Fast Response and Visual Transparency Switching Hydrochromic Film Based on the Rational Structure of Cellulose/Poloxamer Copolymers Design for Smart Window.

The authors are motivated to develop a series of hydrochromic copolymers with fast response, reversibility, repeatability, and visual transparency transition. The hydrochromic block copolymers are based on the rational ratio of hydrophilic segments of poloxamer block and hydrophobic segments of ethyl cellulose according to the preparation method of polyurethane. By tuning the ratio of hydrophilic segments or adding hygroscopic salts, the hydrochromic polymer is endowed with the ability to visualize the transparency in response to the relative humidity. Especially, the response time of the polymer is extremely shortened, up to 1 s for the optimized sample. Within the moisture stimulation, the hygroscopic swelling increases the film thickness, leading to a reversible transparency switching from a highly transparent state (82%) to an opaque white state (20.5%).

Synthesis of Sucrose-HDI Cooligomers: New Polyols for Novel Polyurethane Networks.

Sucrose-1,6-hexamethylene diisocyanate (HDI) cooligomers were synthesized and used as new polyols for poly(ε-caprolactone) (PCL)-based polyurethanes. The polyaddition reaction of sucrose and HDI was monitored by MALDI-TOF MS. It was found that by selecting appropriate reaction conditions, mostly linear oligomer chains containing 16 sucrose units could be obtained. For the synthesis of polyurethane networks, prepolymers were prepared by the reaction of poly(ε-caprolactone) (PCL, 10 kg/mol) with HDI or 4,4'-methylene diphenyl diisocyanate (MDI) and were reacted with sucrose-HDI cooligomers. The so-obtained sucrose-containing polyurethanes were characterized by means of attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FT IR), swelling, mechanical (uniaxial tensile tests) and differential scanning calorimetry (DSC).

Chemical and Mechanical Characterization of Licorice Root and Palm Leaf Waste Incorporated into Poly(urethane-acrylate) (PUA).

A poly(urethane-acrylate) polymer (PUA) was synthesized, and a sufficiently high molecular weight starting from urethane-acrylate oligomer (UAO) was obtained. PUA was then loaded with two types of powdered ligno-cellulosic waste, namely from licorice root and palm leaf, in amounts of 1, 5 and 10%, and the obtained composites were chemically and mechanically characterized. FTIR analysis of final PUA synthesized used for the composite production confirmed the new bonds formed during the polymerization process. The degradation temperatures of the two types of waste used were in line with what observed in most common natural fibers with an onset at 270 °C for licorice waste, and at 290 °C for palm leaf one. The former was more abundant in cellulose (44% vs. 12% lignin), whilst the latter was richer in lignin (30% vs. 26% cellulose). In the composites, only a limited reduction of degradation temperature was observed for palm leaf waste addition and some dispersion issues are observed for licorice root, leading to fluctuating results. Tensile performance of the composites indicates some reduction with respect to the pure polymer in terms of tensile strength, though stabilizing between data with 5 and 10% filler. In contrast, Shore A hardness of both composites slightly increases with higher filler content, while in stiffness-driven applications licorice-based composites showed potential due to an increase up to 50% compared to neat PUA. In general terms, the fracture surfaces tend to become rougher with filler introduction, which indicates the need for optimizing interfacial adhesion.

Vascular Polyurethane Prostheses Modified with a Bioactive Coating-Physicochemical, Mechanical and Biological Properties.

This study describes a method for the modification of polyurethane small-diameter (5 mm) vascular prostheses obtained with the phase inversion method. The modification process involves two steps: the introduction of a linker (acrylic acid) and a peptide (REDV and YIGSR). FTIR and XPS analysis confirmed the process of chemical modification. The obtained prostheses had a porosity of approx. 60%, Young's Modulus in the range of 9-11 MPa, and a water contact angle around 40°. Endothelial (EC) and smooth muscle (SMC) cell co-culture showed that the surfaces modified with peptides increase the adhesion of ECs. At the same time, SMCs adhesion was low both on unmodified and peptide-modified surfaces. Analysis of blood-materials interaction showed high hemocompatibility of obtained materials. The whole blood clotting time assay showed differences in the amount of free hemoglobin present in blood contacted with different materials. It can be concluded that the peptide coating increased the hemocompatibility of the surface by increasing ECs adhesion and, at the same time, decreasing platelet adhesion. When comparing both types of peptide coatings, more promising results were obtained for the surfaces coated with the YISGR than REDV-coated prostheses.

