Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

A Structurally Robust Chiral Borate Ion: Molecular Design,Synthesis, and Asymmetric Catalysis

Catalysis by chiral weakly‐coordinating anions (WCAs) remains underdeveloped due to the lack of a molecular design strategy for exploiting their characteristics, such as the non‐nucleophilic nature. Here, we report the development of a chiral borate ion comprising an O,N,N,O‐tetradentate backbone, which ensures hitherto unattainable structural robustness. Upon pairing with a proton, the hydrogen borate acts as an effective catalyst for the asymmetric Prins‐type cyclization of vinyl ethers, providing access to structurally and stereochemically defined dihydropyrans. The key to selectivity control is the distinct ability of the borate ion to discriminate the prochiral faces of the acyclic oxonium ion intermediate and dictate the regiochemical outcome. We anticipate that this study paves the way for exploring the untapped potential of WCA catalysis for selective chemical synthesis.     

Synthesis,Structures, and Properties of Highly Strained Cyclophenylene–Ethynylenes with Axial and Helical Chirality

Single and double cyclophenylene–ethynylenes (CPEs) with axial and helical chirality have been synthesized by the Sonogashira cross-coupling of di- and tetraethynyl biphenyls with a U-shaped prearomatic diiodoparaphenylene followed by reductive aromatization. X-ray crystallographic analyses and DFT calculations revealed that the CPEs possess highly twisted bent structures. Bend angles on the edge of the paraphenylene units were close to the value of [5]cycloparaphenylene (CPP)—the smallest CPP to date. The double and single CPEs possessed stable chirality despite flexible biphenyl structures because of the high strain in the diethynyl–paraphenylene moiety. In both the single and double CPEs, orbital interactions along the biphenyl axis were observed by DFT calculations in LUMO and LUMO+2 of the single CPE and LUMO+1 of the double CPE, which likely cause lowering of these orbital energies. Concerning chiroptical properties: boosting of the g_abs value was observed in the biphenyl-based double CPE, as well as the binaphthyl-based single CPE, compared to the biphenyl-based single CPE.     

Enthalpy Relaxation Study of Poly(Vinyl Chloride) Films Based on the Time-Temperature Superposition Principle

Abstract

In the enthalpy relaxation of poly(vinyl chloride), a decrease in enthalpy upon the isothermal ageing was measured using the differential scanning calorimetry method as a function of ageing time (t_A) and ageing temperature. The range of the ageing temperature was from 56?°C (T_g ? 25?°C) to 72?°C (T_g ? 9?°C) where T_g denotes the glass transition temperature. The limiting value of the decrease in enthalpy was determined by applying a stretched exponential function to the measured enthalpy data. The relaxation function (?) was derived from the measured enthalpy and the construction of a master curve was tried by shifting the ? ? t_A curves of the respective ageing temperatures horizontally. Although there was no agreement between the shift factors (a_T) and the relaxation times of the ? ? t_A curves, the superposition was successfully constructed and the a_T values obtained for the poly(vinyl chloride) sample were found to be comparable to those reported for viscoelastic experiments over a broad temperature range above and below T_g carried out for different polymers. The origin of the decrease in enthalpy was briefly discussed in terms of the chain dynamics in the isothermal condition.     

An estimated quantitative lateral flow immunoassay for determination of artesunate using monoclonal antibody

There have been reports of fake artesunate (ART), which has led to deaths from untreated malaria in South East Asia. To rapidly screen for fake and adulterated ART products in the drug market, a lateral flow immunoassay (LFIA) based on a colloidal gold–monoclonal antibody probe for detection of ART within samples was developed. With this method, the calibration curve for ART was determined by the intensity ratio of the test and control bands at various ART concentrations. The linearity range was 12.5–200 μg/ml of ART. Samples were tested by the developed LFIA and can be calculated for ART contents. The levels of ART in the samples were also confirmed by enzyme-linked immunosorbent assay. The results of the two methods were in good conformance. The proposed LFIA was demonstrated to be a simple and rapid analytical method for detecting ART in the pharmaceutical formulation.     

Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer

Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 ⁵⁺, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 ⁵⁺ catalyzed ethane oxidation in the presence of H₂O₂ at a relatively low temperature. The site-selective complexation of 3 ⁵⁺ with an additional anionic porphyrin (TPPS⁴⁻) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 ⁵⁺ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS⁴⁻ to 3 ⁵⁺ enhanced the catalytic activity.     

Interpretation of the Role of Composition on the Inclusion Efficiency of Monovalent Cations into Cobalt Hexacyanoferrate

Cobalt hexacyanoferrate of various compositions was prepared in flow mode and the role of the vacancy on the structure, thermogravimetric (TG) properties, and the adsorption efficiency was studied. The material, Na_yCo[Fe(CN)₆]_1−x ⋅ z H₂O, with a minimum vacancy of x=0.014 to the highest x=0.47, was obtained. The TG-differential scanning calorimetry (DSC) profile showed a distinct influence of the vacancy on the water release temperature. Materials with x>0.35 showed a smooth release of water at a relatively lower temperature. However, for the materials with x<0.35, water release took place in multiple steps, suggesting the existence of various forms of water. The FTIR profiles supported the existence of free and bonded water molecules. However, the materials with multiple water peaks in the FTIR spectra showed a shift of the major XRD peaks when heated at 285 °C in N₂ atmosphere. Regarding the effect of the vacancy on the adsorption behavior, for NH₄, the adsorption was found to be proportional to the number of Na atoms in the material, confirming the ion-exchange process. On the contrary, the materials with low vacancy and high Na content showed nominal Cs adsorption capacity. Interestingly, the K adsorption capacity was found to be in between that of the other two ions. This means the ionic size decides the rate of placement into the interstitial sites. For larger ions like Cs, the ease of percolation via the vacancy decides the overall adsorption efficiency.     

Peripheral Modifications of meso-Hydroxyporphyrins: Formation of π-Electronic Anions and Ion-Pairing Assemblies

Phenyl groups were introduced at the β-positions proximal to the meso-hydroxy moiety in hydroxyporphyrin Ni^II complexes by oxidized BINAP Pd^II complexes. Ion-pairing assemblies of deprotonated π-electronic anions, anionic site of which was stabilized by the introduced phenyl moieties with a bulky cation, were formed. They showed charge-by-charge assemblies, assembly modes of which were modulated by the anionic building units.