Catalytic site-selective substrate processing within a tubular nanoreactor

Abstract

Chemists have long sought the ability to modify molecules precisely when presented with several sites of similar reactivity. We reasoned that the confinement of substrates within nanostructures might permit site-selective reactions unachievable in bulk solution, even with sophisticated reagents. In particular, the stretching and alignment of polymers within nanotubes might allow site-specific cleavage or modification. To explore this proposition, macromolecular disulfide substrates were elongated within members of a collection of tubular protein nanoreactors, which contained cysteine residues positioned at different locations along the length of each tube. For each nanoreactor, we defined the reactive location by using a set of polymer substrates (siteselectivity) and which of the two sulfur atoms was attacked (regioselectivity), and found that disulfide interchange occurs with atomic precision. Our strategy has potential for the selective processing of a wide variety of biomacromolecules, and the chemistry and substrates might be generalised yet further by using alternative nanotubes. The control of selectivity at the nanoscale has been a longstanding challenge for synthetic chemists. Two important aspects of this endeavour are site-selectivity-the ability to differentiate between two (or more) similarly reactive positions within a substrate molecule, and regioselectivity-the ability to distinguish between two (or more) sites within a given functional group 1,2. Realising selectivity in synthetic chemistry often requires exploitation Users may view, print, copy, and download text and data-mine the content in such documents, for the purposes of academic research, subject always to the full Conditions of use:

Towards explicit regulating-ion-transport: nanochannels with only function-elements at outer-surface

“…One of the important features of FE is of versatile physical and chemical properties, nanochannel-system adapt to a broad range of applications spanning from osmotic energy conversion devices 15 – 17 , 33 , 38 to biosensors 26 , 27 , 39 – 41 . Meanwhile, a nanochannel system combining with electrochemistry in a confined space is now a crucial promising field 42 , 43 , which is utilized to dynamically monitor the single molecule 44 , understand the chemical reaction 45 , characterize the single particle 46 , and probe single living cell 47 , etc. Here, we investigated whether the nanochannel-system in 3rd stage with FE OS explicit regulating-ion-transport could fulfill the applications above or even with special performances to the 1st and 2nd.…”

A Graphene‐Based Supramolecular Nanoreactor for the Fast Synthesis of Imines in Water

“…[1,2] So far, different types of nanoreactors have been explored: from those that are synthetically generated, such as nanopores or nanoholes, to the ones that are native to biological structures, such as protein pores, channels, or membrane-less organelles. [3][4][5][6][7][8] Micelle-based systems have been widely studied as they mimic the cells, the most relevant confined reactors in terms…”

“…[ 1,2 ] So far, different types of nanoreactors have been explored: from those that are synthetically generated, such as nanopores or nanoholes, to the ones that are native to biological structures, such as protein pores, channels, or membrane‐less organelles. [ 3–8 ]…”

Single‐Molecule Frequency Fingerprint for Ion Interaction Networks in a Confined Nanopore

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“…The microscopic view of this interaction network is important to understand the fundamental principles of ion and molecule transport through a nanopore down to atom‐scale [4] . Especially, the enhanced sensitivity in the nanopore‐based single‐molecule analysis is often achieved by strengthening the interaction between individual molecule and nanopore interface [5–10] . Currently, single‐channel recording is employed to study the molecules and ions transport through the nanopore.…”