PREPARATION AND CHARACTERIZATION OF AFFINITY POLYMER BASIC MICROSPHERES BY SOAP-FREE EMULSION POLYMERIZATION

Poly(styrene-co-glycidyl methacrylate) latex microspheres with uniform size and high-density epoxy groups on the surface were prepared by soap-free emulsion polymerization with batch wise operation mode in the presence of 2.2′- azobis(2-methylpropionamidine) dihydrochloride as an initiator.The kinetics of soap-free emulsion polymerization and the effects of polymerization factors were examined.In addition,the optimum polymerization conditions of poly(styrene-co- glycidyl methacrylate) latex microspheres for...

Preparation of Self-crosslinked Fluorocarbon Polymer Emulsion with Core-shell Structure by the Method of Soap-free Emulsion Polymerization

Using methyl methacrylate （MMA）, butyl acrylate（BA） and hexafluorobutyl acrylate（HFBA） as main raw materials, we prepared self-crosslinked fluorocarbon polymer emulsion with core-shell structure via soap-free emulsion polymerization when the conception of particle design and polymer morphology was adopted. Moreover, the influence of mole ratio of BA to MAA, pH value on the oligomer was studied. And the effects of the added amount of oligomer, self-crosslinked monomer and HFBA, mass ratio of BA to MMA, reaction temperature and the initiator on the polymerization technology and the performance of the product, were investigated and optimized. The structure and performance of the fluorocarbon polymer emulsion were characterized and tested with FTIR, TEM, MFT and contact angle and water absorption of the latex film. The experimental results show that the optimal conditions for preparing fluorocarbon polymer emulsion are as follows： for preparing the oligomer, tool ratio of BA to MAA is equal to 1.0 ： 1.60, and pH value is controlled within the range of 8.0 and 9.0; for preparing fluorocarbon polymer emulsion, the added amount of oligmer[P（BA/MANa）] is 6%; mass ratio of BA to MMA is 40 ＂ 60; the added amount of self-crosslinked monomer is 2%, the added amount of HFBA is 15 %; reaction temperature is 80 ℃; the mixture of potassium persulfate and sodium bisulfite is used as the initiator. The film-forming stability of the fluorocarbon polymer emul- sion and the performance of the latex film, which is prepared with the soap-free emulsion polymerization, are better than that prepared with the conventional emulsion polymerization.

Influences of Electrolytes on the Soap-free Emulsion Copolymerization of St-MMA-AA

Monodisperse functional polymer microspheres with different particle size and with clean surface were prepared by batch soap-free emulsion polymerization of styrene, methyl methacrylate and acrylic acid in the presence of salts, and the influences of type and amount of electrolytes on polymerization process and particle morphology were investigated. Results showed that there was a critical concentration for different electrolyte to make polymerization process and the resultant emulsion stable, and the particle size increased with the increase of electrolyte concentration. The effect of metal ions was Ca^2＋〉〉K^＋〉Na^＋〉Li^＋, and the effect of haloids was Br〉Cl〉F. Keywords： Electrolyte, soap-free emulsion polymerization, polystyrene, latex particle morphology.

Synthesis and Characterization of Poly (Methyl Methacrylate)/Polyethylenimine Grafting Core-Shell Nanoparticles for CO2 Adsorption Using Soap-Free Emulsion Copolymerization

Unlike previous emulsion polymerization, we used grafting reactions in soap-free emulsion systems. In this study, we synthesized grafted PMMA/PEI core-shell nanoparticles by varying the MMA/PEI content and molecular weight of PEI (Mn = 600, 8000, and 10,000). The size and morphology of the core-shell nanoparticles were characterized by a particle size analyzer and scanning electron microscopy. The nanoparticles were 178 - 408 nm in diameter and swelled in water or methanol by 30 - 75 nm. The size of the nanoparticles increased with MMA contents, whereas the size distribution progressively became homogeneous with increasing molecular weight of PEI. Lastly, we measured CO2 adsorption capacity of the grafted PMMA/PEI core-shell nanoparticles, and we found the capacity to be limited at a level of 0.69 mg, which occurred for nanoparticles prepared from emulsions at a pH value of 11.

