New MoS2/Tegafur-Containing Pharmaceutical Formulations for Selective LED-Based Skin Cancer Photo-Chemotherapy.

Non-melanoma skin cancer (NMSC) is one of the most common types of cancer worldwide. Despite the low mortality rate, rising incidence and recurrence rates are a burden on healthcare systems. Standard treatments such as chemotherapy, radiotherapy, and surgery are either invasive or toxic to healthy tissues; therefore, new, alternative, selective treatments are needed. In this work, a combined photothermal and chemotherapeutic approach is proposed. MoS2 was used as photothermal agent. It was prepared by a liquid-phase exfoliation and intercalation method using polyvinylpyrrolidone (PVP), followed by recirculation through a custom-built high-power ultrasonication probe. After 6 h of ultrasonication treatment, the average particle size was 165 ± 170 nm. Near-infrared (NIR) irradiation assays (810 nm, 0.1 W/cm2, 30 min, 180 J/cm2) confirmed that MoS2 nanosheets can efficiently convert NIR light into heat and reach 52 °C. The therapeutic doses of MoS2 (125 µg/mL) and Tegafur (50 µg/mL) were optimized and both were simultaneously incorporated into a Carbopol hydrogel. The cells were brought into contact with the hydrogel and irradiated with a custom-built NIR LED system. In HFF-1 cells (normal human fibroblasts), the metabolic activity was 78% (above the 70% toxicity limit-ISO 10993-5:2009(E)), while in A-431 skin cancer cells, it was 28%. In addition, the MoS2 + Tegafur hydrogels led to a 1.9-fold decrease in A-431 cancer cell metabolic activity, 72 h after irradiation, in comparison to MoS2 hydrogels, indicating a combined effect of photothermal and chemotherapy.

New graphene-containing pharmaceutical formulations for infrared lamps-based phototherapy of skin cancer: In vitro validation and ex-vivo human skin permeation.

Basal cell carcinoma (BCC) is the most common form of human cancer, and treatment usually involves surgery, with alternative strategies being needed. We propose the use of carbopol hydrogels (HG) for topical administration of nanographene oxide (GOn) and partially-reduced nanographene oxide (p-rGOn) for photothermal therapy (PTT) of BCC. GOn and p-rGOn incorporated into the HG present lateral sizes ∼200 nm, being stable for 8 months. After 20 min irradiation with an infrared (IR) photothermal therapy lamp (15.70 mW cm-2), GOn-HG increased temperature to 44.7 °C, while p-rGOn-HG reached 47.0 °C. Human skin fibroblasts (HFF-1) cultured with both hydrogels (250 µg mL-1) maintained their morphology and viability. After 20 min IR irradiation, p-rGOn HG (250 µg mL-1) completely eradicated skin cancer cells (A-431). Ex vivo human skin permeability tests showed that the materials can successfully achieve therapeutic concentrations (250 µg mL-1) inside the skin, in 2.0 h for GO HG or 0.5 h for p-rGOn HG.

Pharmaceutical Formulations Containing Graphene and 5-Fluorouracil for Light-Emitting Diode-Based Photochemotherapy of Skin Cancer.

Nonmelanoma skin cancer (NMSC) is the most common cancer worldwide, among which 80% is basal cell carcinoma (BCC). Current therapies' low efficacy, side effects, and high recurrence highlight the need for alternative treatments. In this work, a partially reduced nanographene oxide (p-rGOn) developed in our laboratory was used. It has been achieved through a controlled reduction of nanographene oxide via UV-C irradiation that yields small nanometric particles (below 200 nm) that preserve the original water stability while acquiring high light-to-heat conversion efficiency. The latter is explained by a loss of carbon-oxygen single bonds (C-O) and the re-establishment of sp2 carbon bonds. p-rGOn was incorporated into a Carbopol hydrogel together with the anticancer drug 5-fluorouracil (5-FU) to evaluate a possible combined PTT and chemotherapeutic effect. Carbopol/p-rGOn/5-FU hydrogels were considered noncytotoxic toward normal skin cells (HFF-1). However, when A-431 skin cancer cells were exposed to NIR irradiation for 30 min in the presence of Carbopol/p-rGOn/5-FU hydrogels, almost complete eradication was achieved after 72 h, with a 90% reduction in cell number and 80% cell death of the remaining cells after a single treatment. NIR irradiation was performed with a light-emitting diode (LED) system, developed in our laboratory, which allows adjustment of applied light doses to achieve a safe and selective treatment, instead of the standard laser systems that are associated with damages in the healthy tissues in the tumor surroundings. Those are the first graphene-based materials containing pharmaceutical formulations developed for BCC phototherapy.

