Supramolecular Zn(II)-Dipicolylamine-Azobenzene-Aminocyclodextrin-ATP Complex: Design and ATP Recognition in Water

Cyclodextrins (CyDs) are water-soluble host molecules possessing a nanosized hydrophobic cavity. In the realm of molecular recognition, this cavity is used not only as a recognition site but also as a reaction medium, where a hydrophobic sensor recognizes a guest molecule. Based on the latter concept, we have designed a novel supramolecular sensing system composed of Zn(II)-dipicolylamine metal complex-based azobenzene (1-Zn) and 3A-amino-3A-deoxy-(2AS,3AS)-γ-cyclodextrin (3-NH₂-γ-CyD) for sensing adenosine-5′-triphosphate (ATP). 1-Zn showed redshifts in the UV-Vis spectra and induced circular dichroism (ICD) only when both ATP and 3-NH₂-γ-CyD were present. Calculations of equilibrium constants indicated that the amino group of 3-NH₂-γ-CyD was involved in the formation of supramolecular 1-Zn/3-NH₂-γ-CyD/ATP. The Job plot of the ICD spectral response revealed that the stoichiometry of 1-Zn/3-NH₂-γ-CyD/ATP was 2:1:1. The pH effect was examined and 1-Zn/3-NH₂-γ-CyD/ATP was most stable in the neutral condition. The NOESY spectrum suggested the localization of 1-Zn in the 3-NH₂-γ-CyD cavity. Based on the obtained results, the metal coordination interaction of 1-Zn and the electrostatic interaction of 3-NH₂-γ-CyD were found to take place for ATP recognition. The “reaction medium approach” enabled us to develop a supramolecular sensing system that undergoes multi-point interactions in water. This study is the first step in the design of a selective sensing system based on a good understanding of supramolecular structures.     

Unique Tube–Ring Interactions: Complexation of Single‐Walled Carbon Nanotubes with Cycloparaphenyleneacetylenes

Carbon nanotubes (CNTs) interlocked by cyclic compounds through supramolecular interaction are promising rotaxane‐like materials applicable as 2D and 3D networks of nanowires and disease‐specific theranostic agents having multifunctionalities. Supramolecular complexation of CNTs with cyclic compounds in a “ring toss'' manner is a straightforward method to prepare interlocked CNTs; however, to date, this has not been reported on. Here, the “ring toss” method to prepare interlocked CNTs by using π‐conjugated carbon nanorings: [8]‐, [9]‐, and [10]cycloparaphenyleneacetylene (CPPA) is reported. CPPAs efficiently interact with CNTs to form CNT@CPPA complexes, while uncomplexed CPPAs can be recovered without decomposition. CNTs, which tightly fit in the cavities of CPPAs through convex–concave interaction, efficiently afford “tube‐in‐ring”‐type CNT@CPPA complexes. “Tube‐in‐ring”‐type and “ring‐on‐tube”‐type complexation modes are successfully distinguished by spectroscopic, thermogravimetric, and microscopic analyses.     

Predictive association of metal–organic systems in the solid-state: the molecular electrostatic potential based approach

Designing crystalline solids with improved properties or performances remains a challenging task, despite great strides that have been made within the field of crystal engineering since its birth several decades ago. Herein, we are bringing examples that illustrate recent successes in taking supramolecular synthetic guidelines from the organic crystal engineering and adjusting those to metal-containing systems, particularly to the lower-dimensional ones. The versatility of calculated molecular electrostatic potential (MEP) as a new crystal engineering tool is demonstrated.     

Effect of matrix−nanoparticle supramolecular interactions on the morphology and mechanical properties of polymer foams

In this study, we report the fabrication of supramolecular polymer nanocomposite foams with a uniform cell structure, high cell density and high expansion ratio using a soft matrix of poly(methyl acrylate‐co‐2‐hydroxyethyl methacrylate) and silica nanoparticle fillers, both functionalized with ureido‐pyrimidinone (UPy) supramolecular groups. Microcellular structures were formed using a batch foaming process at 90 °C under a 9 MPa nitrogen atmosphere. Nanocomposites were characterized and compared before and after the foaming process to investigate the effect of supramolecular interactions on the thermomechanical properties and morphology of the foams. TEM images revealed that while strong inter‐filler supramolecular interactions do not have a positive effect on their dispersion state, matrix?filler interactions derived from hydrogen bonding UPy motifs result in a rather uniform distribution of nanoparticles. Competing filler?filler and matrix?filler supramolecular interactions can be balanced and optimized by adjusting UPy populations along the chains and on the surface of nanoparticles. At a given chain functionality, increasing the nanoparticle loading up to an optimum concentration improves the mechanical properties and formability of the system. Above such concentration strong interactions between fillers, which are not compensated by the matrix, result in large aggregates and consequently undermine the material performance. Supramolecular polymer foams illustrate a similar thermal and viscoelastic behavior to that of neat samples but after foaming, due to the formation of a cellular structure and rearrangement or dissociation of UPy dimers under the foaming conditions, the elastic modulus is reduced. © 2018 Society of Chemical Industry     

