Nanocrystalline cellulose/fluorinated polyacrylate latex via RAFT‐mediated surfactant‐free emulsion polymerization and its application as waterborne textile finishing agent

A simple method for nanocrystalline cellulose (NCC)/fluorinated polyacrylate was developed by RAFT‐mediated surfactant‐free emulsion polymerization, in which the nanocomposites formed a core‐shell spherical morphology. The influence of the content of NCC‐g‐(PAA‐b‐PHFBA) (AA was acrylic acid, HFBA was hexafluorobutyl acrylate) on the properties of latex and film were systematically studied. The monomer conversion, the tensile strength, and water–oil repellency of film increased first and then decreased, the latex particle size decreased first and then decreased, when the content of NCC‐g‐(PAA‐b‐PHFBA) increased from 1 to 6 wt %. Elongation at break and thermal stability distinctly decreased when the content of NCC‐g‐(PAA‐b‐PHFBA) gradually increased. XPS showed that the fluorine‐containing groups well concentrated at the film–air interfaces during the annealing process. SEM analysis revealed that the treated fiber had a rugged surface, and the treated fabric had an excellent water repellency. In addition, this green grafting method in water offered a new perspective for the fabrication of exceptional NCC‐based nanocomposites with NCC as the core and also helped to promote the potential applicability of NCC in a range of multipurpose applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1305–1314     

Self‐emulsion polymerization of amphiphilic monomers—a green route to synthesis of polymeric nanoscaffolds

Self‐emulsion polymerization (SEP), a green route developed by us for the polymerization of amphiphilic monomers, does not require any emulsifier or an organic solvent except that the water‐soluble initiators such as 2,2′‐azobis[2‐(2‐imidazolin‐2‐yl)propane]dihydrochloride (VA‐044) and potassium persulfate (KPS) are only used. We report here the polymer nanoscaffolds from a number of amphiphilic monomers, which can be used for in situ encapsulation of a variety of nanoparticles. As a demonstration of the efficacy of these nanoscaffolds, the synthesis of a biocompatible hybrid nanoparticle (nanohybrid), prepared by encapsulating Fe₃O₄ magnetic nanoparticle (Fe₃O₄ MNPs) in poly(2‐hydroxyethyl methacrylate) in water, for MRI application is presented. The nanohybrid prepared following the SEP in the form of an emulsion does not involve the use of any stabilizing agent, crosslinker, polymeric emulsifier, or surfactant. This water‐soluble, spherical, and stable nanohybrid containing Fe₃O₄ MNPs of average size 10 ± 2 nm has a zeta potential value of ?41.89 mV under physiological conditions. Magnetic measurement confirmed that the nanohybrid shows typical magnetic behavior having a saturation magnetization (Ms) value of 32.3 emu/g and a transverse relaxivity (r2) value of 29.97 mM^?1 s^?1, which signifies that it can be used as a T2 contrast agent in MRI. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019     

Modifying the physicochemical properties,solubility and foaming capacity of milk proteins by ultrasound-assisted alkaline pH-shifting treatment

This study investigated the effects of different treatment of alkaline pH-shifting on milk protein concentrate (MPC), micellar casein concentrate (MCC) and whey protein isolate (WPI) assisted by the same ultrasound conditions, including changes in the physicochemical properties, solubility and foaming capacity. The solubility of milk proteins had a significant increase with gradual enhancement of ultrasound-assisted alkaline pH-shifting (p < 0.05), especially for MCC up to 99.50 %. Also, treatment made a significant decline in the particle size of MPC and MCC, as well as the turbidity of the proteins (p < 0.05). The foaming capacity of MPC, MCC, and WPI was all improved, especially at pH 11, and at this pH, the milk protein also showed the highest surface hydrophobicity. The best foaming capacity at pH 11 was the result of the combined effect of particle size, potential, protein conformation, solubility, and surface hydrophobicity. In conclusion, ultrasound-assisted pH-shifting treatment was found to be effective in improving the physicochemical properties and solubility and foaming capacity of milk proteins, especially MCC, with promising application prospect in food industry.     

Synthesis of poly(n‐butyl acrylate) homopolymer and poly(styrene‐b‐n‐butyl acrylate‐b‐styrene) triblock copolymer via AGET emulsion ATRP using a cationic surfactant

Cationic emulsions of triblock copolymer particles comprising a poly(n‐butyl acrylate) (PⁿBA) central block and polystyrene (PS) outer blocks were synthesized by activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP). Difunctional ATRP initiator, ethylene bis(2‐bromoisobutyrate) (EBBiB), was used as initiator to synthesize the ABA type poly(styrene‐b‐n‐butyl acrylate‐b‐styrene) (PS‐PⁿBA‐PS) triblock copolymer. The effects of ligand and cationic surfactant on polymerizations were also discussed. Gel permeation chromatography (GPC) was used to characterize the molecular weight (M_n) and molecular weight distribution (MWD) of the resultant triblock copolymers. Particle size and particle size distribution of resulted latexes were characterized by dynamic light scattering (DLS). The resultant latexes showed good colloidal stability with average particle size around 100–300 nm in diameter. Glass transition temperature (T_g) of copolymers was studied by differential scanning calorimetry (DSC). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 611–620     

