Search Results (78)

Background/Objectives: Lyotropic liquid crystalline nanoparticles are promising drug delivery nanocarriers, exhibiting significant technological advantages, such as their extended internal morphology. In this study, cationic non-lamellar lyotropic–lipidic liquid crystalline nanoparticles were formulated by phytantriol lipid. Methods: The poly(2-(dimethylamino)ethyl methacrylate)-b-poly(lauryl methacrylate) block copolymer carrying tri-phenyl-phosphine cations (TPP-QPDMAEMA-b-PLMA), was employed as a stabilizer co-assisted by other polymeric guests. The exact qualitative and quantitative formulation of the systems was investigated. Their physicochemical profile was depicted from a variety of light scattering techniques, while their microenvironmental parameters were determined by fluorescence spectroscopy using adequate probe molecules. The effect of environmental conditions was monitored, confirming stimuli-responsiveness properties. Their morphology was illustrated by cryo-TEM, revealing expanded internal assemblies. Resveratrol was incorporated into the nanoparticles and the entrapment efficiency was calculated. Results: Their properties were found to be dependent on the formulation characteristics, such as the lipid used, as well as the architecture of the polymeric stabilizer, also being found to be stealth toward proteins, exhibiting stimuli responsiveness and high entrapment efficiency. Conclusions: The studied liquid crystalline nanoparticles, being stimuli-responsive, with high cationic potential, high loading capacity and showing intriguing 3D structures, are suitable for pharmaceutical applications. Full article

Polyethylenimine (PEI) is a cationic polymer with a high density of amine groups suitable for strong electrostatic interactions with biological molecules to preserve their bioactivities during encapsulation and after delivery for biomedical applications. This review provides a comprehensive overview of PEI as a drug and gene carrier, describing its polymerization methods in both linear and branched forms while highlighting the processing methods to manufacture PEIs into drug carriers, such as nanoparticles, coatings, nanofibers, hydrogels, and films. These various PEI carriers enable applications in non-viral gene and small molecule drug deliveries. The structure–property relationships of PEI carriers are discussed with emphasis on how molecular weights, branching degrees, and surface modifications of PEI carriers impact biocompatibility, transfection efficiency, and cellular interactions. While PEI offers remarkable potential for drug and gene delivery, its clinical translation remains limited by challenges, including cytotoxicity, non-degradability, and serum instability. Our aim is to provide an understanding of PEI and the structure–property relationships of its carrier forms to inform future research directions that may enable safe and effective clinical use of PEI carriers for drug and gene delivery. Full article

Background/Objectives: The endosomal escape of lipid nanoparticles (LNPs) is crucial for efficient mRNA-based therapeutics. Here, we present a cationic polymeric micelle (cPM) as a safe and potent co-delivery system with enhanced endosomal escape capabilities. Methods: We synthesized a cationic and ampholytic di-block copolymer, poly (poly (ethylene glycol)_4-5 methacrylate_a-co-hexyl methacrylate_b)_X-b-poly(butyl methacrylate_c-co-dimethylaminoethyl methacrylate_d-co-propyl acrylate_e)_Y (p(PEG_4-5MA_a-co-HMA_b)_X-b-p(BMA_c-co-DMAEMA_d-co-PAA_e)_Y), via reversible addition–fragmentation chain transfer polymerization. The cPMs were then formulated using the synthesized polymer by the dispersion–diffusion method and characterized by dynamic light scattering (DLS) and cryo-transmission electron microscopy (CryoTEM). The membrane-destabilization activity of the cPMs was evaluated by a hemolysis assay. We performed an in vivo functional assay of firefly luciferase (Fluc) mRNA using two of the most commonly studied LNPs, SM102 LNP and Dlin-MC3-DMA LNPs. Results: With a particle size of 61.31 ± 0.68 nm and a zeta potential of 37.76 ± 2.18 mV, the cPMs exhibited a 2–3 times higher firefly luciferase signal at the injection site compared to the control groups without cPMs following intramuscular injection in mice, indicating the high potential of cPMs to enhance the endosomal escape efficiency of mRNA-LNPs. Conclusions: The developed cPM, with enhanced endosomal escape capabilities, presents a promising strategy to improve the expression efficiency of delivered mRNAs. This approach offers a novel alternative strategy with no modifications to the inherent properties of mRNA-LNPs, preventing any unforeseeable changes in formulation characteristics. Consequently, this polymer-based nanomaterial holds immense potential for clinical applications in mRNA-based vaccines. Full article

