Giving the Green Light to Photochemical Uncaging of Large Biomolecules in High Vacuum

The isolation of biomolecules in a high vacuum enables experiments on fragile species in the absence of a perturbing environment. Since many molecular properties are influenced by local electric fields, here we seek to gain control over the number of charges on a biopolymer by photochemical uncaging. We present the design, modeling, and synthesis of photoactive molecular tags, their labeling to peptides and proteins as well as their photochemical validation in solution and in the gas phase. The tailored tags can be selectively cleaved off at a well-defined time and without the need for any external charge-transferring agents. The energy of a single or two green photons can already trigger the process, and it is soft enough to ensure the integrity of the released biomolecular cargo. We exploit differences in the cleavage pathways in solution and in vacuum and observe a surprising robustness in upscaling the approach from a model system to genuine proteins. The interaction wavelength of 532 nm is compatible with various biomolecular entities, such as oligonucleotides or oligosaccharides.</p

One-pot synthesis and AFM imaging of a triangular aramide macrocycle

Macrocyclizations in exceptionally good yields were observed during the self-condensation of N-benzylated phenyl p-aminobenzoates in the presence of LiHMDS to yield three-membered cyclic aramides that adopt a triangular shape. An ortho-alkyloxy side chain on the N-benzyl protecting group is necessary for the macrocyclization to occur. Linear polymers are formed exclusively in the absence of this Li-chelating group. A model that explains the lack of formation of other cyclic congeners and the demand for an N-(o-alkoxybenzyl) protecting group is provided on the basis of DFT calculations. High-resolution AFM imaging of the prepared molecular triangles on a calcite(10.4) surface shows individual molecules arranged in groups of four due to strong surface templating effects and hydrogen bonding between the molecular triangles