Physical and emulsifying properties of pea protein:influence of combined physical modification by flaxseed gum and ultrasonic treatment

This study characterized and compared the physical and emulsifying properties of pea protein(PP)and its modified proteins(ultrasound treated-PP(PPU),flaxseed gum(FG)treated PP(PPFG)and ultrasound treated-PPFG(PPFGU)).The results showed FG triggered the formation of loosely attached complex with PP via physical modification under gentle magnetic stirring at pH 7.0,while ultrasound played an important role in reducing protein size,increasing surface hydrophobicity and molecular fluidity onto oil-water interface.So ultrasound further enhanced the interaction of PP with FG,and produced the PPFGU complex with smaller droplet size,higherζ-potential and lower turbidity.Further,combination of FG and ultrasound improved the physical properties of PP with higher viscosity,stiffer gels(defined as higher elastic modulus),stronger hydrophobic properties,better thermal stability,and fast protein absorption rate.Therefore,the PPFGU coarse emulsion performed highest emulsifying activity index(EAI)and emulsion stability index(ESI)that the stabilized nanoemulsion obtained smallest droplet size,higherζ-potential,and longest storage stability.The combination of FG and ultrasonic treatment will be an effective approach to improving the emulsifying property and thermal stability of PP,which can be considered as a potential plant-based emulsifier applied in the food industry.

Smart supramolecular vesicles based on glutathione-reactive pillar[6]arene and acid-labile prodrug:Dual drug loading and sequential release

Glutathione thiol-reactive pillar[6]arene(TWP6)is designed and synthesized as the first example of reducing agent-reactive host molecule.TWP6 shows high affinity binding towards suitable anti-tumor drugs and guests.Doxorubicin-based acid-labile prodrugs and TWP6 are used to construct supramolecular vesicles,which are also loaded with camptothecin.The supramolecular vesicles loaded with two drugs demonstrate glutathione-and acid-responsive drug release as well as sequential release to both stimuli types.Supramolecular vesicles show combination therapeutic effect towards tumor cells in vitro.

主客体化学应用于药物拮抗剂设计研究

很多药物在体内残留导致毒副作用.基于残留药物在血液内循环的特征,设计分子、大分子和超分子主体,利用主客体化学原理络合和捕集血液内的残留药物,降低其游离浓度,加速其通过肾脏排泄,实现拮抗和消除这些残留药物毒副作用的目的,是近年来主客体化学研究的重要方向,也是功能超分子体系研究的重要应用出口.本文总结了近年来利用环糊精、杯芳烃、柱芳烃及其类似物、葫芦脲和开环葫芦脲、超分子有机框架和柔性有机框等设计残留药物拮抗剂方面取得的进展,讨论了针对残留药物开展主客体化学的一般原则和识别特征,最后提出了推进针对药物拮抗的主客体体系进一步走向临床前研究需要考虑和解决的挑战.

[5]Rotaxane, linear polymer and supramolecular organic framework constructed by nor-seco-cucurbit[10]uril-based ternary complexation

Here we use nor-seco-cucurbit[10]uril(ns-CB[10]) based ternary complexation to construct [5]rotaxane,linear supramolecular dynamic rotaxane polymers and cubic 3D supramolecular organic framework.A [5]rotaxane is constructed by ns-CB[10], TMe CB[6] and short linear derivatives of 4,4'-bipyridinium(M2). ns-CB[10], CB[7] and long linear derivatives of 4,4'-bipyridinium(M3) self-assemble into a linear supramolecular dynamic rotaxane polymer. ns-CB[10] and tetracationic tetrahedral monomer selfassemble and form a three-dimensional supramolecular organic framework. The above results demonstrate that ns-CB[10]-based ternary complexation is a versatile platform to build various supramolecular systems.

Reactive oxygen specie-induced photodynamic therapy activation by supramolecular strategy

Photodynamic therapy(PDT)agents may accumulate in skin and cause severe skin cytotoxicity.We report a pro-guest-based supramolecular strategy to selectively activate PDT in the reactive oxygen specie(ROS)overexpressed microenvironment,which is often existing in tumor and inflammatory tissues.PDT agents methylene blue(MB)and basic blue 17(BB17)are used as model drugs.When encapsulated by acyclic cucurbit[n]uril(CB[n]),the efficacy of PDT agents is significantly inhibited.By contrast,in the presence of ROS(H_(2)O_(2))and pro-guest,PDT agents are displaced and reactivated to show a dramatically enhanced PDT efficacy in cells.

