in the stability duration for >1 year. Finally, the CS CPs were used as a support to immobilize urease and bovine serum albumin and a stabilizer to prepare W/W emulsion, which were then adopted as a catalysis system and as a spinning solution to fabricate drug-loaded nanofiber. This strategy potentially provides a new oppor-tunity to encapsulate the active molecules at the water-water interface, and enrich the types of usable active molecules in the encapsulation in the W/W emulsions.
功能乳液因含有某种特定功能的功能因子,成为目前研究的热点.生物大分子透明质酸(HA)、溶菌酶(Lys)和微量金属元素锌可静电自组装制备Lys-Zn2+/HA胶体粒子.研究了不同原料浓度对胶体粒子性质的影响,确定最佳组装条件.用纳米粒度仪和扫描电镜对最佳组装条件下胶体粒子的尺寸和形貌进行表征.结果显示:形成的胶体粒子为球形结构,粒径约 300 nm.此胶体粒子具有表面活性,可二次组装在油(含脂溶性维生素D3)-水界面稳定水包油型功能Pickering乳液.详细研究了pH和盐浓度对胶体粒子性质和乳化性能的影响.在最佳乳液性能下,研究了乳液对微量金属和维生素D3功能因子的缓释性能.结果表明:乳液对水溶性和脂溶性功能因子均具有一定的缓释性能.制备的功能乳液在食品、医药和化妆品领域具有潜在的应用.
Thermo-responsive lysozyme/calcium alginate-g-poly-N-isopropylacrylamide nanohydrogels (Lys/CA-g-PNIPAAm NHs) were prepared from the self-assembly of Lys and sodium alginate-g-poly-N-isopropylacrylamide (SA-g-PNIPAAm) and the ionic cross-linking of CaCl2 in aqueous solution. The Lys/CA-g-PNIPAAm NHs were immobilized on the cleaned surface of a transducer to fabricate a Lys molecularly imprinted sensor (Lys@MIP NHs sensor), which can selectively rebind to Lys in a mixture of closely related compounds. The effects of temperature on the size and the morphology of the Lys/CA-g-PNIPAAm NHs, the removal of Lys templates, the rebinding of Lys targets, and the detection performance of the Lys@MIP NHs sensor were investigated by dynamic light scattering, transmission electron microscope, and differential pulse voltammetry measurements. Compared with other Lys sensors, the fabricated Lys@MIP NHs sensor exhibited the wide linear range from 1 × 10−9 to 1 × 10−3 mg·mL−1 at 30 °C and showed short analysis times, high accuracy, satisfactory selectivity, stability, repeatability, reproducibility, and practical application for Lys detection in urine sample.
More recently, growing interests have been focusing on developing biocompatible particulate stabilizers, owing to its commercial value in food, cosmetic, and pharmaceutical industries. The present research was to study the potential of alginate-lysozyme (Alg-Lyz) complex nanoparticles to be used as a kind of food-grade particulate stabilizer for Pickeirng emulsions. The negatively charged polysaccharide alginate (Alg) and positively charged protein lysozyme (Lyz) were self-assembled into complex nanoparticles through electrostatic interactions. The particle size, turbidity, and ζ-potential of Alg-Lyz solutions were fully studied, and the Alg-Lyz nanoparticle had a minimum size of 98 nm at pH 4. Alg-Lyz particles showed excellent emulsify ability for producing Pickering emulsions. The β-carotene was then successfully encapsulated with a Alg-Lyz particles shell by Pickering emulsion technique, and its stability against of UV light were studied through quantifying the content of β-carotene in emulsion based on spectrophotometric measurements.
A molecularly imprinted biosensor for lysozyme based on the polymer nanoparticles self-assembled from watersoluble and electroactive poly (gamma-glutamic acid) modified with 3-aminothiophene copolymer were prepared. The water-soluble copolymer made imprinting of lysozyme in aqueous solution possible and thus facilitated improvement of the activity of LYS. Subsequent electro-polymerization not only locked the recognition site between copolymer and lysozyme but also created a conductive polymer network, which can enhance the electron transfer rate and increase the conductivity of the film. The prepared molecularly imprinted biosensor exhibited a wide linear range from 1 x 10-10 to 1 x 10-5 mg mL-1, and satisfactory selectivity, stability, repeatability for lysozyme detection.
