Nanoparticles made of metal-organic frameworks (nanoMOFs) attract a growing interest in gas storage, separation, catalysis, sensing and more recently, biomedicine. Achieving stable, versatile coatings on highly porous nanoMOFs without altering their ability to adsorb molecules of interest represents today a major challenge. Here we bring the proof of concept that the outer surface of porous nanoMOFs can be specifically functionalized in a rapid, biofriendly and non-covalent manner, leading to stable and versatile coatings. Cyclodextrin molecules bearing strong iron complexing groups (phosphates) were firmly anchored to the nanoMOFs' surface, within only a few minutes, simply by incubation with aqueous nanoMOF suspensions. The coating procedure did not affect the nanoMOF porosity, crystallinity, adsorption and release abilities. The stable cyclodextrin-based coating was further functionalized with: i) targeting moieties to increase the nanoMOF interaction with specific receptors and ii) poly(ethylene glycol) chains to escape the immune system. These results pave the way towards the design of surface-engineered nanoMOFs of interest for applications in the field of targeted drug delivery, catalysis, separation and sensing.

Three novel gold nanoparticles containing multiple long, flexible linkers decorated with lactose, β-cyclodextrin, and both simultaneously have been prepared. The interaction of such nanoparticles with β-d-galactose-recognizing lectins peanut agglutinin (PNA) and human galectin-3 (Gal-3) was demonstrated by UV-vis studies. Gal-3 is well-known to be overexpressed in several human tumors and can act as a biorecognizable target. This technique also allowed us to estimate their loading capability toward the anticancer drug methotrexate (MTX). Both results make these glyconanoparticles potential site-specific delivery systems for anticancer drugs.

Nanoparticles made of metal-organic frameworks (nanoMOFs) are becoming of increasing interest as drug carriers. However, preventing nanoMOFs recognition and clearance by the innate immune system, a prerequisite for biomedical applications, presents an important challenge. In this study we provide a proof of concept that the outer surface of biocompatible iron-based nanoMOFs can be functionalized in a rapid, organic solvent-free and non-covalent manner using a novel family of comb-like copolymers made of dextran (DEX) grafted with both poly(ethylene glycol) (PEG) and alendronate (ALN) moieties. We describe the synthesis and full characterization of DEX-PEG-ALN copolymers by click chemistry, with control of both the amount of grafted PEG and ALN moieties. The copolymers, freely soluble in aqueous media, were used to directly coat the nanoMOFs in water by simple incubation at room temperature. The coating procedure did not affect the nanoMOFs' morphology nor their crystalline structure. As strong iron complexing groups, the ALN moieties ensured multiple cooperative anchoring of the copolymers to the nanoMOFs surface, resulting in stable coatings that substantially decreased their internalization by macrophages in vitro, providing new perspectives for biomedical applications.

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Two citric acid crosslinked γ-cyclodextrin oligomers (pγ-CyD) with a MW of 21-33 kDa and 10-15 γ-CyD units per molecule were prepared by following green chemistry methods and were fully characterized. The non-covalent association of doxorubicin (DOX) with these macromolecules was investigated in neutral aqueous medium by means of circular dichroism (CD), UV-vis absorption and fluorescence. Global analysis of multiwavelength spectroscopic CD and fluorescence titration data, taking into account the DOX monomer-dimer equilibrium, evidenced the formation of 1 : 1 and 1 : 2 pγ-CyD unit-DOX complexes. The binding constants are 1-2 orders of magnitude higher than those obtained for γ-CyD and depend on the characteristics of the oligomer batch used. The concentration profiles of the species in solution evidence the progressive monomerization of DOX with increasing oligomer concentration. Confocal fluorescence imaging and spectral imaging showed a similar drug distribution within the MCF-7 cell line incubated with either DOX complexed to pγ-CyD or free DOX. In both cases DOX is taken up into the cell nucleus without any degradation.

Nanobiosensors are convenient, practical, and sensitive analyzers that detect chemical and biological agents and convert the results into meaningful data between a biologically active molecule and a recognition element immobilized on the surface of the signal transducer by a physicochemical detector. Due to their fast, accurate and reliable operating characteristics, nanobiosensors are widely used in clinical and nonclinical applications, bedside testing, medical textile industry, environmental monitoring, food safety, etc. They play an important role in such critical applications. Therefore, the design of the biosensing interface is essential in determining the performance of the nanobiosensor. The unique chemical and physical properties of nanomaterials have paved the way for new and improved sensing devices in biosensors. The growing demand for devices with improved sensing and selectivity capability, short response time, lower limit of detection, and low cost causes novel investigations on nanobiomaterials to be used as biosensor scaffolds. Among all other nanomaterials, studies on developing nanobiosensors based on metal oxide nanostructures, graphene and its derivatives, carbon nanotubes, and the widespread use of these nanomaterials as a hybrid structure have recently attracted attention. Nanohybrid structures created by combining these nanostructures will directly meet the future biosensors’ needs with their high electrocatalytic activities. This review addressed the recent developments on these nanomaterials and their derivatives, and their use as biosensor scaffolds. We reviewed these popular nanomaterials by evaluating them with comparative studies, tables, and charts.

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