Enantioselective Synthesis of a Chiral Coordination Polymer with Circularly Polarized Visible Laser

Circular dichroism is known to be the feature of a chiral agent which has inspired scientist to study the interesting phenomena of circularly polarized light (CPL) modulated molecular chirality. Although several organic molecules or assemblies have been found to be CPL‐responsive, the influence of CPL on the assembly of chiral coordination compounds remains unknown. Herein, a chiral coordination polymer, which is constructed from achiral agents, was used to study the CPL‐induced enantioselective synthesis. By irradiation with either left‐handed or right‐handed CPL during the reaction and crystallization, enantiomeric excesses of the crystalline product were obtained. Left‐handed CPL resulted in crystals with a left‐handed helical structure, and right‐handed CPL led to crystals with a right‐handed helical structure. It is exciting that the absolute asymmetric synthesis of a chiral coordination polymer could be enantioselective when using CPL, and provides a strategy for the control of the chirality of chiral coordination polymers.     

Inter-laboratory exercise with an aim to compare methods for 90Sr and 239,240Pu determination in environmental soil samples

In order to deliver reliable results for a multitude of different scenarios, e.g. emergency preparedness, environmental monitoring, nuclear decommissioning and waste management, there is a constant process of method development in the field of radioanalytical chemistry. This work presents the results of a method comparison exercise aimed at quantifying ⁹⁰Sr and ^239,240Pu in environmental soil samples, with the intention of evaluating the performance and applicability of different methods. From the methods examined in this work, recommendations are given in order to find a radioanalytical measurement procedure, for ⁹⁰Sr and ^239,240Pu analysis, which is fit-for-purpose for a particular scenario.

     

Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides

We performed a systematic study of soft X-ray absorption spectroscopy in various manganese oxides and fluorides. Both Mn L-edges and ligand (O and F) K-edges are presented and compared with each other. Despite the distinct crystal structure and covalent/ionic nature in different systems, the Mn-L spectra fingerprint the Mn valence and spin states through spectral lineshape and energy position consistently and evidently. The clear O- and F-K pre-edge features in our high resolution spectra enable a quantitative definition of the molecular orbital diagram with different Mn valence. In addition, while the binding energy difference of the O-1s core electrons leads to a small shift of the O-K leading edges between trivalent and quadrivalent manganese oxides, a significant edge shift, with an order of magnitude larger in energy, was found between divalent and trivalent compounds, which is attributed to the spin exchange stabilization of half-filled 3d system. This shift is much enhanced in the ionic fluoride system. This work provides the spectroscopic foundation for further studies of complicated Mn compounds.     

Polymerization of supramonomers: A new way for fabricating supramolecular polymers and materials

Supramolecular polymers and materials are attracting more and more attention nowadays due to their dynamic properties such as reversibility, stimuli-responsiveness and self-healing. Conventionally, bifunctional or multi-functional monomers are first covalently synthesized, followed by the supramolecular complexation to form supramolecular polymers and materials. Recently, we have proposed the supramonomer concept to construct supramolecular polymers and materials in a different way. Supramonomers are bifunctional or multi-functional monomers fabricated by noncovalent synthesis, but can undergo traditional covalent polymerization. In this highlight article, we will summarize and discuss the fabrication of supramonomer and covalent polymerization methods of supramonomers; fabrication of multi-responsive supramolecular polymers from supramonomers; and fabrication of supramolecular materials from supramonomers. It is highly anticipated that the supramonomer concept will enrich the methodology towards supramolecular polymers and materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 604–609     

An efficient electrochemical disinfection of E. coli and S. aureus in drinking water using ferrocene–PAMAM–multiwalled carbon nanotubes–chitosan nanocomposite modified pyrolytic graphite electrode

This work reported an efficient electrochemical treatment for drinking water disinfection using a pyrolytic graphite electrode modified with ferrocenyl tethered poly(amidoamine) dendrimers–multiwalled carbon nanotubes–chitosan nanocomposite. The influence parameters of electrochemical disinfection of Escherichia coli and Staphylococcus aureus, such as applied potential and sterilization time, were investigated. Further investigation indicated that almost all (99.99 %) of the initial bacteria were killed after applying a low potential of 0.4 V for 10 min. During the electrochemical disinfection process, the oxidized form of ferrocene was formed on electrode, which played a key role in the disinfection towards E. coli and S. aureus. Hence, the proposed method may provide potential application for the disinfection of drinking water.

Identification of urinary metabolites of imperatorin with a single run on an LC/Triple TOF system based on multiple mass defect filter data acquisition and multiple data mining techniques

The detection of drug metabolites, especially for minor metabolites, continues to be a challenge because of the complexity of biological samples. Imperatorin (IMP) is an active natural furocoumarin component originating from many traditional Chinese herbal medicines and is expected to be pursued as a new vasorelaxant agent. In the present study, a generic and efficient approach was developed for the in vivo screening and identification of IMP metabolites using liquid chromatography-Triple TOF mass spectrometry. In this approach, a novel on-line data acquisition method mutiple mass defect filter (MMDF) combined with dynamic background subtraction was developed to trace all probable urinary metabolites of IMP. Comparing with the traditionally intensity-dependent data acquisition method, MMDF method could give the information of low-level metabolites masked by background noise and endogenous components. Thus, the minor metabolites in complex biological matrices could be detected. Then, the sensitive and specific multiple data-mining techniques extracted ion chromatography, mass defect filter, product ion filter, and neutral loss filter were used for the discovery of IMP metabolites. Based on the proposed strategy, 44 phase I and 7 phase II metabolites were identified in rat urine after oral administration of IMP. The results indicated that oxidization was the main metabolic pathway and that different oxidized substituent positions had a significant influence on the fragmentation of the metabolites. Two types of characteristic ions at m/z 203 and 219 can be observed in the MS/MS spectra. This is the first study of IMP metabolism in vivo. The interpretation of the MS/MS spectra of these metabolites and the proposed metabolite pathway provide essential data for further pharmacological studies of other linear-type furocoumarins.