This communication presents a partial
historical summary of some
of Iowa State University’s Chemistry Department teaching response
to the shift to online course delivery caused by the COVID-19 pandemic.
The observations reflect discussions between and informal surveys
of an instructor cohort that impacted roughly 1200 undergraduate students.
These students were enrolled in general chemistry I, organic chemistry
II, inorganic chemistry, quantum mechanics, and chemistry for non-physical-science
majors. The paper highlights the challenges faced and describes how
faculty and students met them.
Aspartic
proteases use a pair of carboxylic acids to activate water
molecules for nucleophilic attack. Here we report a nanoparticle catalyst
with a similar catalytic motif capable of generating a hydroxide ion
in its active site even under acidic reaction conditions. The synthetic
enzyme accelerated the hydrolysis of para-nitrophenyl
acetate (PNPA) by 91 000 times and could also hydrolyze nonactivated
aryl esters at pH 7. The distance between the two acids and, in particular,
the flexibility of the catalytic groups in the active site controlled
the catalytic efficiency. The synthetic enzyme readily detected the
addition of a single methyl on the acyl group of the substrate, as
well as the substitution pattern on the phenyl ring.
Distinction
of chemical functionality by their local chemical environment
is a skill mastered by enzymes, evident from the selective synthesis,
cleavage, and transformation of peptides, nucleic acids, and polysaccharides
that abound with the same type of functional group. In contrast, synthetic
catalysts are generally better at differentiating functional groups
based on their electronic and steric properties. Here, we report artificial
epoxidases prepared through the molecular imprinting of surface–core
doubly cross-linked micelles, followed by efficient functionalization
of the imprinted site in the micellar core via photoaffinity labeling.
The size and shape of the active sites are tuned by the modularly
synthesized templates, with the oxygen-delivering peroxy acid group
positioned accurately. These catalysts are used in the epoxidation
of alkenes in water with hydrogen peroxide under mild conditions without
any additional additives. Most importantly, atomic precision is achieved
in the catalysis and enables alkenes to be distinguished that differ
in the position of the carbon–carbon double bond by a single
carbon.
Nature has a remarkable ability to perform selective transformation of complex biological mixtures into desired products using enzymatic catalysts. We report the preparation of nanoparticle catalysts through molecular imprinting within crosslinked micelles. These catalysts were highly selective for their targeted substrates and could selectively hydrolyze less reactive acetals over more reactive ones even under basic conditions. Their catalytic activity and selectivity were tunable through rational postmodification of the active site. These properties enabled the nanoparticle catalysts to produce the desired β-nitro alcohol from a four-component acetal mixture in a tandem deprotection/Henry reaction that required incompatible acidic and basic catalysts in the two steps.
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