Electrospinning of Cyclodextrin-Oligolactide Derivatives.

The materials used for the preparation of electrospun mats exhibit a large variety. Among them, cyclodextrins (CDs) and their derivatives have received thorough attention. Herein, we focus on the preparation of electrospun fibers based on biodegradable cyclodextrin-oligolactide (CDLA) derivatives, which may be qualified as polymer-free cyclodextrin. CDLA was prepared by ring opening of L-lactide initiated by the ß-cyclodextrin. A clear structural image of the high-purity CDLA product was proved by MALDI MS. Preparation of the electrospun mats was optimized by taking into consideration the electrospinning parameters such as applied voltage, needle-to-collector distance, flow rate, the concentration of cyclodextrin solutions, and solvent type. The obtained electrospun fibers were morphologically characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). SEM allowed the optimization of the electrospinning process to obtain beadless fibers with submicronic diameters. Further analysis by TEM and SAXS revealed the inner structural features of the CDLA-based filaments. Our results showed that the high purity CDLA materials, structurally well-defined at the molecular level, are suitable for the preparation of electrospun mats by using dimethylformamide or a water/acetonitrile mixture as electrospinning solvents, similar to lower molecular weight commercial cyclodextrin derivatives.

Atom Transfer Radical Polymerization of Pyrrole-Bearing Methacrylate for Production of Carbonyl Iron Particles with Conducting Shell for Enhanced Electromagnetic Shielding.

The conducting polymer poly(2-(1H-pyrrole-1-yl)ethyl methacrylate (PPEMA) was synthesized by conventional atom transfer radical polymerization for the first time from free as well as surface-bonded alkyl bromide initiator. When grafted from the surface of carbonyl iron (CI) a substantial conducting shell on the magnetic core was obtained. Synthesis of the monomer as well as its polymer was confirmed using proton spectrum nuclear magnetic resonance (1H NMR). Polymers with various molar masses and low dispersity showed the variability of this approach, providing a system with a tailorable structure and brush-like morphology. Successful grafting from the CI surface was elucidate by transmission electron microscopy and Fourier-transform infrared spectroscopy. Very importantly, thanks to the targeted nanometer-scale shell thickness of the PPEMA coating, the magnetization properties of the particles were negligibly affected, as confirmed using vibration sample magnetometry. Smart elastomers (SE) consisting of bare CI or CI grafted with PPEMA chains (CI-PPEMA) and silicone elastomer were prepared and dynamic mechanical properties as well as interference shielding ones were investigated. It was found that short polymer chains grafted to the CI particles exhibited the plasticizing effect, which might be interesting from the magnetorheological point of view, and more interestingly, in comparison to the neat CI-based sample, it provided enhanced electromagnetic shielding of nearly 30 dB in thickness of 500 µm. Thus, SE containing the newly synthesized CI-PPEMA hybrid particles also exhibited considerably enhanced damping factor and proper mechanical performance, which make the material highly promising from various practical application points of view.

Irreversible and Self-Healing Electrically Conductive Hydrogels Made of Bio-Based Polymers.

Electrically conductive materials that are fabricated based on natural polymers have seen significant interest in numerous applications, especially when advanced properties such as self-healing are introduced. In this article review, the hydrogels that are based on natural polymers containing electrically conductive medium were covered, while both irreversible and reversible cross-links are presented. Among the conductive media, a special focus was put on conductive polymers, such as polyaniline, polypyrrole, polyacetylene, and polythiophenes, which can be potentially synthesized from renewable resources. Preparation methods of the conductive irreversible hydrogels that are based on these conductive polymers were reported observing their electrical conductivity values by Siemens per centimeter (S/cm). Additionally, the self-healing systems that were already applied or applicable in electrically conductive hydrogels that are based on natural polymers were presented and classified based on non-covalent or covalent cross-links. The real-time healing, mechanical stability, and electrically conductive values were highlighted.

Combined Therapy with Simvastatin- and Coenzyme-Q10-Loaded Nanoparticles Upregulates the Akt-eNOS Pathway in Experimental Metabolic Syndrome.

