Nanocomposites of PBAT and cellulose nanocrystals modified by in situ polymerization and melt extrusion

Cellulose nanocrystals (CNC) were successfully grafted with a low molecular weight poly(butylene glutarate) through an in situ polymerization procedure. The grafting treatment decreased the CNC hydrophilic character and increased the onset of their thermal degradation by approximately 20°C, thus increasing the possibilities of CNC application. Composites of grafted and nongrafted CNC with a poly(butylene‐adipate‐co‐terephthalate) (PBAT) matrix were prepared by melt extrusion. The CNC addition led to an increase of 50% of the tensile elastic modulus of the PBAT. In addition, dynamic mechanical thermal analysis showed that the composite with CNC retained its high modulus even at temperatures far above the glass transition temperature of PBAT. At 60°C the storage modulus of the composite with CNC was approximately 200% higher than that of the pure PBAT. Thus, in this work, nanocomposites of improved properties were obtained through a combination of in situ polymerization and melt extrusion. POLYM. ENG. SCI., 56:1339–1348, 2016. © 2016 Society of Plastics Engineers     

Sorption of propylene and propane in polyurethane membranes containing silver nanoparticles

The preparation of a facilitated transport membrane of polyurethane (PU) containing silver nanoparticles is reported. The propylene and propane sorption was investigated aiming at the selective separation from C3s mixtures. The silver particles were photogenerated in situ into the polyurethane matrix using UV light radiation and silver triflate (AgCF₃SO₃) as precursor. The morphological properties of these membranes (PUAg) reveled great dispersion of silver particles, which size was smaller than 110 nm. The propylene solubility in PUAg resulted more than four times superior to the one for the pure PU membrane, revealing the high affinity between silver and propylene. Flory–Huggins theory was more accurate to describe the propylene sorption behavior in PUAg than Henry's model. The ideal solubility selectivity of PUAg membrane resulted 24.4, indicating that there is a good potential for an industrial application aiming at the separation of propylene/propane. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42916.     

The Impact of Polyoxyethylene Sorbitan Surfactants in the Microstructure and Rheological Behaviour of Emulsions Made With Melted Fat From Cupuassu (<Emphasis Type="Italic">Theobroma grandiflorum</Emphasis>)

Cupuassu fat is a good candidate for partial substitution of cocoa butter in many products, including emulsions. However, for such use it is necessary to know the characteristics of the products prepared with cupuassu fat. Therefore, the main goal of this work is to characterize emulsions prepared with cupuassu fat using the surfactants Tween^® 60, Tween^® 80 and Tween^® 85 as emulsifiers. The emulsions were prepared at 43 °C with addition of 0.5 or 1.5 % (w/v) of surfactant and compared with an emulsion without surfactant. All emulsions were analysed by conductivity, stability, pH, optical microscopy, rheology and oxidative stability. It was verified that the emulsions prepared with Tween^® 60 and Tween^® 80 have higher stability, smaller droplet size and higher apparent viscosity. Also, these properties are positively influenced by the concentration of the surfactant. On the other hand, emulsions prepared with Tween 85 or without surfactant reached unsatisfactory results. The rheological behaviour of the emulsions was adequately described by both Herschel-Bulkley and Mizhari-Berki models revealing pseudoplastic character. These emulsions also present strong gel behaviour, with storage modulus higher than loss modulus. In conclusion, cupuassu fat can be used as oil phase for emulsions products and this characterization helps to understand their behaviour in order to increase their use in food industry.     

Hydromorphological,hydraulic and ecological effects of restored wood: findings and reflections from an academic partnership approach

Large wood (re)introduction can deliver multiple benefits in river restoration, but there is a dearth of the detailed and longer‐term post‐project monitoring and evaluation required for improving best practice. We present findings from an academic partnership approach to post‐project evaluation, based on successive MSc research projects on restored large wood in the Loddon catchment, UK. Field and modelling data reveal: (i) key differences in large wood features between restored and natural reaches; (ii) increased hydraulic retention and changes to mesohabitats associated with large wood; (iii) differences in macroinvertebrate community composition around large wood but a lack of site‐level effects; (iv) interactions between macrophytes and large wood that may be specific to restored reaches; (v) a need for further field and modelling studies to inform the accurate representation of large wood in hydraulic models. Some key challenges in partnership working are identified to aid planning and effectiveness of future collaborations.     

