A Dual Threat: Redox-Activity and Electronic Structures of Well-Defined Donor–Acceptor Fulleretic Covalent-Organic Materials

The effect of donor (D)–acceptor (A) alignment on the materials electronic structure was probed for the first time using novel purely organic porous crystalline materials with covalently bound two- and three-dimensional acceptors. The first studies towards estimation of charge transfer rates as a function of acceptor stacking are in line with the experimentally observed drastic, eight-fold conductivity enhancement. The first evaluation of redox behavior of buckyball- or tetracyanoquinodimethane-integrated crystalline was conducted. In parallel with tailoring the D-A alignment responsible for “static” changes in materials properties, an external stimulus was applied for “dynamic” control of the electronic profiles. Overall, the presented D–A strategic design, with stimuli-controlled electronic behavior, redox activity, and modularity could be used as a blueprint for the development of electroactive and conductive multidimensional and multifunctional crystalline porous materials.     

Five Years of ChemRxiv: Where We Are and Where We Go From Here**

ChemRxiv was launched on August 15, 2017 to provide researchers in chemistry and related fields a home for the immediate sharing of their latest research. In the past five years, ChemRxiv has grown into the premier preprint server for the chemical sciences, with a global audience and a wide array of scholarly content that helps advance science more rapidly. On the service's fifth anniversary, we would like to reflect on the past five years and take a look at what is next for ChemRxiv.     

A robust spin-coated optical sensing device for rapid determination of predominant metal ions in wastewater streams

The potential of an optical sensing material for determination of metal ions in wastewater streams is presented. The initial results in the development of a chromo-ionophore-based optical sensor for metal ions are detailed. An azo dye species, 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (BrPADAP), together with an ionophore and plasticiser was immobilised in a film of poly(vinyl chloride) (PVC). Initial investigations using the dye-impregnated sensing film showed a reproducible and reversible response to Pb(II) ions in aqueous solution. The response of this sensing film to Pb(II) at pH 6 was found to be linear in the 0.1-10 mg/L range, with a %RSD of 1.55%. The film can be regenerated by immersion in a low-pH buffer solution. The authors demonstrate how this method shows potential for analysis using once-off sensing probes. The sensing film response for Pb(II) occurs within 30 s.     

A multilayer composite separator consisting of non-woven mats and ceramic particles for use in lithium ion batteries

Battery separator is a porous membrane that is placed between the positive and negative electrodes to avoid their electric contact, while maintaining a good ionic flow through the liquid electrolyte filled in its pores. Non-woven mats have been evaluated as battery separators due to their highly porous structures. In this study, composite non-woven mats were fabricated through electrospinning and lamination with a ceramic layer, and evaluated as lithium ion battery separators. The lamination with the ceramic layer provides not only improved separator dimensional stability at elevated temperatures but also the potential to increase the production rate of electrospun separators. The electrospun mats keep ceramic particles from dropping avoiding the non-uniform current density distribution caused by the loss of the ceramic particles. The composite separators enabled good ionic conductivity when saturated with a liquid electrolyte. Coin cells with this type of separators showed not only stable cycling performance but also good rate capabilities at room temperature.     

Paper spray tandem mass spectrometry: A rapid approach for the assay of parabens in cosmetics and drugs

A fast methodology for the assay of parabens in drug and cosmetic preparations has been presented. The procedure developed is based on paper spray tandem mass spectrometry and isotope dilution approach. For each investigated paraben, the corresponding labeled standard has been used in order to improve the accuracy and reproducibility of the analyses. The MS experiments have been performed under MRM conditions, monitoring the transitions [M‐H]^? → m/z 92 and [M‐H]^? → m/z 98, respectively, for each analyte and the corresponding labeled internal standard. The quantitative assay has been performed using a calibration curve built from 2 to 15 mg/L. The method accuracy, in all case near 100%, was evaluated using fortified samples at two concentration levels, which are representative of the lower and the higher portion of calibration curve. The good values of LOQ, LOD, and reproducibility confirm the consistency of the developed approach.     

Reaction of α-Pinene and β-Pinene with Diethyl Hydrogen Phosphite Under Free Radical Conditions

We have found that α-pinene and β-pinene react with diethyl hydrogen phosphite (DEHP) and di-tert-butyl peroxide (TOOT) to form both mono- and diphosphonates. When the reaction was catalyzed by TOOT at 140-150[ddot]C, the major products were diphosphonates. Under comparatively mild initiation by benzoyl. peroxide at 80[ddot]C monophosphonate adducts were the major products.     

Ritter Reactions between Alcohols and Acetonitrile Mediated by the Conducting Polymer Poly-(3,4-ethylenedioxy Thiophene) (PEDOT)

Herein, we report new reactivity of the conducting polymer, poly-(3,4-ethylenedioxy thiophene) (PEDOT), where PEDOT mediates a Ritter reaction between alcohols and acetonitrile. The yields were variable and in most cases competitive with results obtained using sulfuric acid. Attempts at a stoichiometric reaction between benzonitrile and diphenylmethanol are also reported herein. Finally, described here are preliminary mechanistic studies that suggest PEDOT is behaving as an alcohol-selective or specific Lewis acid.

Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for full experimental and spectral details.     

Kinetic aspects of non-linear effects in asymmetric synthesis,catalysis, and autocatalysis

The Kagan ML_n models developed for rationalizing non-linear effects of catalyst enantiopurity have become a valuable mechanistic tool for probing complex asymmetric catalytic reactions. This work demonstrates how these models also provide clues about reactivity that may be used for further evidence to test a mechanistic hypothesis. Special considerations for probing non-linear effects in asymmetric synthesis using stoichiometric chiral auxiliaries and in asymmetric autocatalysis are highlighted in comparison with asymmetric catalysis.