Eco-Friendly Ether and Ester-Urethane Prepolymer: Structure, Processing and Properties.

This study concerns bio-based urethane prepolymers. The relationship between the chemical structure and the thermal and processing parameters of bio-based isocyanate-terminated ether and ester-urethane prepolymers was investigated. Bio-based prepolymers were obtained with the use of bio-monomers such as bio-based diisocyanate, bio-based polyether polyol or polyester polyols. In addition to their composition, the bio-based prepolymers were different in the content of iso-cyanate groups content (ca. 6 and 8%). The process of pre-polymerization and the obtained bio-based prepolymers were analyzed by determining the content of unreacted NCO groups, Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, thermogravimetry, and rheological measurements. The research conducted facilitated the evaluation of the properties and processability of urethane prepolymers based on natural components. The results indicate that a significant impact on the processability has the origin the polyol ingredient as well as the NCO content. The thermal stability of all of the prepolymers is similar. A prepolymer based on a poly-ether polyol is characterized by a lower viscosity at a lower temperature than the prepolymer based on a polyester polyol. The viscosity value depends on the NCO content.

Design, Synthesis, Antibacterial, and Antitumor Activity of Linear Polyisocyanide Quaternary Ammonium Salts with Different Structures and Chain Lengths.

The development of organic polymer materials for disinfection and sterilization is thought of as one of the most promising avenues to solve the growth and spread of harmful microorganisms. Here, a series of linear polyisocyanide quaternary ammonium salts (L-PQASs) with different structures and chain lengths were designed and synthesized by polymerization of phenyl isocyanide monomer containing a 4-chloro-1-butyl side chain followed by quaternary amination salinization. The resultant compounds were characterized by 1H NMR and FT-IR. The antibacterial activity of L-PQASs with different structures and chain lengths against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) was evaluated by determining the minimum inhibitory concentrations (MICs). The L-POcQAS-M50 has the strongest antimicrobial activity with MICs of 27 µg/mL against E. coli and 32 µg/mL against S. aureus. When the L-PQASs had the same polymerization degree, the order of the antibacterial activity of the L-PQASs was L-POcQAS-Mn > L-PBuQAS-Mn > L-PBnQAS-Mn > L-PDBQAS-Mn (linear, polyisocyanide quaternary ammonium salt, monomer, n = 50,100). However, when L-PQASs had the same side chain, the antibacterial activity reduced with the increase of the molecular weight of the main chain. These results demonstrated that the antibacterial activity of L-PQASs was dependent on the structure of the main chain and the length of the side chain. In addition, we also found that the L-POcQAS-M50 had a significant killing effect on MK-28 gastric cancer cells.

Effect of New Eco-Polyols Based on PLA Waste on the Basic Properties of Rigid Polyurethane and Polyurethane/Polyisocyanurate Foams.

The aim of the presented research was to obtain two new eco-polyols based on waste polylactide (PLA) and to check the effect on the properties of rigid polyurethane (RPU) foams and, based on these, rigid polyurethane/polyisocyanurate (RPU/PIR) foams. The synthesis of eco-polyols was based on the transesterification reaction of melted PLA with diethylene glycol in the presence of an organometallic catalyst. Properties of the obtained eco-polyols were examined for their potential as raw materials for synthesis of rigid polyurethane and polyisocyanurate foams, i.e., hydroxyl value, acid value, density, viscosity, pH, water content. Spectroscopic studies (FTIR, 1H NMR and 13C NMR) were also carried out. Results of these tests confirmed the assumed chemical structure of the new polyols. RPU and RPU/PIR foam formulations were developed based on the obtained analytical results. Partial replacement of petrochemical polyol by eco-polyols in RPU and RPU/PIR foams decreased the value of apparent density, compressive strength, brittleness and water absorption. Moreover, all foams modified by eco-polyols showed higher resistance to aging. All RPU/PIR foams and most PRU foams modified by eco-polyols from waste PLA had better functional properties than the reference foams based on petrochemical polyol.