Synthesis and Theoretical Study of New Guanylated Cyclophosphazenes and Their Use in the CO2 Fixation into Styrene Carbonate

Three new guanylated cyclophosphazenes G1–G3 have been synthesized through the catalytic guanylation of three different bi, tetra and hexa (p-aminophenoxy)-cyclophosphazenes by using N,N’-diisopropylcarbodiimide as guanylating agent, ZnEt₂ as catalyst and dry tetrahydrofuran as solvent. The resulting products have been characterized by ¹H, ¹³C{¹H} and ³¹P{¹H} NMR spectroscopy. The hexaguanylated cyclophosphazenes exhibit a deep purple colour, unusual for this type of compounds. The electronic structure of these compounds was investigated by carrying out density functional calculations at PBE-D3(BJ)/TZP level of theory. The molecular structural analysis reveals that aromatic rings are stacked and time dependent density functional calculations show that a charge transfer electronic transition occurs between the aromatic rings which absorb light around 500–700 nm. Finally, the catalytic usefulness of guanylated cyclophosphazene compounds G1–G3 has been proven by the preparation of styrene carbonate from the reaction between styrene oxide and carbon dioxide.

     

Senescent CD4+CD28− T Lymphocytes as a Potential Driver of Th17/Treg Imbalance and Alveolar Bone Resorption during Periodontitis

Senescent cells express a senescence-associated secretory phenotype (SASP) with a pro-inflammatory bias, which contributes to the chronicity of inflammation. During chronic inflammatory diseases, infiltrating CD4⁺ T lymphocytes can undergo cellular senescence and arrest the surface expression of CD28, have a response biased towards T-helper type-17 (Th17) of immunity, and show a remarkable ability to induce osteoclastogenesis. As a cellular counterpart, T regulatory lymphocytes (Tregs) can also undergo cellular senescence, and CD28⁻ Tregs are able to express an SASP secretome, thus severely altering their immunosuppressive capacities. During periodontitis, the persistent microbial challenge and chronic inflammation favor the induction of cellular senescence. Therefore, senescence of Th17 and Treg lymphocytes could contribute to Th17/Treg imbalance and favor the tooth-supporting alveolar bone loss characteristic of the disease. In the present review, we describe the concept of cellular senescence; particularly, the one produced during chronic inflammation and persistent microbial antigen challenge. In addition, we detail the different markers used to identify senescent cells, proposing those specific to senescent T lymphocytes that can be used for periodontal research purposes. Finally, we discuss the existing literature that allows us to suggest the potential pathogenic role of senescent CD4⁺CD28⁻ T lymphocytes in periodontitis.     

Physicochemical and Theoretical Characterization of a New Small Non-Metal Schiff Base with a Differential Antimicrobial Effect against Gram-Positive Bacteria

Searching for adequate and effective compounds displaying antimicrobial activities, especially against Gram-positive bacteria, is an important research area due to the high hospitalization and mortality rates of these bacterial infections in both the human and veterinary fields. In this work, we explored (E)-4-amino-3-((3,5-di-tert-butyl-2-hydroxybenzylidene)amino) benzoic acid (SB-1, harboring an intramolecular hydrogen bond) and (E)-2-((4-nitrobenzilidene)amino)aniline (SB-2), two Schiff bases derivatives. Results demonstrated that SB-1 showed an antibacterial activity determined by the minimal inhibitory concentration (MIC) against Staphylococcus aureus, Enterococcus faecalis, and Bacillus cereus (Gram-positive bacteria involved in human and animal diseases such as skin infections, pneumonia, diarrheal syndrome, and urinary tract infections, among others), which was similar to that shown by the classical antibiotic chloramphenicol. By contrast, this compound showed no effect against Gram-negative bacteria (Klebsiella pneumoniae, Escherichia coli, and Salmonella enterica). Furthermore, we provide a comprehensive physicochemical and theoretical characterization of SB-1 (as well as several analyses for SB-2), including elemental analysis, ESMS, ¹H and ¹³C NMR (assigned by 1D and 2D techniques), DEPT, UV-Vis, FTIR, and cyclic voltammetry. We also performed a computational study through the DFT theory level, including geometry optimization, TD-DFT, NBO, and global and local reactivity analyses.     