In addition to their LDL-cholesterol-lowering effect, statins have pleiotropic beneficial effects on the cardiovascular system. However, long-term treatment with statins may be associated with serious side effects. With the aim to make statin therapy more effective, we studied the effects of simvastatin- and coenzyme-Q10-loaded polymeric nanoparticles on the lipid profile and nitric oxide (NO)/reactive oxygen species (ROS) balance in the heart and aorta of adult male obese Zucker rats. The rats were divided into an untreated group, a group treated with empty nanoparticles, and groups treated with simvastatin-, coenzyme Q10 (CoQ10)-, or a combination of simvastatin- and CoQ10-loaded nanoparticles (SIMV+CoQ10). After 6 weeks, the lipid profile in the plasma and the concentration of conjugated dienes in the liver were determined. Nitric oxide synthase (NOS) activity, Akt, endothelial NOS (eNOS), phosphorylated eNOS (p-eNOS), nicotinamide adenine dinucleotide phosphate (NADPH) oxidase, and nuclear factor kappaB (NF-kappaB) protein expressions were measured in the heart and aorta. All simvastatin, CoQ10, and SIMV+CoQ10 treatments decreased plasma LDL levels, but only the combined SIMV+CoQ10 treatment increased NOS activity and the expression of Akt, eNOS, and p-eNOS in both the heart and the aorta. Interestingly, NADPH oxidase in the heart and NF-kappaB protein expression in the aorta were decreased by all treatments, including nanoparticles alone. In conclusion, only combined therapy with SIMV- and CoQ10-loaded nanoparticles increased NOS activity and upregulated the Akt-eNOS pathway in obese Zucker rats, which may represent a promising tool for the treatment of cardiometabolic diseases.

Properties and Degradation Performances of Biodegradable Poly(lactic acid)/Poly(3-hydroxybutyrate) Blends and Keratin Composites.

From environmental aspects, the recovery of keratin waste is one of the important needs and therefore also one of the current topics of many research groups. Here, the keratin hydrolysate after basic hydrolysis was used as a filler in plasticized polylactic acid/poly(3-hydroxybutyrate) blend under loading in the range of 1-20 wt%. The composites were characterized by infrared spectroscopy, and the effect of keratin on changes in molar masses of matrices during processing was investigated using gel permeation chromatography (GPC). Thermal properties of the composites were investigated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The effect of keratin loading on the mechanical properties of composite was investigated by tensile test and dynamic mechanical thermal analysis. Hydrolytic degradation of matrices and composites was investigated by the determination of extractable product amounts, GPC, DSC and NMR. Finally, microbial growth and degradation were investigated. It was found that incorporation of keratin in plasticized PLA/PHB blend provides material with good thermal and mechanical properties and improved degradation under common environmental conditions, indicating its possible application in agriculture and/or packaging.

Fabrication, Modification, and Characterization of Lignin-Based Electrospun Fibers Derived from Distinctive Biomass Sources.

From the environmental point of view, there is high demand for the preparation of polymeric materials for various applications from renewable and/or waste sources. New lignin-based spun fibers were produced, characterized, and probed for use in methylene blue (MB) dye removal in this study. The lignin was extracted from palm fronds (PF) and banana bunch (BB) feedstock using catalytic organosolv treatment. Different polymer concentrations of either a plasticized blend of renewable polymers such as polylactic acid/polyhydroxybutyrate blend (PLA-PHB-ATBC) or polyethylene terephthalate (PET) as a potential waste material were used as matrices to generate lignin-based fibers by the electrospinning technique. The samples with the best fiber morphologies were further modified after iodine handling to ameliorate and expedite the thermostabilization process. To investigate the adsorption of MB dye from aqueous solution, two approaches of fiber modification were utilized. First, electrospun fibers were carbonized at 500 °C with aim of generating lignin-based carbon fibers with a smooth appearance. The second method used an in situ oxidative chemical polymerization of m-toluidine monomer to modify electrospun fibers, which were then nominated by hybrid composites. SEM, TGA, FT-IR, BET, elemental analysis, and tensile measurements were employed to evaluate the composition, morphology, and characteristics of manufactured fibers. The hybrid composite formed from an OBBL/PET fiber mat has been shown to be a promising adsorbent material with a capacity of 9 mg/g for MB dye removal.

