Development of lactic acid based chain extender and soybean oil-derived polyurethanes for ecofriendly sustained drug delivery systems.

In the present study, a range of sustainable, biocompatible and biodegradable polyurethanes (PU-1 to PU-4) were synthesized using different combinations of biobased polyol (obtained through the epoxidation of soybean oil, followed by ring opening with ethanol) and polyethylene glycol (PEG) and isophorone diisocyanate. The sustainable chain extender used in this study was synthesized by the esterification of lactic acid with ethylene glycol (EG). The synthesized PU samples were characterized through scanning electron microscopy (SEM), Fourier transformed infrared (FTIR) and nuclear magnetic resonance (1H NMR and 13C NMR) spectroscopy. Wetting ability and thermal degradation analysis (TGA) of the samples were also studied. Subsequently, these PUs were examined as potential drug delivery systems using Gabapentin as a model drug, which was loaded in the polymer matrix using the solvent evaporation method. The drug release studies were carried out in 0.06 N HCl as a release medium according to the method outlined in the United States Pharmacopeia. The maximum drug release was observed for sample PU-P1, which was found to be 53.0 % after 6 h. Moreover, a comparison of different PU samples revealed a trend wherein the values of drug release were decreased with an increase in the PEG content.

Decrease of radiation-induced skin reactions in breast cancer patients by preventive application of film dressings-a systematic review.

PURPOSE: Radiation-induced skin reactions remain one of the most frequent side effects of adjuvant radiotherapy for breast cancer, which is the most common global malignancy. In individual cases, we observed a decrease in radiation dermatitis under film dressings used for skin marking purposes. Therefore, we decided to revise the available evidence regarding the prophylactic use of film dressings to reduce radiation dermatitis in breast cancer patients. METHODS: On 20 March 2023, we conducted a systematic review of literature for randomized controlled trials published in the English, German, French, or Spanish language, available in the PubMed database. RESULTS: Of 82 publications, 9 full texts were assessed and 6 randomized controlled trials were included in the final synthesis. Two trials analyzed the application of polyurethane film (Hydrofilm, Paul Hartmann AG, Heidenheim, Germany), the other four of silicone-based polyurethane film (Mepitel film, Molnlycke Health Care Limited, Milton Keynes, United Kingdom). The evaluation scales Common Terminology Criteria for Adverse Events (CTCAE), Radiation Therapy Oncology Group (RTOG), and the Radiation-Induced Skin Reaction Assessment Scale (RISRAS) were used for assessment. All six trials, with a total of 788 patients yielding data for analysis, demonstrate a significant decrease in radiation-induced skin reactions by use of the film (mainly p < 0.001). CONCLUSION: Our analysis demonstrates a significant decrease in radiation-induced skin reactions by prophylactically applied film dressings in breast cancer patients. Consequent preventive use of film dressings might systematically reduce acute radiation-induced skin reactions in these patients.

The effect of chemical bond and solvent solubility parameter on stability and absorption value of functionalized PU sponge.

Seawater pollution from various sources such as industrial effluents, ship washing at sea, and oil spills harm humans and the marine environment. Therefore, finding ways to eliminate this pollution is crucial. This study successfully modified a polyurethane sponge through a simple dip-coating method with functionalized graphene oxide incorporating octadecylamine and oleic acid, resulting in a hydrophobic sponge capable of absorbing crude oil and various organic solvents. Characterization analyses confirmed the synthesis. The absorption capacity of the modified sponges was examined, for example, the PU sponge has absorbed 4 g/g engine oil, while the modified GO-ODA-PU sponge has increased its absorption to 36 g/g. The GO-ODA-PU sponge demonstrated great reusability compared to the GO-OA-PU sponge owing to the strong covalent bond formed between GO and ODA, which is superior to the weak hydrogen bond formed between GO and OA. The absorption capacity of the GO-OA-PU sponge decreased by 30%. The contact angle test showed that GO-ODA-PU and GO-OA-PU sponges had contact angles of 131° and 115°, respectively. Additionally, the GO-ODA-PU sponge performed optimally for semi-polar solvents in the solubility parameter range of 18-19, with its absorption capacity reaching its maximum value. The amount of oil recycling is even possible up to 98%.