Electrospun curcumin/polycaprolactone/copolymer F-108 fibers as a new therapy for wound healing

The application of fibers associated with drugs is a promising alternative to meet the clinical needs of tissue repair. Curcumin exhibits great cicatricial potential because it has numerous pharmacological properties. This research aimed to produce fibers of polycaprolactone and copolymer F-108 associated with curcumin and to evaluate in vivo their action on the process of wound healing. The fibers were produced by electrospinning technique and characterized by scanning electron microscopy (SEM), X-ray diffractometry (XRD), and fluorescence microscopy. They were applied in cutaneous wounds of rats for the analysis of photoacoustic permeation and histological study. The characterization showed that the electrospinning allowed the preparation of homogeneous material with curcumin. The fibers benefited healing of the wounds and allowed the permeation of curcumin at all stages. The use of PCL/F-108 fibers allowed the elaboration of a new curcumin delivery system, improving its bioavailability and action in the healing of excisional wound. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48415.     

Formulation of a Biodegradable Detergent for Cleaning Oily Residues Generated during Industrial Processes

The use of toxic petroleum-based heavy oils is common in industrial processes. The cleaning of machines, equipment, and other surface covered in these oils is achieved with expensive products that are often also toxic and harmful to both the health of workers and the environment. The present paper proposes the development of a sustainable biodetergent made from plant-based materials. Tests were performed to determine the properties of the biodetergent in terms of its surfactant and emulsifying capacities, stability, toxicity, and the removal of heavy oil from glass plates and metallic surfaces. The formulation was composed of a natural solvent (cottonseed oil), a plant-based surfactant agent (saponin), and two natural stabilizers (carboxymethylcellulose and glycerine). The formulation was stable, nontoxic, and highly efficient, removing 100% of the heavy oil from glass and metallic surfaces. This solution developed in this study could be used in diverse industries with the need to clean machines and parts encrusted with oil and grease as well as the cleaning of floors covered with petroleum-based residues. A preliminary analysis of the economic feasibility of using the detergent was carried out at a Brazilian power plant. Besides the reduction in environmental impact due to the use of a nontoxic, biodegradable product as well as the reduction in health risks to workers associated with toxic cleaning products, this new product can have a considerable impact on the market as an environmentally friendly solution.     

New Formulation of a Methylseleno-Aspirin Analog with Anticancer Activity Towards Colon Cancer

Aspirin (ASA) has attracted wide interest of numerous scientists worldwide thanks to its chemopreventive and chemotherapeutic effects, particularly in colorectal cancer (CRC). Incorporation of selenium (Se) atom into ASA has greatly increased their anti-tumoral efficacy in CRC compared with the organic counterparts without the Se functionality, such as the promising antitumoral methylseleno-ASA analog (1a). Nevertheless, the efficacy of compound 1a in cancer cells is compromised due to its poor solubility and volatile nature. Thus, 1a has been formulated with native α-, β- and γ-cyclodextrin (CD), a modified β-CD (hydroxypropyl β-CD, HP-β-CD) and Pluronic F127, all of them non-toxic, biodegradable and FDA approved. Water solubility of 1a is enhanced with β- and HP- β-CDs and Pluronic F127. Compound 1a forms inclusion complexes with the CDs and was incorporated in the hydrophobic core of the F127 micelles. Herein, we evaluated the cytotoxic potential of 1a, alone or formulated with β- and HP- β-CDs or Pluronic F127, against CRC cells. Remarkably, 1a formulations demonstrated more sustained antitumoral activity toward CRC cells. Hence, β-CD, HP-β-CD and Pluronic F127 might be excellent vehicles to improve pharmacological properties of organoselenium compounds with solubility issues and volatile nature.