Fabrication and Stability Improvement of Monoglyceride Oleogel/Polyglycerol Polyricinoleate-Stabilized W/O High Internal Phase Pickering Emulsions.

To decrease the lipid content in water-in-oil (W/O) emulsions, high internal phase Pickering W/O emulsions (HIPPE) were fabricated using magnetic stirring using a combination of monoglyceride (MAG) oleogel and polyglycerol polyacrylate oleate (PGPR) as stabilizers. Effects of MAGs (glyceryl monostearate-GMS, glycerol monolaurate-GML and glycerol monocaprylate-GMC) and internal phase components on the formation and properties of HIPPEs were investigated. The results showed that milky-white stabilized W/O HIPPE with up to 85 wt% aqueous phase content was successfully prepared, and the droplet interfaces presented a network of MAG crystals, independent of the MAG type. All HIPPEs exhibited great stability under freeze-thaw cycles but were less plastic. Meanwhile, GML-oleogel-based HIPPEs had larger particle size and were less thermal stable than GMS and GMC-based HIPPEs. Compared to guar gum, the internal phase components of sodium chloride and sucrose were more effective in reducing the particle size of HIPPEs, improving their stability and plasticity, and stabilizing them during 100-day storage. HIPPEs presented great spreadability, ductility and plasticity after whipping treatment. This knowledge provides a new perspective on the use of oleogels as co-stabilizers for the formation of W/O HIPPEs, which can be used as a potential substitute for creams.

Advances in emulsion-based delivery systems for nutraceuticals: Utilization of interfacial engineering approaches to control bioavailability.

Designing functional foods fortified with nutraceuticals is an important focus of modern food science with the aim of improving human health and wellbeing. However, many nutraceuticals have a low water solubility and poor physiochemical stability, which makes it challenging to incorporate into food matrices. Moreover, nutraceuticals may also have a low bioavailability after oral administration because they can either precipitate or chemically degrade, and/or might not be absorbed in the gastrointestinal tract. Numerous strategies have been developed and applied to encapsulate and deliver nutraceuticals. Emulsions are a kind of colloid delivery system where one phase is dispersed into another immiscible phase in the form of small droplets. These droplets have been widely used as carriers to improve the dispersibility, stability, and absorption of nutraceuticals. Many factors affect the formation and stability of emulsions, with the interfacial coating formed around the droplets by emulsifiers and other stabilizers being one of the most important. Hence, interfacial engineering principles are needed for the design and development of emulsions. Different approaches to interfacial engineering have been developed, which can help to modulate the dispersibility, stability, and bioavailability of nutraceuticals. This chapter summarizes recent research in developing interfacial engineering approaches and their impacts on the bioavailability of nutraceuticals.

Crystallization Behavior and Physical Properties of Monoglycerides-Based Oleogels as Function of Oleogelator Concentration.

Oleogels have been shown as a promising replacer of hydrogenated vegetable oil. Fatty acid glycerides, including some typical mono- and di-glycerides, were used to form oleogels. The concentration effects of fatty acid glycerides on the crystallization behavior and physical properties of oleogels were investigated by using different analysis techniques. The results showed that all the oleogels formed by saturated fatty acid glycerides (glyceryl monostearate (GMS), glyceryl monolaurate (GML), glycerol monocaprylate (GMC)) exhibited a solid-like behavior and were thermally reversible systems, while a higher amount of unsaturated fatty acid glycerides (monoolein (GMO), diolein (GDO)) were needed to form oleogels. The onset gelation concentration of GMS and GMC was found to be 2 wt% (w/w), while that of GML was 4 wt% by the inverted tube method. The crystallization results illustrated that the GMS and GMC formed small needle-like crystals with the presence of ß and ß' crystals, while GML formed large flake-like crystals with α crystals in oleogels, and faster cooling rates caused smaller crystals. GMS- and GMC-based oleogels had higher crystallinity, resulting in higher thermal stability and better mechanical properties than GML-based ones at the same monoglyceride (MAG) level. With the increasing MAG content, the oleogels showed a more compact three-dimensional network leading to higher mechanical properties and better thermal stability and resistance to deformations. Hence, MAG-based oleogels, especially GMC ones with medium chain fatty acid, could be a promising replacer for hydrogenation vegetable oils.

