The cover image, by James Gardiner et al., is based on the Research Article 4‐Halogeno‐3,5‐dimethyl‐1H‐pyrazole‐1‐carbodithioates: versatile reversible addition fragmentation chain transfer agents with broad applicability, DOI: . Note: MAMs and LAMs are acronyms for more and less activated monomers.
Pyrazole-based dithiocarbamates are versatile reversible addition fragmentation chain transfer (RAFT) agents that provide molar mass and dispersity (Ð) control over the radical polymerization of both more and less activated monomers (MAMs and LAMs). In this paper we report on theoretical and experimental findings demonstrating that their activity as RAFT agents can be significantly enhanced by introducing electron-withdrawing substituents to the pyrazole ring. This enhancement is most noticeable in methyl methacrylate polymerization where product molar masses are more accurately predicted by the RAFT agent concentration, and significantly lower Ð values, with respect to those seen with the parent RAFT agent under similar conditions, are observed. Thus, use of 4-chloro-3,5-dimethyl-1H-pyrazole-1-carbodithioate provides a poly(methyl methacrylate) with the anticipated molar mass and Ð as low as 1.3 at high monomer conversion. Good control is retained for monosubstituted MAMs, styrene, methyl acrylate and N,N-dimethylacrylamide. Low dispersities and less molar mass control are also achieved for homoand copolymerizations with the LAM vinyl acetate, albeit with some retardation.
The self-organizing map with relational perspective mapping
(SOM-RPM)
is an unsupervised machine learning method that can be used to visualize
and interpret high-dimensional hyperspectral data. We have previously
used SOM-RPM for the analysis of time-of-flight secondary ion mass
spectrometry (ToF-SIMS) hyperspectral images and three-dimensional
(3D) depth profiles. This provides insightful visualization of features
and trends of 3D depth profile data, using a slice-by-slice view,
which can be useful for highlighting structural flaws including molecular
characteristics and transport of contaminants to a buried interface
and characterization of spectra. Here, we apply SOM-RPM to stitched
ToF-SIMS data sets, whereby the stitched data are used to train the
same model to provide a direct comparison in both 2D and 3D. We conduct
an analysis of spin-coated polyaniline (PANI) films on indium tin
oxide-coated glass slides that were subjected to heat treatment under
atmospheric conditions to model PANI as a conformal aerospace industry
coating. Replicates were shown to be precisely equivalent, both spatially
and by composition, indicating a clear threshold for annealing of
the film. Quantitative assessment was performed on the chemical breakdown
trends accompanying annealing based on peak ratios, while spectral
analysis alone shows only very subtle differences which are difficult
to evaluate quantitatively. The SOM-RPM method considers data sets
in their totality and highlights subtle differences between samples
often simply differences in peak intensity ratios.
This work describes the Diels–Alder reaction of the naturally occurring substituted butadiene, myrcene, with a range of different naturally occurring and synthetic dienophiles. The synthesis of the Diels–Alder adduct from myrcene and acrylic acid, containing surfactant properties, was scaled-up in a plate-type continuous-flow reactor with a volume of 105 mL to a throughput of 2.79 kg of the final product per day. This continuous-flow approach provides a facile alternative scale-up route to conventional batch processing, and it helps to intensify the synthesis protocol by applying higher reaction temperatures and shorter reaction times.
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