Self-Propelling Hybrid Gels Incorporating an Active Self-Assembled,Low-Molecular-Weight Gelator

Hybrid gel beads based on combining a low-molecular-weight gelator (LMWG) with a polymer gelator (PG) demonstrate an enhanced ability to self-propel in water, with the LMWG playing an active role. Hybrid gel beads were loaded with ethanol and shown to move in water owing to the Marangoni effect changes in surface tension caused by the expulsion of ethanol – smaller beads move farther and faster than larger beads. Flat shapes of the hybrid gel were cut using a “stamp” – circles moved the furthest, whereas stars showed more rotation on their own axes. Comparing hybrid LMWG/PG gel beads with PG-only beads demonstrated that the LMWG speeds up the beads, enhancing the rate of self-propulsion. Self-assembly of the LMWG into a “solid-like” network prevents its leaching from the gel. The LMWG also retains its own unique function – specifically, remediating methylene blue pollutant dye from basic water as a result of noncovalent interactions. The mobile hybrid beads accumulate this dye more effectively than PG-only beads. Self-propelling gel beads have potential applications in removal/delivery of active agents in environmental or biological settings. The ability of self-assembling LMWGs to enhance mobility and control removal/delivery suggests that adding them to self-propelling systems can add significant value.     

Hierarchical assemblies of Si3N4 nanostructures

In the present work, for the first time, we report the growth of hierarchical assemblies of Si₃N₄ nanostructures via catalyst-assisted pyrolysis of a polymeric precursor on the Si substrates. The synthesized products were characterized by using field emission scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. It is found that the size of the catalytic droplet plays a critical role on the formation of hierarchical assemblies of Si₃N₄ nanostructures rather than common single nanowire. A mechanism based on the Vapor–Liquid–Solid (VLS) process was proposed for the assembly of hierarchical Si₃N₄ nanostructures.     

Synthesis and mesomorphism of ionic self-assembled complexes of anthraquinones

Anthraquinones are known to exhibit mesomorphism upon appropriate substitutions. In this report, the concept of ionic self-assembly has been applied to design and synthesise new anthraquinone-based liquid crystals. Four different anthraquinones were used as polyelectrolytes which form ionic complexes with double-tail ammonium surfactants. The chemical structures were characterised by spectral techniques and elemental analysis. The thermal behaviour of the complexes was investigated by polarising optical microscopy, differential scanning calorimetry, thermogravimetric analysis and X-ray diffraction studies. All these complexes display lamellar mesomorphism. The amphotropic nature of the complexes has also been studied.     

Synthesis of the Functional Hydrogels: Poly(N-isopropylacrylamide) Threaded onto the PEG Backbones Via RAFT

Functional poly(N-isopropylacrylamide) (PNIPAM) hydrogels were prepared by reversible addition fragmentation chain transfer (RAFT) polymerization of NIPAM in the presence of four-arm poly(ethylene glycol) (4A-PEG) as backbone and 4-cyanopentanoic acid dithiobenzoate functional α -cyclodextrin threaded onto the PEG as chain transfer reagent (CTA).The structure of the hydrogels was characterized in detail with FTIR techniques. The analytical results demonstrated that α -cyclodextrin remains in as-obtained hydrogels. The swelling behavior was investigated and the functional hydrogels (functional gels) showed accelerated shrinking kinetics and higher swelling ratio comparing with conventional hydrogel (CG). It could be attributed to the presence of dangling chains. The hydrogel exhibited rapid swelling and deswelling kinetics. In principle, the hydrogel might find a number of applications including an on-off system and drug delivery systems.     

Self-Assembling Catalytic Peptide Nanomaterials Capable of Highly Efficient Peroxidase Activity

The self-assembly of short peptides gives rise to versatile nanomaterials capable of promoting efficient catalysis. We have shown that short, seven-residue peptides bind hemin to produce functional catalytic materials which display highly efficient peroxidation activity, reaching a catalytic efficiency of 3×10⁵ m ⁻¹ s⁻¹. Self-assembly is essential for catalysis as non-assembling controls show no activity. We have also observed peroxidase activity even in the absence of hemin, suggesting the potential to alter redox properties of substrates upon association with the assemblies. These results demonstrate the practical utility of self-assembled peptides in various catalytic applications and further support the evolutionary link between amyloids and modern-day enzymes.     

