Messages de Rogue Scholar

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Publié in Henry Rzepa's Blog

The topic of this post originates from a recent article which is attracting much attention.[cite]10.1038/s41586-019-1059-9[/cite] The technique uses confined light to both increase the spatial resolution by around three orders of magnitude and also to amplify the signal from individual molecules to the point it can be recorded. To me, Figure 3 in this article summarises it nicely (caption: visualization of vibrational normal modes ).

Publié in Henry Rzepa's Blog

Students learning organic chemistry are often asked in examinations and tutorials to devise the mechanisms (as represented by curly arrows) for the core corpus of important reactions, with the purpose of learning skills that allow them to go on to improvise mechanisms for new reactions.

Publié in Henry Rzepa's Blog

The title of this post comes from the site www.crossref.org/members/prep/ Here you can explore how your favourite publisher of scientific articles exposes metadata for their journal. Firstly, a reminder that when an article is published, the publisher collects information about the article (the “metadata”) and registers this information with CrossRef in exchange for a DOI.

Publié in Henry Rzepa's Blog

The Book of Kells is a spectacularly illuminated gospel manuscript dating from around 800AD and held in Trinity College library in Dublin. Some idea of the colours achieved can be seen below.  #gallery-2 { margin: auto; } #gallery-2 .gallery-item { float: left; margin-top: 10px; text-align: center; width: 33%; } #gallery-2 img { border: 2px solid #cfcfcf;

Publié in Henry Rzepa's Blog

There is emerging interest in cyclic conjugated molecules that happen to have triplet spin states and which might be expected to follow a 4n rule for aromaticity.[cite]10.1002/anie.201705228[/cite] The simplest such system would be the triplet state of cyclobutadiene, for which a non or anti-aromatic singlet state is always found to be lower in energy. Here I explore some crystal structures containing this motif for possible insights.

Publié in Henry Rzepa's Blog

Five years back, I speculated about the mechanism of the epoxidation of ethene by a peracid, concluding that kinetic isotope effects provided interesting evidence that this mechanism is highly asynchronous and involves a so-called “hidden intermediate”. Here I revisit this reaction in which a small change is applied to the atoms involved. Below are two representations of the mechanism.

Publié in Henry Rzepa's Blog

Here is the concluding part of my exploration of a recently published laboratory experiment for undergraduate students.[cite]10.1021/acs.jchemed.7b00566[/cite] I had previously outlined a possible mechanistic route, identifying TS3 (below) as the first transition state in which C-C bond formation creates two chiral centres.

Publié in Henry Rzepa's Blog

Recently, the 100th anniversary of the birth of the famous chemist Derek Barton was celebrated with a symposium. One of the many wonderful talks presented was by Tobias Ritter and entitled “ Late-stage fluorination for PET imaging ” and this resonated for me. The challenge is how to produce C-F bonds under mild conditions quickly so that 18 F-labelled substrates can be injected for the PET imaging.

Publié in Henry Rzepa's Blog

I am exploring the fascinating diverse facets of a recently published laboratory experiment for undergraduate students.[cite]10.1021/acs.jchemed.7b00566[/cite] Previously I looked at a possible mechanistic route for the reaction between an enal (a conjugated aldehyde-alkene) and benzyl chloride catalysed by base and a chiral amine, followed by the use of NMR coupling constants to assign relative stereochemistries.