Theoretical analysis of the thermoelectric properties of penta-PdX2 (X = Se, Te) monolayer.

Based on the successful fabrication of PdSe2 monolayers, the electronic and thermoelectric properties of pentagonal PdX2 (X = Se, Te) monolayers were investigated via first-principles calculations and the Boltzmann transport theory. The results showed that the PdX2 monolayer exhibits an indirect bandgap at the Perdew-Burke-Ernzerhof level, as well as electronic and thermoelectric anisotropy in the transmission directions. In the PdTe2 monolayer, P-doping owing to weak electron-phonon coupling is the main reason for the excellent electronic properties of the material. The low phonon velocity and short phonon lifetime decreased the thermal conductivity (κ l) of penta-PdTe2. In particular, the thermal conductivity of PdTe2 along the x and y transmission directions was 0.41 and 0.83 Wm-1K-1, respectively. Owing to the anisotropy of κ l and electronic structures along the transmission direction of PdX2, an anisotropic thermoelectric quality factor ZT appeared in PdX2. The excellent electronic properties and low lattice thermal conductivity (κ l) achieved a high ZT of the penta-PdTe2 monolayer, whereas the maximum ZT of the p- and n-type PdTe2 reached 6.6 and 4.4, respectively. Thus, the results indicate PdTe2 as a promising thermoelectric candidate.

Separation of chemical constituents in Bidens pilosa Linn. var. radiata Sch. Bip. by elution-extrusion counter-current chromatography using two new three-phase solvent systems.

Two new three-phase solvent systems combined with elution-extrusion counter-current chromatography mode were used to study the chemical constituents in Bidens pilosa Linn. var. radiata Sch. Bip. The first novel solvent system consisted of n-hexane, acetonitrile, chloroform, and water in a ratio of 5:5:1:5, which was selected for elution-extrusion counter-current chromatography to separate the n-hexane extraction part. A total of six constituents were obtained from this part in the up phase as the stationary phase and the middle phase as the mobile phase. The second novel solvent system, composed of n-hexane-butyl acetate-acetonitrile-water (3:1:4:3, v/v/v/v), was used for separating ethyl acetate extract of Bidens pilosa Linn. var. radiata Sch. Bip. Eight compounds were successfully isolated using elution-extrusion counter-current chromatography elution-extrusion mode. Fourteen chemical constituents were identified as 2-ß-D-glucopyranosytoxy-1-hydroxy-5(E)-tridecene-7,9,11-triyne (Y1), 3-ß-D-glucopyranosyloxy -1-hydroxy-6(E)-tetradecene-8,10,12-triyne (Y2), 1, 2-dihydroxy-5(E)-tridecene-7,9, 11-triyne (Y3), isorhamnetin (Y4), kaempferol (Y5), icthyothereolacetate (Y6), quercetin-3-O-ß-D- galactopyranosyl-7-O-ß-D-glucopyranoside (W1), quercetin 3-O-ß-L-rhamnopyranoside (W2), neosperidin dihydrochalcone (W3), quercetin (W4), quercetagetin-3,6,4' -trimethoxyl- 7-O-ß-D-glucopyranoside (W5), taxifolin (W6), luteolin (W7), and apigenin (W8) by spectra of 1 H-NMR and 13 C-NMR data. Among them, compounds Y1, Y2, Y3, and Y6 belong to polyacetylene compounds, and the rest were flavonoids. In addition, counter-current chromatography has been used to separate polyacetylene compounds for the first time. All compounds in this method were isolated from Bidens pilosa Linn. var. radiata Sch. Bip. for the first time.

SCKs as nanoparticle carriers of doxorubicin: investigation of core composition on the loading, release and cytotoxicity profiles.