Sulfobetaine-based polydisulfides with tunable upper critical solution temperature (UCST) in water alcohols mixture, depolymerization kinetics and surface wettability.

HYPOTHESIS: Synthesis of a new family of polymers having a polydisulfide structure can be conducted from sulfobetaine-based derivative of natural (R)-lipoic acid. A polydisulfide backbone of polymer can be depolymerized by response to external stimuli and sulfobetaine pendant groups ensure the upper critical solution temperature (UCST) behaviour temperatures that can be modulated according to the nature of the solvent and concentration. EXPERIMENTS: Sulfobetaine-bearing polydisulfides were synthesized from dithiolane derivatives and then characterized. UCST behavior of the polymers in water and in mixtures containing different alcohols (methanol, ethanol, isopropanol) was investigated. The regeneration of monomers from the polymers in response to external stimuli was examined using UV-vis and circular dichroism (CD) spectroscopy. Tunable surface wettability were shown on the grafted polymers. FINDINGS: Decreasing polarity and/or increasing alcohol percentage in the water mixtures induced an increase in the cloud points of the polymers in the solutions. Thermoresponsive behaviour were repeatable and fully reversible with negligible hysteresis from aggregate to unimer state. The regeneration of monomers by depolymerization was tunable by temperature and sunlight. A thickness dependence on surface wettability was observed on wafers covalently modified with polydisulfides. This is the first report of sulfobetaine-based polydisulfides showing tunable UCST behavior and surface wettability.

Properties and Degradation of Novel Fully Biodegradable PLA/PHB Blends Filled with Keratin.

The utilization of keratin waste in new materials formulations can prevent its environmental disposal problem. Here, novel composites based on biodegradable blends consisting of poly(lactic acid) (PLA) and poly(3-hydroxybutyrate) (PHB), and filled with hydrolyzed keratin with loading from 1 to 20 wt % were prepared and their properties were investigated. Mechanical and viscoelastic properties were characterized by tensile test, dynamic mechanical thermal analysis (DMTA) and rheology measurements. The addition of acetyltributyl citrate (ATBC) significantly affected the mechanical properties of the materials. It was found that the filled PLA/PHB/ATBC composite at the highest keratin loading exhibited similar shear moduli compared to the un-plasticized blend as a result of the much stronger interactions between the keratin and polymer matrix compared to composites with lower keratin content. The differences in dynamic moduli for PLA/PHB/ATBC blend filled with keratin depended extensively on the keratin content while loss the factor values progressively decreased with keratin loading. Softening interactions between the keratin and polymer matrix resulted in lower glass transitions temperature and reduced polymer chain mobility. The addition of keratin did not affect the extent of degradation of the PLA/PHB blend during melt blending. Fast hydrolysis at 60 °C was observed for composites with all keratin loadings. The developed keratin-based composites possess properties comparable to commonly used thermoplastics applicable for example as packaging materials.

Effect of Structure of Polymers Grafted from Graphene Oxide on the Compatibility of Particles with a Silicone-Based Environment and the Stimuli-Responsive Capabilities of Their Composites.

This study reports the utilization of controlled radical polymerization as a tool for controlling the stimuli-responsive capabilities of graphene oxide (GO) based hybrid systems. Various polymer brushes with controlled molecular weight and narrow molecular weight distribution were grafted from the GO surface by surface-initiated atom transfer radical polymerization (SI-ATRP). The modification of GO with poly(n-butyl methacrylate) (PBMA), poly(glycidyl methacrylate) (PGMA), poly(trimethylsilyloxyethyl methacrylate) (PHEMATMS) and poly(methyl methacrylate) (PMMA) was confirmed by thermogravimetric analysis (TGA) coupled with online Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Various grafting densities of GO-based materials were investigated, and conductivity was elucidated using a four-point probe method. Raman shift and XPS were used to confirm the reduction of surface properties of the GO particles during SI-ATRP. The contact angle measurements indicated the changes in the compatibility of GOs with silicone oil, depending on the structure of the grafted polymer chains. The compatibility of the GOs with poly(dimethylsiloxane) was also investigated using steady shear rheology. The tunability of the electrorheological, as well as the photo-actuation capability, was investigated. It was shown that in addition to the modification of conductivity, the dipole moment of the pendant groups of the grafted polymer chains also plays an important role in the electrorheological (ER) performance. The compatibility of the particles with the polymer matrix, and thus proper particles dispersibility, is the most important factor for the photo-actuation efficiency. The plasticizing effect of the GO-polymer hybrid filler also has a crucial impact on the matrix stiffness and thus the ability to reversibly respond to the external light stimulation.