Cationic vaccines of nanometric sizes can directly perform the delivery of antigen(s) and immunomodulator(s) to dendritic cells in the lymph nodes. The positively charged nanovaccines are taken up by antigen-presenting cells (APCs) of the lymphatic system often originating the cellular immunological defense required to fight intracellular microbial infections and the proliferation of cancers. Cationic molecules imparting the positive charges to nanovaccines exhibit a dose-dependent toxicity which needs to be systematically addressed. Against the coronavirus, mRNA cationic nanovaccines evolved rapidly. Nowadays cationic nanovaccines have been formulated against several infections with the advantage of cationic compounds granting protection of nucleic acids in vivo against biodegradation by nucleases. Up to the threshold concentration of cationic molecules for nanovaccine delivery, cationic nanovaccines perform well eliciting the desired Th 1 improved immune response in the absence of cytotoxicity. A second strategy in the literature involves dilution of cationic components in biocompatible polymeric matrixes. Polymeric nanoparticles incorporating cationic molecules at reduced concentrations for the cationic component often result in an absence of toxic effects. The progress in vaccinology against cancer involves in situ designs for cationic nanovaccines. The lysis of transformed cancer cells releases several tumoral antigens, which in the presence of cationic nanoadjuvants can be systemically presented for the prevention of metastatic cancer. In addition, these local cationic nanovaccines allow immunotherapeutic tumor treatment. Full article

Aggregation-induced emission dyes (AIEs) have gained significant interest due to their unique optical properties. Upon aggregation, AIEs can exhibit remarkable fluorescence enhancement. These systems are ideal candidates for applications in bioimaging, such as image-guided drug delivery or surgery. Encapsulation of AIEs in polymeric nanocarriers can result in biocompatible and efficient nanosystems. Herein, we report the fabrication of novel nanoaggregates formulated by amino terpolymer and tetraphenylethylene (TPE) AIE in aqueous media. Poly(di(ethylene glycol) methyl ether methacrylate-co-2-(dimethylamino)ethylmethacrylate-co-oligoethylene glycol methyl ether methacrylate), P(DEGMA-co-DMAEMA-co-OEGMA) hydrophilic terpolymer was utilized for the complexation of the sodium tetraphenylethylene 4,4′,4″,4‴-tetrasulfonate AIE dye. Fluorescence spectroscopy, physicochemical studies, and self-assembly in aqueous and fetal bovine serum media were carried out. The finely dispersed nanoparticles exhibited enhanced fluorescence compared to the pure dye. To investigate the role of tertiary amino groups in the aggregation phenomenon, the polymer was quaternized, and quaternized polymer nanocarriers were fabricated. The increase in fluorescence intensity indicated stronger interaction between the cationic polymer analog and the dye. A stronger interaction between the nanoparticles and fetal bovine serum was observed in the case of the quaternized polymer. Thus, P(DEGMA-co-DMAEMA-co-OEGMA) formulations are better candidates for bioimaging applications than the quaternized ones, presenting both aggregation-induced emission and less interaction with fetal bovine serum. Full article

Poly(L-lactic acid) (PLLA) and poly(ε-caprolactone) (PCL), two biodegradable and biocompatible polymers that are commonly used for biomedical applications, are, respectively, the result of the ring-opening polymerization of LA and ε-CL, cyclic esters, which can be produced according to several mechanisms (cationic, monomer-activated cationic, anionic, and coordination-insertion), except for L-lactide, which is polymerized only by anionic, cationic, or coordination-insertion polymerization. A series of well-defined PLLA-b-PCL block copolymers have been obtained starting from the same PLLA homopolymer, having a molar mass of 2500 g·mol⁻¹, and being synthesized by coordination-insertion in the presence of tin octoate. PCL blocks were obtained via a cationic-activated monomer mechanism to limit transesterification reactions, and their molar masses varied from 1800 to 18,500 g·mol⁻¹. The physicochemical properties of the copolymers were determined by ¹H NMR, SEC, and DSC. Moreover, a series of nanoparticles (NPs) were prepared starting from these polyester-based copolymers by an emulsification/evaporation method. The sizes of the obtained NPs varied between 140 and 150 nm, as a function of the molar mass of the copolymers. Monomodal distribution curves with PDI values under 0.1 were obtained by Dynamic Light Scattering (DLS) and their spherical shape was confirmed by TEM. The increase in the temperature from 25 to 37 °C induced only a very slight decrease in the NP sizes. The results obtained in this preliminary study indicate that NPs have a temperature stability, allowing us to consider their use as drug-loaded nanocarriers for biomedical applications. Full article