SCK nanoparticles having differing core thermal characteristics were designed and evaluated as thermoresponsive drug delivery systems of doxorubicin for the killing of cancerous cells.

Facile, efficient approach to accomplish tunable chemistries and variable biodistributions for shell cross-linked nanoparticles.

The in vivo behavior of shell cross-linked knedel-like (SCK) nanoparticles is shown to be tunable via a straightforward and versatile process that advances SCKs as attractive nanoscale carriers in the field of nanomedicine. Tuning of the pharmacokinetics was accomplished by grafting varied numbers of methoxy-terminated poly(ethylene glycol) (mPEG) chains to the amphiphilic block copolymer precursors, together with chelators for the radioactive tracer and therapeutic agent (64)Cu, followed by self-assembly into block copolymer micelles and chemical cross-linking throughout the shell regions. (64)Cu-radiolabeling was then performed to evaluate the SCKs in vivo by means of biodistribution experiments and positron emission tomography (PET). It was found that the blood retention of PEGylated SCKs could be tuned, depending on the mPEG grafting density and the nanoparticle surface properties. A semiquantitative model of the density of mPEG surface coverage as a function of in vivo behavior was applied to enhance the understanding of this system.

Labeling of Polymer Nanostructures for Medical Imaging: Importance of crosslinking extent, spacer length, and charge density.

Radiolabeling studies were employed to investigate the influence of structure on the efficiency of surface functionalization for poly(acrylic acid)-coated shell crosslinked nanoparticles (SCKs) with two types of amine-terminated DOTA chelators. An intricate interplay between the chemical and physical properties of both the DOTA derivative and the SCK nanostructures was revealed, demonstrating the importance of structural control.

Photo-Fries rearrangements of 1-naphthyl (R)-2-phenylpropanoate in poly(vinyl acetate) and ethyl acetate. Influence of medium polarity and polymer relaxation on motions of singlet radical pairs.

Both the regio- and stereo-chemistries of the photoreactions of 1-naphthyl (R)-2-phenylpropanoate have been investigated in poly(vinyl acetate) films in their glassy (at 5 degrees C) and melted (at 50 degrees C) states and in ethyl acetate. These results are compared with those from irradiations in polyethylene films and in n-hexane. The regioselectivity of the intermediate 1-naphthoxy/(R)-2-phenylpropanoyl radical pair combinations is much higher in both the melt and glassy states of poly(vinyl acetate) films than that in the melt state of completely amorphous polyethylene films, but the stereoselectivity of intermediate prochiral 1-naphthoxy/1-phenylethyl radical pair combinations is much lower in poly(vinyl acetate). The results emphasize the need to control the ratio between the rates of radical tumbling and translation, as well as the ratio between the rates of in-cage motions and cage-escape, if high stereo- and regio-selectivities of combination products are to be achieved. A mechanistic picture of how the radicals of the intermediate pairs are affected by and interact with the various media is advanced.

Combinations of chiral and prochiral singlet radical-pairs in reaction cavities of polyethylene films. Control and analysis of radical tumbling and translation.

The regio- and stereo-chemistries of combination products from chiral 1-naphthoxy/(R)-2-phenylpropanoyl and prochiral 1-naphthoxy/1-phenylethyl singlet radical-pairs (radical-pairs A and B, respectively) have been studied at different temperatures in polyethylene (PE) films with different crystallinities. The radical-pairs have been generated as intermediates along the photo-Fries reaction course of 1-naphthyl (R)-2-phenylpropanoate ((R)-1) and the photo-Claisen reaction course of 1-naphthyl (R)-1-phenylethyl ether ((R)-2). Radical-pair was produced directly upon lysis of the first excited singlet state of (R)-2 and indirectly after irradiation of (R)-1 and subsequent decarbonylation of the 2-phenylpropanoyl radical of radical-pair A. Comparison of the fates of the directly and indirectly formed radical-pairs provides detailed information about the nature of the reaction cavities within the polyethylene hosts and how the combinations of the radical-pairs are influenced by their initial locations within a cavity. The results, especially when taken with those from irradiations in n-alkanes, indicate that the cavities are "templated" by the (R)-1 and (R)-2 guest molecules and that the templated shapes are retained in some form for periods that are at least as long as the time required for decarbonylation of a 2-phenylpropanoyl radical. In addition, the enantiomeric excesses of the decarbonylated photoproducts from (R)-1(2, 2-(1-phenylethyl)-1-naphthol (2BN), and 4-(1-phenylethyl)-1-naphthol (4BN)) or 2BN and 4 BN from (R)-2 indicate different influences of temperature on translational and tumbling motions of the radicals of radical-pairs B within their polyethylene cages.

