Anionic boron cluster compounds (ABCCs) are intrinsically amphiphilic building blocks suitable for nanochemistry. ABCCs are involved in atypical weak interactions, notably dihydrogen bonding, due to their peculiar polyhedral structure, consisting of negatively charged B–H units. The most striking feature of ABCCs that differentiates them from typical surfactants is the lack of head-and-tail structure. Furthermore, their structure can be described as intrinsically amphiphilic or aquaneutral. Therefore, classical terms established to describe self-assembly of classical amphiphiles are insufficient and need to be reconsidered. The opinions and theories focused on the solution behavior of ABCCs are briefly discussed. Moreover, a comparison between ABCCs with other amphiphilic systems is made focusing on the explanation of enthalpy-driven micellization or relations between hydrophobic and chaotropic effects. Despite the unusual structure, ABCCs still show self- and coassembly properties comparable to classical amphiphiles such as ionic surfactants. They self-assemble into micelles in water according to the closed association model. The most typical features of ABCCs solution behavior is demonstrated on calorimetry, NMR spectroscopy, and tensiometry experiments. Altogether, the unique features of ABCCs makes them a valuable inclusion into the nanochemisty toolbox to develop novel nanostructures both alone and with other molecules.

The present study describes the synthesis, self-assembly and responsiveness to glucose and lactic acid of biocompatible and biodegradable block copolymer micelles using phenylboronic ester as the linkage between hydrophobic poly(ε-caprolactone) (PCL) and hydrophilic poly(ethylene oxide) (PEO). The PCL block with pendant phenylboronic acid (PCLBA) was synthesized by combining ε-caprolactone (ε-CL) ring-opening polymerisation (ROP), using 4-hydroxymethyl(phenylboronic) acid pinacolate as the initiator, and pinacol deprotection. The glucose-terminated PEO (PEOGlc) was prepared by 1,3-dipolar, Cu(I)-catalysed, alkyne–azide cycloaddition of α-methoxy-ω-propargyl poly(ethylene oxide) and 1-azido-1-deoxy-D-glucopyranose. All new compounds were evaluated by ¹H NMR spectroscopy and by SEC analysis. PCLBA and PEOGlc blocks were linked in NaOH acetone solution, which was indirectly confirmed by Alizarin Red S fluorescence and directly by ¹H NMR spectroscopy. Dialysis against Milli-Q water induced the self-assembly of PCLBA-b-PEOGlc nanoparticles, which were characterised by static (SLS) and dynamic (DLS) light scattering and by cryogenic transmission electron microscopy (cryo-TEM). Furthermore, the microscopic properties of the charged interface between the hydrophobic PCLBA core and the hydrophilic PEOGlc shell were examined by electrophoretic light scattering (zeta potential) and by fluorescence spectroscopy using the fluorescent probe 5-(N-dodecanoyl)aminofluorescein (DAF) as a pH indicator. Subsequently, the nanoparticles were transferred to a phosphate buffer saline (PBS) solution supplemented with different concentrations of glucose to simulate the physiological conditions in blood or lactic acid to simulate acidic cytosolic or endosomal conditions in tumour cells. Adding a surplus of glucose or lactic acid, which competitively binds to PBA, removes the stabilising hydrophilic PEOGlc blocks, thereby triggering marked nanoparticle aggregation. However, the rate of aggregation induced by lactic acid is considerably faster than that induced by glucose, as confirmed by light scattering. Thus, this novel block copolymer may contribute to the field of selective, lactic acid- and/or glucose-responsive drug delivery vehicle design under both pathological and physiological conditions.

Amphiphilic triblock terpolymers have attractive applications in the preparation of nanoparticles with controlled morphology. An additional level of morphology control can be provided by reactive blocks, whose interactions with the solvent vary under different stimuli. In this work, we synthesized a triblock terpolymer (poly(acrylic acid)-b-poly(4-hydroxystyrene)-b-poly{1-[4-(1-methyl-1,2-dicarba-closo-dodecaborane-2-yl methyl)-phenyl]ethylene}) (PAA-b-PHS-b-PSC) containing carboranes as pendant groups by reversible addition fragmentation chain transfer (RAFT) polymerization and subsequently studied its behavior in aqueous solution. Once the nanoparticles were formed, the solubility of the second and third blocks was changed via pH and CsF reactions, respectively. The resulting micelles work as an ON/OFF system, using changes in fluorescence intensity at different pH values.