Starch-based isocyanate- and non-isocyanate polyurethane hybrids: A review on synthesis, performance and biodegradation.

The challenges related to the persistence of plastics in natural ecosystems fostered strong interest in developing biodegradable bioplastics. Among natural biopolymers, starch gained both academic and industrial interest owing to its impressive physicochemical properties. The use of starch in production of polyurethane (PU) composites not only yields PUs with outstanding mechanical properties but also makes the final PU products biodegradable. The hydrophilic nature of starch limits its dispersion in hydrophobic PU polymers, although it is a significant benefit in creating starch-embedded non-isocyanate polyurethane (NIPU) composites. We present a comprehensive overview to highlight important strategies that are used to improve the compatibility of starch with various PU matrices. This review also gives an overview of the recent advances in the synthesis of starch-NIPU hybrids. Moreover, we aim to deliver critical insight into strategies that boost the biodegradation characteristics of PUs along with a discussion on various methods to assess their biodegradation.

Biobased Polyurethane Composite Foams Reinforced with Plum Stones and Silanized Plum Stones.

In the following study, ground plum stones and silanized ground plum stones were used as natural fillers for novel polyurethane (PUR) composite foams. The impact of 1, 2, and 5 wt.% of fillers on the cellular structure, foaming parameters, and mechanical, thermomechanical, and thermal properties of produced foams were assessed. The results showed that the silanization process leads to acquiring fillers with a smoother surface compared to unmodified filler. The results also showed that the morphology of the obtained materials is affected by the type and content of filler. Moreover, the modified PUR foams showed improved properties. For example, compared with the reference foam (PUR_REF), the foam with the addition of 1 wt.% of unmodified plum filler showed better mechanical properties, such as higher compressive strength (~8% improvement) and better flexural strength (~6% improvement). The addition of silanized plum filler improved the thermal stability and hydrophobic character of PUR foams. This work shows the relationship between the mechanical, thermal, and application properties of the obtained PUR composites depending on the modification of the filler used during synthesis.

Bio-based Poly(hydroxy urethane)s: Synthesis and Pre/Post-Functionalization.

New and emerging demand for polyurethane (PU) continues to rise over the years. The harmful isocyanate binding agents and their integrated PU products are at the height of environmental concerns, in particular PU (macro and micro) pollution and their degradation problems. Non-isocyanate poly(hydroxy urethane)s (NIPUs) are sustainable and green alternatives to conventional PUs. Since the introduction of NIPU in 1957, the market value of NIPU and its hybridized materials has increased exponentially in 2019 and is expected to continue to rise in the coming years. The secondary hydroxyl groups of these NIPU's urethane moiety have revolutionized them by allowing for adequate pre/post functionalization. This minireview highlights different strategies and advances in pre/post-functionalization used in biobased NIPU. We have performed a comprehensive evaluation of the development of new ideas in this field to achieve more efficient synthetic biobased hybridized NIPU processes through selective and kinetic understanding.

Improved in vivo stability of silicon-containing polyurethane by fluorocarbon side chain modulation of the surface structure.

As a class of widely used biomedical materials, polyurethanes suffer from their insufficient stability in vivo. Although the commercialized silicone-polyetherurethanes (SiPEUs) have demonstrated excellent biostability compared with polyetherurethanes (PEUs) for long-term implantation, the usage of polydimethylsiloxane (PDMS) inevitably decreased the mechanical properties and unexpected breaches were observed. In this study, we introduced a fluorinated diol (FDO) into SiPEU to modulate the molecular interactions and micro-separated morphology. The fluorinated silicon-containing polyurethane (FSiPEU) was achieved with desirable silicone- and fluorine-enriched surfaces and mechanical properties at a low silicon content. As evidenced by in vitro culture of macrophages and in vivo hematoxylin-eosin (H&E) staining, FSiPEU demonstrated a minimized inflammatory response. After implantation in mice for 6 months, the material was devoid of significant surface degradation and had the least chain cleavage of soft segments. The results indicate that FSiPEU could be promising candidates for long-term implantation considering the combination of biostability, biocompatibility and mechanical performances.

Synthesis and molecular characterization of chitosan/alginate blends based polyurethanes biocomposites.

