Effect of the molecular weight on the sensing mechanism in polyethylene glycol diacrylate/gold nanocomposite optical transducers.

The combination of plasmonic nanoparticles and hydrogels results in nanocomposite materials with unprecedented properties that give rise to powerful platforms for optical biosensing. Herein, we propose a physicochemical characterization of plasmonic hydrogel nanocomposites made of polyethylene glycol diacrylate (PEGDA) hydrogels with increasing molecular weights (700-10000 Da) and gold nanoparticles (AuNPs, ∼60 nm). The swelling capability, mechanical properties, and thermal responses of the nanocomposites are analyzed and the combination with the resulting optical properties is elucidated. The different optomechanical properties of the proposed nanocomposites result in different transduction mechanisms, which can be exploited for several biosensing applications. A correlation between the polymer molecular weight, the effective refractive index of the material, and the optical response is found by combining experimental data and numerical simulations. In particular, the localized surface plasmon resonance (LSPR) position of the AuNPs was found to follow a parabolic profile as a function of the monomer molecular weight (MW), while its absorbance intensity was found as inversely proportional to the monomer MW. Low MW PEGDA nanocomposites were found to be responsive to refractive index variations for small molecule sensing. Differently, high MW PEGDA nanocomposites exhibited absorbance intensity increase/decrease as a function of the hydrophobicity/hydrophilicity of the targeted small molecule. The proposed optomechanical model paves the way to the design of innovative platforms for real-life applications, such as wearable sensing, point-of-care testing, and food monitoring via smart packaging devices.

Advances in Transdermal Drug Delivery Systems: A Bibliometric and Patent Analysis.

Transdermal drug delivery systems have become an intriguing research topic in healthcare technology and one of the most frequently developed pharmaceutical products in the global market. In recent years, researchers and pharmaceutical companies have made significant progress in developing new solutions in the field. This study sheds light on current trends, collaboration patterns, research hotspots, and emerging frontiers of transdermal drug delivery. Herein, a bibliometric and patent analysis of data recovered from Scopus and The Lens databases, respectively, is reported over the last 20 years. From 2000 to 2022, the annual global publications increased from 131 in 2000 to 659 in 2022. Researchers in the United States, China, and India produced the highest number of publications. Likewise, most patent applications have been filed in the USA, China, and Europe. The recovered patents are 7275, grouped into 2997 patent families, of which 314 were granted. This study could support the work of decision-makers, scientific managers, or scientists to create new business opportunities or save money, time, and intellectual capital, thereby defining when a research or technology project should be a priority or not.

An Investigation of the Healing Efficiency of Epoxy Vitrimer Composites Based on Zn2+ Catalyst.

The need to recycle carbon-fibre-reinforced composite polymers (CFRP) has grown significantly to reduce the environmental impact generated by their production. To meet this need, thermoreversible epoxy matrices have been developed in recent years. This study investigates the performance of an epoxy vitrimer made by introducing a metal catalyst (Zn2+) and its carbon fibre composites, focusing on the healing capability of the system. The dynamic crosslinking networks endow vitrimers with interesting rheological behaviour; the capability of the formulated resin (AV-5) has been assessed by creep tests. The analysis showed increased molecular mobility above a topology freezing temperature (Tv). However, the reinforcement phase inhibits the flow capability, reducing the flow. The fracture behaviour of CFRP made with the vitrimeric resin has been investigated by Mode I and Mode II tests and compared with the conventional system. The repairability of the vitrimeric CFRP has been investigated by attempting to recover the delaminated samples, which yielded unsatisfactory results. Moreover, the healing efficiency of the modified epoxy composites has been assessed using the vitrimer as an adhesive layer. The joints were able to recover about 84% of the lap shear strength of the pristine system.

Influence of Catalyst Content and Epoxy/Carboxylate Ratio on Isothermal Creep of Epoxy Vitrimers.

In the present work, a commercial epoxy based on epoxy anhydride and tertiary amine was modified by a metallic catalyst (Zn2+) to induce vitrimeric behavior by promoting the transesterification reaction. The effect of two different epoxy/acid ratios (1 and 0.6) at two different zinc acetate amounts (Zn(Ac)2) on the thermomechanical and viscoelastic performances of the epoxy vitrimers were investigated. Creep experiments showed an increase in molecular mobility above the critical "Vitrimeric" temperature (Tv) of 170 °C proportionally to the amount of Zn(Ac)2. A procedure based on Burger's model was set up to investigate the effect of catalyst content on the vitrimer ability to flow as the effect of the dynamic exchange reaction. The analysis showed that in the case of a balanced epoxy/acid formulation, the amount of catalyst needed for promoting molecular mobility is 5%. This system showed a value of elastic modulus and dynamic viscosity at 170 °C of 9.50 MPa and 2.23 GPas, respectively. The material was easily thermoformed in compression molding, paving the way for the recyclability and weldability of the thermoset system.