The present study concerns the preparation of hybrid nanostructures composed of carbon dots (CDs) synthesized in our lab and a double-hydrophilic poly(2-dimethylaminoethyl methacrylate-co-oligo(ethylene glycol) methyl ether methacrylate) (P(DMAEMA-co-OEGMA)) random copolymer through electrostatic interactions between the negatively charged CDs and the positively charged DMAEMA segments of the copolymer. The synthesis of P(DMAEMA-co-OEGMA) copolymer was conducted through RAFT polymerization. Furthermore, the copolymer was converted into a strong cationic random polyelectrolyte through quaternization of the amine groups of DMAEMA segments with methyl iodide (CH₃I), and it was subsequently utilized for the complexation with the carbon dots. The molecular, physicochemical, and photophysical characterization of the aqueous solution of the copolymers and their hybrid nanoparticles was conducted using dynamic and electrophoretic light scattering (DLS, ELS) and spectroscopic techniques, such as UV-Vis, fluorescence (FS), and FT-IR spectroscopy. In addition, studies of their aqueous solution using DLS and ELS showed their responsiveness to external stimuli (pH, temperature, ionic strength). Finally, the interaction of selected hybrid nanoparticles with iron (III) ions was confirmed through FS spectroscopy, demonstrating their potential application for heavy metal ions sensing. Full article

Inorganic–organic hybrid biomaterials have been proposed for bone tissue repair, with improved mechanical flexibility compared with scaffolds fabricated from bioceramics. However, obtaining hybrids with osteoinductive properties equivalent to those of bioceramics is still a challenge. In this work, we present for the first time the synthesis of a class II hybrid modified with bioactive glass nanoparticles (nBGs) with osteoinductive properties. The nanocomposite hybrids were produced by incorporating nBGs in situ into a polytetrahydrofuran (PTHF) and silica (SiO₂) hybrid synthesis mixture using a combined sol–gel and cationic polymerization method. nBGs ~80 nm in size were synthesized using the sol–gel technique. The structure, composition, morphology, and mechanical properties of the resulting materials were characterized using ATR-FTIR, ²⁹Si MAS NMR, SEM-EDX, AFM, TGA, DSC, mechanical, and DMA testing. The in vitro bioactivity and degradability of the hybrids were assessed in simulated body fluid (SBF) and PBS, respectively. Cytocompatibility with mesenchymal stem cells was assessed using MTS and cell adhesion assays. Osteogenic differentiation was determined using the alkaline phosphatase activity (ALP), as well as the gene expression of Runx2 and Osterix markers. Hybrids loaded with 5, 10, and 15% of nBGs retained the mechanical flexibility of the PTHF–SiO₂ matrix and improved its ability to promote the formation of bone-like apatite in SBF. The nBGs did not impair cell viability, increased the ALP activity, and upregulated the expression of Runx2 and Osterix. These results demonstrate that nBGs are an effective osteoinductive nanoadditive for the production of class II hybrid materials with enhanced properties for bone tissue regeneration. Full article

The popularity of Glycosaminoglycans (GAGs) in drug delivery systems has grown as their innate ability to sequester and release charged molecules makes them adept in the controlled release of therapeutics. However, peptide therapeutics have been relegated to synthetic, polymeric systems, despite their high specificity and efficacy as therapeutics because they are rapidly degraded in vivo when not encapsulated. We present a GAG-based nanoparticle system for the easy encapsulation of cationic peptides, which offers control over particle diameter, peptide release behavior, and swelling behavior, as well as protection from proteolytic degradation, using a singular, organic polymer and no covalent linkages. These nanoparticles can encapsulate cargo with a particle diameter range spanning 130–220 nm and can be tuned to release cargo over a pH range of 4.5 to neutral through the modulation of the degree of sulfation and the molecular weight of the GAG. This particle system also confers better in vitro performance than the unencapsulated peptide via protection from enzymatic degradation. This method provides a facile way to protect therapeutic peptides via the inclusion of the presented binding sequence and can likely be expanded to larger, more diverse cargo as well, abrogating the complexity of previously demonstrated systems while offering broader tunability. Full article