Polyurethane Foam as a Novel Material for Ochratoxin A Removal in Tea and Herbal Infusions-A Quantitative Approach.

A novel solid-phase extraction methodology followed by UHPLC-MS/MS has been developed for Ochratoxin A (OTA) analysis in herbal infusions. For this purpose, a commercial polyurethane foam (PUF) was used as sorbent, and the experimental conditions were fully optimized. The strategy was satisfactory for reducing the matrix effect and allowed for OTA quantification in black tea and herbal infusions, with suitable recoveries and quantitation limits in agreement with those required by the maximum levels allowed by current regulations. The achieved results demonstrated the unprecedented use of polyurethane foam as an effective alternative for OTA retention and quantification in herbal infusions with the advantages of simple preparation, time saving, sustainability, and low cost for routine analysis.

Polyols and Polyurethane Foams Based on Water-Soluble Chitosan.

At present, majority of polyols used in the synthesis of polyurethane foams are of petrochemical origin. The decreasing availability of crude oil imposes the necessity to convert other naturally existing resources, such as plant oils, carbohydrates, starch, or cellulose, as substrates for polyols. Within these natural resources, chitosan is a promising candidate. In this paper, we have attempted to use biopolymeric chitosan to obtain polyols and rigid polyurethane foams. Four methods of polyol synthesis from water-soluble chitosan functionalized by reactions of hydroxyalkylation with glycidol and ethylene carbonate with variable environment were elaborated. The chitosan-derived polyols can be obtained in water in the presence of glycerol or in no-solvent conditions. The products were characterized by IR, 1H-NMR, and MALDI-TOF methods. Their properties, such as density, viscosity, surface tension, and hydroxyl numbers, were determined. Polyurethane foams were obtained from hydroxyalkylated chitosan. The foaming of hydroxyalkylated chitosan with 4,4'-diphenylmethane diisocyanate, water, and triethylamine as catalysts was optimized. The four types of foams obtained were characterized by physical parameters such as apparent density, water uptake, dimension stability, thermal conductivity coefficient, compressive strength, and heat resistance at 150 and 175 °C. It has been found that the obtained materials had most of the properties similar to those of classic rigid polyurethane foams, except for an increased thermal resistance up to 175 °C. The chitosan-based polyols and polyurethane foams obtained from them are biodegradable: the polyol is completely biodegraded, while the PUF obtained thereof is 52% biodegradable within 28 days in the soil biodegradation oxygen demand test.

Self-healing waterborne polyurethane coatings with high transparence and haze via cellulose nanocrystal stabilized linseed oil Pickering emulsion.

Protection coatings with self-healing ability can significantly enhance their anti-corrosion properties and service life. In this study, self-healing waterborne polyurethane (WPU) coatings with high transparence and haze were facile fabricated via cellulose nanocrystal (CNC) stabilized linseed oil (LO) Pickering emulsion. Sustainable CNCs displayed outstanding emulsifying ability and stability to stabilize LO Pickering emulsion. The size of LO Pickering emulsion droplets decreases with the CNC concentration, while the emulsion fraction and surface coverage by CNCs increase with CNC concentration, leading to a more stable Pickering emulsion. The self-healing rates of WPU coatings at varied time, temperature, CNC and catalyst concentration were investigated. Higher temperature, larger emulsion droplets, and with driers employed as catalysts generally lead to faster self-healing rate. The WPU self-healing coatings displayed much better abrasion resistance and mechanical properties than pristine WPU due to the incorporation of CNCs. Moreover, the WPU self-healing coatings show a high transparence and haze due to light scattering, and their applications as coatings of lamp covers and glass to achieve uniform light distribution and privacy protection with high light transmission were further demonstrated.

Wound healing and antibacterial capability of electrospun polyurethane nanofibers incorporating Calendula officinalis and Propolis extracts.