Reaction cavities of liquid and solid phases of a long n-alkane, n-nonadecane, as probed by the regio- and stereo-chemical fates of two singlet radical pairs.

The regio- and stereo-chemistries of photo-Fries reactions of 1-naphthyl (R)-2-phenylpropanoate ((R)-1) and photo-Claisen reactions of 1-naphthyl (R)-1-phenylethyl ether ((R)-2) have been investigated in the liquid and solid phases of n-nonadecane. The results are compared with those obtained in a lower and higher viscosity liquid n-alkane. Irradiation of (R)-1 yields a prochiral singlet 1-naphthoxy-1-phenylethyl radical pair (radical pair B) indirectly, after decarbonylation of the initially formed chiral singlet 1-naphthoxy-2-phenylpropanoyl radical pair (radical pair A). Radical pair B is generated directly upon lysis of the excited singlet state of (R)-2. The restricted environments of the solid phases enable both the directly and indirectly formed radical pairs to maintain much (but not all) of the memory of their initial orientations. Thus, the in-cage combination products from indirectly formed radical pair B contain up to 33% enantiomeric excess. However, the combinations of directly formed radical pair B lack complete stereo-specificity due to their disturbing influence on their local environments in the solid phases. A discussion of the dynamics of the radical pair motions in the different environments is presented.

Analyses of in-cage singlet radical-pair motions from irradiations of 1-naphthyl (R)-1-phenylethyl ether and 1-naphthyl -2-phenylpropanoate in n-alkanes.

[reaction: see text] The regio- and stereochemistries of photo-Claisen reactions of 1-naphthyl (R)-1-phenylethyl ether ((R)-2), in combination with photo-Fries and photo-Claisen-type reactions of 1-naphthyl (R)-2-phenylpropanoate ((R)-1), have been investigated in n-alkanes of different viscosities and at several temperatures. Analyses of the results provide detailed information about the in-cage motions of the singlet prochiral 1-naphthoxy/1-phenylethyl radical pairs (radical-pair B) that are formed directly from (R)-2 and indirectly from (R)-1 via decarbonylation of singlet chiral 1-naphthoxy/2-phenylpropanoyl radical pairs (radical-pair A). In hexane at 23 degrees C, the photo-Claisen products from irradiations of (R)-2 retain up to 31% enantiomeric excess (ee), but the ees of the same photoproducts from (R)-1 are near 0%. This disparity is attributed to differences between the initial orientations of the constituent radicals of radical-pair B at the moment of their "birth". The regio- and stereoselectivities reach plateau values as the solvent viscosity increases, indicating that the relationships between the rates of radical-radical bond formation and either translational or tumbling motions within a solvent cage reach an asymptotic limit. Detailed analyses are presented of the various motions that are in competition within a solvent cage during the very short lifetimes of the radical pairs. The data, in toto, present interesting insights into how radical pairs move during short periods and over short distances when their solvent cages have walls of varying flexibility.

Enantioselectivity of prochiral radical-pair recombinations. Reaction cavity differentiation in polyethylene films.

reaction: see text] Recombinations of prochiral radical pairs from irradiations of 1-naphthyl (R)-2-phenylpropanoate in polyethylene films occur with significant enantioselectivity due to templating effects in the reaction cavities. Photoreactions in PE films in their unstretched or stretched states and of different crystallinity have been employed to distinguish between the characteristics of reaction cavities in amorphous and interfacial regions of the polymer.