Effect of Graphene Characteristics on Morphology and Performance of Composite Noble Metal-Reduced Graphene Oxide SERS Substrate.

Graphene/noble metal substrates for surface enhanced RAMAN scattering (SERS) possess synergistically improved performance, due to the strong chemical enhancement mechanism accounted to graphene and the electromagnetic mechanism raised from the metal nanoparticles. However, only the effect of noble metal nanoparticles characteristics on the SERS performance was studied so far. In attempts to bring a light to the effect of quality of graphene, in this work, two different graphene oxides were selected, slightly oxidized GOS (20%) with low aspect ratio (1000) and highly oxidized (50%) GOG with high aspect ratio (14,000). GO and precursors for noble metal nanoparticles (NP) simultaneous were reduced, resulting in rGO decorated with AgNPs and AuNPs. The graphene characteristics affected the size, shape, and packing of nanoparticles. The oxygen functionalities actuated as nucleation sites for AgNPs, thus GOG was decorated with higher number and smaller size AgNPs than GOS. Oppositely, AuNPs preferred bare graphene surface, thus GOS was covered with smaller size, densely packed nanoparticles, resulting in the best SERS performance. Fluorescein in concentration of 10-7 M was detected with enhancement factor of 82 × 104. This work demonstrates that selection of graphene is additional tool toward powerful SERS substrates.

Gramicidin ion channels in a lipid bilayer supported on polyelectrolyte multilayer films: an electrochemical impedance study.

Supported membranes on polymer cushions are of fundamental interest as models for cell membranes. The use of polyelectrolyte multilayers (PEMs) assembled by the layer by layer (LbL) technique as supports for a bilayer allows for easy integration of the lipid bilayer on surfaces and devices and for nanoscale tunable spacing of the lipid bilayer. Controlling ionic permeability in lipid bilayers supported on PEMs triggers potential applications in sensing and as models for transport phenomena in cell membranes. Lipid bilayers displaying gramicidin channels are fabricated on top of polyallylamine hydrochloride (PAH) and polystyrene sulfonate (PSS) multilayer films, by the assembly of vesicles of phosphatidylcholine and phosphatidylserine, 50 : 50 M/M, carrying gramicidin (GA). Quartz crystal microbalance with dissipation shows that the vesicles with GA fuse into a bilayer. Atomic force microscopy reveals that the presence of GA alters the bilayer topography resulting in depressions in the bilayer of around 70 nm in diameter. Electrochemical impedance spectroscopy (EIS) studies show that supported bilayers carrying GA have smaller resistances than the bilayers without GA. Lipid layers carrying GA display a higher conductance for K+ than for Na+ and are blocked in the presence of Ca2+.

Responsive Copolymer Brushes of Poly[(2-(Methacryloyloxy)Ethyl) Trimethylammonium Chloride] (PMETAC) and Poly((1)H,(1)H,(2)H,(2)H-Perfluorodecyl acrylate) (PPFDA) to Modulate Surface Wetting Properties.

Polymer brushes have a large potential for controlling properties such as surface lubrication or wetting through facile functionalization. Polymer chemistry, chain density, and length impact on the wetting properties of brushes. This study explores the use of diblock copolymer brushes with different block length and spatial arrangement of the blocks to tune surface wettability. Block copolymer brushes of the polyelectrolyte [2-(methacryloyloxy)ethyl] trimethylammonium chloride (PMETAC) with a contact angle of 17° and a hydrophobic block of (1)H, (1)H, (2)H, (2)H-perfluorodecyl Acrylate (PPFDA) with a contact angle of 130° are synthesized by RAFT polymerization. By changing the sequence of polymerization either block is synthesized as top or bottom block. By varying the concentration of initiator the length of the blocks is varied. Contact angle values with intermediate values between 17° and 130° are measured. In addition, by changing solvent pH and in presence of a different salt the contact angle of the copolymer brushes can be fine tuned. Brushes are characterized by atomic force microscopy, Raman confocal microscopy, and X-ray photoelectron spectroscopy.

pH-responsive ion transport in polyelectrolyte multilayers of poly(diallyldimethylammonium chloride) (PDADMAC) and poly(4-styrenesulfonic acid-co-maleic acid) (PSS-MA) bearing strong- and weak anionic groups.