Synthesis and characterization of Au nanoshells with a magnetic core and betaine derivatives.

The article describes preparation, characterization and further modification of hybrid magnetic particles (Au nanoshells with a magnetic core (MPs@silica@Au)) by zwitterionic molecules bearing diazonium functional groups. Such hybrid magnetic particles modified by zwitterionic molecules exhibit the following features: •Responsiveness towards external magnetic field applicable for various enrichment strategies due to magnetic core;•Golden outer layer exhibiting free surface plasmons could be used for grafting of zwitterionic molecules via diazonium functionality;•Zwitterionic interface on such particles provides resistivity towards non-specific protein binding; and at the same time such interface was applied for immobilization of antibodies against prostate specific antigen (PSA) applied for selective enrichment of PSA from serum samples with subsequent electrochemical assays. The approach presented here using hybrid magnetic particles can be easily applied for immobilization of antibodies using a highly robust surface patterning protocols i.e. by formation of a self-assembled monolayer with delivery of functional groups on the outer surface of magnetic particles. Hybrid magnetic particles with immobilized antibodies are applied for highly efficient and quick separation of protein of interest i.e. PSA from complex sample. Finally, hybrid magnetic particles with "fished-out" protein molecules could be incubated with lectins to form a sandwich configuration for glycoprofiling of PSA.

Tailoring the interparticle distance in Langmuir nanoparticle films.

The ability to control the interparticle distance in self-assembled arrays of nanoparticles plays an important role in a large number of applications, which require tunable electronic and photonic properties. Importantly, practical applications in real devices rely on arrays satisfying more stringent requirements of lateral homogeneity controlled over a large scale. Herein, the interparticle distance in ordered nanoparticle assemblies was controlled by varying the nanoparticle effective size via the molecular chemical nature and chain length of the ligand. Iron oxide nanoparticles (IONPs) were functionalized by three types of ligands, namely (i) a mixture of oleic acid/oleylamine (OA/OAm), (ii) poly(n-butyl acrylate) (PBA) and (iii) polystyrene (PS), while two different molar masses of PBA and PS were used. The polymeric ligands with narrow dispersity and bearing phosphonic chain-end groups were prepared by atom transfer radical polymerization. Functionalization of the IONPs with polymeric ligands was achieved using a ligand exchange method. Both the hydrodynamic diameter and size distribution of the nanoparticles in colloidal solution were determined by dynamic light scattering (DLS). The mean interparticle distances in Langmuir-Schaefer monolayers prepared on solid substrates were assessed by means of the pair correlation function calculated from the atomic force microscopy (AFM) images. Furthermore, the lateral ordering, homogeneity, and interparticle distances averaged over a mesoscopic scale of the ordered monolayers were studied by the grazing-incidence small-angle X-ray scattering (GISAXS) technique. We demonstrate that the (nanoparticle) centre-to-centre distance in the ordered assemblies constituted by the IONPs with the core diameter of about 6 nm can be varied from 7.6 to about 12 nm with the resulting interparticle gap change by a factor of about 4.

Enhanced and Tunable Electrorheological Capability using Surface Initiated Atom Transfer Radical Polymerization Modification with Simultaneous Reduction of the Graphene Oxide by Silyl-Based Polymer Grafting.

