Supramolecular chemistry

  • Article
    | Open Access

    Encapsulating large and contorted nanographenes inside artificial receptors remain challenging. This work reports the synthesis, characterization and binding properties of a trigonal prismatic cage compound that can serve as a receptor for contorted nanographene derivatives.

    • Huang Wu
    • , Yu Wang
    •  & J. Fraser Stoddart
  • Article
    | Open Access

    Mechanical motions in hybrid sp2/sp3 -hybrid nanocarbon peapods might lead to promising materials applications, but have been insufficiently explored. Here the authors demonstrate that a diamondoid molecule trapped inside a carbonaceous cylinder undergoes solid-state rotations at terahertz frequencies.

    • Taisuke Matsuno
    • , Seiya Terasaki
    •  & Hiroyuki Isobe
  • Article
    | Open Access

    Tetrel bonds are noncovalent interactions between electron donors and group 14 elements; in these situations, C(sp3) atoms can act as Lewis acids, accepting electron density. Here, the authors show that methyl groups, when bound to atoms less electronegative than carbon, can participate in noncovalent interactions as electron density donors.

    • Oliver Loveday
    •  & Jorge Echeverría
  • Article
    | Open Access

    Dissipative self-assembly, which requires a continuous supply of fuel to maintain the assembled states far from equilibrium, is the foundation of biological systems but it remains a challenge to introduce light as fuel into artificial dissipative self-assemblies. Here, the authors report an artificial dissipative self-assembly system that is constructed from light-induced amphiphiles.

    • Xu-Man Chen
    • , Xiao-Fang Hou
    •  & Quan Li
  • Article
    | Open Access

    Self-assembling peptides have a range of potential applications but developing self-assembling sequences can be challenging. Here, the authors report on a one-bead one-compound combinatorial library where fluorescence is used to detect the potential for self-assembly and identified candidates are evaluated.

    • Pei-Pei Yang
    • , Yi-Jing Li
    •  & Kit S. Lam
  • Article
    | Open Access

    The development of tissue-like materials which replicate the mechanical properties of tissue is of interest for a range of applications. Here, the authors report on the development of radial asters that form a gel network to stiffen in compression and soften in extension, resembling tissue mechanics.

    • Qingqiao Xie
    • , Yuandi Zhuang
    •  & Lingxiang Jiang
  • Article
    | Open Access

    Nucleic acid-based constitutional dynamic networks (CDNs) enable control of various catalytic processes, but it is challenging to achieve intercommunication between different CDNs and by that mimic complex cell biology networks. Here, the authors report two CDNs that control the integration of photochemical and dark-operating processes, and show their intercommunication afforded by environmental components.

    • Chen Wang
    • , Michael P. O’Hagan
    •  & Itamar Willner
  • Article
    | Open Access

    Despite their great utility in synthetic and materials chemistry, Diels-Alder and retro Diels-Alder reactions have been vastly unexplored in promoting self-assembly processes. Here the authors show the release of steric bulkiness associated with a bridged bicyclic Diels Alder adduct by the retro Diels-Alder reaction that allowed generation of two building blocks that spontaneously self-assembled to form a supramolecular polymer.

    • Jaeyoung Park
    • , Jung-Moo Heo
    •  & Jong-Man Kim
  • Article
    | Open Access

    The preparation of artificial host–guest systems that display dynamic adaptation during guest binding is challenging. Here the authors report a chiral self-assembled tetrahedral cage featuring curved walls that reconfigures stereochemically to fit fullerene guests, regulates corannulene inversion, and enables the determination of co-guest enantiomeric excess by NMR spectroscopy.

    • Yang Yang
    • , Tanya K. Ronson
    •  & Jonathan R. Nitschke
  • Article
    | Open Access

    Synthetic polymer nano-objects with well-defined hierarchical structures are important for a wide range of applications such as nanomaterial synthesis, catalysis, and therapeutics. Here the authors demonstrate the strategy of fabricating controlled hierarchical structures through self-assembly of folded synthetic polymers.

    • Chaojian Chen
    • , Manjesh Kumar Singh
    •  & Tanja Weil
  • Article
    | Open Access

    Mechanically flexible single crystals are promising materials for advanced technological applications. Here, the authors study the high pressure response of a plastically flexible coordination polymer and provide indication of an overall disparate mechanical response of bulk flexibility and quasi-hydrostatic compression within the same crystal lattice.