3D Printed Magneto-Active Microfiber Scaffolds for Remote Stimulation and Guided Organization of 3D In Vitro Skeletal Muscle Models.

This work reports the rational design and fabrication of magneto-active microfiber meshes with controlled hexagonal microstructures via melt electrowriting (MEW) of a magnetized polycaprolactone-based composite. In situ iron oxide nanoparticle deposition on oxidized graphene yields homogeneously dispersed magnetic particles with sizes above 0.5 µm and low aspect ratio, preventing cellular internalization and toxicity. With these fillers, homogeneous magnetic composites with high magnetic content (up to 20 weight %) are obtained and processed in a solvent-free manner for the first time. MEW of magnetic composites enabled the creation of skeletal muscle-inspired design of hexagonal scaffolds with tunable fiber diameter, reconfigurable modularity, and zonal distribution of magneto-active and nonactive material, with elastic tensile deformability. External magnetic fields below 300 mT are sufficient to trigger out-of-plane reversible deformation. In vitro culture of C2C12 myoblasts on three-dimensional (3D) Matrigel/collagen/MEW scaffolds showed that microfibers guided the formation of 3D myotube architectures, and the presence of magnetic particles does not significantly affect viability or differentiation rates after 8 days. Centimeter-sized skeletal muscle constructs allowed for reversible, continued, and dynamic magneto-mechanical stimulation. Overall, these innovative microfiber scaffolds provide magnetically deformable platforms suitable for dynamic culture of skeletal muscle, offering potential for in vitro disease modeling.

2D Nanomaterials and Their Drug Conjugates for Phototherapy and Magnetic Hyperthermia Therapy of Cancer and Infections.

Photothermal therapy (PTT) and magnetic hyperthermia therapy (MHT) using 2D nanomaterials (2DnMat) have recently emerged as promising alternative treatments for cancer and bacterial infections, both important global health challenges. The present review intends to provide not only a comprehensive overview, but also an integrative approach of the state-of-the-art knowledge on 2DnMat for PTT and MHT of cancer and infections. High surface area, high extinction coefficient in near-infra-red (NIR) region, responsiveness to external stimuli like magnetic fields, and the endless possibilities of surface functionalization, make 2DnMat ideal platforms for PTT and MHT. Most of these materials are biocompatible with mammalian cells, presenting some cytotoxicity against bacteria. However, each material must be comprehensively characterized physiochemically and biologically, since small variations can have significant biological impact. Highly efficient and selective in vitro and in vivo PTTs for the treatment of cancer and infections are reported, using a wide range of 2DnMat concentrations and incubation times. MHT is described to be more effective against bacterial infections than against cancer therapy. Despite the promising results attained, some challenges remain, such as improving 2DnMat conjugation with drugs, understanding their in vivo biodegradation, and refining the evaluation criteria to measure PTT or MHT effects.

Long-term in vivo degradation and biocompatibility of degradable pHEMA hydrogels containing graphene oxide.