Synthesis of submicron-sized peanut-shaped poly(methyl methacrylate)/polystyrene particles by seeded soap-free emulsion polymerization

Submicron-sized peanut-shaped poly（methyl methacrylate）/polystyrene （PMMA/PS） particles were successfully synthesized by seeded soap-free emulsion polymerization of styrene on the spherical crosslinked PMMA seed particles. The obtained peanut- shaped particles showed a novel internal morphology： PS phase formed one domain which linked to the other domain having PMMA core encased by PS shell.

PREPARATION OF MICRON-SIZED NONSPHERICAL POLYSTYRENE/POLY(STYRENE-co-ETHYLENEGLYCOL DIMETHACRYLATE) PARTICLES BY SEEDED SOAP-FREE EMULSION POLYMERIZATION

Micron-sized nonspherical polymer particles having different morphologies were synthesized by seeded soap-free emulsion polymerization of styrene （St） and ethyleneglycol dimethacrylate （EGDMA, used as a crosslinker） on spherical, linear polystyrene （PS） seed particles. The morphology of the resulting PS/poly（St-co-EGDMA） particles was dependent on the crosslinker concentration and polymerization temperature.

Effect of sodium starch octenyl succinate-based Pickering emulsion on the physicochemical properties of hairtail myofibrillar protein gel subjected to multiple freeze-thaw cycles

A Pickering emulsion based on sodium starch octenyl succinate(SSOS)was prepared and its effects on the physicochemical properties of hairtail myofibrillar protein gels(MPGs)subjected to multiple freeze-thaw(F-T)cycles were investigated.The whiteness,water-holding capacity,storage modulus(G')and texture properties of the MPGs were significantly improved by adding 1%-2%Pickering emulsion(P<0.05).Meanwhile,Raman spectral analysis demonstrated that Pickering emulsion promoted the transformation of secondary structure,enhanced hydrogen bonds and hydrophobic interactions,and promoted the transition of disulfide bond conformation from g-g-g to g-g-t and t-g-t.At an emulsion concentration of 2%,theα-helix content decreased by 10.37%,while theβ-sheet content increased by 7.94%,compared to the control.After F-T cycles,the structure of the MPGs was destroyed,with an increase in hardness and a decrease in whiteness and water-holding capacity,however,the quality degradation of MPGs was reduced with 1%-2%Pickering emulsion.These findings demonstrated that SSOS-Pickering emulsions,as potential fat substitutes,can enhance the gel properties and the F-T stability of MPGs.

INFLUENCES OF ACID POST-TREATMENT ON THE MORPHOLOGY OF SOAP-FREE P(MMA-EA-MAA)PARTICLES PREPARED BY SEEDED EMULSION POLYMERIZATION

Soap-free poly（methyl methacrylate-ethyl acrylate-methacrylic acid） latex particles with narrow size distribution were synthesized by seeded emulsion polymerization, and the porous particles were created by a stepwise alkali/acid treatment method. Effects of acid treatment conditions on the particle morphology were investigated. Results show that one to three pores were formed inside most of particles after post-treatment. At pH 7.0, when the treatment temperature was lower than 70℃, the size of particles and the volume of pores remained almost unchanged, and these two values increased significantly when the temperature was higher than 70℃. Both the particle size and the pore volume decreased with the increase of initial pH value and treatment time in the acid treatment. As the pH was below 4.0 and the treatment time was longer than 180 min, the particles shrunk in size.

Oil-in-water nanoemulsions loaded with lycopene extracts encapsulated by spray drying:Formulation,characterization and optimization

