Peptide-Functionalized Organotin Sulfide Clusters

Abstract

We report the first successful attachment of peptides to tin sulfide clusters. For proof of principle, H-L-Phe hydrazide and Boc-protected dipeptide hydrazides (Boc-L-Ala-L-Ala hydrazide and Boc-L-Val-L-Phe hydrazide) were reacted with keto-functionalized tin sulfide clusters [(R 1 Sn) 4 S 6 ] (A; R 1 = CMe 2 CH 2 C(O)Me) and [(R 1 Sn) 3 S 4 Cl] (B). In the first case, we obtained single crystals of an amino acid functionalized Sn/S cluster, [R 2 2 Sn 4 S 5 ] (1; R 2 = (CMe 2 CH 2 C(Me)-N 2 C(O)CH(CH 2 Ph)NC(Me)CH 2 CMe 2 ), formed after inorganic cluster rearrangement and intramolecular condensation of the amino acid ligand. By means of NMR spectroscopic investigations and ESI/LIFDI mass spectrometry, we demonstrate that both dipeptides are attached to B under retention of the original cluster architecture to yield [(R 3 Sn) 3 S 4 Cl] (2; R 3 = CMe 2 CH 2 C(NNH-Ala-Ala-Boc)Me) and [(R 4 Sn) 3 S 4 Cl] (3; R 4 = CMe 2 CH 2 C(NNH-Phe-Val-Boc)Me), as evident from mass spectrometric data of their cations [(R 3 Sn) 3 S 4 ] + (2 + ) and [(R 4 Sn) 3 S 4 ] + (3 + ).

Amino Acid Functionalized Organotin Trichlorides and Their Tin Sulfide Clusters

“…Reactions of compounds 1-3 with 1.00 eq of Na 2 S in an acetone water mixture at -10°C served to prepare clusters with "doppeldecker"-type structure, [(R AAc Sn) 4 S 6 ] (17)(18)(19). In contrast to the synthesis of the related keto functionalized compound [(R 1 Sn) 4 S 6 ], which precipitates after a few minutes from the reaction solution, [23] the clusters equipped with R AAc ligands do not precipitate at all.…”

“…[17][18][19] For reaching this goal two strategies are generally feasible: First, post-functionalization of pre-functionalized organotin sulfide clusters by an amino acid derivatives (AAc; Equation 1), and second, cluster formation under employment of CMe 2 CH 2 C(O)Me] and determined its structure by means of Xray diffraction. [17][18][19] For reaching this goal two strategies are generally feasible: First, post-functionalization of pre-functionalized organotin sulfide clusters by an amino acid derivatives (AAc; Equation 1), and second, cluster formation under employment of CMe 2 CH 2 C(O)Me] and determined its structure by means of Xray diffraction.…”

“…Beyond this background, we are currently interested in the formation of tin sulfide clusters with bio‐organic decoration to enable a more targeted study under physiological conditions . For reaching this goal two strategies are generally feasible: First, post‐functionalization of pre‐functionalized organotin sulfide clusters by an amino acid derivatives (AAc; Equation 1), and second, cluster formation under employment of corresponding bio‐organotin trichloride reactants (Equation 2).…”

Behavior of Organotin Sulfide Clusters towards Zinc Compounds

“…Furthermore, it enables derivatization of the organic ligand sphere by condensation reactions with hydrazines, hydrazones or hydrazides. This way, many different versions of ligand extensions have been realized, including biomolecules, chelating ligands and metallocenes, which were successfully attached to the clusters.…”

Specific Decoration of a Discrete Bismuth Oxido Cluster by Selected Peptides towards the Design of Metal Tags

“…Attachments of peptides to, for example, metals,m etal clusters, or to nanoparticles have been previously described in the literature and suggest interesting opportunities for (bio)functionalization. [15] Particularly,t he progressive exploitation of combinatorial strategies has enabled material scientists to select peptides equences from large libraries, which are precisely tailored for as pecific material/molecule of interestr anging from soft to hard matter over ab road range of sizes. [16] Here, we present an approach for identifying strongp eptide bindersf or 1,a llowing functionalization and attachment of the cluster to thiols, which are, besides for example amines, [9b, 10f, 17] often presented by biomolecules.…”