Supramolecular Chiral Aggregates Exhibiting Nonlinear CD–ee Dependence

Although a linear relationship between the optical activity (normally the CD signal) and the enantiomeric excess (ee) of chiral auxiliaries has been the most commonly observed dependence in dynamic supramolecular helical aggregates, positive nonlinear CD–ee dependence, known as the “majority-rules effect” (MRE), indicative of chiral amplification, has also been well documented and to some extent understood. In sharp contrast, the negative nonlinear CD–ee dependence has been much less reported and is not well understood. Here, the state of the art of both the positive and negative nonlinear CD–ee dependence in noncovalently bound supramolecular helical aggregates is summarized, with the hope that the vast examples of supramolecular aggregates showing positive nonlinear dependence, in terms of the methods of investigations, variations in the structure of the building block (single species or multiple species), and theoretical modeling using the mismatch penalty energy and helix reversal penalty energy, would help to guide the design of building blocks to form aggregates showing negative nonlinear dependence, and thus to understand the mechanisms. The potential applications of those functional supramolecular aggregates are also discussed.     

Supramolecular Poly(cyclotriphosphazene) Functionalized Graphene Oxide/Polypropylene Composites with Simultaneously Improved Thermal Stability,Flame Retardancy,and Viscoelastic Properties

A novel crosslinkable supramolecular poly(cyclotriphosphazene) functionalized graphene oxide (FGO) is synthesized and melt‐processed with polypropylene (PP), which results in a PP composite with simultaneously improved flame retardancy, smoke‐suppression, and thermal and viscoelastic properties. The cone‐calorimetry test results reveal that the peak heat‐release rate and total heat release of the composite (2 wt% FGO) are reduced by 39.7% and 29.9%, respectively, compared to those of the neat PP. Meanwhile, the total smoke released and total smoke production of PP are significantly (42.7% and 34.9%, respectively) reduced after composite formation with 2 wt% FGO. Similarly, the PP/FGO composite shows an improved maximum weight loss temperature of 392.4 °C, compared to that of neat PP (361.4 °C). Thermogravimetric Fourier‐transform infrared spectroscopy (TG‐FTIR) analysis further confirms that the composite reduces the evolution of the flammable components and toxic gases, especially CO gas, indicating that the FGO significantly decreases the fire hazards of the PP. The thermomechanical and melt‐rheological analyses reveal that the composite has higher mechanical stiffness and viscoelastic properties than the neat polymer. In summary, FGO is shown to have potential as an advanced additive to obtain PP composites with multifunctional properties; however, higher FGO loading would be needed to improve UL‐94 rating from V‐2 to V‐0.     

超分子作用阻尼材料的动态力学模型修正

为提高飞机起落架载荷实测精度，以支柱式起落架结构为研究对象，探讨处理其载荷标定数据的工程方法。首先，对实际受载情况和单向加载工况标定数据的分析，挖掘出三向载荷、缓冲支柱压缩行程与应变码值间的数学关系，将预测的数学关系代入到多向工况的标定数据中，验证了它们的准确性;其次，根据两种标定数据回归方法，提出了对应使用的支柱式起落架载荷-应变标定方程的数学模型;最后，将两种标定方程代回到标定数据中，计算起落架三向载荷，所有反算载荷的误差均在可控范围内，表明标定方程满足精度要求。将标定方程代入实测数据中，实测曲线符合变化规律。该处理方法的应用能有力提高支柱式起落架的起飞-着陆载荷实测和载荷谱编制的准确度。     

Supramolecular Architectures of Nucleic Acid/Peptide Hybrids

Supramolecular architectures that are built artificially from biomolecules, such as nucleic acids or peptides, with structural hierarchical orders ranging from the molecular to nano-scales have attracted increased attention in molecular science research fields. The engineering of nanostructures with such biomolecule-based supramolecular architectures could offer an opportunity for the development of biocompatible supramolecular (nano)materials. In this review, we highlighted a variety of supramolecular architectures that were assembled from both nucleic acids and peptides through the non-covalent interactions between them or the covalently conjugated molecular hybrids between them.