Developing biocompatible, non-fouling and biodegradable hydrogels for blood-contacting devices remains a demanding challenge. Such materials should promote natural healing, prevent clotting, and undergo controlled degradation. This study evaluates the biocompatibility and biodegradation of degradable poly(2-hydroxyethyl methacrylate) (d-pHEMA) hydrogels with or without reinforcement with oxidized few-layer graphene (d-pHEMA/M5ox) in a long term implantation in rats, assessing non-desired side-effects (irritation, chronic toxicity, immune response). Subcutaneous implantation over 6 months revealed degradation of both hydrogels, despite slower for d-pHEMA/M5ox, with degradation products found in intracellular vesicles. No inflammation nor infection at implantation areas were observed, and no histopathological findings were detected in parenchymal organs. Immunohistochemistry confirmed d-pHEMA and d-pHEMA/M5ox highly anti-adhesiveness. Gene expression of macrophages markers revealed presence of both M1 and M2 macrophages at all timepoints. M1/M2 profile after 6 months reveals an anti-inflammatory environment, suggesting no chronic inflammation, as also demonstrated by cytokines (IL-α, TNF-α and IL-10) analysis. Overall, modification of pHEMA towards a degradable material was successfully achieved without evoking a loss of its inherent properties, specially its anti-adhesiveness and biocompatibility. Therefore, these hydrogels hold potential as blank-slate for further modifications that promote cellular adhesion/proliferation for tissue engineering applications, namely for designing blood contacting devices with different load bearing requirements. STATEMENT OF SIGNIFICANCE: Biocompatibility, tunable biodegradation kinetics, and suitable immune response with lack of chronic toxicity and irritation, are key features in degradable blood contact devices that demand long-term exposure. We herein evaluate the 6-month in vivo performance of a degradable and hemocompatible anti-adhesive hydrogel based in pHEMA, and its mechanically reinforced formulation with few-layer graphene oxide. This subcutaneous implantation in a rat model, shows gradual degradation with progressive changes in material morphology, and no evidence of local inflammation in surrounding tissue, neither signs of inflammation or adverse reactions in systemic organs, suggesting biocompatibility of degradation products. Such hydrogels exhibit great potential as a blank slate for tissue engineering applications, including for blood contact, where cues for specific cells can be incorporated.

Nanomaterials for Skin Cancer Photoimmunotherapy.

Skin cancer is one of the most common types of cancer, and its incidence continues to increase. It is divided into two main categories, melanoma and non-melanoma. Treatments include surgery, radiation therapy, and chemotherapy. The relatively high mortality in melanoma and the existing recurrence rates, both for melanoma and non-melanoma, create the need for studying and developing new approaches for skin cancer management. Recent studies have focused on immunotherapy, photodynamic therapy, photothermal therapy, and photoimmunotherapy. Photoimmunotherapy has gained much attention due to its excellent potential outcomes. It combines the advantages of photodynamic and/or photothermal therapy with a systemic immune response, making it ideal for metastatic cancer. This review critically discusses different new nanomaterials' properties and mechanisms of action for skin cancer photoimmunotherapy and the main results obtained in the field.

Novel Approach for a Controlled Delivery of Essential Oils during Long-Term Maize Storage: Clove Bud and Pennyroyal Oils Efficacy to Control Sitophilus zeamais, Reducing Grain Damage and Post-Harvest Losses.

Maize grains represent a significant contribution for assuring food safety all over the globe. Sitophilus zeamais (Motschulsky) (Coleoptera: Curculionidae), also known as the maize weevil, is one of the most destructive pests in stored maize, causing qualitative and quantitative losses. To control S. zeamais populations in maize storage sites, synthetical chemical insecticides are applied. However, these are often used wastefully, have environmental implications, and can induce the development of resistant populations. In this work, the insecticidal and grain protecting efficacy of an innovative macro-capsule delivery device, loaded with essential oils from Clove bud and Pennyroyal, as well as their combined solutions, was tested against naturally S. zeamais-infested maize grains. The blend of both compounds incorporated in a controlled release device reduced losses by more than 45% over a long storage period of twenty weeks, diminishing the survivability of maize weevils by over 90%. The usage of the blend at a concentration of 370 µL⋅Lair-1 with an antioxidant showed the best results, however, by halving the concentration (185 µL⋅Lair-1), a significant control of S. zeamais populations was still achieved.

Poly(2-hydroxyethyl methacrylate) hydrogels containing graphene-based materials for blood-contacting applications: From soft inert to strong degradable material.