    • Xiaojiao Liu
    • , Adam A. L. Michalchuk
    •  & Colin R. Pulham
  • Article
    | Open Access

    Artificial self-assembling systems such as anion receptors or ‘binders’ are largely unexplored for therapeutic applications. Here, the authors report self-assembling trimetallic cryptands containing copper, zinc or manganese that encapsulate a range of anions, are highly toxic to human cancer cell lines and show metal-dependent selectivity towards cancer vs. healthy cells linked to the selective inhibition of multiple kinases.

    • Simon J. Allison
    • , Jaroslaw Bryk
    •  & Craig R. Rice
  • Article
    | Open Access

    Active coacervate droplets are droplets coupled to a chemical reaction that maintains them out of equilibrium, which can be used to drive active processes, but coacervates are still subject to passive processes that compete with or mask growth. Here, the authors present a nucleotide-based model for active coacervate droplets that form and grow by fuel-driven synthesis of ATP, and, importantly, do not undergo Ostwald ripening.

    • Karina K. Nakashima
    • , Merlijn H. I. van Haren
    •  & Evan Spruijt
  • Article
    | Open Access

    The removal of ethane from ethylene is of importance in the petrochemical industry, but similar physicochemical properties of these molecules makes separation a challenging task. Here, the authors demonstrate that a robust octahedral calix[4]resorcinarene-based porous organic cage can separate high-purity ethylene from ethane/ethylene mixtures.

    • Kongzhao Su
    • , Wenjing Wang
    •  & Daqiang Yuan
  • Article
    | Open Access

    In hybrid perovskites, the driving forces of an order–disorder transition that arise from the organic cation and inorganic framework cannot be easily untangled. Here, the authors introduce a cage-in-framework structure in which reorientation of the cage cation does not alter the cubic symmetry of the perovskite lattice.

    • Zhifang Shi
    • , Zheng Fang
    •  & Qixi Mi
  • Article
    | Open Access

    Self-assembling peptides (SAPs) can be used to build biomaterials, but genetically encoded SAPs have rarely been used as building blocks in cells. Here, the authors design a SAP that can be genetically fused to target proteins to induce their intracellular clustering and modulate their signaling functions.

    • Takayuki Miki
    • , Taichi Nakai
    •  & Hisakazu Mihara
  • Article
    | Open Access

    It remains a challenge to achieve a balance between performance and stability, as well as addressing the environmental impact of perovskite solar cells. Here, the authors propose a multimodal host-guest complexation strategy enabling these shortcomings to be addressed simultaneously.

    • Hong Zhang
    • , Felix Thomas Eickemeyer
    •  & Michael Grätzel
  • Article
    | Open Access

    Living supramolecular polymerization can produce precise covalent polymers, but the scope of monomers is still narrow. Here the authors show a molecular platform for living supramolecular polymerization that is based on the unique structure of all-cis 1,2,3,4,5,6- 22 hexafluorocyclohexane, the most polar aliphatic compound reported to date.

    • Oleksandr Shyshov
    • , Shyamkumar Vadakket Haridas
    •  & Max von Delius
  • Article
    | Open Access

    Artificial molecular systems can show complex kinetics of reproduction, however their integration into larger ensembles remains a challenge towards evolving higher order functionality. Here authors use show that self-reproducing lipids can initiate and accelerate octanol droplet movement and that reciprocally chemotactic movement of these droplets increases the rate of lipid reproduction substantially.

    • Dhanya Babu
    • , Robert J. H. Scanes
    •  & Nathalie Katsonis
  • Article
    | Open Access

    Communication of chirality at a molecular level is the fundamental for transmitting chirality information but one-step communication modes in many artificial systems limits further processing the chirality information. Here, the authors report chirality communication of aromatic oligoamide sequences within interpenetrated helicate architecture in a hierarchical manner.

    • Jiajia Zhang
    • , Dan Luo
    •  & Quan Gan
  • Article
    | Open Access

    Realizing overtemperature protection with a molecular device is challenging. Here, the authors demonstrate an overtemperature protection function by integrating thermo- and photoresponsive functions into a pillar[6]arene based pseudocatanene.