The present work aims to examine the structural properties of polyurethanes bio-composites with mole ratios of alginate and chitosan. For this concern, a two-step reaction mechanism was carried out; in the first step isocyanate (-NCO) terminated pre-polymer was synthesized by the reaction of hexamethylene diisocyanate (HMDI) and hydroxyl-terminated polybutadiene (HTPB). The pre-polymer was further extended with 1,4-butanediol (BDO), chitosan (CS) and alginate (ALG) in the second step. Structural and functional group elucidation was done by using Fourier Transform Infra-red (FT-IR) and proton nuclear magnetic resonance (1H NMR) spectroscopy. The crystallinity of the prepared samples was investigated by using X-ray diffraction (XRD) method, the maximum observed intensity was 7704 a.u. The thermal properties of polyurethane composites were carried out using thermogravimetric analysis (TGA) and differential scanning calorimeter (DSC). The TGA results showed that thermal stability of RPU-5 was 20 °C more than RPU-1 at each corresponding degradation temperature. It is observed all physical parameters like crystallinity, glass transition temperature, melting point are much dependent on ratio of chain extenders. Overall, CS based samples along with small amount of ALG showed better thermal properties.

Light-Activated Antimicrobial Surfaces Using Industrial Varnish Formulations to Mitigate the Incidence of Nosocomial Infections.

Evidence has shown that hospital surfaces are one of the major vehicles of nosocomial infections caused by drug-resistant pathogens. Smart surface coatings presenting multiple antimicrobial activity mechanisms have emerged as an advanced approach to safely prevent this type of infection. In this work, industrial waterborne polyurethane varnish formulations containing for the first time cationic polymeric biocides (SPBs) combined with photosensitizer curcumin were developed to afford contact-active and light-responsive antimicrobial surfaces. SPBs were prepared by atom transfer radical polymerization, which allows control over the polymer features that influence antimicrobial efficiency (e.g., molecular weight), while natural curcumin was employed to impart photodynamic activity to the surface. Antibacterial testing against Gram-negative Escherichia coli revealed that glass surfaces coated with the new formulations displayed photokilling effect under white-light (42 mW/cm2) irradiation within only 15 min of exposure. In addition, it was observed a combined antimicrobial effect between the two biocides (cationic SPB and curcumin), with a higher reduction in the number of viable bacteria observed for the surfaces containing cationic SPB/curcumin mixtures in comparison with the one obtained for surfaces only with polymer or without biocides. The waterborne industrial varnish formulations allowed the formation of homogeneous films without the need for addition of a coalescing agent, which can be potentially applied in diverse surface substrates to reduce bacterial transmission infections in healthcare environments.

A Biodegradable Chitosan-Polyurethane Cryogel with Switchable Shape Memory.

Cryogels are matrices that are formed in moderately frozen solutions of monomeric or polymeric precursors. They have the advantages of interconnected macropores, structural stability, and compressibility. Meanwhile, thermally induced shape memory is an attractive feature of certain functional materials. Although there have been several studies concerning shape-memory cryogels, little work has been conducted on shape-memory cryogels with biodegradability. In this study, a water-based biodegradable difunctional polyurethane with a shape-memory property was synthesized and used as the nanoparticulate crosslinker to react with chitosan to form a shape-memory cryogel. The thermally induced shape-memory mechanism was clarified using in situ wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS) during the shape-memory process. The in situ WAXS showed the changes of crystallinity in the crosslinker and the cryogel during the shape fixation and recovery processes. The in situ SAXS revealed the orientation of crystallinity of the crosslinker and the cryogel as the mechanism for shape memory. The strip-shape cryogel was deformed at 50 °C to U-shape and fixed at - 20 °C, which was squeezable at 25 °C and returned to the strip-shape at 50 °C in air. The shape recovery was further tested in water at two different temperatures. The injected cryogel recovered the U-shape in 4 °C water, representing elastic recovery, and transformed to a long strip in 37 °C water, representing the switchable shape memory. Moreover, the shape-memory cryogel sheet with a large dimension (10 mm × 10 mm × 1.1 mm cryogel sheet) or with complex structures (N, T, and U shapes) could be fixed as a rod, injected through a 16 G needle, and return to its original shape in 37 °C water, all of which could not be achieved by the conventional cryogel. Human mesenchymal stem cells grown in the shape-memory cryogel scaffolds displayed long-term proliferation and chondrogenic potential. Their unique injectability and cytocompatibility suggested potential applications of shape-memory cryogels as injectable and expandable templates for tissue engineering and minimally invasive surgery.

