After uptake by U87 MG and A375 cancer cells, cobaltabisdicarbollide [COSAN] distributes between membrane and nucleus and presents no relevant cytotoxicity against both cell lines even for long incubation times. The cytotoxicity of Na[COSAN] was also tested towards one normal cell line, the V79 fibroblasts, in order to ascertain the noncytotoxic profile of the compound. As the cell's nucleus contains DNA, the interaction between [COSAN] and double-stranded calf thymus DNA (CT-dsDNA) has been investigated. There is a strong interaction between both molecules forming a nanohybrid CT-dsDNA-[COSAN] biomaterial, which was fully characterized. Moreover, Na[COSAN] shows characteristic redox peaks ascribed to the oxidation/reduction of Co at a formal potential of -1.444 V and it can be accumulated at a surface-immobilized DNA layer of glassy carbon electrodes. The equilibrium surface-binding constants (K /K ), which confirm that [COSAN] interacts with DNA by an intercalative or electrostatic mode, depending on the ionic strength of the solution, were estimated. In addition, high binding affinity of Na[COSAN] to proteins was observed by B{ H} NMR and confirmed in vivo. Finally, biodistribution studies of [COSAN] in normal mice were run. After administration, Na[COSAN] was distributed into many organs but mainly accumulated in the reticuloendothelial system (RES), including liver and spleen. After 1 h, the formation of aggregates by plasma protein interaction plays a role in the biodistribution profile; the aggregates accumulate mostly in the lungs. Na[COSAN], which displays low toxicity and high uptake by relevant cancer cells accumulating boron within the nucleus, could act as a suitable compound for further developments as boron neutron capture therapy (BNCT) agents.
Nature provides copious examples of self-assembling supramolecular nanofibers. Among them, amyloid structures have found amazing applications as advanced materials in fields such as biomedicine and nanotechnology. Prions are a singular subset of proteins able to switch between a soluble conformation and an amyloid state. The ability to transit between these two conformations is encoded in the so-called prion domains (PrDs), which are long and disordered regions of low complexity, enriched in polar and uncharged amino acids such as Gln, Asn, Tyr, Ser, and Gly. The polar nature of PrDs results in slow amyloid formation, which allows kinetic control of fiber assembly. This approach has been exploited for fabrication of multifunctional materials because in contrast to most amyloids, PrDs lack hydrophobic stretches that can nucleate their aggregation, their assembly depends on the establishment of a large number of weak interactions along the complete domain. The length and low complexity of PrDs make their chemical synthesis for applied purposed hardly affordable. Here, we designed four minimalist polar binary patterned peptides inspired in PrDs, which include the [Q/N/G/S]-Y-[Q/N/G/S] motif frequently observed in these domains: NYNYNYN, QYQYQYQ, SYSYSYS, and GYGYGYG. Despite their small size, they all recapitulate the properties of full-length PrDs, self-assembling into nontoxic amyloids under physiological conditions. Thus, they constitute small building blocks for the construction of tailored prion-inspired nanostructures. We exploited Tyr residues in these peptides to generate highly stable dityrosine cross-linked assemblies for the immobilization of metal nanoparticles in the fibrils surface and to develop an electrocatalytic amyloid scaffold. Moreover, we show that the shorter and more polar NYNNYN, QYQQYQ, and SYSSYS hexapeptides also self-assemble into amyloid-like structures, consistent with the presence of these tandem motifs in human prion-like proteins.
An inorganic sandwich molecule, Na[Co(C 2 B 9 H 11 ) 2 ], able to produce vesicles through self-assembly and known to produce strong dihydrogen-bond interactions with amine groups is capable of interacting with proteins.T his dual non-bonding ability of Na[Co(C 2 B 9 H 11 ) 2 ]i sw hat makes this molecule unique:i tc an be firmly anchored to ap rotein surface and is capable of extending over it. To prove this, the widely available bovine serum albumin( BSA), which has many pendanta mino groups in its structure, has been taken as the model protein. It has been found that around 100 molecules of Na[Co(C 2 B 9 H 11 ) 2 ]p reserve the native structure of BSA, while endorsing it with as ignificantly increased sta-bility with respectt oc hemical-and thermal-inducedd enaturation due to efficient encapsulation. The advantages of this encapsulation technique are two-fold; the first is its simplicity as it relies on the anchoring capacity of Na[Co(C 2 B 9 H 11 ) 2 ] to the surface of the protein through the amine-containing residues and the second is its self-assembling capacity allowing it to spread across the surface. The dense shield of protection offered by Na[Co(C 2 B 9 H 11 ) 2 ]h as been demonstrated by the inhibition of BSA pseudo-esterase activity,w hich indicates that the inorganic corset around BSA protects its reactive surface residues,thereby preventing their acetylation.
The electrochemical behaviour of metallocarborane sodium salts and their interactions with DNA have been studied. They are shown to be selective redox indicators with wide-ranging potential as electrochemical indicators in DNA biosensors.
The development of new types of ion conducting materials is one of the most important challenges in the field of energy. Lithium salt polymer electrolytes have been the most convenient, and thus the most widely used in the design of the new generation of batteries. However, in this work, we have observed that Na ions provide a higher conductivity, or at least a comparable conductivity to that of Li ions in the same basic material. This provides an excellent possibility to use Na ions in the design of a new generation of batteries, instead of lithium, to enhance conductivity and ensure wide supply. Our results indicate that the dc-conductivity is larger when the anion is [Co(CBH)], [COSANE], compared to tetraphenylborate, [TPB]. Our data also prove that the dc-conductivity behavior of Li and Na salts is opposite with the two anions. At 40 °C, the conductivity values change from 1.05 × 10 S cm (Li[COSANE]) and 1.75 × 10 S cm (Na[COSANE]) to 2.8 × 10 S cm (Li[TPB]) and 1.5 × 10 S cm (Na[TPB]). These findings indicate that metallacarboranes can be useful components of mixed matrix membranes (MMMs), providing excellent conductivity when the medium contains sufficient amounts of ionic components and a certain degree of humidity.
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