A novel ferrocenium capped amphiphilic pillar[5]arene (FCAP) was synthesized and self-assembled to cationic vesicles in aqueous solution. The cationic vesicles, displaying low cytotoxicity and significant redox-responsive behavior due to the redox equilibrium between ferrocenium cations and ferrocenyl groups, allow building an ideal glutathione (GSH)-responsive drug/siRNA co-delivery system for rapid drug release and gene transfection in cancer cells in which higher GSH concentration exists. This is the first report of redox-responsive vesicles assembled from pillararenes for drug/siRNA co-delivery; besides enhancing the bioavailability of drugs for cancer cells and reducing the adverse side effects for normal cells, these systems can also overcome the drug resistance of cancer cells. This work presents a good example of rational design for an effective stimuli-responsive drug/siRNA co-delivery system.

This article summarizes pillararene-based supramolecular delivery systems constructed through host–guest interactions and outlines the future challenges for their broader applications.

The inflammatory response is induced by the overexpression of inflammatory cytokines, mainly interleukin (IL)-1β, and is one of the main causes of intervertebral disc degeneration (IVDD). NLR pyrin domain containing 3 (NLRP3) inflammasome activation is an important source of IL-1β. As an anti-inflammatory neuroendocrine hormone, melatonin plays various roles in different pathophysiological conditions. However, its roles in IVDD are still not well understood and require more examination. First, we demonstrated that melatonin delayed the progression of IVDD and relieved IVDD-related low back pain in a rat needle puncture IVDD model; moreover, NLRP3 inflammasome activation (NLRP3, p20, and IL-1β levels) was significantly upregulated in severely degenerated human discs and a rat IVDD model. Subsequently, an IL-1β/NF-κB-NLRP3 inflammasome activation positive feedback loop was found in nucleus pulposus (NP) cells that were treated with IL-1β. In these cells, expression of NLRP3 and p20 was significantly increased, NF-κB signaling was involved in this regulation, and mitochondrial reactive oxygen species (mtROS) production increased. Furthermore, we found that melatonin disrupted the IL-1β/NF-κB-NLRP3 inflammasome activation positive feedback loop in vitro and in vivo. Melatonin treatment decreased NLRP3, p20, and IL-1β levels by inhibiting NF-κB signaling and downregulating mtROS production. Finally, we showed that melatonin mediated the disruption of the positive feedback loop of IL-1β in vivo. In this study, we showed for the first time that IL-1β promotes its own expression by upregulating NLRP3 inflammasome activation. Furthermore, melatonin disrupts the IL-1β positive feedback loop and may be a potential therapeutic agent for IVDD.

Pillar[n]arenes (n = 5-15) are a novel class of macrocyclic molecules with hydroquinone as the repeating unit linked by methylene bridges at para-positions. Introduced by T. Ogoshi for the first time in 2008, pillararenes have attracted increasing interest and have been widely studied during the last eight years, due to their unique structural advantages as host molecules, such as symmetrical rigid architecture, electron-rich cavities and facile functional modification. In this review, we first describe the syntheses of pillar[n]arenes including cyclooligomerization of pillar[n]arenes and modification of pillar[n]arenes after cyclooligomerization, summarising almost twenty different kinds of guest motifs and dividing them into three types: cationic, neutral and anionic motifs. The main section of this review examines the applications of pillar[n]arenes based on the host-guest interactions in different research fields, including biology, materials science and environmental science. Finally, future research directions and potential for novel applications are discussed.

Photoderivatized polymer-coated gold surfaces have been developed following a perfluorophenylazide-based double ligation strategy. Gold-plated quartz crystal microbalance (QCM) crystals were initially covalently functionalized with a monolayer of poly(ethylene glycol) (PEG), using photo-or thermolytic nitrene formation and insertion. The polymer surfaces were subsequently used as substrates for photoinsertion of carbohydrate-derivatized photoprobes, yielding different recognition motifs for selective protein binding. The resulting robust and biocompatible sensor surfaces were applied to a flow-through QCM instrument for monitoring lectin-carbohydrate interactions in real time. The results clearly show the predicted lectin selectivity, demonstrating the applicability of the approach.Selective surface generation and functionalization form the basis for intense research in a number of diverse areas such as chemical sensors, interface engineering, and nanotechnology. A versatile method to covalent derivatization is based on the specific chemistry of arylazides. Upon thermal activation or light irradiation, the azide functionality in these structures becomes converted to a highly reactive nitrene species that readily inserts into CH and NH bonds. 1 Especially perfluorophenylazides (PFPAs), 2 which produce markedly enhanced insertion yields, have thus been used to thermo-and photochemically introduce functional groups in a range of entities, including proteins, nanostructures, and synthetic polymers. [3][4][5][6][7][8][9] The versatility of the PFPA chemistry makes it an attractive choice for surface modification. Surfaces can either be globally modified by the technique, or discrete areas can be addressed by arraying techniques such as photomasking and conventional printing devices. HHS Public Access Author Manuscript Author ManuscriptAuthor Manuscript Author ManuscriptThe surface presentation of recognition motifs based on bioactive compounds is central for many applications in bioanalytical and biomaterials science, and carbohydrates and glycomimetic structures are in this context attracting increasing interest. [10][11][12][13][14] Interactions between cellular glycans and proteins have been found to be of special importance in many biological processes, being involved in cell-cell interactions, cell communication, cell proliferation, and cell death. This emerging significance prompts for new means to analytically study these interactions. To date, various methods have been developed to analyze interactions of carbohydrates and proteins, including biosensors, enzyme-linked lectin assays (ELLAs) and cell assays, nuclear magnetic resonance, calorimetric techniques, and, more recently, microarray technologies. [15][16][17][18][19][20][21][22][23] Among these methods, the quartz crystal microbalance (QCM) biosensor format is being increasingly adopted due to its convenient means of operation coupled with high performance. [24][25][26][27][28][29][30][31][32][33] Measurements can also be performed in real tim...