Recent Advances in Stimuli-Responsive Hydrogel-Based Wound Dressing.

Polymeric materials have found increasing use in biomedical applications in the last decades. Among them, hydrogels represent the chosen class of materials to use in this field, in particular as wound dressings. They are generally non-toxic, biocompatible, and biodegradable, and they can absorb large amounts of exudates. Moreover, hydrogels actively contribute to skin repair promoting fibroblast proliferation and keratinocyte migration, allowing oxygen to permeate, and protecting wounds from microbial invasion. As wound dressing, stimuli-responsive systems are particularly advantageous since they can be active only in response to specific environmental stimuli (such as pH, light, ROS concentration, temperature, and glucose level). In this review, we briefly resume the human skin's structure and functions, as well as the wound healing phases; then, we present recent advances in stimuli-responsive hydrogels-based wound dressings. Lastly, we provide a bibliometric analysis of knowledge produced in the field.

Thermally Mendable Self-Healing Epoxy Coating for Corrosion Protection in Marine Environments.

Polymeric coatings represent a well-established protection system that provides a barrier between a metallic substrate and the environment. The development of a smart organic coating for the protection of metallic structures in marine and offshore applications is a challenge. In the present study, we investigated the use of self-healing epoxy as an organic coating suitable for metallic substrates. The self-healing epoxy was obtained by mixing Diels-Alder (D-A) adducts with a commercial diglycidyl ether of bisphenol-A (DGEBA) monomer. The resin recovery feature was assessed through morphological observation, spectroscopic analysis, and mechanical and nanoindentation tests. Barrier properties and anti-corrosion performance were evaluated through electrochemical impedance spectroscopy (EIS). The film on a metallic substrate was scratched and subsequently repaired using proper thermal treatment. The morphological and structural analysis confirmed that the coating restored its pristine properties. In the EIS analysis, the repaired coating exhibited diffusive properties similar to the pristine material, with a diffusivity coefficient of 1.6 × 10-6 cm2/s (undamaged system 3.1 × 10-6 cm2/s), confirming the restoration of the polymeric structure. These results reveal that a good morphological and mechanical recovery was achieved, suggesting very promising applications in the field of corrosion-resistant protective coatings and adhesives.

Effect of microneedles shape on skin penetration and transdermal drug administration.

Microneedle (MN) patches are highly efficient and versatile tools for transdermal drug administration, in particular for pain-free, self-medication and rapid local applications. Diffraction ultraviolet (UV) light lithography offers an advanced method in fabricating poly(ethylene glycol)-based MNs with different shapes, by changing both the UV-light exposure time and photomask design. The exposure time interval is limited at obtaining conical structures with aspect ratio < 1:3, otherwise MNs exhibit reduced fracture load and poor indentation ability, not suitable for practical application. Therefore, this work is focused on a systematic analysis of the MN's base shapes effects on the structural characteristics, skin penetration and drug delivery. Analyzing four different base shapes (circle, triangle, square and star), it has been found that the number of vertices in the polygon base heavily affects these properties. The star-like MNs reveal the most efficient skin penetration ability (equal to 40 % of -their length), due to the edges action on the skin during the perforation. Furthermore, the quantification of the drug delivered by the MNs through ex-vivo porcine skin shows that the amounts of small molecules released over 24 h by star-like MNs coated by local anesthetic (Lidocaine) and an anti-inflammatory (Diclofenac epolamine) drugs are 1.5× and 2× higher than the circular-MNs, respectively.

Crystal structure of the trigonal form of isotactic polypropylene as an example of density-driven polymer structure.

Propene-hexene copolymers crystallize in a new polymorphic form of isotactic polypropylene when the concentration of hexene is higher than nearly 10-15 mol %. The hexene units are included in the crystals, inducing an increase of density that allows crystallization of 3-fold helical chains in a trigonal unit cell according to the space group R3c or Rc, where the helical symmetry of the chains is maintained in the crystal lattice. The structure of this new form is similar to those of isotactic polybutene and polystyrene and does not crystallize in polypropylene homopolymer because it would have too low density. The crystal structure of isotactic polypropylene is therefore no longer an exception to the principles of polymer crystallography, but the new structure represents the fulfillment of these principles and indicates that the packing of polymer molecules is mainly driven by density.