This manuscript presents the synthesis of hyperbranched amphiphilic poly (lauryl methacrylate-co-tert-butyl methacrylate-co-methacrylic acid), H-P(LMA-co-tBMA-co-MAA) copolymers via reversible addition fragmentation chain transfer (RAFT) copolymerization of tBMA and LMA, and their post-polymerization modification to anionic amphiphilic polyelectrolytes. The focus is on investigating whether the combination of the hydrophobic characters of LMA and tBMA segments, as well as the polyelectrolyte and hydrophilic properties of MAA segments, both distributed within a unique hyperbranched polymer chain topology, would result in intriguing, branched copolymers with the potential to be applied in nanomedicine. Therefore, we studied the self-assembly behavior of these copolymers in aqueous media, as well as their ability to form complexes with cationic proteins, namely lysozyme (LYZ) and polymyxin (PMX). Various physicochemical characterization techniques, including size exclusion chromatography (SEC) and proton nuclear magnetic resonance (¹H-NMR), verified the molecular characteristics of these well-defined copolymers, whereas light scattering and fluorescence spectroscopy techniques revealed promising nanoparticle (NP) self- and co-assembly properties of the copolymers in aqueous media. Full article

Globally the overall oil recovery factors for primary and secondary recovery range from 35% to 45%, and a tertiary recovery method that can enhance the recovery factor by 10–30% could contribute to the energy supply. The use of nanoparticles in enhanced oil recovery (EOR) processes comprises an emerging and well-promising approach. Polymer-coated nanoparticles (PNPs) were synthesized through the free radical polymerization (FRP) of the monomers 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPSA) and dodecyl methacrylate (DMA) on the surface of acrylic-modified spherical silica nanoparticles. The obtained PNPs were characterized using Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR) and thermogravimetric analysis (TGA). Dispersions of PNPs were prepared in salt (NaCl, CaCl₂) aqueous solutions, the static oil/water interfacial tension were measured using the Du Nouy ring method, and changes caused based on the oil/water contact angle were recorded optically. The PNP dispersions were used to stabilize and characterize shear-thinning oil-in-water Pickering emulsions. The capacity of the PNP dispersions and Pickering emulsions to mobilize the trapped ganglia of viscous paraffin oil, which remained after successive tests of drainage and primary imbibition, was tested with visualization experiments of the secondary imbibition in a transparent glass-etched pore network. The synthesized SiO₂-P(AMPSA-co-DMA) nanoparticles were stable even at high temperatures (~200–250 °C) and displayed excellent stability in aqueous dispersions at high ionic strengths with the presence of divalent cations, and their dispersions generated stable oil-in-water Pickering emulsions with a shear-thinning viscosity. The oil-recovery efficiency is maximized when the most viscous Pickering emulsion is selected, but if energy cost factors are also taken into account, then the less viscous Pickering emulsion is preferable. Full article

Superparamagnetic iron oxide nanoparticles (SPION) with a “non-fouling” surface represent a versatile group of biocompatible nanomaterials valuable for medical diagnostics, including oncology. In our study we present a synthesis of novel maghemite (γ-Fe₂O₃) nanoparticles with positive and negative overall surface charge and their coating by copolymer P(HPMA-co-HAO) prepared by RAFT (reversible addition–fragmentation chain-transfer) copolymerization of N-(2-hydroxypropyl)methacrylamide (HPMA) with N-[2-(hydroxyamino)-2-oxo-ethyl]-2-methyl-prop-2-enamide (HAO). Coating was realized via hydroxamic acid groups of the HAO comonomer units with a strong affinity to maghemite. Dynamic light scattering (DLS) demonstrated high colloidal stability of the coated particles in a wide pH range, high ionic strength, and the presence of phosphate buffer (PBS) and serum albumin (BSE). Transmission electron microscopy (TEM) images show a narrow size distribution and spheroid shape. Alternative coatings were prepared by copolymerization of HPMA with methyl 2-(2-methylprop-2-enoylamino)acetate (MMA) and further post-polymerization modification with hydroxamic acid groups, carboxylic acid and primary-amino functionalities. Nevertheless, their colloidal stability was worse in comparison with P(HPMA-co-HAO). Additionally, P(HPMA-co-HAO)-coated nanoparticles were subjected to a bio-distribution study in mice. They were cleared from the blood stream by the liver relatively slowly, and their half-life in the liver depended on their charge; nevertheless, both cationic and anionic particles revealed a much shorter metabolic clearance rate than that of commercially available ferucarbotran. Full article