Combinatorial and approximative analyses in a spatially random division process

For a spatial characteristic, there exist commonly fat-tail frequency distributions of fragment-size and -mass of glass, areas enclosed by city roads, and pore size/volume in random packings. In order to give a new analytical approach for the distributions, we consider a simple model which constructs a fractal-like hierarchical network based on random divisions of rectangles. The stochastic process makes a Markov chain and corresponds to directional random walks with splitting into four particles. We derive a combinatorial analytical form and its continuous approximation for the distribution of rectangle areas, and numerically show a good fitting with the actual distribution in the averaging behavior of the divisions.     

From Binuclear Complexes to Molecular Necklaces: Incorporating Flexible Ligands into Rotaxanes

The conversion of binuclear complexes into larger molecular necklaces can be achieved through rigidifying flexible ligands by threading them through a crown ether to form either an interpenetrated [2]pseudorotaxane or a permanently interlocked [2]rotaxane. The resulting complexes and assemblies are characterized by ¹H and DOSY NMR in solution and single‐crystal X‐ray diffraction in the solid‐state.     

Inhomogeneous Distribution of Cationic Surfactants around Anionic Molecular Clusters

An interesting phenomenon is reported when uranyl peroxide nanoclusters U₆₀ (Li_48+mK₁₂(OH)_m[UO₂(O₂)(OH)]₆₀ (H₂O)_n, m≈20 and n≈310) interact with a small number of cationic surfactant molecules. Cationic surfactant molecules do not distribute evenly around the U₆₀ clusters during the interaction as expected. Instead, a small fraction of U₆₀ clusters attract almost all the surfactant molecules, leading to the self-assembly into supramolecular structures by using surfactant–U₆₀ complexes as building locks, and later further aggregate and precipitate based on hydrophobic interaction, whereas the rest of the clusters remained unbounded soluble macroions in bulk dispersion. This phenomenon nicely demonstrates a unique feature of macroion solutions. Considering that Debye–Hückel approximation is no longer valid in such solutions, the competition between the local electrostatic interaction and hydrophobic interaction becomes important to regulate the solution behaviors of macroions.     

Dynamic Molecular Metamorphism Involving Palladium-Assisted Dimerization of π-Cation Radicals

A dynamic supramolecular approach is developed to promote the π-dimerization of viologen radicals at room temperature and in standard concentration ranges. The approach involves cis- or trans-protected palladium centers serving as inorganic hinges linking two functionalized viologens endowed with metal-ion coordinating properties. Based on detailed spectroscopic, electrochemical and computational data, we show that the one-electron electrochemical reduction of the viologen units in different dynamic metal/ligand mixtures leads to the formation of the same intramolecular π-dimer, regardless of the initial environment around the metallic precursor and of the relative ratio between metal and ligand initially introduced in solution. The large-scale electron-triggered reorganization of the building blocks introduced in solution thus involves drastic changes in the stoichiometry and stereochemistry of the palladium/viologen complexes proceeding in some cases through a palladium centered trans→cis isomerization of the coordinated ligands.     

Exploring the Effect of Ligand Structural Isomerism in Langmuir–Blodgett Films of Chiral Luminescent EuIII Self‐Assemblies

Here we have investigated the influence of the antenna group position on both the formation of chiral amphiphilic Eu^III‐based self‐assemblies in CH₃CN solution and, on the ability to form monolayers on the surface of quartz substrates using the Langmuir–Blodgett technique, by changing from the 1‐naphthyl ( 2(R) , 2(S) ) to the 2‐naphthyl ( 1(R) , 1(S) ) position. The evaluation of binding constants of the self‐ assemblies in CH₃CN solution was achieved using conventional techniques such as UV/Visible and luminescence spectroscopies along with more specific circular dichroism (CD) spectroscopy. The binding constants obtained for EuL , EuL₂ and EuL₃ species in the case of 2‐naphthyl derivatives were comparable to those obtained for 1‐naphthyl derivatives. The analysis of the changes in the CD spectra of 1(R) and 1(S) upon addition of Eu^III not only allowed us to evaluate the values of the binding constants but the resulting recalculated spectra may also be used as fingerprints for assignment of the chiral self‐assembly species formed in solution. The obtained monolayers were predominantly formed from EuL₃ (≈85 %) with the minor species present in ≈15 % EuL₂ .