Lycopene is very susceptible to degradation once released from the protective chromoplast environment.In this study,oil-in-water(O/W)nanoemulsions coupled with spray drying technology were applied for the encapsulation and stabilization of lycopene extracted from tomato waste.Tomato extract was obtained by ultrasound-assisted extraction.Nanoemulsions were prepared by a high-speed rotor stator using isopropyl myristate as the oil phase and Pluronic F-127 as the emulsifier for the aqueous external phase.The effect of emulsification process parameters was investigated.Spray drying of the produced emulsions was attempted to obtain a stabilized dry powder after the addition of a coating agent.The effect of different coating agents(maltodextrin,inulin,gum arabic,pectin,whey and polyvinylpyrrolidone),drying temperature(120-170℃),and feed flow rate(3-9 ml·min^(-1))on the obtained particles was evaluated.Results revealed that the emulsion formulation of 20/80(O/W)with 1.5%(mass fraction)of Pluronic F-127 as stabilizer in the aqueous phase resulted in a stable nanoemulsion with droplet sizes in the range of 259-276 nm with a unimodal and sharp size distribution.The extract in the nanoemulsion was well protected at room temperature with a degradation rate of lycopene of about 50%during a month of storage time.The most stable emulsions were then processed by spray drying to obtain a dry powder.Spray drying was particularly successful when using maltodextrin as a coating agent,obtaining dried spherical particles with mean diameters of(4.87±0.17)μm with a smooth surface.The possibility of dissolving the spray dried powder in order to repristinate.The original emulsion was also successfully verified.

Insights into the enhancement of food flavor perception:strategies,mechanism and emulsion applications

The core drivers of the modern food industry are meeting consumer demand for tasty and healthy foods.The application of food flavor perception enhancement can help to achieve the goals of salt-and sugar-reduction,without compromising the sensory quality of the original food,and this has attracted increasing research attention.The analysis of bibliometric results from 2002 to 2022 reveals that present flavor perception enhancement strategies(changing ingredient formulations,adding salt/sugar substitutes,emulsion delivery systems)are mainly carry out based on sweetness,saltiness and umami.Emulsion systems is becoming a novel research foci and development trends of international food flavor perception-enhancement research.The structured design of food emulsions,by using interface engineering technology,can effectively control,or enhance the release of flavor substances.Thus,this review systematically summarizes strategies,the application of emulsion systems and the mechanisms of action of food flavor perception-enhancement technologies,based on odor-taste cross-modal interaction(OTCMI),to provide insights into the further structural design and application of emulsion systems in this field.

Anti-abrasion collagen fiber-based membrane functionalized by UiO-66-NH_(2)with ultra-high efficiency and stability for oil-in-water emulsions separation

Membrane separation strategies offer promising platform for the emulsion separation.However,the low mechanical strength of membrane separation layers and the trade-off between separation flux and efficiency present significant challenges.In this study,we report a CFM@UiO-66-NH_(2)membrane with high separation flux,efficiency and stability,through utilizing a robust anti-abrasion collagen fiber membrane(CFM)as the multifunctional support and UiO-66-NH_(2)by an in-situ growth as the separation layer.The high mechanical strength of the CFM compensated for the weakness of the separation layer,while the charge-breaking effect of UiO-66-NH_(2),along with the size sieving of its constituent separating layers and the capillary effect of the collagen fibers,contributed to the potential for efficient separation.Additionally,the CFM@UiO-66-NH_(2)membrane exhibited superhydrophilic properties,making it suitable for separating oil-in-water microemulsions and nanoemulsions stabilized by anionic surfactants.The membrane demonstrated remarkable separation efficiencies of up to 99.960%and a separation flux of370.05 L·m^(-2)·h^(-1).Moreover,it exhibits stability,durability,and abrasion resistance,maintaining excellent separation performance even when exposed to strong acids and alkalis without any damage to its structure and performance.After six cycles of reuse,it achieved a separation flux of 417.97 L·m^(-2)·h^(-1)and a separation efficiency of 99.747%.Furthermore,after undergoing 500 cycles of strong abrasion,the separation flux remained at 124.39 L·m^(-2)·h^(-1),with a separation efficiency of 99.992%.These properties make it suitable for the long-term use in harsh operating environments.We attribute these properties to the electrostatic effect resulting from the amino group on UiO-66-NH_(2)and its in-situ growth on the CFM,which forms a size-screening separation layer.Our work highlights the potential of the CFM@UiO-66-NH_(2)membrane as an environmentally friendly size-screening material for the efficient emulsion wastewater separation.