In this study, a verified process of the "grafting from" approach using surface initiated atom transfer radical polymerization was applied for the modification of a graphene oxide (GO) surface. This approach provides simultaneous grafting of poly(2-(trimethylsilyloxy)ethyl methacrylate) (PHEMATMS) chains and a controllable reduction of the GO surface. This allows the fine tuning of its electrical conductivity, which is a crucial parameter for applications of such hybrid composite particles in electrorheological (ER) suspensions. The successful coating was confirmed by transmission electron microscopy and Fourier-transform infrared spectroscopy. The molecular characteristics of PHEMATMS were characterized by gel permeation chromatography. ER performance was elucidated using a rotational rheometer under various electric field strengths and a dielectric spectroscopy to demonstrate the direct impact of both the relaxation time and dielectric relaxation strength on the ER effectivity. Enhanced compatibility between the silicone oil and polymer-modified GO particles was investigated using contact angle measurements and visual sedimentation stability determination. It was clearly proven that the modification of the GO surface improved the ER capability of the system due to the tunable conductivity during the surface-initiated atom transfer radical polymerization (SI-ATRP) process and the enhanced compatibility of the GO particles, modified by polymer containing silyl structures, with silicone oil. These unique ER properties of this system appear very promising for future applications in the design of ER suspensions.

Advanced impedimetric biosensor configuration and assay protocol for glycoprofiling of a prostate oncomarker using Au nanoshells with a magnetic core.

In this paper several advances were implemented for glycoprofiling of prostate specific antigen (PSA), what can be applied for better prostate cancer (PCa) diagnostics in the future: 1) application of Au nanoshells with a magnetic core (MP@silica@Au); 2) use of surface plasmons of Au nanoshells with a magnetic core for spontaneous immobilization of zwitterionic molecules via diazonium salt grafting; 3) a double anti-fouling strategy with integration of zwitterionic molecules on Au surface and on MP@silica@Au particles was implemented to resist non-specific protein binding; 4) application of anti-PSA antibody modified Au nanoshells with a magnetic core for enrichment of PSA from a complex matrix of a human serum; 5) direct incubation of anti-PSA modified MP@silica@Au with affinity bound PSA to the lectin modified electrode surface. The electrochemical impedance spectroscopy (EIS) signal was enhanced 43 times integrating Au nanoshells with a magnetic core compared to the biosensor without them. This proof-of-concept study shows that the biosensor could detect PSA down to 1.2 fM and at the same time to glycoprofile such low PSA concentration using a lectin patterned biosensor device. The biosensor offers a recovery index of 108%, when serum sample was spiked with a physiological concentration of PSA (3.5 ng mL-1).

Electrorheology of SI-ATRP-modified graphene oxide particles with poly(butyl methacrylate): effect of reduction and compatibility with silicone oil.

Surface-initiated atom transfer radical polymerization (SI-ATRP) was used to modify graphene oxide (GO) particles with poly(butyl methacrylate) (PBMA) chains. This procedure facilitated the single-step fabrication of a hybrid material with tailored conductivity for the preparation of a suspension in silicone oil with enhanced sedimentation stability and improved electrorheological (ER) activity. PBMA was characterized using various techniques, such as gel permeation chromatography (GPC) and 1H NMR spectroscopy. Thermogravimetric analysis through on-line investigation of the Fourier transform infrared spectra, together with transmission electron microscopy, X-ray photoelectron microscopy, and atomic force microscopy, were successfully used to confirm GO surface modification. The ER performance was investigated using optical microscopy images and steady shear rheometry, and the mechanism of the internal chain-like structure formation was elucidated. The dielectric properties confirmed enhanced ER performance owing to an increase in relaxation strength to 1.36 and decrease in relaxation time to 5 × 10-3 s. The compatibility between GO and silicone oil was significantly influenced by covalently bonded PBMA polymer brushes on the GO surface, showing enhanced compatibility with silicone oil, which resulted in the considerably improved sedimentation stability. Furthermore, a controlled degree of reduction of the GO surface ensured that the suspension had improved ER properties.

Functional Polymers and Polymeric Materials From Renewable Alpha-Unsaturated Gamma-Butyrolactones.

