taBOX: A water-soluble tetraanionic rectangular molecular container for conjugated molecules and taste masking for berberine and palmatine

A water-soluble macrocycle that bears four carboxylate anions has been designed and prepared,which forms a rectangular cavity that can efficiently encapsulate discrete electron-deficient aromatic compounds,including berberine and palmatine.This macrocycle is revealed to be highly biocompatible and able to inhibit the bitter taste of the two drugs.

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.

芳香大分子和超分子螺旋管构筑及其功能

疏溶剂作用、氢键、静电作用、卤键和配位作用等非共价键作用力都可以用于控制芳香大分子和超分子的折叠和螺旋,由此形成的芳香聚合物螺旋管内径尺寸相对固定,内穴深度可调,作为主体分子可以识别或包结多种客体分子,通过络合能够产生手性诱导与传递和跨膜输送功能,也能够促进有机化学转化等。本文综述了由芳香砌块构筑的这类大分子和超分子螺旋管的构筑和功能。首先介绍了通过不同策略形成管状结构的背景,以及超分子和大分子方法的特点,着重介绍了由芳香酰胺、酰肼、三唑和乙炔重复链段的不同低聚物分子形成的分子管,并总结了形成超分子管的自组装策略,最后讨论了长高分子管的合成挑战以及这种结构独特的结构家族的新的潜在应用。

药物输送体系构筑中的超分子组装策略

超分子组装提供了药物输送体系设计的新原理。以高效的分子间非共价键作用为驱动力,超分子药物输送体系能够利用结构简单的分子单体获得精确的成分控制,并使得载体结构易于预测,形貌与体积易于调控,有利于实现药物的控制释放。本文首先总结超分子药物输送体系的研究背景,之后重点介绍基于环糊精、杯芳烃、柱芳烃和葫芦脲的主-客体体系的超分子药物输送体系的构建与药物输送功能,然后介绍水溶性的超分子有机框架在药物输送方面的应用,最后提出了超分子药物载体实用化需要克服的若干挑战性问题。

Ruthenium(Ⅱ)-cored supramolecular organic framework-mediated recyclable visible light photoreduction of azides to amines and cascade formation of lactams

Ru(bpy)3]2+-cored supramolecular organic framework SMOF-1, assembled from a [Ru(bpy)3]2+-derived hexaarmed molecule and cucurbit[8]uril, has been demonstrated to heterogeneously catalyze visible light-induced reduction of phenyl, benzyl, 2-phenylethyl and 3-phenylpropyl azides in acetonitrile to produce the corresponding amines in good to high yields. For the last two kinds of azides that bear a CO2Me group at the para-position of the benzene ring, cascade reactions take place to generate the corresponding lactams in high yields. Compared with homogeneous control [Ru(bpy)3]Cl2, SMOF-1 exhibits remarkably increased photocatalysis activity as a result of synergistic effect of the [Ru(bpy)3]2+ units that form cubic cages to host the azide molecules and related intermediates. Moreover, SMOF-1 displays high recyclability and considerable photocatalysis activity after 3 to 12 runs.

A stable metal-covalent-supramolecular organic framework hybrid: enrichment of catalysts for visible light-induced hydrogen production

Cubic metal-covalent-supramolecular organic framework(MCSOF-1)hybrid has been created from the reaction of two molecular components and subsequent co-assembly with cucurbit[8]uril(CB[8])in water.In the presence of CB[8],[Ru(bpy)_3]^(2+)-based acylhydrazine 1·2Cl reacted with aldehyde 2·Cl to quantitatively yield six-armed precursor 3·8Cl through the generation of MCSOF-1.MCSOF-1 combines the structural features of metal-,covalent-and supramolecular organic frameworks.Its periodicity in water and in the solid state was confirmed by synchrotron X-ray scattering and diffraction experiments.MCSOF-1could enrich discrete anionic polyoxometalates(POMs),maintain periodicity in acidic medium,and remarkably facilitate visible light-induced electron transfer from its[Ru(bpy)_3]^(2+)units to enriched POMs,leading to enhanced catalysis of the POMs for the reduction of proton to H_2in both aqueous(homogeneous)and organic(heterogeneous)media.