Rhein-based Pickering emulsion for hepatocellular carcinoma:Shaping the metabolic signaling and immunoactivation in transarterial chemoembolization

The efficacy of transarterial chemoembolization(TACE)has been limited by insufficient embolization and a high incidence of tumor recurrence.Herein,we iden-tified that aberrant metabolic reprogramming and immunosuppression contribute to TACE refractoriness and Rhein,as a potential glycolytic metabolism inhibitor and immunoactivation inducer,was optimized to sensitize tumors to TACE therapy.To achieve efficient embolization,we developed an oil-in-water lipiodol embolic emulsion by stabilizing the self-assembled Rhein nanogel.The assembled Rhein exhibited a nanofiber network,and its integration enhanced the mechanical stability and viscoelasticity of the lipiodol embolic agent.With the synergistic advantages of solid and liquid embolic agents,this carrier-free Pickering emulsion exhibits effi-cient embolization and sustained drug release in models of unilateral renal artery embolization,rabbit ear tumor embolization,rabbit orthotopic liver cancer,and rat orthotopic liver cancer.Compared to conventional three-way catheter mixing meth-ods,multimodal imaging corroborates a marked enhancement in local drug retention and tumor suppression.Importantly,the incorporation of Rhein-mediated syner-gistic immunoembolization in this strategy achieved efficient embolization while robustly activating anti-tumor immune responses,including inducing immunogenic cell death,dendritic cell activation,and major histocompatibility complex class I pre-sentation to CD8+T cells for tumor killing.Together,thesefindings reveal a novel strategy for the application of self-assembled Rhein nanofiber-stabilized lipiodol emulsion to control metabolic signaling and immunoactivation in TACE.

Pickering emulsion transport in skeletal muscle tissue:A dissipative particle dynamics simulation approach

Lymph node targeting is a commonly used strategy for particulate vaccines,particularly for Pickering emulsions.However,extensive research on the internal delivery mechanisms of these emulsions,especially the complex intercellular interactions of deformable Pickering emulsions,has been surprisingly sparse.This gap in knowledge holds significant potential for enhancing vaccine efficacy.This study aims to address this by summarizing the process of lymph-node-targeting transport and introducing a dissipative particle dynamics simulation method to evaluate the dynamic processes within cell tissue.The transport of Pickering emulsions in skeletal muscle tissue is specifically investigated as a case study.Various factors impacting the transport process are explored,including local cellular tissue environmental factors and the properties of the Pickering emulsion itself.The simulation results primarily demonstrate that an increase in radial repulsive interaction between emulsion particles can decrease the transport efficiency.Additionally,larger intercellular gaps also diminish the transport efficiency of emulsion droplet particles due to the increased motion complexity within the intricate transport space compared to a single channel.This study sheds light on the nuanced interplay between engineered and biological systems influencing the transport dynamics of Pickering emulsions.Such insights hold valuable potential for optimizing transport processes in practical biomedical applications such as drug delivery.Importantly,the desired transport efficiency varies depending on the specific application.For instance,while a more rapid transport might be crucial for lymph-node-targeted drug delivery,certain applications requiring a slower release of active components could benefit from the reduced transport efficiency observed with increased particle repulsion or larger intercellular gaps.

Hyperspectral remote sensing identification of marine oil emulsions based on the fusion of spatial and spectral features