Small interfering RNA (siRNA) molecules have limited transfection efficiency and stability, necessitating the use of delivery systems to be effective in gene knockdown therapies. In this regard, lipid–polymeric nanocarriers have emerged as a promising class of nanoparticles for siRNA delivery, particularly for topical applications. We proposed the use of solid lipid–polymer hybrid nanoparticles (SLPHNs) as topical delivery systems for siRNA. This approach was evaluated by assessing the ability of SLPHNs–siRNA complexes to internalize siRNA molecules and both to penetrate skin layers in vitro and induce gene knocking down in a skin cell line. The SLPHNs were formed by a specific composition of solid lipids, a surfactant polymer as a dispersive agent, and a cationic polymer as a complexing agent for siRNA. The optimized nanocarriers exhibited a spherical shape with a smooth surface. The average diameter of the nanoparticles was found to be 200 nm, and the zeta potential was measured to be +20 mV. Furthermore, these nanocarriers demonstrated excellent stability when stored at 4 °C over a period of 90 days. In vitro and in vivo permeation studies showed that SLPHNs increased the cutaneous penetration of fluorescent-labeled siRNA, which reached deeper skin layers. Efficacy studies were conducted on keratinocytes and fibroblasts, showing that SLPHNs maintained cell viability and high cellular uptake. Furthermore, SLPHNs complexed with siRNA against Firefly luciferase (siLuc) reduced luciferase expression, proving the efficacy of this nanocarrier in providing adequate intracellular release of siRNA for silencing specific genes. Based on these results, the developed carriers are promising siRNA delivery systems for skin disease therapy. Full article

The effect of semiconducting tungsten disulfide (WS₂) nanoparticles (NPs), functionalized by either methacryloxy, glycidyl, vinyl, or amino silanes, has been studied in photocuring of acrylate and epoxy resins (the latter photocured according to a cationic mechanism). The curing time, degree of curing (DC), thermal effects, and mechanical properties of the radiation-cured resins were investigated. X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses confirmed that a silane coating was formed (1–4 nm) on the NPs’ surface having a thickness of 1–4 nm. Fourier transition infrared (FTIR) was used to determine the DC of the nanocomposite resin. The curing time of the epoxy resin, at 345–385 nm wavelength, was 10 to 20 s, while for acrylate, the curing time was 7.5 min, reaching 92% DC in epoxy and 84% in acrylate. The glass transition temperature (Tg) of the photocured acrylates in the presence of WS₂ NPs increased. In contrast to the acrylate, the epoxy displayed no significant variations of the Tg. It was found that the silane surface treatments enhanced the DC. Significant increases in impact resistance and enhancement in shear adhesion strength were observed when the NPs were treated with vinyl silane. A previous study has shown that the addition of WS₂ NPs at a concentration of 0.5 wt.% is the optimal loading for improving the resin’s mechanical properties. This study supports these earlier findings not only for the unmodified NPs but also for those functionalized with silane moieties. This study opens new vistas for the photocuring of resins and polymers in general when incorporating WS₂ NPs. Full article

In this work, polymeric microspheres derived from polystyrene-co-methyl methacrylate embedded with magnetic ZnO nanoparticles (poly(styrene-co-MMA)-3MPS-Fe (ZnO)) were synthesized using the suspension polymerization method. The surfaces of polymeric Fe(ZnO) microspheres were improved by functionalization with amino and sulphonate groups. The physicochemical analysis indicated a large number of positively charged (anion exchange) groups (91 mmol/g) on the amine-modified polymeric microsphere (MFZPI) and a large number of negatively charged (cation exchange) groups (90 mmol/g) on the sulphonate-modified polymeric microsphere (SMFZPI)—revealing ambivalent character of obtained sorbent. The characterization of the synthesized compounds using various analytical techniques such as TGA, FTIR, XRD, SEM/EDX, UV-VIS and VSM indicated that synthesized microspheres were thermally stable, semi-crystalline in structure with hollow irregular morphology, optically active in UV region and slightly magnetic in nature. Due to the introduction of groups having ion exchange properties, these modified poly(styrene-co-MMA)-3MPS-Fe(ZnO) microspheres were used for the ion exchange sorptive removal of Cr(III) and fluorescein from aqueous matrix. The equilibrium sorption capacity of Cr(III) was 16.79 mg/g whereas of fluorescein was 12.03 mg/g under optimized conditions. Therefore, SMFZPI was found to be a promising sorbent for both cationic heavy metals and anionic dyes due to the presence of both acidic and basic groups. The mathematical modelling revealed that the sorption phenomenon followed pseudo-second-order kinetics with Freundlich equilibrium isotherm, indicating multilayer chemisorption of the pollutants on the synthesized ion exchange sorbents. This work establishes the utilization of polymeric magnetic ZnO-based ion exchange sorbents to effectively remove harmful toxins from wastewater. Full article