The layer-by-layer construction of interfacial architectures displaying stimuli-responsive control of mass transport is attracting increasing interest in materials science. In this work, we describe the creation of interfacial architectures displaying pH-dependent ionic transport properties which until now have not been observed in polyelectrolyte multilayers. We describe a novel approach to create pH-controlled ion-rectifying systems employing polyelectrolyte multilayers assembled from a copolymer containing both weakly and strongly charged pendant groups, poly(4-styrenesulfonic acid-co-maleic acid) (PSS-MA), alternately deposited with poly(diallyldimethylammonium chloride) (PDADMAC). The conceptual framework is based on the very contrasting and differential interactions of PSS and MA units with PDADMAC. In our setting, sulfonate groups play a structural role by conferring stability to the multilayer due to the strong electrostatic interactions with the polycations, while the weakly interacting MA groups remain "silent" within the film and then act as on-demand pH-responsive units. When these multilayers are combined with a strong cationic capping layer that repels the passage of cationic probes, a pH-gateable rectified transport of anions is observed. Concomitantly, we also observed that these functional properties are significantly affected when multilayers are subjected to extensive pH cycling as a consequence of irreversible morphological changes taking place in the film. We envision that the synergy derived from combining weak and strong interactions within the same multilayer will play a key role in the construction of new interfacial architectures displaying tailorable ion transport properties.

Bringing innovative wound care polymer materials to the market: Challenges, developments, and new trends.

The development of innovative products for treating acute and chronic wounds has become a significant topic in healthcare, resulting in numerous products and innovations over time. The growing number of patients with comorbidities and chronic diseases, which may significantly alter, delay, or inhibit normal wound healing, has introduced considerable new challenges into the wound management scenario. Researchers in academia have quickly identified promising solutions, and many advanced wound healing materials have recently been designed; however, their successful translation to the market remains highly complex and unlikely without the contribution of industry experts. This review article condenses the main aspects of wound healing applications that will serve as a practical guide for researchers working in academia and industry devoted to designing, evaluating, validating, and translating polymer wound care materials to the market. The article highlights the current challenges in wound management, describes the state-of-the-art products already on the market and trending polymer materials, describes the regulation pathways for approval, discusses current wound healing models, and offers a perspective on new technologies that could soon reach consumers. We envision that this comprehensive review will significantly contribute to highlighting the importance of networking and exchanges between academia and healthcare companies. Only through the joint of these two actors, where innovation, manufacturing, regulatory insights, and financial resources act in harmony, can wound care products be developed efficiently to reach patients quickly and affordably.

Resembling Graphene/Polymer Aerogel Morphology for Advancing the CO2/N2 Selectivity of the Postcombustion CO2 Capture Process.

The separation of CO2 from N2 remains a highly challenging task in postcombustion CO2 capture processes, primarily due to the relatively low CO2 content (3-15%) compared to that of N2 (70%). This challenge is particularly prominent for carbon-based adsorbents that exhibit relatively low selectivity. In this study, we present a successfully implemented strategy to enhance the selectivity of composite aerogels made of reduced graphene oxide (rGO) and functionalized polymer particles. Considering that the CO2/N2 selectivity of the aerogels is affected on the one hand by the surface chemistry (offering more sites for CO2 capture) and fine-tuned microporosity (offering molecular sieve effect), both of these parameters were affected in situ during the synthesis process. The resulting aerogels exhibit improved CO2 adsorption capacity and a significant reduction in N2 adsorption at a temperature of 25 °C and 1 atm, leading to a more than 10-fold increase in selectivity compared to the reference material. This achievement represents the highest selectivity reported thus far for carbon-based adsorbents. Detailed characterization of the aerogel surfaces has revealed an increase in the quantity of surface oxygen functional groups, as well as an augmentation in the fractions of micropores (<2 nm) and small mesopores (<5 nm) as a result of the modified synthesis methodology. Additionally, it was found that the surface morphology of the aerogels has undergone important changes. The reference materials feature a surface rich in curved wrinkles with an approximate diameter of 100 nm, resulting in a selectivity range of 50-100. In contrast, the novel aerogels exhibit a higher degree of oxidation, rendering them stiffer and less elastic, resembling crumpled paper morphology. This transformation, along with the improved functionalization and augmented microporosity in the altered aerogels, has rendered the aerogels almost completely N2-phobic, with selectivity values ranging from 470 to 621. This finding provides experimental evidence for the theoretically predicted relationship between the elasticity of graphene-based adsorbents and their CO2/N2 selectivity performance. It introduces a new perspective on the issue of N2-phobicity. The outstanding performance achieved, including a CO2 adsorption capacity of nearly 2 mmol/g and the highest selectivity of 620, positions these composites as highly promising materials in the field of carbon capture and sequestration (CCS) postcombustion technology.