Marine oil spill emulsions are difficult to recover,and the damage to the environment is not easy to eliminate.The use of remote sensing to accurately identify oil spill emulsions is highly important for the protection of marine environments.However,the spectrum of oil emulsions changes due to different water content.Hyperspectral remote sensing and deep learning can use spectral and spatial information to identify different types of oil emulsions.Nonetheless,hyperspectral data can also cause information redundancy,reducing classification accuracy and efficiency,and even overfitting in machine learning models.To address these problems,an oil emulsion deep-learning identification model with spatial-spectral feature fusion is established,and feature bands that can distinguish between crude oil,seawater,water-in-oil emulsion(WO),and oil-in-water emulsion(OW)are filtered based on a standard deviation threshold–mutual information method.Using oil spill airborne hyperspectral data,we conducted identification experiments on oil emulsions in different background waters and under different spatial and temporal conditions,analyzed the transferability of the model,and explored the effects of feature band selection and spectral resolution on the identification of oil emulsions.The results show the following.(1)The standard deviation–mutual information feature selection method is able to effectively extract feature bands that can distinguish between WO,OW,oil slick,and seawater.The number of bands was reduced from 224 to 134 after feature selection on the Airborne Visible Infrared Imaging Spectrometer(AVIRIS)data and from 126 to 100 on the S185 data.(2)With feature selection,the overall accuracy and Kappa of the identification results for the training area are 91.80%and 0.86,respectively,improved by 2.62%and 0.04,and the overall accuracy and Kappa of the identification results for the migration area are 86.53%and 0.80,respectively,improved by 3.45%and 0.05.(3)The oil emulsion identification model has a certain degree of transferability and can effectively identify oil spill emulsions for AVIRIS data at different times and locations,with an overall accuracy of more than 80%,Kappa coefficient of more than 0.7,and F1 score of 0.75 or more for each category.(4)As the spectral resolution decreasing,the model yields different degrees of misclassification for areas with a mixed distribution of oil slick and seawater or mixed distribution of WO and OW.Based on the above experimental results,we demonstrate that the oil emulsion identification model with spatial–spectral feature fusion achieves a high accuracy rate in identifying oil emulsion using airborne hyperspectral data,and can be applied to images under different spatial and temporal conditions.Furthermore,we also elucidate the impact of factors such as spectral resolution and background water bodies on the identification process.These findings provide new reference for future endeavors in automated marine oil spill detection.

Influence of the Powder on the Properties of the Liquid Crystal Emulsions

The purpose of study was to evaluate the effect of four powder including titanium dioxide,bismuth oxychloride,silica,and kaolin on the properties of the liquid crystal emulsions.The results show that the addition of titanium dioxide and bismuth oxychloride had no obvious effect on the liquid crystal structure.In addition,the addition of Kaolin and silica have an effect on the stability of the liquid crystal structure.Sensory evaluation and Texture analyzer results shown that the addition of titanium dioxide and bismuth oxychloride had no obvious effect on the spreadability of liquid crystal system.The addition of silica and Kaolin was increased the hardness and adhesive of the liquid crystal system.Rheological experiments shown that the kaolin system had lower structural stability.the system with titanium dioxide,bismuth oxychloride,and silica has good stability.This paper provides data support for the application of powders in the formulation of liquid crystal system,which aims to provide a data basis for the preparation and applications of liquid crystal emulsion.

Experimental investigation on using CO_(2)/H_(2)O emulsion with high water cut in enhanced oil recovery

CO_(2) emulsions used for EOR have received a lot of interest because of its good performance on CO_(2)mobility reduction.However,most of them have been focusing on the high quality CO_(2) emulsion(high CO_(2) fraction),while CO_(2) emulsion with high water cut has been rarely researched.In this paper,we carried out a comprehensive experimental study of using high water cut CO_(2)/H_(2)O emulsion for enhancing oil recovery.Firstly,a nonionic surfactant,alkyl glycosides(APG),was selected to stabilize CO_(2)/H_(2)O emulsion,and the corresponding morphology and stability were evaluated with a transparent PVT cell.Subsequently,plugging capacity and apparent viscosity of CO_(2)/H_(2)O emulsion were measured systematically by a sand pack displacement apparatus connected with a 1.95-m long capillary tube.Furthermore,a high water cut(40 vol%) CO_(2)/H_(2)O emulsion was selected for flooding experiments in a long sand pack and a core sample,and the oil recovery,the rate of oil recovery,and the pressure gradients were analyzed.The results indicated that APG had a good performance on emulsifying and stabilizing CO_(2) emulsion.An inversion from H_(2)O/CO_(2) emulsion to CO_(2)/H_(2)O emulsion with the increase in water cut was confirmed.CO_(2)/H_(2)O emulsions with lower water cuts presented higher apparent viscosity,while the optimal plugging capacity of CO_(2)/H_(2)O emulsion occurred at a certain water cut.Eventually,the displacement using CO_(2)/H_(2)O emulsion provided 18.98% and 13.36% additional oil recovery than that using pure CO_(2) in long sand pack and core tests,respectively.This work may provide guidelines for EOR using CO_(2) emulsions with high water cut.