Degradable biomaterials for blood-contacting devices (BCDs) are associated with weak mechanical properties, high molecular weight of the degradation products and poor hemocompatibility. Herein, the inert and biocompatible FDA approved poly(2-hydroxyethyl methacrylate) (pHEMA) hydrogel was turned into a degradable material by incorporation of different amounts of a hydrolytically labile crosslinking agent, pentaerythritol tetrakis(3-mercaptopropionate). In situ addition of 1wt.% of oxidized graphene-based materials (GBMs) with different lateral sizes/thicknesses (single-layer graphene oxide and oxidized forms of few-layer graphene materials) was performed to enhance the mechanical properties of hydrogels. An ultimate tensile strength increasing up to 0.2 MPa (293% higher than degradable pHEMA) was obtained using oxidized few-layer graphene with 5 µm lateral size. Moreover, the incorporation of GBMs has demonstrated to simultaneously tune the degradation time, which ranged from 2 to 4 months. Notably, these features were achieved keeping not only the intrinsic properties of inert pHEMA regarding water uptake, wettability and cytocompatibility (short and long term), but also the non-fouling behavior towards human cells, platelets and bacteria. This new pHEMA hydrogel with degradation and biomechanical performance tuned by GBMs, can therefore be envisioned for different applications in tissue engineering, particularly for BCDs where non-fouling character is essential. STATEMENT OF SIGNIFICANCE: Suitable mechanical properties, low molecular weight of the degradation products and hemocompatibility are key features in degradable blood contacting devices (BCDs), and pave the way for significant improvement in the field. In here, a hydrogel with outstanding anti-adhesiveness (pHEMA) provides hemocompatibility, the presence of a degradable crosslinker provides degradability, and incorporation of graphene oxide reestablishes its strength, allowing tuning of both degradation and mechanical properties. Notably, these hydrogels simultaneously provide suitable water uptake, wettability, cytocompatibility (short and long term), no acute inflammatory response, and non-fouling behavior towards endothelial cells, platelets and bacteria. Such results highlight the potential of these hydrogels to be envisioned for applications in tissue engineered BCDs, namely as small diameter vascular grafts.

Metal-Organic Frameworks Applications in Synergistic Cancer Photo-Immunotherapy.

Conventional cancer therapies, such as radiotherapy and chemotherapy, can have long-term side effects. Phototherapy has significant potential as a non-invasive alternative treatment with excellent selectivity. Nevertheless, its applicability is restricted by the availability of effective photosensitizers and photothermal agents, and its low efficacy when it comes to avoiding metastasis and tumor recurrence. Immunotherapy can promote systemic antitumoral immune responses, acting against metastasis and recurrence; however, it lacks the selectivity displayed by phototherapy, sometimes leading to adverse immune events. The use of metal-organic frameworks (MOFs) in the biomedical field has grown significantly in recent years. Due to their distinct properties, including their porous structure, large surface area, and inherent photo-responsive properties, MOFs can be particularly useful in the fields of cancer phototherapy and immunotherapy. MOF nanoplatforms have successfully demonstrated their ability to address several drawbacks associated with cancer phototherapy and immunotherapy, enabling an effective and low-side-effect combinatorial synergistical treatment for cancer. In the coming years, new advancements in MOFs, particularly regarding the development of highly stable multi-function MOF nanocomposites, may revolutionize the field of oncology.

Comparative Study of Friction and Wear Performance of PEK, PEEK and PEKK Binders in Tribological Coatings.

Tribological coatings are widely used in industry, particularly when the conventional oil lubrication of sliding surfaces has to be replaced by maintenance-free contacts. This work studies the tribological performance of waterborne tribological coatings based on three binders of the polyaryletherketone (PAEK) family: polyetherketone (PEK), PEEK, and polyetherketoneketone (PEKK). Even though PEEK is a well-known commercial solution for this type of tribological coatings, PEK and PEKK have never been studied in such a context. PTFE particles were added to all coatings as a solid lubricant. High thermal resistance of the binder materials was confirmed, with decomposition starting above 550 °C, under either N2 or O2 atmosphere. XRD analysis showed that PEK and PEEK are semi-crystalline after being subjected to the coating curing conditions, while PEKK is amorphous. The coatings were successfully applied with thicknesses of 20-30 µm. Tribological measurements showed that the PEK-based coating possesses a coefficient of friction (COF) of 0.08 under high load and pressure conditions (hertzian point contact), which is lower than the reference PEEK-based coating (around 0.11). The PEKK-based coating showed an impressive wear resistance with almost no wear measured compared to the 105 µm wear obtained for PEEK-based coating, while showing a similar COF. These results suggest that PEK and PEKK seem to be interesting alternatives to PEEK and should be further studied for use in tribological coatings.