Block Copolymers in 3D/4D Printing: Advances and Applications as Biomaterials.

3D printing is a manufacturing technique in constant evolution. Day by day, new materials and methods are discovered, making 3D printing continually develop. 3D printers are also evolving, giving us objects with better resolution, faster, and in mass production. One of the areas in 3D printing that has excellent potential is 4D printing. It is a technique involving materials that can react to an environmental stimulus (pH, heat, magnetism, humidity, electricity, and light), causing an alteration in their physical or chemical state and performing another function. Lately, 3D/4D printing has been increasingly used for fabricating materials aiming at drug delivery, scaffolds, bioinks, tissue engineering (soft and hard), synthetic organs, and even printed cells. The majority of the materials used in 3D printing are polymeric. These materials can be of natural origin or synthetic ones of different architectures and combinations. The use of block copolymers can combine the exemplary properties of both blocks to have better mechanics, processability, biocompatibility, and possible stimulus behavior via tunable structures. This review has gathered fundamental aspects of 3D/4D printing for biomaterials, and it shows the advances and applications of block copolymers in the field of biomaterials over the last years.

Advances and Applications of Block Copolymers.

Polymers are materials that have constantly evolved from the beginning of their discovery until the present day [...].

Tailoring of Textural Properties of 3D Reduced Graphene Oxide Composite Monoliths by Using Highly Crosslinked Polymer Particles toward Improved CO2 Sorption.

The main constraint on developing a full potential for CO2 adsorption of 3D composite monoliths made of reduced graphene oxide (rGO) and polymer materials is the lack of control of their textural properties, along with the diffusional limitation to the CO2 adsorption due to the pronounced polymers' microporosity. In this work, the textural properties of the composites were altered by employing highly crosslinked polymer particles, synthesized by emulsion polymerization in aqueous media. For that aim, waterborne methyl methacrylate (MMA) particles were prepared, in which the crosslinking was induced by using different quantities of divinyl benzene (DVB). Afterward, these particles were combined with rGO platelets and subjected to the reduction-induced self-assembly process. The resulting 3D monolithic porous materials certainly presented improved textural properties, in which the porosity and BET surface area were increased up to 100% with respect to noncrosslinked composites. The crosslinked density of MMA polymer particles was a key parameter controlling the porous properties of the composites. Consequently, higher CO2 uptake than that of neat GO structures and composites made of noncrosslinked MMA polymer particles was attained. This work demonstrates that a proper control of the microstructure of the polymer particles and their facile introduction within rGO self-assembly 3D structures is a powerful tool to tailor the textural properties of the composites toward improved CO2 capture performance.

Toward enhanced catalytic activity of magnetic nanoparticles integrated into 3D reduced graphene oxide for heterogeneous Fenton organic dye degradation.

