We present a new versatile route toward biomoleculefunctionalized tin sulfide clusters. A novel bifunctional orthogonal spacer was developed and used for the formation of a trifold azido-adamantylterminated cluster, serving as a building block for click reactions. The azido cluster was quantitatively bioconjugated via a strain-promoted 1,3-dipolar cycloaddition, affording a peptide-decorated cluster.
Azide–alkyl decorated organotin sulfide clusters were synthesized and further reacted to form peptide-decorated derivatives in solution via strain-promoted azide–alkyne cycloaddition as the key step.
Layered metal halides like BiI 3 are of current interest in connection with both 2D materials and photovoltaics.Here, we present a facile new method for the preparation of millimeter-sized BiI 3 single crystals. We use these crystals to study the surface reactivity of their (001) cleavage planes toward various environmental conditions by measuring morphological changes using atomic force microscopy and analyzing the formed species by means of X-ray photoelectron spectroscopy and X-ray diffraction methods. We find that freshly cleaved samples show atomically flat surface regions extending over several micrometers and reveal steps corresponding to single BiI 3 layers. However, we also find that the surface deteriorates in air on a time scale of hours. By studying samples cleaved and stored under different conditions, we identify water as the agent initiating the changes in surface morphology, while under inert gas and dry oxygen, the surface stays intact. On the basis of the analysis of deteriorated long-term-stored samples we identify BiOI as the main product of hydrolysis. We also observe a second long-term decomposition route for samples stored under dynamic vacuum, where formation of BiI whiskers occurs. Overall, our findings emphasize the challenges associated with the surface reactivity of BiI 3 but also demonstrate that well-ordered BiI 3 surfaces can be obtained, which indicates that preparation of extended, atomically smooth BiI 3 monolayers by exfoliation from bulk crystals should be possible.
In order to gain information about the behavior of tin sulfide clusters with bio‐organic ligand shells under acidic conditions, such as found in undesirable cells for instance, we systematically treated amino acid‐functionalized tin sulfide clusters with different acids. For Boc‐protected amino acid derivatives, we could show that this treatment causes either cleavage of the protecting group of the amino acid or protolysis of the tin sulfide core under release of H2S and formation of the correspondingly functionalized organotin trichloride, depending on the nature of the acid. This points towards a potential future use of such species for targeted cytotoxic applications.
We present a new synthesis of functionalized tin sulfide clusters via organotin trichlorides with boc-protected amino acids (R AAc SnCl 3 ). In this work we used non-polar (alanine, valine, leucine, phenylalanine and methionine), polar/neutral (serine and tyrosine) and basic (histidine) amino acids. We obtained single crystals from a Boc-protected valine derivative of the originally used organotin trichloride R 1 SnCl 3 [R 1 = [a]
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