    • Jiabin Yao
    • , Wanhua Wu
    •  & Cheng Yang
  • Article
    | Open Access

    Semi-conducting two-dimensional polymer nanoobjects are promising materials but examples of self-assembled 2D nanosheets with controlled dimensions has not been shown before. Here, the authors precisely tune the length of 2D sheets of conjugated polymers by using blending, heating, and seeded-growth strategies.

    • Sanghee Yang
    • , Sung-Yun Kang
    •  & Tae-Lim Choi
  • Article
    | Open Access

    Efficient stimulus-responsive phosphorescence organic materials are attractive, but are extremely rare because of unclear design principles and intrinsically spin-forbidden intersystem crossing. Here, the authors present a facile strategy to achieve ultraviolet irradiation-responsive ultralong room-temperature phosphorescence in several simple amorphous polymer materials.

    • Yongfeng Zhang
    • , Liang Gao
    •  & Yanli Zhao
  • Article
    | Open Access

    Rationally designing and precisely constructing the dimensions, configurations and compositions of organic micro- and nanomaterials are key issues in material chemistry, but remain challenging. Here, the authors realize the fine synthesis of organic superstructure microwires via a hierarchical epitaxial-growth approach.

    • Ming-Peng Zhuo
    • , Guang-Peng He
    •  & Liang-Sheng Liao
  • Article
    | Open Access

    Investigating biomembrane curvature formation is important for studying intracellular processes, but the instability of liposome models mimicking these membranes restricts exploration of membrane processes. Here, the authors demonstrate control over the curvature formation in polymersome membranes by insertion of PNIPAm as stimuli responsive polymer.

    • Jiawei Sun
    • , Sjoerd J. Rijpkema
    •  & Daniela A. Wilson
  • Article
    | Open Access

    Induced motion has emerged as a method to increase the efficacy of delivery and therapeutic outcomes using nanomaterials. Here, the authors report on a Janus gold shell polymersome with aggregation-induced emission molecules for phototactic and photodynamic therapy applications.

    • Shoupeng Cao
    • , Jingxin Shao
    •  & Jan C. M. van Hest
  • Article
    | Open Access

    Incommensurate pairing is a type of stereoisomerism, observed in carbon bilayers, that arises from the twisted orientations of the graphitic layers. Here, the authors create a finite molecular version of an incommensurate carbon bilayer in the form of two concentrically assembled cylindrical molecules.

    • Taisuke Matsuno
    • , Yutaro Ohtomo
    •  & Hiroyuki Isobe
  • Article
    | Open Access

    Macrocycles are molecular structures extensively used in the design of catalysts, therapeutics and supramolecular assemblies but synthesis procedures that can produce macrocycles in high yield under high reaction concentrations are rare. Here the authors report the use of dynamic hindered urea bond for the construction of urea macrocycles with high efficiency.

    • Yingfeng Yang
    • , Hanze Ying
    •  & Jianjun Cheng
  • Article
    | Open Access

    Photoluminescence printing is a widely applied anticounterfeiting technique but there are still challenges in developing new generation anticounterfeiting materials providing a high security level. Here, the authors demonstrate coordination dependent photochromic luminescence in a supramolecular coordination polyelectrolyte for multiple information authentication.

    • Zhiqiang Li
    • , Xiao Liu
    •  & Yanli Zhao
  • Article
    | Open Access

    The coexistence of single-crystallinity with a multidomain morphology is a paradoxical crystallographic phenomenon. Here, the authors introduce a crystallographic morphology never reported before. The single-crystals with a curved and hollow morphology offer opportunities to generate a class of synthetic multidomain crystals.

    • Maria Chiara di Gregorio
    • , Merna Elsousou
    •  & Milko E. van der Boom
  • Article
    | Open Access

    Organic ferroelectrics are of potential use in state-of-the-art ferroelectric devices but mechanistic insight in generating ferroelectricity remains limited. Here, the authors demonstrate that a bowl-to-bowl inversion of a bowl shaped organic molecule generates ferroelectric dipole relaxation, extending the concept of ferroelectricity in small organic molecules.

    • Shunsuke Furukawa
    • , Jianyun Wu
    •  & Tomoyuki Akutagawa
  • Article
    | Open Access

    Physical networks typically employ enthalpy-dominated crosslinking interactions that become more dynamic at elevated temperatures. Here, the authors report an entropy-driven physical network based on polymer-nanoparticle interactions that exhibits mechanical properties that are invariant with temperature.