Composite Fenton nanocatalyst was prepared by water-based in situ creation of Fe3O4 nanoparticles integrated within the self-assembly 3D reduced graphene oxide (rGO) aerogel. The hybrid applied for the degradation of Acid Green 25 (AG-25) organic dye in an aqueous solution, in the presence of H2O2. By investigating the conditions that maximize the dye adsorption by the 3D composite, it was found that the pH of the solution should be adjusted between the pKa of the functional groups present on the rGO surface (carboxylic acid) and that of the dye (sulfonic acid) to promote electrostatic interactions dye-3D structure. Performed under these conditions, Fenton degradation of AG-25 in presence of H2O2 was completed in less than 30 min, including all the intermediate products, as demonstrated by MALDI-TOF-MS analysis of the aqueous solution after discoloration. Moreover, this was achieved in a solution with as high a dye concentration of 0.5 mg/mL, with only 10 mg of 3D composite catalyst, at room temperature and without additional energy input. The high performance was attributed to the creation of charge-transfer complex between rGO and Fe3O4 nanoparticles throughout covalent bond C-O-Fe, the formation of which was promoted by the in situ synthesis procedure. For the first time, up to the authors' knowledge, AG-25 degradation mechanism was proposed.

Synthesis, Characterization and Structure Properties of Biobased Hybrid Copolymers Consisting of Polydiene and Polypeptide Segments.

Novel hybrid materials of the PB-b-P(o-Bn-L-Tyr) and PI-b-P(o-Bn-L-Tyr) type (where PB: 1,4/1,2-poly(butadiene), PI: 3,4/1,2/1,4-poly(isoprene) and P(o-Bn-L-Tyr): poly(ortho-benzyl-L-tyrosine)) were synthesized through anionic and ring-opening polymerization under high-vacuum techniques. All final materials were molecularly characterized through infrared spectroscopy (IR) and proton and carbon nuclear magnetic resonance (1H-NMR, 13C-NMR) in order to confirm the successful synthesis and the polydiene microstructure content. The stereochemical behavior of secondary structures (α-helices and ß-sheets) of the polypeptide segments combined with the different polydiene microstructures was also studied. The influence of the α-helices and ß-sheets, as well as the polydiene chain conformations on the thermal properties (glass transition temperatures, thermal stability, α- and ß-relaxation) of the present biobased hybrid copolymers, was investigated through differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dielectric spectroscopy (DS). The obtained morphologies in thin films for all the synthesized materials via atomic force microscopy (AFM) indicated the formation of polypeptide fibrils in the polydiene matrix.

Molecular and Structure-Properties Comparison of an Anionically Synthesized Diblock Copolymer of the PS-b-PI Sequence and Its Hydrogenated or Sulfonated Derivatives.

An approach to obtaining various nanostructures utilizing a well-studied polystyrene-b-poly(isoprene) or PS-b-PI diblock copolymer system through chemical modification reactions is reported. The complete hydrogenation and partial sulfonation to the susceptible carbon double bonds of the PI segment led to the preparation of [polystyrene-b-poly(ethylene-alt-propylene)] as well as [polystyrene-b-poly(sulfonated isoprene-co-isoprene)], respectively. The hydrogenation of the polyisoprene block results in enhanced segmental immiscibility, whereas the relative sulfonation induces an amphiphilic character in the final modified material. The successful synthesis of the pristine diblock copolymer through anionic polymerization and the relative chemical modification reactions were verified using several molecular and structural characterization techniques. The thin film structure-properties relationship was investigated using atomic force microscopy under various conditions such as different solvents and annealing temperatures. Small-angle X-ray scattering was employed to identify the different observed nanostructures and their evolution upon thermal annealing.

Reduced Graphene Oxide/Polymer Monolithic Materials for Selective CO2 Capture.

Polymer composite materials with hierarchical porous structure have been advancing in many different application fields due to excellent physico-chemical properties. However, their synthesis continues to be a highly energy-demanding and environmentally unfriendly process. This work reports a unique water based synthesis of monolithic 3D reduced graphene oxide (rGO) composite structures reinforced with poly(methyl methacrylate) polymer nanoparticles functionalized with epoxy functional groups. The method is based on reduction-induced self-assembly process performed at mild conditions. The textural properties and the surface chemistry of the monoliths were varied by changing the reaction conditions and quantity of added polymer to the structure. Moreover, the incorporation of the polymer into the structures improves the solvent resistance of the composites due to the formation of crosslinks between the polymer and the rGO. The monolithic composites were evaluated for selective capture of CO2. A balance between the specific surface area and the level of functionalization was found to be critical for obtaining high CO2 capacity and CO2/N2 selectivity. The polymer quantity affects the textural properties, thus lowering its amount the specific surface area and the amount of functional groups are higher. This affects positively the capacity for CO2 capture, thus, the maximum achieved was in the range 3.56-3.85 mmol/g at 1 atm and 25 °C.