In order to produce a healing accelerator antibacterial wound dressing, different electrospun polyurethane (PU)-based nanofibers inclusive Calendula officinalis and Propolis ethanolic extracts were fabricated. The measurement of minimum inhibitory concentrations (MIC) against Methicillin-resistant Staphylococcus aureus (MRSA) determined the concentrations of incorporating extracts. Then the morphological properties of the produced polyurethane (PU), polyurethane/C. officinalis (PU/CO), polyurethane/Propolis (PU/PR), polyurethane/C. officinalis/Propolis (PU/CO/PR) were analyzed by scanning electron microscopy (SEM). The physicochemical features and biological characteristics of the fabricated nanofibers were evaluated. Subsequently, the antibacterial and wound-healing efficiency of electrospun wound dressings were tested under in vivo situation. The electrospun PU/CO/PR nanofiber illustrated the most degree of antibacterial, antioxidant, and cell proliferation efficiencies. In vivo examination and histological analysis confirmed significant improvement in the complete, well-organized wound-healing process in MRSA-infected wounds treated with PU/CO/PR. These outcomes described PU/CO/PR electrospun nanofibers as a wound dressing that can significantly facilitate wound healing with notable antibacterial, antioxidant, and cell proliferation properties.

Influence of Phosphorus Structures and Their Oxidation States on Flame-Retardant Properties of Polyhydroxyurethanes.

This article focuses on the synthesis of polyhydroxyurethane (PHU) materials containing novel phosphorus flame retardants (FR). Four different phosphorus compounds were grafted onto cyclic carbonate: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), diethyl phosphite (DEP), diphenyl phosphite (DPP) and dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO). Thus, three novel phosphorus reactive cyclic carbonates which have never been reported so far were synthetized. Phosphorus FR containing PHU materials were characterized by FTIR to evidence the total conversion of the cyclic carbonate. Moreover, the gel contents up to 80% confirmed the formation of the polymer network. Then, the thermal stability and the flame-retardant properties were investigated by thermogravimetric analyses, cone calorimeter and pyrolysis combustion flow calorimeter. The mode of action of phosphorus compounds, depending on the oxidation state, was especially highlighted. Phosphonate (+III) provided better action in a condensed phase than phosphinate thanks to a more efficient char formation. Among phosphonates, differences were observed in terms of char-formation rate and expansion. DEP provided the best flame-retardant properties, with a reduction of 76% of pHRR with 2 wt% of phosphorus in cone calorimeter analysis. Therefore, this article highlighted the different modes of action of phosphorus flame retardants, depending on the oxidation state of phosphorus, in PHU materials.

Castor oil-based waterborne polyurethane/tunicate cellulose nanocrystals nanocomposites for wearable strain sensors.

In this study, tunicate cellulose nanocrystals (TCNCs) were introduced into castor oil-based waterborne polyurethane (WPU) to prepare bio-based nanocomposites through a simple solution blending method. The effect of TCNCs content on the particle size and stability of the composite dispersions, as well as the thermophysical and mechanical properties of the composite films were studied and discussed. The unique structure and properties of TCNCs, such as high crystallinity, large aspect ratio and high modulus, not only greatly improved the storage stability of WPU, but also showed significant reinforcing/toughening effects and excellent compatibility to WPU. By drip-coating silver nanowires (AgNWs) on the surface of the composite films, the flexible strain sensors were fabricated, which showed excellent sensitivity in monitoring human movement.

Enhanced biological nitrogen and phosphorus removal from sewage driven by fermented glycerol: comparative assessment between sequencing batch- and continuously fed-structured fixed bed reactor.

The nutrient biological removal from sewage, especially from anaerobic reactor effluents, still represents a major challenge in conventional sewage treatment plants. In this work, the nitrogen and phosphorus removal from anaerobic pre-treated domestic sewage in an up-flow anaerobic sludge blanket (UASB) reactor was assessed in a structured fixed bed reactor (SFBR) operated in a continuous and in a batch mode using polyurethane foam as material support for biomass and fermented glycerol as the exogenous carbon source. The SFBR was operated as a sequencing batch reactor with cycles of 90, 120, and 150 min under anaerobic, oxic, and anoxic conditions, respectively, reaching average efficiencies for total nitrogen and phosphorus removal of 88% and 56%, respectively. Fermented glycerol was added during the non-aerated periods. Under continuous feeding, the SFBR was operated with aeration/non-aeration periods of 2/1 (h) and 3/1 (h), hydraulic retention time of 12 h, and a recirculation ratio of 3. Without fermented glycerol addition, the maximum removal of total nitrogen (TN) reached 42%, while adding glycerol in the non-aerated period improved TN removal to 64.9% (2/1 h) and 69.5% (3/1 h). During continuous operation, no phosphorus removal was observed, which was released during the non-aerated period, remaining in the effluent. Optical microscopy analyses confirmed the presence of polyphosphate granules and of the phosphorus accumulating organisms in the reactor biofilm. It was concluded that the batch feeding method was determinant for phosphorus removal. The structured fixed bed reactor with polyurethane foam proved to be feasible in the removal of organic matter and nutrients remaining in the UASB reactor effluent.

