Over the last three decades, proteins and peptides have attracted great interest as drugs of choice for combating a broad spectrum of diseases, including diabetes mellitus, cancer, and infectious and neurological diseases. However, the delivery of therapeutic proteins to target sites should take into account the obstacles and limitations related to their intrinsic sensitivity to different environmental conditions, fragile tertiary structures, and short half-life. Polymeric nanostructures have emerged as competent vehicles for protein delivery, as they are multifunctional and can be tailored according to their peculiarities. Thus, the enhanced bioavailability and biocompatibility, the adjustable control of physicochemical features, and the colloidal stability of polymer-based nanostructures further enable either the embedding or conjugation of hydrophobic or hydrophilic bioactive molecules, which are some of the features of paramount importance that they possess and which contribute to their selection as vehicles. The present review aims to discuss the prevalent nanostructures composed of block copolymers from the viewpoint of efficient protein hospitality and administration, as well as the up-to-date scientific publications and anticipated applications of polymeric nanovehicles containing proteins and peptides.

This review article aims to cover the most recent advances regarding the synthesis of linear ABC-type triblock terpolymers and star-shaped polymers by RAFT polymerization, as well as their self-assembly properties in aqueous solutions. RAFT polymerization has received extensive attention, as it is a versatile technique, compatible with a great variety of functional monomers and reaction conditions, while providing exceptional and precise control over the final structure, with well-defined side-groups and post-polymerization engineering potential. Linear triblock terpolymers synthesis can lead to very interesting novel ideas, since there are countless combinations of stimuli/non-stimuli and hydrophilic/hydrophobic monomers that someone can use. One of their most interesting features is their ubiquitous ability to self-assemble in different nanostructures depending on their degree of polymerization (DP), block composition, solubilization protocol, internal and external stimuli. On the other hand, star-shaped polymers exhibit a more stable nanostructure, with a distinct crosslinked core and arm blocks that can also incorporate stimuli-responsive blocks for “smart” applications.

We report on the utilization of the amphiphilic poly[quaternized (2-(N,N-dimethylamino) ethyl methacrylate)]-co-(lauryl methacrylate))-b-poly[(oligo ethylene glycol) methyl ether methacrylate] QP(DMAEMA-co-LMA)-b-POEGMA cationic diblock terpolymer aggregates as nanocarriers for insulin delivery applications. QP(DMAEMA-co-LMA)-b-POEGMA random diblock terpolymer is derived from the chemical modification of the precursor amino diblock copolymer via quaternization, producing permanent positive charges on the macromolecular chain. The QP(DMAEMA-co-LMA)-b-POEGMA diblock terpolymer as well as its amino precursor investigated self-assemble in aqueous media, forming aggregates. In vitro cytotoxicity and in vivo biocompatibility studies on QP(DMAEMA-co-LMA)-b-POEGMA and its amino precursor aggregates, showed good cytocompatibility and biocompatibility. QP(DMAEMA-co-LMA)-b-POEGMA aggregates were chosen to be complexed with insulin due to their self-assembly features and the permanent positive charge in each amino group. QP(DMAEMA-co-LMA)-b-POEGMA aggregates were complexed with insulin through electrostatic interactions. Light scattering techniques were used in order to study the ability of the polymer aggregates to complex with insulin, to determine critical physicochemical parameters such as size, mass, and surface charge of the stable complexes and study the effect of salt addition on their properties. The results showed that in both cases, the complexation process was successful and as the insulin concentration increases, nanosized complexes of different physicochemical characteristics (mass, size, surface charge) and spherical morphology are formed. UV-Vis and fluorescence spectroscopy studies showed that no conformational changes of insulin occurred after the complexation.