Pulegone and Eugenol Oral Supplementation in Laboratory Animals: Results from Acute and Chronic Studies.

Essential oils are natural compounds used by humans for scientific purposes due to their wide range of properties. Eugenol is mostly present in clove oil, while pulegone is the main constituent of pennyroyal oil. To guarantee the safe use of eugenol and pulegone for both humans and animals, this study addressed, for the first time, the effects of these compounds, at low doses (chronic toxicity) and high doses (acute toxicity), in laboratory animals. Thirty-five FVB/n female mice were randomly assigned to seven groups (n = 5): group I (control, non-additive diet); group II (2.6 mg of eugenol + 2.6 mg of pulegone); group III (5.2 mg of eugenol + 5.2 mg of pulegone); group IV (7.8 mg of eugenol + 7.8 mg of pulegone); group V (7.8 mg of eugenol); group VI (7.8 mg of pulegone); and group VII (1000 mg of eugenol + 1000 mg of pulegone). The compounds were administered in the food. Groups I to VI were integrated into the chronic toxicity study, lasting 28 days, and group VII was used in the acute toxicity study, lasting 7 days. Animals were monitored to assess their general welfare. Water and food intake, as well as body weight, were recorded. On the 29th day, all animals were euthanized by an overdose of ketamine and xylazine, and a complete necropsy was performed. Blood samples were collected directly from the heart for microhematocrit and serum analysis, as well as for comet assay. Organs were collected, weighed, and fixed in formaldehyde for further histological analysis and enzymatic assay. Eugenol and pulegone induced behavioral changes in the animals, namely in the posture, hair appearance and grooming, and in mental status. These compounds also caused a decrease in the animals' body weight, as well as in the food and water consumption. A mortality rate of 20% was registered in the acute toxicity group. Both compounds modulated the serum levels of triglycerides and alanine aminotransferase. Eugenol and pulegone induced genetic damage in all animals. Eugenol increased the activity of the CAT enzyme. Both compounds increased the GR enzyme at the highest dose. Moreover, pulegone administered as a single compound increased the activity of the GST enzyme. Histopathological analysis revealed inflammatory infiltrates in the lungs of groups II, III, and IV. The results suggest that eugenol and pulegone may exert beneficial or harmful effects, depending on the dose, and if applied alone or in combination.

Flexible Composite Films Made of EMAA-Na+ Ionomer: Evaluation of the Influence of Piezoelectric Particles on the Thermal and Mechanical Properties.

Studies that aim to produce flexible films of composite materials based on ionomers-PZT, and volume fractions lower than 10% PZT, in order to monitor damage in aeronautical structures are seldom investigated. The growing emphasis on the use of polymers capable of self-healing after damage or activation by heating has motivated the application of self-healing ionomers as polymeric matrices in composites with piezoelectric particles aiming to monitor damage. Flexible composite films were developed based on the self-healing polymer matrix Surlyn® 8940 ionomer (DuPontTM-Wilmington, DE, USA) and PZT particles (connectivity 2-3) in volume fractions of 1, 3, 5 and 7%, with thickness around 50-100 µm. The choice of PZT volume fractions followed the preliminary requirement that establishes a final density, which is lower or at least close to the density of the materials used in aeronautical structures. Since the application of composites based on epoxy resin/carbon fibers has been increasing in the aeronautical segment, this material (with density lower than 1500 kg/m3) was chosen as a reference for the present work. Thus, due to self-healing (a characteristic of the matrix Surlyn® 8940) combined with recyclability, high flexibility and low thickness, the flexible composite films showed advantages to be applied on aeronautical structures, which present complex geometries and low-density materials. The manufactured films were characterized by SEM, XRD, DMA and mechanical tensile tests. The results were discussed mainly in terms of the volume fraction of PZT. X-ray diffraction patterns showed coexistent rhombohedral and tetragonal phases in the PZT particles-dispersed composite, which can potentialize the alignment of ferroelectric domains during polarization under strong electrical field, enhancing dielectric and piezoelectric properties toward sensing applications. DMA and tensile testing results demonstrated that the addition of PZT particles did not impair either dynamic or quasi-static mechanical performance of the flexible composite films. It was concluded that the PZT volume fraction should be lower than 3% because, for higher values, the molecular mobility of the polymer would suffer significant reductions. These findings, combined with the high flexibility and low density of the ceramic particle-filled thermoplastic polymer, render the developed flexible composite film a very promising candidate for strain and damage sensing in aeronautical structures.