A green synthesis of nanocatalysts based on reduced graphene oxide/magnetic nanoparticles for the degradation of Acid Red 1.

The increasing amount of organic dye-polluted wastewater from the textile industry makes the development of techniques for the efficient purification and reuse of wastewater an urgent issue. Accordingly, solid adsorbents based on three-dimensional (3D) reduced graphene oxide (rGO) aerogels combined with magnetic nanoparticles (rGO@Fe3O4) appear to be potential materials, which offer fast and efficient discoloration of dye solutions by dye adsorption, simultaneously acting as Fenton reaction nanocatalysts, and thus may eliminate organic dyes. In this work, 3D rGO@Fe3O4 aerogel nanocatalysts were synthesized via a low-energy, simple, one-step in situ method, in which GO and FeSO4·7H2O were simultaneously reduced. Consequently, monolithic porous nanocatalyst 3D structures were obtained, with a specific surface area of 241 m2 g-1 and pore volume 0.39 cm3 g-1. The nanocatalysts were applied for the degradation of Acid Red 1 azo-dye in aqueous solution in the presence of hydrogen peroxide, without the need for external energy. The effect of the adsorbent dose, and concentration of dye and peroxide on the dye removal was studied. The degradation of the dye was monitored by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. It was found that an increase in the amount of peroxide allowed complete degradation of the dye together with high molar mass side-products with a conjugated aromatic structure. The good nanocatalyst performance was explained based on the charge-transfer complex established between rGO and the magnetic nanoparticles, allowing the regeneration of ferrous ions during the Fenton process.

In vivo toxicological evaluation of polymer brush engineered nanoceria: impact of brush charge.

Nanoceria has a broad variety of industrial and pharmacological applications due to its antioxidant activity. Nanoceria can be modified by surface coating with polyelectrolyte brushes. Brushes can increase the surface charge of nanoceria, providing greater aqueous stability while reducing agglomeration. However, surface-coating also behaves as a barrier around nanoceria, affecting its redox equilibrium and, hence, its biological and toxicological properties. In the present study, we examined whether bare nanoceria (CeO2; 80-150 nm) and nanoceria modified by surface polymer brush, using negatively charged polyacrylic acid (CeO2@PAA) and positively charged poly (2-(methacryloyloxy)ethyl-trimethyl-ammonium chloride (CeO2@PMETAC), could induce systemic toxicity. As CeO2 has limited colloidal stability, which might result in vascular occlusion, intraperitoneal injection was used instead of intravenous administration. C57Bl/6 mice were four times injected with three different doses of each nanoceria-based sample (corresponding to 1.8, 5.3 and 16 mg Ce/kg BW/administration) for a total period of 14 days. CeO2@PMETAC induced a significant dose-dependent neutrophilia. Histopathological evaluation showed inflammatory processes in the capsule of liver, kidney, and spleen of animals at all doses of CeO2@PMETAC, and with the highest dose of CeO2@PAA and CeO2. However, none of the nanoceria-based samples tested increased the level of DNA damage or micronuclei in blood cells, even though Ce was detected by inductively coupled plasma mass spectrometry analyses in the bone marrow. Only CeO2@PMETAC induced the presence of megakaryocytes in the spleen. A higher accumulation of Ce in mononuclear phagocyte system organs (liver, spleen and bone marrow) was observed after CeO2@PMETAC treatment compared with CeO2@PAA and CeO2.

Exploring the Self-Assembly Capabilities of ABA-Type SBS, SIS, and Their Analogous Hydrogenated Copolymers onto Different Nanostructures Using Atomic Force Microscopy.