Recent Advances in Polyurethane/POSS Hybrids for Biomedical Applications.

Advanced organic-inorganic materials-composites, nanocomposites, and hybrids with various compositions offer unique properties required for biomedical applications. One of the most promising inorganic (nano)additives are polyhedral oligomeric silsesquioxanes (POSS); their biocompatibility, non-toxicity, and phase separation ability that modifies the material porosity are fundamental properties required in modern biomedical applications. When incorporated, chemically or physically, into polyurethane matrices, they substantially change polymer properties, including mechanical properties, surface characteristics, and bioactivity. Hence, this review is dedicated to POSS-PU composites that have recently been developed for applications in the biomedical field. First, different modes of POSS incorporation into PU structure have been presented, then recent developments of PU/POSS hybrids as bio-active composites for scaffolds, cardiovascular stents, valves, and membranes, as well as in bio-imaging and cancer treatment, have been described. Finally, characterization and methods of modification routes of polyurethane-based materials with silsesquioxanes were presented.

Favorable Antibacterial, Antibiofilm, Antiadhesion to Cells, and Biocompatible Polyurethane by Facile Surface Functionalization.

It is of paramount importance to prohibit biofilm formation in a wide range of implant devices, such as thermoplastic polyurethane (PU)-based catheters. It is possible only by means of a multifunctional material that provides fast and effective antibacterial activity, proper biocompatibility, and low bacterial and cell adhesion. In this paper, a facile chemistry approach has been developed to modify biomedical-grade PU with PU species, containing reactive uretdione functional groups for functionalization with the contact-type polyguanidine bactericidal agent and oxidized dextran as an antifouling polymer without sacrificing the thermal and mechanical properties. The resulting PU possesses broad-spectrum contact-active antibacterial activity against Gram-negative and Gram-positive bacteria with fast kinetics. The excellent antifouling capacity was confirmed by low nonspecific protein adsorption and reduced adhesion of fibroblast cells by ≥ 90%. In addition to antiadhesive and antibiofilm properties, high cell viability (>90%) and low hemolysis rate (HR < 1%) verified favorable cytocompatibility. Hence, the strategy followed to functionalize PUs in this paper might be considered to modify PU-based biomedical devices.

Microbial oversecretion of (R)-3-hydroxybutyrate oligomer with diethylene glycol terminal as a macromonomer for polyurethane synthesis.

Poly((R)-3-hydroxybutyrate) (P(3HB)) is a polyester that is synthesized and accumulated in many prokaryotic cells. Recently, a new culture method for the secretion of the intracellularly synthesized (R)-3-hydroxybutyrate oligomer (3HBO) from recombinant Escherichia coli cells was developed. In this study, we attempted to produce microbial 3HBO capped with a diethylene glycol terminal (3HBO-DEG) as a macromonomer for polymeric materials. First, we prepared recombinant E. coli strains harboring genes encoding various polyhydroxyalkanoate (PHA) synthases (PhaC, PhaEC or PhaRC) that can incorporate chain transfer (CT) agents such as DEG into the polymer's terminal and generate CT end-capped oligomers. To this end, each strain was cultivated under DEG supplemental conditions, and the synthesis of 3HBO-DEG was confirmed. As a result, the highest secretory production of 3HBO-DEG was observed for the PHA synthase derived from Bacillus cereus YB-4 (PhaRCYB4). To evaluate the usability of the secreted 3HBO-DEG as a macromonomer, 3HBO-DEG was purified from the culture medium and polymerized with 4,4'-diphenylmethane diisocyanate as a spacer compound. Characterization of the polymeric products revealed that 3HBO-based polyurethane was successfully obtained and was a flexible and transparent noncrystalline polymer, unlike P(3HB). These results suggested that microbial 3HBO-DEG is a promising platform building block for synthesizing polyurethane and various other polymers.

Black phosphorus quantum dots encapsulated in anionic waterborne polyurethane nanoparticles for enhancing stability and reactive oxygen species generation for cancer PDT/PTT therapy.