New Polymeric Composites Based on Two-Dimensional Nanomaterials for Biomedical Applications.

The constant evolution and advancement of the biomedical field requires robust and innovative research. Two-dimensional nanomaterials are an emerging class of materials that have risen the attention of the scientific community. Their unique properties, such as high surface-to-volume ratio, easy functionalization, photothermal conversion, among others, make them highly versatile for a plethora of applications ranging from energy storage, optoelectronics, to biomedical applications. Recent works have proven the efficiency of 2D nanomaterials for cancer photothermal therapy (PTT), drug delivery, tissue engineering, and biosensing. Combining these materials with hydrogels and scaffolds can enhance their biocompatibility and improve treatment for a variety of diseases/injuries. However, given that the use of two-dimensional nanomaterials-based polymeric composites for biomedical applications is a very recent subject, there is a lot of scattered information. Hence, this review gathers the most recent works employing these polymeric composites for biomedical applications, providing the reader with a general overview of their potential.

Fabrication of Polymer/Graphene Biocomposites for Tissue Engineering.

Graphene-based materials (GBM) are considered one of the 21st century's most promising materials, as they are incredibly light, strong, thin and have remarkable electrical and thermal properties. As a result, over the past decade, their combination with a diverse range of synthetic polymers has been explored in tissue engineering (TE) and regenerative medicine (RM). In addition, a wide range of methods for fabricating polymer/GBM scaffolds have been reported. This review provides an overview of the most recent advances in polymer/GBM composite development and fabrication, focusing on methods such as electrospinning and additive manufacturing (AM). As a future outlook, this work stresses the need for more in vivo studies to validate polymer/GBM composite scaffolds for TE applications, and gives insight on their fabrication by state-of-the-art processing technologies.

Grape Canes (Vitis vinifera L.) Applications on Packaging and Particleboard Industry: New Bioadhesive Based on Grape Extracts and Citric Acid.

The main by-product generated in the wine industry are the grape canes, derived from the pruning process. In order to increase the valorisation possibilities of this highly polyphenolic lignocellulosic material, this work focuses on its applicability in the materials industry. As a first step, we demonstrate the viability of using grape cane particles as raw material for particleboard production, combined with a melamine formaldehyde urea (MFU) binder. In addition, looking for the application of these particleboards in the food packaging industry, particleboards based on grape canes were also produced using a new bioadhesive, obtained from the grape cane extract and citric acid. The self-condensation reaction of the grape cane extracts, and the curing reaction with citric acid, were studied by FTIR-ATR and ABES showing the feasibility of this new bioadhesive formulation. Looking for a zero-waste process, the effect of the type of raw material (fresh grape cane, solid by-product of the extraction) and of the extract used on the properties of particleboard were also studied. Citric acid was demonstrated to be a good crosslinking agent for grape cane extract. This work shows that it is possible to produce a new lignocellulosic product based only on grape cane particles using a binder based on grape cane extracts and citric acid. The implemented methodology allowed producing particleboards with applicability in the food-packaging industry, minimizing the waste generated in the process.

Using Graphene-Based Materials for Stiff and Strong Poly(ethylene glycol) Hydrogels.