Development of a polyurethane-coated thin film solid phase microextraction device for multi-residue monitoring of pesticides in fruit and tea beverages.

A novel solid-phase microextraction device coated with an efficient and cheap thin film of polyurethane was developed for trace determination of 13 widely used pesticides in fruit and tea beverages. A round-shaped polyurethane film covering the bottom of a glass vial was fabricated as the sorbent to exhibit a superior capacity for preconcentrating target compounds and reducing matrix interferences. After optimization of the key parameters including the film type, extraction time, solution pH, ionic strength, desorption solvent, and conditions, this device allowed an efficient adsorption-desorption cycle for the pesticides accomplished in one vial. Coupled with gas chromatography-electron capture detection, the polyurethane-coated thin film microextraction method was successfully established and applied for the analysis of real fruit and tea drinks, showing low limits of detection (0.001-0.015 µg/L), wide linear ranges (1.0-500.0 µg/L, r2  > 0.9931), good relative recoveries (77.2%-106.3%) and negligible matrix effects (86.1%-107.5%) for the target pesticides. The proposed approach revealed strong potential of extending its application by flexibly modifying the type or size of the coating film. This study provides insights into the enrichment of contaminants from complex samples using inexpensive and reusable microextraction devices that can limit the environmental and health impact of the sample preparation protocol.

Bio-based Polyurethane Based on a Dynamic Covalent Network with Damage Tolerance for Controlled Release of Fertilizers.

Bio-based polyurethanes are promising for the controlled release of nutrients and fertilizers, but their toughness and plasticity need to be improved. We developed a smooth, dense, elastic, and indestructible bio-based polyurethane (BPU) coating with a nutrient controlled release ∼150% superior, a tensile strength ∼300% higher, and a toughness ∼1200% higher than those for the original BPU coating. Through a one-step reaction of soybean oil polyols (accounting for more than 60%), isocyanate, and benzil dioxime, the dynamic covalent network based on oxime-carbamate replaces part of irreversible covalent cross-linking. The dynamic fracture-bonding reaction in the modified coating BPU can effectively promote the hydrogen bond recombination and oxime-carbamate chain migration in the coating process, which avoids the structural defects caused by coating tear and fertilizer collision. This work provides a simple and versatile strategy for building controlled-release fertilizer coatings.

Thermal Insulating Rigid Polyurethane Foams with Bio-Polyol from Rapeseed Oil Modified by Phosphorus Additive and Reactive Flame Retardants.

In this article, rigid polyurethane foams obtained with the addition of a bio-polyol from rapeseed oil, were modified with the dimethyl propane phosphonate as additive flame retardant and two reactive flame retardants diethyl (hydroxymethyl)phosphonate and diethyl bis-(2-hydroxyethyl)-aminomethylphosphonate. The influence of used flame retardants on the foaming process and characteristic processing times of tested polyurethane systems were determined. The obtained foams were tested in terms of cell structure, physical and mechanical properties, as well as flammability. Modified foams had worse mechanical and thermal insulation properties, caused by lower cellular density and higher anisotropy coefficient in the cross-section parallel to the foam rise direction, compared to unmodified foam. However, the thermal conductivity of all tested foam materials was lower than 25.82 mW/m∙K. The applied modifiers effectively reduced the flammability of rigid polyurethane foams, among others, increasing the oxygen index above 21.4 vol.%, reducing the total heat released by about 41-51% and the rate of heat release by about 2-52%. A correlation between the limiting oxygen index values and both total heat released parameters from the pyrolysis combustion flow calorimetry and cone calorimetry was observed. The correlation was also visible between the value of the heat release capacity (HRC) parameter obtained from the pyrolysis combustion flow calorimetry and the maximum average rate of heat emission (MARHE) from the cone calorimeter test.