Loading-free supramolecular organic framework drug delivery systems(sof-DDSs) for doxorubicin:normal plasm and multidrug resistant cancer cell-adaptive delivery and release

Four water-soluble porous supramolecular organic framework drug delivery systems（sof-DDSs） have been used to adsorb doxorubicin（DOX） in water at physiological pH of 7.4,which is driven exclusively by hydrophobicity.The resulting complexes DOX@SOFs are formed instantaneously upon dissolving the components in water.The drug-adsorbed sof-DDSs can undergo plasm circulation with important maintenance of the drug and overcome the multidrug resistance of human breast MCF-7/Adr cancer cells.DOX is released readily in the cancer cells due to the protonation of its amino group in the acidic medium of cancer cells.In vitro and in vivo experiments reveal that the delivery of SOF-a-d remarkably improve the cytotoxicity of DOX for the MCF-7/Adr cells and tumors,leading to 13-19-fold reduction of the 1C_（50）values as compared with that of DOX.This new sof-DDSs strategy omits the indispensable loading process required by most of reported nano-scaled carriers for neutral hydrophobic chemotherapeutic agents,and thus should be highly valuable for future development of low-cost delivery systems.

Conjugated radical cation dimerization-driven generation of supramolecular architectures

This paper summarizes the recent advance in utilizing conjugated radical cation dimerization （CRCD） for constructing new unimolecular, such as foldamers, and supramolecular ordered structures, such as three-dimensional supramolecular polymers and two-dimensional supramolecular organic framework. Particularly, the stacking or dimerization of tetrathiafulvalene and 4,4＇-dipyridium subunits has been highlighted, and the approaches for enhancing the stability of their radical cation dimers have been discussed.

Self-assembly of supramolecular polymers in water from tetracationic and tetraanionic monomers in water through cooperative electrostatic attraction and aromatic stacking

The cooperative electrostatic attraction and π-π aromatic stacking interactions between tetrahedral tetrapyridinium TP and three tetraanionic tetraphenylethylene derivatives TPE-1～3 led to the formation of a new kind of supramolecular polymer networks in water, which have been confirmed by^1 H NMR,fluorescence, isothermal titration calorimetric(ITC) and dynamic light scattering(DLS) experiments. ITC studies show that the contributions of enthalpy and entropy were comparable, reflecting the importance of hydrophobicity in driving the intermolecular aromatic stacking. DLS experiments indicate that the linear supramolecular polymers formed by these tetratopic monomers further aggregated into networks of 10~2-nm size.

In situ-prepared homogeneous supramolecular organic framework drug delivery systems(sof-DDSs)：Overcoming cancer multidrug resistance and controlled release

Water-soluble three-dimensional porous supramolecular organic frameworks（SOFs） have been demonstrated as a new generation of homogeneous polycationic platforms for anti-cancer drug delivery.The new SOF drug delivery systems（sof-DDSs） can adsorb dianionic pemetrexed（PMX）,a clinically used chemotherapeutic agent instantaneously upon dissolving in water,which is driven by both electrostatic attraction and hydrophobicity.The in situ-prepared PMX@SOFs are highly stable and can avoid important release of the drug during plasm circulation and overcome the multidrug resistance of human breast MCF-7/Adr cancer cells to enter the cancer cells.Acidic microenvironment of cancer cells promotes the release of the drug in cancer cells.Both in vitro and in vivo studies have revealed that sofDDSs considerably improve the treatment efficacy of PMX,leading to 6-12-fold reduction of the IC50 values,as compared with that of PMX alone.The new drug delivery strategy omits the loading process required by most of reported nanoparticle-based delivery systems and thus holds promise for future development of low-cost drug delivery systems

A periodic metallo-supramolecular polymer from a flexible building block: self-assembly and photocatalysis for organic dye degradation

A water-soluble metallo-supramolecular polymer MSP-f-6Np,which possesses a regular pore aperture of 1.4 nm,has been assembled from a structurally flexible naphthalene-appended[Ru(bipy)3]^2+complex and cucurbit[8]uril.As the first periodic metallo-supramolecular polymer formed by a flexible building block,MSP-f-6Np exhibits a hydrodynamic diameter of 122 and 164 nm at 0.1 and 2.0 mM of the monomer concentrations.Synchrotron small angle X-ray scattering experiments confirm that MSP-f-6Np possesses porosity periodicity in both the solution and solid states.Compared with a control,the new highly ordered porous system displays enhanced photocatalytic activity for the degradation of organic dyes.

Pleated polymeric foldamers driven by donor–acceptor interaction and conjugated radical cation dimerization

Two naphthalene（NP） and bipyridinium（BIPY^2＋） alternately incorporated polymers P1 and P2 have been prepared through the formation of dynamic hydrazone bonds. The polymers formed NP–BIPY^2＋donor–acceptor interaction-induced pleated secondary structure. Upon reducing the BIPY^2＋units to radical cation BIPY＋, intramolecular dimerization of the BIPY＋units induced the backbones to afford another pleated secondary structure. Adding electron-rich macrocyclic polyether bis-1,5-dinaphtho[38]crown-10 or electron-deficient cyclobis（paraquat-p-phenylene） cyclophane did not break the first foldamer by complexing the BIPY^2＋or NP units of the polymers, whereas the di（radical cationic）ring of the second cyclophane could break the second foldamer by forming threading complexes with the BIPY＋units of the polymers.