Blood-contacting devices are increasingly important for the management of cardiovascular diseases. Poly(ethylene glycol) (PEG) hydrogels represent one of the most explored hydrogels to date. However, they are mechanically weak, which prevents their use in load-bearing biomedical applications (e.g., vascular grafts, cardiac valves). Graphene and its derivatives, which have outstanding mechanical properties, a very high specific surface area, and good compatibility with many polymer matrices, are promising candidates to solve this challenge. In this work, we propose the use of graphene-based materials as nanofillers for mechanical reinforcement of PEG hydrogels, and we obtain composites that are stiffer and stronger than, and as anti-adhesive as, neat PEG hydrogels. Results show that single-layer and few-layer graphene oxide can strengthen PEG hydrogels, increasing their stiffness up to 6-fold and their strength 14-fold upon incorporation of 4% w/v (40 mg/mL) graphene oxide. The composites are cytocompatible and remain anti-adhesive towards endothelial cells, human platelets and Staphylococcus aureus, similar to neat hydrogels. To the best of our knowledge, this is the first work to report such an increase of the tensile properties of PEG hydrogels using graphene-based materials as fillers. This work paves the way for the exploitation of PEG hydrogels as a backbone material for load-bearing applications.

The Potential of Visible Spectroscopy as a Tool for the In-Line Monitoring of Lignin Methylolation.

Out of the 50 to 70 million tons of lignin that are produced annually, only 1 to 2% are used for value-added products. Currently, 90% of the total market of this compound corresponds to lignosulphonates (LS). The most successful industrial attempts to use lignin for wood adhesives rely on using it as a partial substitute in phenol-formaldehyde or urea-formaldehyde resins. However, lignin's aromatic ring presents a low number of reactive sites. Several methods have been proposed to improve its reactivity, such as prior methylolation with formaldehyde. Off-line methods are commonly applied to monitor this reaction's progress, but this introduces a significant delay in the analysis. This study proposes a new method for in-line monitoring of the methylolation reaction using visible spectroscopy. In order to monitor the reaction progress, principal component analysis was applied to the spectra, and the obtained scores were analyzed. When these results were plotted against those obtained by the off-line methods, a satisfactory regression was obtained at 50 °C (R2 = 0.97) and 60 °C (R2 = 0.98) for two different LS samples. Therefore, it was concluded that visible spectroscopy is a promising technique for studying lignin methylolation.

Lignosulphonates as an Alternative to Non-Renewable Binders in Wood-Based Materials.

Lignin is a widely abundant renewable source of phenolic compounds. Despite the growing interest on using it as a substitute for its petroleum-based counterparts, only 1 to 2% of the global lignin production is used for obtaining value-added products. Lignosulphonates (LS), derived from the sulphite pulping process, account for 90% of the total market of commercial lignin. The most successful industrial attempts to use lignin for wood adhesives are based on using this polymer as a partial substitute in phenol-formaldehyde or urea-formaldehyde resins. Alternatively, formaldehyde-free adhesives with lignin and lignosulphonates have also been developed with promising results. However, the low number of reactive sites available in lignin's aromatic ring and high polydispersity have hindered its application in resin synthesis. Currently, finding suitable crosslinkers for LS and decreasing the long pressing time associated with lignin adhesives remains a challenge. Thus, several methods have been proposed to improve the reactivity of lignin molecules. In this paper, techniques to extract, characterize, as well as improve the reactivity of LS are addressed. The most recent advances in the application of LS in wood adhesives, with and without combination with formaldehyde, are also reviewed.

Graphene Oxide Topical Administration: Skin Permeability Studies.

Nanostructured carriers have been widely used in pharmaceutical formulations for dermatological treatment. They offer targeted drug delivery, sustained release, improved biostability, and low toxicity, usually presenting advantages over conventional formulations. Due to its large surface area, small size and photothermal properties, graphene oxide (GO) has the potential to be used for such applications. Nanographene oxide (GOn) presented average sizes of 197.6 ± 11.8 nm, and a surface charge of -39.4 ± 1.8 mV, being stable in water for over 6 months. 55.5% of the mass of GOn dispersion (at a concentration of 1000 µg mL-1) permeated the skin after 6 h of exposure. GOn dispersions have been shown to absorb near-infrared radiation, reaching temperatures up to 45.7 °C, within mild the photothermal therapy temperature range. Furthermore, GOn in amounts superior to those which could permeate the skin were shown not to affect human skin fibroblasts (HFF-1) morphology or viability, after 24 h of incubation. Due to its large size, no skin permeation was observed for graphite particles in aqueous dispersions stabilized with Pluronic P-123 (Gt-P-123). Altogether, for the first time, Gon's potential as a topic administration agent and for delivery of photothermal therapy has been demonstrated.