Supramolecular Vesicles Based on Water-Soluble 2,6-Helic[6]arene:High Affinity Binding,Stimuli Responsiveness and Delivery of Doxorubicin to Cancer Cells

Water-soluble 2,6-helic[6]arene was used to construct supramolecular vesicles via host-guest interaction. Water-soluble 2,6-helic[6]arene was discovered to be high affinity host for suitable biomarkers. Supramolecular vesicles were responsive to multiple stimuli types, including temperature, pH, Ca^2+, CO2 bubbling and biomarker displacement. Supramolecular vesicles were used to load and deliver anti-tumor drug doxorubicin to HeLa cells in vitro.

AND molecular logic gates based on host-guest complexation operational in live cells

We report supramolecular AND logic gates based on host-guest complexation between acid-labile acyclic cucurbit[n]uril(CB[n]) molecular container and Na Cl O-responsive dye. Supramolecular AND logic gate is turned on due to acid-triggered degradation of molecular container and the release of the dye, followed by Na Cl O-induced fluorescence “switch on” effect of the dye. The reason for AND molecular logic gate is discovered to be the combination of oxidation inhibition and fluorescence “switch off” effect. Supramolecular AND logic gate is confirmed to be operational in live MCF-7 and He La cancer cells.

Cucurbit[7]uril-threaded flexible organic frameworks: Quantitative polycatenation through dynamic covalent chemistry

A three-dimensional flexible organic framework FOF-1 has been synthesized from the condensation of a tetratopic acylhydrazine and a rigid 4,4-diphenyl-4,4-bipyridinium dialdehyde in water through the quantitative formation of hydrazone bond. FOF-1 is further applied to construct a polycatenane framework FOF-pc-1 through the quantitative cucurbit[7]uril encapsulation for the diphenylbipyridinium subunits of the framework by making use of the dynamic nature of the hydrazone bond in water. The bipyridinium subunits in both frameworks can be reduced their radical cation counterparts to produce conjugated radical cation-linked dynamic organic frameworks rc-FOF-1 or rc-FOF-pc-1. Polycatenation is revealed to enhance the stability of the dynamic frameworks in water, whereas depolycatenation can be reached for both FOF-pc-1 and rc-FOF-pc-1 by using a ferrocene guest to form a more stable complex with CB[7].

Ultra-stable and multistimuli-responsive nanoparticles coated with zwitterionic pillar[n]arene for enhanced cellular uptake

Nanoparticle surface property is crucial for circulation stability,cellullar uptake and other biological characteristics.Zwitte rionic pillar[n]arenes(ZPns)we re used to coat gold nanopa rticles(GNPs)via hostguest interaction.The resulting GNPs demonstrated higher stability in blood serum compared to polyethylene glycol(PEG)-coated GNPs.ZPn-coated GNPs were responsive to UV-irradiation,competitive displacement and acidic pH.UV-irradiation or competitive displacement could lead to the removal of ZPn coating to expose GNPs,which enhanced cell uptake efficiency by 5.9-and 7.4-fold,respectively.

A self-assembled framework that interpenetrates in crystal but does not interpenetrate in solution

A porous supramolecular framework has been for the first time revealed to undergo interpenetration in crystal and noninterpenetration in solution.A new supramolecular organic framework Bu-SOF has been constructed from the co-assembly of a tetracationic tetrahedral monomer and cucurbit[8]uril(CB[8])in water through the encapsulation of two anti-parallel n-butyl chains by CB[8].X-ray diffraction analysis reveals that Bu-SOF forms 3-fold interpenetrated networks in crystals grown by evaporation of its solution in water.1 H NMR,dynamic light scattering and isothermal titration calorimetric experiments confirm that Bu-SOF is also formed in water.Solid samples,prepared by lyophilizing the aqueous solution of Bu-SOF,can adsorb nanoscaled organic dyes,supporting the porosity of the framework and thus non-interpenetration in solution.The avoidance of interpenetration of Bu-SOF in solution has been attributed to the filling of water inside the porous framework as well as the electrostatic repulsion of the appended bipyridinium units of the tetrahedral building block.