Black phosphorus quantum dots (BPQDs) with excellent biocompatibility, outstanding photothermal and photodynamic efficacies have attracted significant attention in cancer therapy. However, the low environmental stability and poor dispersity of BPQDs limit their practical applications. In the present work, biocompatible anionic waterborne polyurethane (WPU) nanoparticles were synthesized from castor oil to encapsulate the BPQDs. The WPU-BPQDs with a BPQDs loading capacity of about 13.8% (w/w) exhibited significantly improved dispersion and environmental stability without affecting the photothermal efficiency of BPQDs. Intriguingly, it was found that WPU encapsulation led to significant enhancement in the reactive oxygen species (ROS) generation of BPQDs, which indicated the enhanced photodynamic efficacy of the encapsulated BPQDs as compared to the bare BPQDs. The effect of solution pH on the ROS generation efficiency of BPQDs and the pH variation caused by BPQDs degradation was then investigated to explore the possible mechanism. In acidic solution, ROS generation was suppressed, while BPQDs degradation led to the acidification of the solution. Fortunately, after being encapsulated inside the WPU nanoparticles, the degradation rate of BPQDs became slower, while the acidic environment around BPQDs was favorably regulated by WPU nanoparticles having a special electrochemical double layer consisting of interior COO- and exterior NH(Et3)+, thus endowing the WPU-BPQDs-boosted production of ROS as compared to the bare BPQDs. Considering the undesired acidic tumor environment, this unique pH regulation effect of WPU-BPQDs would be beneficial for in vivo photodynamic efficacy. Both in vitro and in vivo experiments showed that WPU-BPQDs could effectively improve photodynamic therapy (PDT) and maintain outstanding photothermal therapy (PTT) effects. Together with the excellent dispersity, biocompatibility, and easy biodegradability, WPU-BPQDs can be a promising agent for PDT/PTT cancer treatments.

A biostable, anti-fouling zwitterionic polyurethane-urea based on PDMS for use in blood-contacting medical devices.

Polydimethylsiloxane (PDMS) is commonly used in medical devices because it is non-toxic and stable against oxidative stress. Relatively high blood platelet adhesion and the need for chemical crosslinking through curing, however, limit its utility. In this research, a biostable PDMS-based polyurethane-urea bearing zwitterion sulfobetaine (PDMS-SB-UU) was synthesized for potential use in the fabrication or coating of blood-contacting devices, such as a conduits, artificial lungs, and microfluidic devices. The chemical structure and physical properties of synthesized PDMS-SB-UU were confirmed by 1H-nuclear magnetic resonance (1H-NMR), X-ray diffraction (XRD), and uniaxial stress-strain curve. In vitro stability of PDMS-SB-UU was confirmed against lipase and 30% H2O2 for 8 weeks, and PDMS-SB-UU demonstrated significantly higher resistance to fibrinogen adsorption and platelet deposition compared to control PDMS. Moreover, PDMS-SB-UU showed a lack of hemolysis and cytotoxicity with whole ovine blood and rat vascular smooth muscle cells (rSMCs), respectively. The PDMS-SB-UU was successfully processed into small-diameter (0.80 ± 0.05 mm) conduits by electrospinning and coated onto PDMS- and polypropylene-based blood-contacting biomaterials due to its unique physicochemical characteristics from its soft- and hard- segments.

Assessment of interfacial interactions between starch and non-isocyanate polyurethanes in their hybrids.

Manufacturing of multifunctional materials through blending is a promising route for improving performance of biopolymers including starch. Non-isocyanate polyurethanes (NIPUs) are an emerging group of green materials. Understanding the mechanism of interaction between starch and NIPU not only highlights underlying chemistry but also offers an opportunity to tailor the properties and functions of starch-NIPU hybrids. We investigated the interfacial interactions between starch and NIPU to pave the way towards development of high-performance green materials. Multiple analyses revealed that NIPU interacted effectively with starch chains via intermolecular hydrogen bonds. We showed that NIPU domains can efficiently interact with the small portion of starch skeleton at interfacial region and they are only moderately miscible. Incorporation of either component above certain ratio resulted in a phase separation. This work contributes towards understanding of interfacial chemistry between starch and NIPUs and enables tailoring the interface for facile engineering of starch-NIPU hybrids.