Sustainable chemistry requires application of green processes and often starting materials originate from renewable resources. Biomass-derived monomers based on five-membered γ-butyrolactone ring represent suitable candidates to replace sources of fossil origin. α-Methylene-γ-butyrolactone, ß-hydroxy-α-methylene-γ-butyrolactone, and ß- and γ-methyl-α-methylene-γ-butyrolactones bearing exocyclic double bond are available directly by isolation from plants or derived from itaconic or levulinic acids available from biomass feedstock. Exocyclic double bond with structural similarity with methacrylates is highly reactive in chain-growth polymerization. Reaction involves the linking of monomer molecules through vinyl double bonds in the presence of initiators typical for radical, anionic, zwitterionic, group-transfer, organocatalytic, and coordination polymerizations. The formed polymers containing pendant ring are characterized by high glass transition temperature (T g > 195°C) and render decent heat, weathering, scratch, and solvent resistance. The monomers can also be hydrolyzed to open the lactone ring and form water-soluble monomers. Subsequent radical copolymerization in the presence of cross-linker can yield to hydrogels with superior degree of swelling and highly tunable characteristics, depending on the external stimuli. The five-membered lactone ring allows copolymerization of these compounds by ring opening polymerization to provide polyesters with preserved methylene functionality. In addition, both the lactone ring and the methylene double bond can be attacked by amines. Polyaddition with di- or multi-amines leads to functional poly(amidoamines) with properties tunable by structure of the amines. In this mini-review, we summarize the synthetic procedures for preparation of polymeric materials with interesting properties, including thermoplastic elastomers, acrylic latexes, stimuli-sensitive superabsorbent hydrogels, functional biocompatible polyesters, and poly(amidoamines).

Structural Architectural Features of Cyclodextrin Oligoesters Revealed by Fragmentation Mass Spectrometry Analysis.

Cyclodextrins (CDs) were used in the present study for the ring-opening oligomerization (ROO) of l-lactide (LA) in order to synthesize biodegradable products with possible applications in pharmaceutical and medical fields. The practical importance of ROO reactions may reside in the possibility of synthesizing novel CD derivatives with high purity due to the dual role played by CDs, the role of the initiator through the hydroxylic groups, and the role of the catalyst by monomer inclusion in the CD cavity. The analyzed compounds were CDs modified with oligolactides obtained through ROO reactions of l-lactide in dimethylformamide. The resulting CD isomeric mixtures were investigated using classical characterization techniques such as gel permeation chromatography and nuclear magnetic resonance. Moreover, advanced mass spectrometry (MS) techniques were employed for the determination of the average number of monomer units attached to the cyclodextrin and the architecture of the derivatives (if the monomer units were attached as a single chain or as multiple chains). Thus, fragmentation studies effectuated on two different instruments (ESI Q-TOF and MALDI TOF) allowed us to correlate the size of the oligolactide chains attached to the CD with the observed fragmentation patterns.

Polyglobalide-Based Porous Networks Containing Poly(ethylene glycol) Structures Prepared by Photoinitiated Thiol-Ene Coupling.

The high interest in polymers from natural resources prompted us to investigate the use of enzymatically synthesized polyglobalide (PGL) in the preparation of polymer networks with potential applications as biomaterials for drug delivery devices. Polymer networks were obtained under mild conditions by photoinitiated thiol-ene coupling between PGL and a poly(ethylene glycol- co-thiomalate) (PEG-SH) copolymer obtained by polycondensation. The obtained polymer networks were thoroughly characterized by Raman spectroscopy, scanning electron microscopy, titration of thiol groups and elemental analysis. Our study took into consideration the synthesis parameters for the polymer networks, such as the total polymer concentration and the SH/C=C functionality molar ratio. Swelling in both THF and water was assessed, and the potential of the materials for drug delivery was determined. The scanning electron microscopy images showed that the prepared polymer networks may have different morphologies ranging from homogeneous polymer materials to macroporous structures. Additionally, the prepared materials were found to be suitable from a cytotoxicity point of view, enabling their application as biomaterials for drug delivery devices.

Bioactive polymeric formulations for wound healing.

