Pillar[5]arene-modified peptide-guanidiniocarbonylpyrrol amphiphiles with gene transfection properties

Pillar[5]arene-modified amphiphilic peptides with varying numbers of guanidiniocarbonylpyrrol(GCP)moieties have been successfully synthesized,which can self-assemble to multivalent cationic superstructures in aqueous solutions.These assembled peptides can condense DNA into various compact multimolecular aggregates to achieve successful intracellular DNA delivery and demonstrate great potential for gene transfection.Transfection efficiencies of the self-assembled superstructures have been evaluated in vitro with He La and HEK 293T cells.We demonstrate that GCP moiety could enhance the cell transfection ability,owing to its excellent binding towards cytomembrane.It was also found that subtle structure difference in peptides 2 and 3 could result in distinct transfection efficacy,which makes it possible to gain an in-depth understanding of their structure-activity relationship.This work presents a good example of rational structural design in achieving effective gene transfection vectors.

State-of-the-art and recent progress in resorcinarene-based cavitand

Compartmentalization in the biological world brings excellent efficiency and specificity to the formation of complex compounds,inspiring supramolecular chemists to continuously search for defined spaces that can mimic such natural binding sites.Bowl-shaped cavitands built up from resorcinarenes(RA)present rigid and preorganized concave surfaces,which are capable of mimicking the molecular recognition properties of enzymes.The versatile scaffold of RA endows the cavitand with terrific variety and excellent binding behavior.This review provides a comprehensive overview over the structural modification to date in the high attention field of RA-based cavitands development.Different strategies for synthesizing diverse cavitands,such as small cavity cavitands,wider cavity cavitands,deep cavity cavitands,biscavitands,and asymmetric cavitands,are discussed in details.Furthermore,insights into their applications including catalysis,separations and sensing are provided.

杯芳烃和柱芳烃桥梁部位的衍生及其功能化

随着大环化学的快速发展,对杯芳烃、柱芳烃及其他类似化合物的桥梁亚甲基部位进行高效修饰的方法日益引起人们的关注.桥梁部位修饰后的大环衍生物,在不改变其原有属性的基础上增加了新的功能,不仅可以引入更多的功能基团,而且可以通过主客体的自组装行为,进一步拓展杯芳烃和柱芳烃等超分子大环在药物递送、化学传感、荧光体系构建等诸多领域的应用.本文对杯芳烃和柱芳烃桥梁部位修饰的研究进展进行了综述.按照修饰方法的不同进行分类,系统阐述了杯芳烃和柱芳烃桥梁部位修饰的方法、修饰后结构的变化,以及相应的应用拓展,并进一步讨论了其未来发展所面临的机遇与挑战.

Supramolecular Nanohelix Fabricated by Pillararene-Based Host–Guest System for Chirality Amplification, Transfer, and Circularly Polarized Luminescence in Water

Amplified chirality and Förster resonance energy transfer(FRET)-assisted chirality transfer frommolecular to nanoscale level have been shown to play a vital role in co-assembled nanohelix for potential energy transfer in biological systems.Herein,we have constructed a chiral host–guest complex donor system for chiral amplification via induced chirality of pillar[5]arene host and loaded it with an achiral dye acceptor to demonstrate how chirality-assisted excitation energy transfer occurred in the supramolecular nanohelix system in an aqueous medium.

The emerging applications of pillararene architectures in supramolecular catalysis

Over the last decade,numerous research efforts have been devoted to pillar[n]arenes since their debut.The popularity of pillararenes is a reflection of current research trend in supramolecular and macrocyclic chemistry in general.Among the vast applications(such as chemosensors,drug delivery,transmembrance channels,and separation)of pillararenes,their utilization in catalysis is a relatively less explored area.However,soaring attention has been paid by researchers in recent years and this field has seen gradual increasing publications.Therefore,in this review we will discuss progress in the emerging applications of pillararene architectures in catalysis based on various reaction genre including reduction,oxidation,coupling,decomposition and others.Furthermore,this review not only focuses on the pillararenes based current progress in catalysis,but also provides the signs for future development in this research field.

An AIE singlet oxygen generation system based on supramolecular strategy

The design of supramolecular system s with efficient singlet oxygen generation has attracted considerable interests.Herein,an AIE-based singlet oxygen generation system with chemiluminescence properties is reported in aqueous media based on supramolecular host-guest assembly between a water-soluble pillar[5]arene(WP5)and an AIE photosensitizer(TPEDM).The formed supramolecular nanoparticles exhibit significant singlet oxygen generation ability as well as enhanced fluorescence.In addition,by introducing catalase,this H_(2) O_(2)-responsive supramolecular system shows increased~1 O_(2) generation efficiency compared with the blank nanoparticles.An efficient chemiluminescence system can also be achieved by entrapping an energy donor adamantane derivative(AMPPD).Moreover,the present system can function as nanoreactors to perform the photooxidation of dopamine to form polydopamine with visible light irradiation.This wo rk provides a new strategy for the construction of~1 O_(2) generation system based on supramolecular nanomaterials,which has potential applications in the fields such as chemiluminescence imaging and controlled photocatalysis.

Control of secondary structure and morphology of peptide-guanidiniocarbonylpyrrole conjugates by variation of the chain length

Peptide amphiphiles with well-organized secondary structure are an important family of molecules that are known to assemble into a variety of nanostructures.In this work,we present three guanidiniocarbonylpyrrole(GCP)containing peptide amphiphiles,which show versatile morphology and secondary structure changes as a result of different chain lengths and in different concentration regimes.The random coil conformation,α-helix,andβ-sheet are obtained for peptide 1,peptide 2,and peptide 3,respectively under neutral aqueous conditions.Furthermore,all peptide amphiphiles can aggregate to form nanoparticles at low concentrations.However,at high concentrations,peptide 1 selfassembles into left-ha nded twisted helical fibers,while longer bamboo-like mo rphology can be obse rved exclusively for peptide 2.For peptide 3,freshly prepared samples show uniform spherical morphology,whereas an obvious morphological transition from original nanoparticles to disordered fibers was realized after incubating for one week.These fascinating morphology changes were determined by the combination of circular dichroism,dynamic light scattering,transmission electron microscopy,atomic force microscopy,and theoretical calculations.