Supertough poly(lactic acid)/bio-polyurethane blends fabricated by dynamic self-vulcanization of dual difunctional monomers.

In this work, a facile and efficient strategy known as 'dynamic self-vulcanization of dual difunctional monomers' was reported to toughen poly(lactic acid) (PLA) with in-situ formed crosslinked bio-polyurethane (PCPUE) phase from plant oil-derived hydrogenated dimer diol (Pripol) and hexamethylene diisocyanate (HDI). By simply adjusting equivalent ratios (nNCO/nOH) of complementary functional groups between these two difunctional toughening monomers from 1.0 to 2.2 while fixing their total feeding content at 20 wt%, the notched impact strength (IS) and phase morphologies of PLA blends can be tailored in a broad range. When the ratio reached 1.6, the maximum IS value up to 87.1 kJ/m2 (about 28 times that of neat PLA) was achieved with an elongation-at-break of ~223 %. Based on the analysis on reaction mechanism and phase morphologies, the optimum interfacial compatibility between PLA and PCPUE phases in junction with the proper crosslinking density of rubbery PCPUE phase was considered to be responsible for such a remarkable improvement in impact toughness.

Anti-smudge and self-cleaning characteristics of waterborne polyurethane coating and its construction.

A novel anti-smudge coating, based on waterborne polyurethane (WPU), Polydimethylsiloxane (PDMS) and Hexamethoxymethylmelamine (HMMM) was constructed. Specifically, hydroxyl capped WPU emulsions grafted with PDMS (WPU-g-PDMSX) were prepared firstly, then the Hexamethoxymethylmelamine (HMMM) was used as the crosslinking agent to block the polar hydrophilic hydroxyl groups and the carboxyl groups in WPU-g-PDMSX and increase the cross-linking density of the coating. Oily markers, water, hexadecane, fingerprint liquid, and common liquids in life (milk, coffee, ink and cooking oil) were utilized to demonstrate the anti-graffiti and self-cleaning characteristics of coatings. Aside from having great transparency and exceptional resistance to liquid corrosion, the coating still retains its anti-smudge capabilities even when bent or impacted, and they also exhibit 5B adhesion and 5H pencil hardness. This work provides novel idea and strategy for the preparation of WPU anti-smudge coatings.

Improvement of bio-based polyurethane and its optimal application in controlled release fertilizer.

In the past decades, polyurethane has emerged as a new material that has been widely developed and applied in coated controlled release fertilizers (CRFs). Particularly in recent years, the excessive consumption of petroleum resources and increasing demand for sustainable development have resulted in considerable interest in bio-based polyurethane coated controlled-release fertilizers. This review article focuses on the application and progress of environmentally friendly bio-based materials in the polyurethane-coated CRF industry. We also explore prospects for the green and sustainable development of coated CRFs. Using animal and plant oils, starch, lignin, and cellulose as raw materials, polyols can be produced by physical, chemical, and biological means to replace petroleum-based materials and polyurethane film coating for CRFs can be prepared. Various modifications can also improve the hydrophobicity and degradability of polyurethane film. A growing body of research on bio-based polyurethane has revealed its great potential in the production and application of coated CRFs. The purpose of this review is to highlight the practicality of bio-based materials in the application of polyurethane-coated CRFs and to clarify their current limitations.

Selective Separation and Preconcentration of Caffeine from Natural and Pharmaceutical Products using New Polyurethane Foams