In this work, the self-assembled morphologies obtained for poly(styrene-b-butadiene-b-styrene) (SBS) and poly(styrene-b-isoprene-b-styrene) (SIS) ABA-type copolymers were investigated before and after hydrogenation of the polydiene block, which led to poly(styrene-b-ethylene)/poly(ethylene-b-styrene) (SEES) and poly(styrene-b-ethylene)/poly(propylene-b-styrene) (SEPS) copolymers, respectively. The evaluation of different morphologies was carried out using atomic force microscopy (AFM), analyzing the effect of various parameters such as the solvent and polymer concentrations employed for film casting (toluene, cyclohexane, or tetrahydrofurane with concentrations of 1 and 3 wt%), together with that of the annealing treatment (thermal annealing at room temperature, and 60, 80, and 100 °C). The effect of these parameters in combination with the chemical nature of the polydiene block led to different morphologies with different topographic aspects affecting the roughness (Ra) of the film.

Exploring the pH Sensitivity of Poly(allylamine) Phosphate Supramolecular Nanocarriers for Intracellular siRNA Delivery.

Silencing RNA (siRNA) technologies emerge as a promising therapeutic tool for the treatment of multiple diseases. An ideal nanocarrier (NC) for siRNAs should be stable at physiological pH and release siRNAs in acidic endosomal pH, fulfilling siRNA delivery only inside cells. Here, we show a novel application of polyamine phosphate NCs (PANs) based on their capacity to load negatively charged nucleic acids and their pH stability. PANs are fabricated by complexation of phosphate anions from phosphate buffer solution (PB) with the amine groups of poly(allylamine) hydrochloride as carriers for siRNAs. PANs are stable in a narrow pH interval, from 7 to 9, and disassemble at pH's higher than 9 and lower than 6. siRNAs are encapsulated by complexation with poly(allylamine) hydrochloride before or after PAN formation. PANs with encapsulated siRNAs are stable in cell media. Once internalized in cells following endocytic pathways, PANs disassemble at the low endosomal pH and release the siRNAs into the cytoplasm. Confocal laser scanning microscopy (CLSM) images of Rhodamine Green labeled PANs (RG-PANs) with encapsulated Cy3-labeled siRNA in A549 cells show that siRNAs are released from the PANs. Colocalization experiments with labeled endosomes and either labeled siRNAs prove the translocation of siRNAs into the cytosol. As a proof of concept, it is shown that PANs with encapsulated green fluorescence protein (GFP) siRNAs silence GFP in A549 cells expressing this protein. Silencing efficacy was evaluated by flow cytometry, CLSM, and Western blot assays. These results open the way for the use of poly(allylamine) phosphate nanocarriers for the intracellular delivery of genetic materials.

Fabrication of hybrid graphene oxide/polyelectrolyte capsules by means of layer-by-layer assembly on erythrocyte cell templates.

A novel and facile method was developed to produce hybrid graphene oxide (GO)-polyelectrolyte (PE) capsules using erythrocyte cells as templates. The capsules are easily produced through the layer-by-layer technique using alternating polyelectrolyte layers and GO sheets. The amount of GO and therefore its coverage in the resulting capsules can be tuned by adjusting the concentration of the GO dispersion during the assembly. The capsules retain the approximate shape and size of the erythrocyte template after the latter is totally removed by oxidation with NaOCl in water. The PE/GO capsules maintain their integrity and can be placed or located on other surfaces such as in a device. When the capsules are dried in air, they collapse to form a film that is approximately twice the thickness of the capsule membrane. AFM images in the present study suggest a film thickness of approx. 30 nm for the capsules in the collapsed state implying a thickness of approx. 15 nm for the layers in the collapsed capsule membrane. The polyelectrolytes used in the present study were polyallylamine hydrochloride (PAH) and polystyrenesulfonate sodium salt (PSS). Capsules where characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light scattering (DLS) and Raman microscopy, the constituent layers by zeta potential and GO by TEM, XRD, and Raman and FTIR spectroscopies.