Ricinoleic acid (RA) has potential to promote wound healing because of its analgesic and anti-inflammatory properties. This study investigates the synthesis and characterization of RA liposomes infused in a hydrogel for topical application. Lecithin liposomes containing RA were prepared and incorporated into a chitosan solution and were subsequently cross-linked with dialdehyde ß-cyclodextrin (Di-ß-CD). Chitosan/Di-ß-CD concentrations and reaction temperatures were varied to alter gelation time, water content, and mechanical properties of the hydrogel in an effort to obtain a wide range of RA release profiles. Hydrogel cross-linking was confirmed by spectroscopy, and liposome and carrier hydrogel morphology via microscopy. Chitosan, Di-ß-CD, and liposome concentrations within the formulation affected the extent of matrix swelling, mechanical strength, and pore and overall morphology. Higher cross-linking density of the hydrogel led to lower water uptake and slower release rate of RA. Optimized formulations resulted in a burst release of RA followed by a steady release pattern accounting for 80% of the encapsulated RA over a period of 48 hours. However, RA concentrations above 0.1 mg/mL were found to be cytotoxic to fibroblast cultures in vitro because of the oily nature of RA. These formulations promoted wound healing when used to treat full thickness skin wounds (2 cm2) in Wister male rats. The wound contraction rates were significantly higher compared to a commercially available topical cream after a time period of 21 days. Histopathological analysis of the RA-liposomal chitosan hydrogel group showed that the epidermis, dermis, and subcutaneous skin layers displayed an accelerated yet normal healing compared to control group.

Reversible Actuation Ability upon Light Stimulation of the Smart Systems with Controllably Grafted Graphene Oxide with Poly (Glycidyl Methacrylate) and PDMS Elastomer: Effect of Compatibility and Graphene Oxide Reduction on the Photo-Actuation Performance.

This study is focused on the controllable reduction of the graphene oxide (GO) during the surface-initiated atom transfer radical polymerization technique of glycidyl methacrylate (GMA). The successful modification was confirmed using TGA-FTIR analysis and TEM microscopy observation of the polymer shell. The simultaneous reduction of the GO particles was confirmed indirectly via TGA and directly via Raman spectroscopy and electrical conductivity investigations. Enhanced compatibility of the GO-PGMA particles with a polydimethylsiloxane (PDMS) elastomeric matrix was proven using contact angle measurements. Prepared composites were further investigated through the dielectric spectroscopy to provide information about the polymer chain mobility through the activation energy. Dynamic mechanical properties investigation showed an excellent mechanical response on the dynamic stimulation at a broad temperature range. Thermal conductivity evaluation also confirmed the further photo-actuation capability properties at light stimulation of various intensities and proved that composite material consisting of GO-PGMA particles provide systems with a significantly enhanced capability in comparison with neat GO as well as neat PDMS matrix.

Light-Induced Actuation of Poly(dimethylsiloxane) Filled with Graphene Oxide Grafted with Poly(2-(trimethylsilyloxy)ethyl Methacrylate).

This study serves to combine two approaches into one single step, to achieve a significant improvement of the light-induced actuation capabilities. Graphene oxide (GO) is an inert material, from the electrical and thermal conductivity point of view, and is incompatible with the usually-used poly(dimethylsiloxane) (PDMS) matrix. During surface-modification by surface-initiated atom transfer radical polymerization, the GO was transformed into a conducting and compatible material with the PDMS showing enormous light-induced actuation capability. The GO surface-modification with poly(2-(trimethylsilyloxy)ethyl methacrylate) (PHEMATMS) chains was confirmed by transmission electron microscopy and thermogravimetric analysis, with an on-line monitoring of gasses using FTIR. The improved compatibility was elucidated using contact angle and dielectric properties measurements. The PHEMATMS shell was investigated using gel permeation chromatography and nuclear magnetic resonance. The improved electric conductivity was measured using the four-point probe method and by Raman spectroscopy. The very important mechanical properties were elucidated using dynamic mechanical analysis, and with the help of thermo-mechanic analysis for the light-induced actuation. The excellent actuation capabilities observed, with changes in the length of around 0.8% at 10% pre-strain, are very promising from the point of view of applications.