In this work, the synthesis and the aqueous solution self-assembly behavior of novel partially hydrophobically modified poly(2-(dimethylamino) ethyl methacrylate)-b-poly(oligo(ethylelene glycol) methyl ether methacrylatetabel) pH and temperature responsive random diblock copolymers (P(DMAEMA-co-Q_6/12DMAEMA)-b-POEGMA), are reported. The chemical modifications were accomplished via quaternization with 1-iodohexane (Q₆) and 1-iodododecane (Q₁₂) and confirmed by ¹H-NMR spectroscopy. The successful synthesis of PDMAEMA-b-POEGMA precursor block copolymers was conducted by RAFT polymerization. The partial chemical modification of the diblocks resulted in the permanent attachment of long alkyl chains on the amine groups of the PDMAEMA block and the presence of tertiary and quaternary amines randomly distributed within the PDMAEMA block. Light scattering techniques confirmed that the increased hydrophobic character results in the formation of nanoaggregates of high mass and tunable pH and temperature response. The characteristics of the aggregates are also affected by the aqueous solution preparation protocol, the nature of the quaternizing agent and the quaternization degree. The incorporation of long alkyl chains allowed the encapsulation of indomethacin within the amphiphilic diblock copolymer aggregates. Nanostructures of increased size were detected due to the encapsulation of indomethacin into the interior of the hydrophobic domains. Drug release studies demonstrated that almost 50% of the encapsulated drug can be released on demand by aid of ultrasonication.

The purity and safety of water as a finite resource is highly important in order to meet current and future human needs. To address this issue, the usage of environmentally friendly and biodegradable adsorbers and flocculants is essential. Chitosan, as a biopolymer, features tremendous properties as an adsorber and flocculant for water treatment. For the application of chitosan as an adsorber under acidic aqueous conditions, such as acid mine drainage, chitosan has been modified with hydrophobic hexanoyl chloride (H-chitosan) to reduce the solubility at a lower pH. In order to investigate the influence of the substitution of the hexanoyl chloride on the adsorption properties of chitosan, two chitosans of different molecular weights and of three different functionalization degrees were analyzed for the adsorption of CdSO_4(aq) and Al₂(SO₄)_3(aq). Among biobased adsorbents, H-chitosan derived from the shorter Chitosan exhibited extraordinarily high maximum adsorption capacities of 1.74 mmol/g and 2.06 mmol/g for Cd²⁺ and sulfate, and 1.76 mmol/g and 2.60 mmol/g for Al³⁺ and sulfate, respectively.

Development of graphene/perovskite heterostructures mediated by polymeric materials may constitute a robust strategy to resolve the environmental instability of metal halide perovskites and provide barrierless charge transport. Herein, a straightforward approach for the growth of perovskite nano-crystals and their electronic communication with graphene is presented. Methylammonium lead bromide (CH₃NH₃PbBr₃) nano-crystals were grown in a poly[styrene-co-(2-(dimethylamino)ethyl methacrylate)], P[St-co-DMAEMA], bi-functional random co-polymer matrix and non-covalently immobilized on graphene. P[St-co-DMAEMA] was selected as a bi-modal polymer capable to stabilize the perovskite nano-crystals via electrostatic interactions between the tri-alkylamine amine sites of the co-polymer and the A-site vacancies of the perovskite and simultaneously enable Van der Waals attractive interactions between the aromatic arene sites of the co-polymer and the surface of graphene. The newly synthesized CH₃NH₃PbBr₃/co-polymer and graphene/CH₃NH₃PbBr₃/co-polymer ensembles were formed by physical mixing of the components in organic media at room temperature. Complementary characterization by dynamic light scattering, microscopy, and energy-dispersive X-ray spectroscopy revealed the formation of uniform spherical perovskite nano-crystals immobilized on the graphene nano-sheets. Complementary photophysical characterization by UV-Vis absorption, steady-state, and time-resolved fluorescence spectroscopy unveiled the photophysical properties of the CH₃NH₃PbBr₃/co-polymer colloid perovskite solution and verified the electronic communication within the graphene/CH₃NH₃PbBr₃/co-polymer ensembles at the ground and excited states.