    • Anthony C. Yu
    • , Huada Lian
    •  & Eric A. Appel
  • Article
    | Open Access

    Organic agents with activity in the second near infrared region (NIR-II) are needed for precise treatment of cancer. Here, the authors develop boron difluoride formazanate nanosystem as a theranostic agent active in the NIR-II region for treating deep-seated hepatocellular carcinoma in mice.

    • Huijing Xiang
    • , Lingzhi Zhao
    •  & Yanli Zhao
  • Article
    | Open Access

    Thiol-disulfide exchange is an extensively used reversible reaction in dynamic combinatorial chemistry, but usually requires long time to reach equilibrium. Here, the authors employ selenocystine as a catalyst of thiol-disulfide exchange at low temperatures and basic pH, and show that it can promote disulfide bond formation during folding of a scrambled RNase A.

    • Andrea Canal-Martín
    •  & Ruth Pérez-Fernández
  • Article
    | Open Access

    Design of artificial catalysts to mimic enzyme activity and selectivity is a challenge in the catalysis field. Here, the authors design a platinum catalyst with a porous cage ligand which shows enzyme-like properties, such as high hydrosilylation activity and substrate size selectivity, while being recyclable.

    • Ganghuo Pan
    • , Chunhua Hu
    •  & Yuzhou Liu
  • Article
    | Open Access

    Selectivity in carbene insertion reactions promoted by Ru(II)porphyrinates is achieved only upon careful control of substrate stoichiometry. Here, the authors demonstrate that endotopic catalysis and formation of mechanical bonds enables carbene insertions to occur selectively and in quantitative yield regardless of substrate stoichiometry.

    • Liniquer A. Fontana
    • , Marlon P. Almeida
    •  & Jackson D. Megiatto Jr.
  • Article
    | Open Access

    Mimicking the crowded cytosol of cells in synthetic cells has been a major limitation to the functionality. Here, the authors used the interaction between nickel, nitrilotriacetic acid and histidine tagged proteins to control loading of macromolecules into spatially programmed coacervate-based protocells.

    • Wiggert J. Altenburg
    • , N. Amy Yewdall
    •  & Jan C. M. van Hest
  • Article
    | Open Access

    Xenon binding carries potential for xenon separation and emerging applications in magnetic resonance imaging. Here, the authors report a rare example of a tight yet soft capsule, assembled from two chiral bisurea-bisthiourea macrocycle components, that can efficiently and adaptively bind xenon in both the solid state and solution.

    • Shi-Xin Nie
    • , Hao Guo
    •  & Qi-Qiang Wang
  • Article
    | Open Access

    Knowledge about kinetically favored intermediate states in self-assembly processes can provide information about the self-assembly process but trapping these states without changing the reaction conditions is challenging. Here, the authors report a method for trapping metastable intermediates in self-assembly processes that is based on a photopolymerization strategy.

    • Joonsik Seo
    • , Joonyoung F. Joung
    •  & Jong-Man Kim
  • Article
    | Open Access

    DNA-templated synthesis takes advantage of sequence-specific hybridization to accelerate chemical reactions. Here, the authors present templated synthesis controlled through antibody-antigen interactions.

    • Lorena Baranda Pellejero
    • , Malihe Mahdifar
    •  & Francesco Ricci
  • Article
    | Open Access

    The collective properties of atomically precise nanoclusters bear vast potential for electronic materials by design. Here, the authors describe the self-assembly of Au32 nanoclusters into micro-crystals, which improves the electric conductivity and invokes new optical transitions caused by the high structural order.

    • Florian Fetzer
    • , Andre Maier
    •  & Marcus Scheele
  • Article
    | Open Access

    Typical micelles are molecular assemblies composed of amphiphiles bearing linear alkyl chains. Herein, the authors present an uncommon type of cycloalkane-based bent amphiphile and its micelle which encapsulates large metal- complexes with high uptake efficiency, selectivity, and emissivity in water.

    • Mamiko Hanafusa
    • , Yamato Tsuchida
    •  & Michito Yoshizawa
  • Article
    | Open Access

    The development of techniques capable of orchestrating the assembly of living cells into multicellular ensembles with synergistic and function is challenge. Here, the authors construct algal or algal/bacterial cells-based core shell-like structure based on aqueous two-phase system for synergic photosynthetic H2 production.

    • Zhijun Xu
    • , Shengliang Wang
    •  & Stephen Mann