Vitamin K1 distribution following intravenous vitamin K1–fat emulsion administration in rats

This study investigated vitamin K₁ (VK₁) distribution following intravenous vitamin K₁–fat emulsion (VK₁–FE) administration and compared it with that after VK₁ injection. Rats were intravenously injected with VK₁–FE or VK₁. The organ and tissue VK₁ concentrations were determined using high‐performance liquid chromatography method at 0.5, 2 and 4 h to determine distribution, equilibrium and elimination phases, respectively. In the VK₁–FE group, the plasma, heart and spleen VK₁ concentrations decreased over time. However, other organs like liver, lung, kidney, muscle and testis, reached peak VK₁ concentrations at 2 h. In the VK₁ injection group, the liver VK₁ concentrations were significantly higher than those in other organs at the three time points. However, VK₁ concentrations in the other organs peaked at 2 h. In addition, in VK₁–FE group, the heart, spleen and lung VK₁ concentrations were significantly higher than those in the VK₁ injection group at the three time points, and the liver VK₁ concentration was significantly higher than that in the VK₁ injection group at 4 h. The VK₁ amount was greatest in the liver compared with the other organs. Thus, the liver is the primary organ for VK₁ distribution. The distribution of VK₁ is more rapid when injected as VK₁–FE than as VK₁. Copyright © 2015 John Wiley & Sons, Ltd.     

Emulsion Copolymerization of Vinyl Acetate and Vinyl Silanes: Kinetics and Development of Microstructure

The batch emulsion copolymerization of vinyl acetate with different vinyl silane functional monomers (vinyl trimethoxysilane [VTMS], vinyl triethoxysilane [VTES], and vinyl silanetriol [VSTO]) is studied. The nature of the silane strongly affects the development of the microstructure and crosslinking ability of the latexes. A combination of techniques (Soxhlet extraction, centrifugation, assymetric‐flow field flow fractionation AF4/MALS/RI) shows that the factor controlling the molar mass and crosslinking density is the degree of hydrolysis of the alkoxysilane, producing higher molar masses and degrees of crosslinking when the degree of hydrolysis is high. Thus, the copolymer containing VSTO produced a very crosslinked latex, the one with VTMS produced a latex with a low degree of crosslinking in the wet state that can yield high degrees of crosslinking upon drying, and the latex with VTES do not produce significant amounts of crosslinking neither before nor after drying.     

Front face synchronous fluorescence as a tool for the quality assurance of Greek milk

This research focuses on implementing the low cost and rapid front face synchronous fluorescence (SyFS) in order to ensure the quality assurance of Greek milk. Specifically, samples originated from the Greek domestic production of goat, sheep, cow, as well as foreign cow milk samples and adulterated cow milk samples. SyFS spectra were acquired in the excitation area of 250–500 nm with (Δλ)= 100 nm. Greek and foreign cow milk samples were differentiated based on intensity variations at wavelengths 350–515 nm, 540–579 nm, and 580–600 nm. The emissions at these wavelength positions correspond to tryptophan, vitamin A, and riboflavin. The supervised model with 94 samples exhibited p-value = 7,98E-11, RMSEE= 0,29171, RMSEcv= 0,29284 and RMSEP= 0,98013, AUROC for Greek samples= 0,61 and AUROC for foreign= 0,85. We differentiated milk samples according to the animal type with PCA and OPLS-DA models of 107 samples exhibiting RMSEE= 0,225842, RMSEcv= 0,228054 and RMSEP= 0,518635, AUROC for sheep samples= 0,99, AUROC for goat samples= 0,98 and AUROC for cow samples= 0,96. In fact, the emission band 350–591 nm characterized sheep milk and corresponds to aminoacids and fatty acids, cow milk was related to the 350–600 nm emission band related to the b-carotene and to the goat milk the emission bands 350–505 nm and 520–600 nm were attributed to tryptophan, NADH and Rivoflabin. Finally, we investigated whether SyFS coupled with chemometrics may provide preliminary evidence on adulterated cow milk samples. All models were validated with permutation testing, p-values and ROC curves.     

Forces between a hard surface and an air–aqueous interface with and without films

The adsorption of particles to air–aqueous interfaces is vital in many applications, such as mineral flotation and the stabilization of food foams. The forces in the system determine whether a particle will attach to an air–aqueous interface. The forces between a particle and an air–aqueous interface are influenced by Derjaguin–Landau–Verwey–Overbeek forces (i.e. van der Waals and electrostatic forces), non–Derjaguin–Landau–Verwey–Overbeek forces (e.g. hydrophobic, hydrodynamic, structural, and capillary forces), liquid drainage, and liquid flow. As an air–aqueous interface can be deformed by a particle, the forces measured between an air–aqueous interface and a particle can differ from those measured between two hard surfaces separated by liquid. The presence of a film at an air–aqueous interface can also change the forces.     

Effect of Butyl α-Hydroxymethyl Acrylate Monomer Structure on the Morphology Produced via Aqueous Emulsion Polymerization-induced Self-assembly

Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl(n BHMA) and tert-butyl(t BHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of n BHMA and t BHMA employing poly(ethylene glycol) macromolecular chain transfer agents(macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for t BHMA, which has a higher water solubility than that of n BHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.