Water-Soluble Three-Dimensional Polymers:Non-Covalent and Covalent Synthesis and Functions

Water-soluble three-dimensional(3D)polymers are structurally ideal for the construction of ordered porous materials for in-situ and tunable loading and release of guests.For many years,studies on ordered porous materials have been confined to crystalline solids.Since 2014,self-assembly has been developed as a robust strategy for the preparation of water-soluble 3D polymers that possess defined and intrinsic porosity.

In Situ Loading and Delivery of Short Single- and Double-Stranded DNA by Supramolecular Organic Frameworks

Short DNA represents an important class of bioma-cromolecules that arewidely applied in gene therapy,editing,and modulation.However,the development of simple and reliable methods for their intracellular delivery remains a challenge.Herein,we describe that seven water-soluble,homogeneous supramole-cular organic frameworks(SOFs)with a well-defined pore size and high stability in water that can accom-plish in situ inclusion of single-stranded(ss)and double-stranded(ds)DNA(21,23,and 58 nt)and effective intracellular delivery(including two non-cancerous and six cancerous cell lines).

Halogen bonding-driven formation of supramolecular macrocycles and double helix

The crystal structures of three intramolecularly hydrogen bonded rigid aromatic amide derivatives,which all bear one iodine atom at one end as the donor and one pyridine unit at the other end as the acceptor,have been described to reveal the utility of halogen bonding in inducing the formation of supramolecular macrocycles.All the three compounds formed intermolecular I···N halogen bonding.For short compound 1,halogen bonding induced the formation of an extended supramolecular array.For longer folded compounds 2 and 3,halogen bonding could hold two molecules to form supramolecular macrocycles even by adopting a highly distorted,energetically less favorable conformation(for 3).Depending on the solvent for the growth of crystals,compound 3 could also gave rise to a halogen bonded supramolecular double helix.

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].

Interplay of nonreciprocity and nonlinearity on mean-field energy and dynamics of a Bose–Einstein condensate in a double-well potential

We investigate the mean-field energy spectrum and dynamics in a Bose–Einstein condensate in a double-well potential with non-Hermiticity from the nonreciprocal hopping,and show that the interplay of nonreciprocity and nonlinearity leads to exotic properties.Under the two-mode and mean-field approximations,the nonreciprocal generalization of the nonlinear Schrödinger equation and Bloch equations of motion for this system are obtained.We analyze the PT phase diagram and the dynamical stability of fixed points.The reentrance of PT-symmetric phase and the reformation of stable fixed points with increasing the nonreciprocity parameter are found.Besides,we uncover a linear selftrapping effect induced by the nonreciprocity.In the nonlinear case,the self-trapping oscillation is enhanced by the nonreciprocity and then collapses in the PT-broken phase,and can finally be recovered in the reentrant PT-symmetric phase.

Non-Hermitian topological Anderson insulators

Non-Hermitian systems can exhibit exotic topological and localization properties.Here we elucidate the non-Hermitian effects on disordered topological systems using a nonreciprocal disordered Su-Schrieffer-Heeger model.We show that the non-Hermiticity can enhance the topological phase against disorders by increasing bulk gaps.Moreover,we uncover a topological phase which emerges under both moderate non-Hermiticity and disorders,and is characterized by localized insulating bulk states with a disorder-averaged winding number and zero-energy edge modes.Such topological phases induced by the combination of non-Hermiticity and disorders are dubbed non-Hermitian topological Anderson insulators.We reveal that the system has unique non-monotonous localization behavior and the topological transition is accompanied by an Anderson transition.These properties are general in other non-Hermitian models.

A cucurbit[8]uril-stabilized 3D charge transfer supramolecular polymer with a remarkable confinement effect for enhanced photocatalytic proton reduction and thioether oxidation

A highly water-soluble tetrahedral compound T1 that contains one tetraphenylmethane core and four 2-oxynaphthelene-CH_(2)-4,4’-bipyridinium(NP-CH_(2)-DIPY)side arms has been prepared.Control experi-ments reveal that NP-CH_(2)-BIPY undergoes antiparallel dimerization which is stabilized by two charge transfer interactions with NP as an electron-rich donor and BIPY as an electron-deficient acceptor.