用海藻酸(ALG)和溶菌酶(Lys)静电自组装制各胶体粒子,用纳米粒度仪和透射电镜对其尺寸和形貌进行表征,研究了溶菌酶和海藻酸的质量比(WR)对胶体粒子性质的影响,得到了具有最佳WR的胶体粒子.胶体粒子具有球形结构,粒径约为143 nm.这种胶体粒子可二次组装在油水界面稳定水包油型Pickering乳液,研究了pH值和盐浓度对胶体粒子性质和乳化性能的影响.随着pH值的增大胶体粒子和乳液滴粒径均逐渐增大而乳化性能逐渐降低;随着盐浓度的提高胶体粒子和乳液滴的粒径先减小后增大,乳化性能先提高后降低.乳液均保留了一定的活性.
用透明质酸(HA)和溶菌酶(Lys)静电自组装制备胶体粒子.研究了溶菌酶和透明质酸的质量比(WR)对胶体粒子性质的影响,得到最佳质量比下的胶体粒子.用纳米粒度仪和透射电镜对胶体粒子的尺寸和形貌进行表征.结果显示,形成的胶体粒子为球形结构,粒径约250 nm.此胶体粒子可二次组装在油水界面稳定水包油型类凝胶Pickering乳液.详细研究了pH和盐浓度对胶体粒子性质和乳化性能的影响.结果表明,随着pH增加,胶体粒子粒径先减小后增加;乳液滴粒径逐渐减小,乳化性能逐渐增加.随着盐浓度增加,胶体粒子和乳液滴粒径先降低后增加,乳化性能先增加后降低.进一步研究了pH和盐浓度对乳液中溶菌酶活性的影响.研究表明,制备的乳液均保留了一定的活性,在食品、医药和化妆品领域具有潜在的应用.
An electroconductive nanoparticles (NPs) film consisting of sodium poly(γ-glutamate) (γ-PGANa) and 3,4-diaminothiophene dihydrochloride (DATh) was simply prepared through macromolecular self-assembly and electropolymerization methods. Firstly, the γ-PGANa and the DATh underwent a complexation to form DATh/γ-PGANa composites through the electrostatic interaction; the DATh/γ-PGANa composites were then self-assembled into DATh/γ-PGANa NPs through decreasing the pH value in aqueous solution. Next, an electroconductive NPs film was formed on the surface of a gold electrode by casting the DATh/γ-PGANa NPs and subsequently electropolymerizing the DATh. Last, horseradish peroxidase and Nafion were cast onto the NPs film to obtain an enzymatic biosensor for H2O2 detection. The electroconductive DATh/γ-PGANa NPs film endowed the biosensor with high sensitivity. Under the optimal conditions, the prepared biosensor showed a linear range from 1 × 10−11 to 1 × 10−4 mol·L−1 with a detection limit of 3 × 10−12 mol·L−1 for H2O2 detection. The biosensor can retain its detection performance for 4 weeks. The response currents of the biosensor changed little after adding the interferent into the analyte. The standard deviation of the response between different biosensors did not exceed 2.5%.
An oil-in-water (O/W) Pickering emulsion catalysis system was prepared using a self-assembled of lipase/chitosan nanoparticles (CRL/CS NPs). The CRL/CS NPs functioned as both a stabilizer and a catalyst, and every droplet of the emulsion was used as a microreactor for the reactants in the oil phase. Due to an adequate oil–water interface for the “lid” opening of lipase and rapid mass transfer in the CRL/CS NPs, the Pickering emulsion exhibited excellent enzymatic activity toward the hydrolysis of olive oil, achieving 72.80% and 99.62% hydrolysis rates after 15 min and 120 min, respectively. Immobilizing lipase in the self-assembled CS NPs endowed the lipase with exceptional recyclability and provided a shield to protect the enzyme from deactivation.