Abstract Two polyurethane foam-based sorbents (PUF) were synthesized by imprinting and grafting techniques and examined for selective separation and preconcentration of caffeine (CAF) in some pharmaceutical products and in black tea. Molecularly imprinted PUF was synthesized based on hydrogen-bonding interactions between CAF and alizarin yellow G (AYG) and subsequent polymerization into PUF. The static experiments indicated optimum sorption conditions at pH=6.5 and 5.5 for imprinted PUF (AY-IPUF) and grafted PUF (AY-GPUF), respectively. In the online experiments, the suitable preconcentration time was found to be 40 and 20s for (AY-IPUF) and (AY-GPUF), respectively, at a flow rate of 1.75 mL.min-1. Desorption of CAF has been affected by passing 500 µL of 0.05, 0.01 mol.L−1 HCl eluent onto (AY-IPUF) and (AY-GPUF), respectively. The online methods have provided satisfactory enrichment factors of 8.4 and 10.5 for (AY-IPUF) and (AY-GPUF), respectively. The time consumed for preconcentartion, elution and determination steps was 1.48 and 1.05 min, thus, the throughput was 42 and 57 h-1, for (AY-IPUF) and (AY-GPUF), respectively. The developed sorbents were studied for the determination of CAF in pharmaceutical samples which will be helpful to minimize caffeinism. Finally, in silico bioactivity, ADMET and drug-likeness predictive computational studies of caffeine were also carried out

Friction Dynamics of Wood Coated with Vegetable Oil.

Surface treatment of wood surface is an effective method to improve the physical properties. The friction dynamics of wood coated with vegetable oil were evaluated and compared to wood treated with polyurethane and untreated wood. The kinetic friction coefficient, µ k , was 0.39±0.01, which was smaller than the values for polyurethane-treated wood and untreated oak. The effect of the surface treatment was also observed in the dependence of velocity on the friction coefficient. The friction profile of the wood surface treated with vegetable oil was similar to that of untreated wood, and the friction coefficient was nearly constant, except in the static friction region of sliding out. These results suggest that wood treated with vegetable oil is suitable for inducing a smooth feel.

Combination of polyurethane and polymethyl methacrylate thin films as a microextraction sorbent for rapid adsorption and sensitive determination of neonicotinoid insecticides in fruit juice and tea by ultra high performance liquid chromatography with tandem mass spectrometry.

An economical and effective thin film microextraction (TFME) for simultaneous analysis of ten neonicotinoid insecticides and metabolites in fruit juice and tea, was developed based on the combination of polyurethane (PU) and polymethyl methacrylate (PMMA) films as the sorbent followed by ultra high performance liquid chromatography with tandem mass spectrometry. The PU/PMMA composite was evidenced to possess rapid adsorption and strong accumulation towards neonicotinoids compared with the films used alone. A series of parameters were optimized, and the agitation mode, film size, ionic strength, desorption solvent and sample pH were found to dominate the microextraction process rather than the extraction temperature, agitation time and sample volume. The thin films are cost effective and efficient for single use analysis, but still can be reused at least 8 times with no significant loss in performance. The ten neonicotinoids were measured with good recoveries (81.1-107.9%), high enrichment factors (up to 135), low limits of detection (0.001-0.1 µg L-1), and wide linearity range (1-500 µg L-1, r2>0.9981) in fruit juice (apple, lemon, and pomegranate) and tea (green tea and black tea) samples. The proposed method was successfully applied to commercial fruit and tea drinks, and no samples were tested positive on target neonicotinoids. The PU/PMMA based TFME has shown great potential as an alternative to exhaustive extraction techniques for routine screening of trace neonicotinoids in fruit juice and tea by simplifying the analytical procedure, shortening the operation time, and lowering the material expense.

Vermiculite Filler Modified with Casein, Chitosan, and Potato Protein as a Flame Retardant for Polyurethane Foams.

In this study, polyurethane (PU) composite foams were modified with 2 wt.% of vermiculite fillers, which were themselves modified with casein, chitosan, and potato protein. The impact of the fillers on selected properties of the obtained composites, including their rheological (foaming behavior, dynamic viscosity), thermal (temperature of thermal decomposition stages), flame-retardant (e.g., limiting oxygen index, ignition time, heat peak release), and mechanical properties (toughness, compressive strength (parallel and perpendicular), flexural strength) were investigated. Among all the modified polyurethane composites, the greatest improvement was noticed in the PU foams filled with vermiculite modified with casein and chitosan. For example, after the addition of modified vermiculite fillers, the foams' compressive strength was enhanced by ~6-18%, their flexural strength by ~2-10%, and their toughness by ~1-5%. Most importantly, the polyurethane composites filled with vermiculite filler and modified vermiculite fillers exhibited improved flame resistance characteristics (the value of total smoke release was reduced by ~34%, the value of peak heat release was reduced by ~25%).