Progress in Preparation and Application of Gel-Emulsions

Compared to conventional emulsions, gel-emulsions have a higher internal phase volume fraction, unique structures and properties, higher viscosity, and tunable internal structures. These advantages make them widely applicable in the cosmetics industry, food industry, aerospace, and biomedicine, with significant potential in the development of new materials and high-performance products. The factors affecting the stability of gel-emulsions, as well as the types of stabilizers required for their preparation (including solid particles, surfactants, and small molecule gelators), and the corresponding preparation methods (including the one-step method, two-step method, and phase inversion method) are reviewed in this article. The applications of gel-emulsions in porous materials, food, cosmetics, and stimuli-responsive materials are introduced, and future research directions are also discussed.

Preparation of multihollow P(St-MAA) particles by sequence soap-free/soap emulsion polymerization and followed by stepwise alkali/acid posttreatment

The effects of ionic emulsifier, sodium dodecylbenzene sulfate (SDBS), on the formation of the multihollow structures in sub-micron sized polymer particles produced by alkali/acid posttreatment were investigated. The original latex particles with narrow size distribution were synthesized by a new sequence emulsifier-free/emulsifier emulsion copolymerization of styrene (St) and methacrylic acid (MAA). Results indicated that the pore size decreased and the pore number increased with the increase of SDBS amount, and the morphology of the posttreated latex particles was also significantly influenced by the introducing time of SDBS in the preparation of the original latex particles, and a suitable introducing time was 3 h of polymerization. (c) 2007 Cheng You Kan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

The use of bacterial cellulose from kombucha to produce curcumin loaded Pickering emulsion with improved stability and antioxidant properties

Curcumin is a bioactive molecule with limited industrial application because of its instability and poor solubility in water.Herein,curcumin-loaded Pickering emulsion was produced using purified bacterial cellulose from fermented kombucha(KBC).The morphology,particle size,stability,rheological properties,and antioxidant activities of the curcumin-loaded Pickering emulsion were investigated.The fluorescence microscope and scanning electron microscopy images showed that the curcumin-loaded Pickering emulsion formed circular droplets with good encapsulation.The curcumin-load Pickering emulsion exhibited better stability under a wide range of temperatures,low p H,sunlight,and UV-365 nm than the free curcumin,indicating that the KBC after high-pressure homogenization improved the stability of the CPE.The encapsulated curcumin retained its antioxidant capacity and exhibited higher functional potential than the free curcumin.The study demonstrated that the KBC could be an excellent material for preparing a Pickering emulsion to improve curcumin stability and antioxidant activity.

Rheo-optic in situ synchronous study on the gelation behaviour and mechanism of waxy crude oil emulsions

An improved rheo-optic in situ synchronous measurement system was employed to investigate the gelation behaviour and mechanism of waxy crude oil emulsions. By combining transmitted natural light and reflected polarized light microscopy, a multiangle composite light source was built to achieve the simultaneous observation of wax crystals and emulsified water droplets, as well as their dynamic aggregation process. Main outcomes on the microscopic mechanism were obtained by developed microscopic image processing method. It was found that the microstructure of W/O waxy crude oil emulsion has the evolution of “individual structure--homogeneous aggregate structure--heterogeneous coaggregate structure--floc structure” during the static cooling, which results in the four stages during gelation process. Different from previous studies, the aggregation of emulsified water droplets was found to be more significant and contributes to the formation and development of the wax crystals-emulsified water droplets coaggregate, which plays a decisive role in the further evolution of the gelled microstructure. Time series microscopic images show the dynamic aggregation of emulsified water droplets and wax crystals. Two different aggregation behaviours between wax crystals and water droplets were observed. That wax crystals can not only embed in gaps between adjacent water droplets and enhance the structure, but also surround the outside of the water droplets and continue to grow resulting in the interconnection of different coaggregates to form a larger floc structure. In addition, correlation between viscoelasticity and microstructure evolution of waxy crude oil emulsions of different water contents was discussed. With increasing water contents, the microstructure is changed from wax crystal flocculation structure as the main skeleton and the emulsified water droplets embedded in it, into the aggregation of emulsified water droplets occupying the main position. When the number of wax crystals and water droplets reaches a certain ratio, did wax crystals form coaggregates with emulsified water droplets, and the remaining wax crystals formed an overall flocculation structure, the viscoelasticity of the waxy crude oil emulsion is the highest.