Effect of oral exposure on chemical, physical, mechanical, and morphologic properties of clear orthodontic aligners

The dental industry is heavily committed to developing more esthetic solutions for orthodontic treatments. Invisalign is a system of transparent orthodontic aligners introduced as an alternative to conventional orthodontic fittings with brackets and metal wires. This study aimed to assess the chemical, physical, mechanical and morphologic changes in these polymeric aligners after exposure to the oral environment. Twenty-four Invisalign orthodontic aligners were equally divided into 2 groups: an in vivo aged group in which patients used aligners for 14 days and the reference group, unexposed to the oral environment. Different experimental techniques were used to study the chemical structure, the color changes and translucency, the density and subsequent volume of the aligners, mechanical properties, surface roughness, morphology and elemental composition. The data were subjected to several statistical analyses. Clear orthodontic aligners exhibit chemical stability but undergo a statistically significant optical change in color and translucency. There was a gradual increase in the water absorption rate and the dimensional variation of the polymer, indicating a strong correlation among these factors. The mechanical properties of the polymer showed a statistically significant decrease in its elastic modulus and hardness. There was a slight tendency toward increased surface roughness of the material, but no statistical differences were found between reference and aged groups. The surface morphology of the used aligners demonstrates microcracks, distortions and biofilm formation. Intraoral aging adversely affected the physical, mechanical, and morphologic properties of the Invisalign appliance.

Evaluation of the Ecotoxicity of New Polyurethane Composites on Target Organisms for Aquatic and Atmospheric Environments.

The present study investigated if new biocomposite materials, polyurethanes (PURs) added with functionalized cellulose fibers, produce potential toxic effects on two target organisms currently used in biomonitoring the quality of two different environmental compartments. Natural fibers were extracted from the species Spartium junceum L., a shrub commonly found in the southern region of the Mediterranean having a high cellulose content. All PURs produced were characterized by Fourier-transform infrared spectroscopy, and their structure was analyzed by scanning electron microscopy. We measured the effects of exposure to aromatic and aliphatic PUR composites (containing or not cellulose fibers) on the aquatic model organism Daphnia magna Straus, a freshwater crustacean (Cladocera), and a biomonitor of air quality, the fruticose epiphytic lichen Pseudevernia furfuracea (L.) Zopf. Leachates from aliphatic PUR composite not containing cellulose are more toxic to D. magna than all others, showing a slight acute toxicity in the case of the shortest exposure (24 h) and a moderate acute toxicity in the longer one (48 h). This effect is most likely due to the presence of free organic ammines and amides, which, in their turn, are immobilized in composites containing cellulosic fibers because of the considerable amount of chemical functional groups. Regarding lichens, both types of aliphatic PURs resulted in a toxic effect. Formulate not added with cellulose strongly promoted fungal peroxidation, whereas that which was functionalized affected the pigment concentration of the algal partner. Our results suggest that the use of cellulose in PUR production, in general, can limit the ecotoxicological effects on both test organisms and reduce the potential environmental impact due to this type of polymer. Environ Toxicol Chem 2023;42:421-436. © 2022 SETAC.

Exploring structure/property relationships to health and environmental hazards of polymeric polyisocyanate prepolymer substances-1. Design of experiments, aquatic exposure, and acute aquatic toxicity.

Polymeric polyisocyanate prepolymer substances are reactive intermediates used in the manufacture of various polyurethane products. Knowledge of their occupational and environmental hazard properties is essential for product stewardship and industrial hygiene purposes. This work reports on the systematic design of a program to explore how structural features (i.e., types of polymeric polyol and diisocyanate reactants, functionality) and physical-chemical properties (i.e., octanol-water partition coefficient [log Kow], viscosity, molecular weight) of a group of 10 toluene diisocyanate (TDI)- and methylene diphenyl diisocyanate (MDI)-based monomer-depleted prepolymer substances can be related to their exposure and hazard potentials. The revelation of trends or thresholds in such relationships could form a basis for regulatory screening of existing or new prepolymer substances, while also informing the design of substances having reduced exposure and/or hazard profiles. As a first step, the aquatic exposure and hazard potentials of these 10 substances were investigated. The results of this investigation showed that yields of dissolved reaction products (derived from non-purgeable organic carbon measurements and carbon contents of the parent prepolymers) were inversely correlated with the calculated log Kow of the substances. For prepolymer loading rates of both 100 and 1000 mg/L in water, the average dissolved reaction product yields ranged from ≤1% to 32% and from ≤0.1% to 25%, respectively, over calculated log Kow values ranging from -4.8 to 45. For both loading rates, dissolved reaction products were not quantifiable where the calculated log Kow value was >10. Yet, none of the 10 prepolymers and tested loading rates exhibited acute adverse effects on the aquatic invertebrate, Daphnia magna, in the 48-h acute immobilization test. From a product stewardship perspective, polymeric prepolymers of TDI and MDI within the investigated domain and concentration range are not expected to be hazardous in the aquatic environment.

Exploring structure/property relationships to health and environmental hazards of polymeric polyisocyanate prepolymer substances-2. Dermal sensitization potential in the mouse local lymph node assay.

The sensitization potencies of twenty custom-designed monomer-depleted polymeric polyisocyanate prepolymer substances and their associated toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) monomer precursors were investigated by means of the mouse Local Lymph Node Assay (LLNA). These polymeric prepolymers were designed to represent the structural features and physical-chemical properties exhibited by a broad range of commercial polymeric polyisocyanate prepolymers that are produced from the reaction of aromatic and aliphatic diisocyanate monomers with aliphatic polyether and polyester polyols. The normalization of LLNA responses to the applied (15-45-135 mM) concentrations showed that the skin sensitization potency of polymeric polyisocyanate prepolymers is at least 300 times less than that of the diisocyanate monomers from which they are derived. The sensitization potency of the prepolymers was shown to be mainly governed by their hydrophobicity (as expressed by the calculated octanol-water partition coefficient, log Kow) and surfactant properties. Neither hydrophilic (log Kow <0) nor very hydrophobic (log Kow >25) prepolymers stimulated lymphocyte proliferation beyond that of the dosing vehicle control. The findings of this investigation challenge the generally held assumption that all isocyanate (-N=C=O) bearing substances are potential skin (and respiratory) sensitizers. Further, these findings can guide the future development of isocyanate chemistries and associated polyurethane applications toward reduced exposure and health hazard potentials.

Functionalizing Ti3C2Tx for enhancing fire resistance and reducing toxic gases of flexible polyurethane foam composites with reinforced mechanical properties.

Flexible polyurethane foam (FPUF) is the most used polyurethane, but the highly flammable characteristic limits its widespread usage. In this work, ZIF-8@Ti3C2Txwas synthesized to reduce the heat and toxic gases of FPUF. Flame-retardant FPUF was characterized by cone calorimeter (Cone), thermogravimetric analysis/fourier-transform infrared spectroscopy (TG-FTIR), tensileand compression tests. Compared with pure FPUF, these results showed that the peak of heat release rate (PHRR), total heat release (THR), CO and HCN of FPUF6 decreased by 46%, 69%, 27% and 43.5%, respectively. Moreover, the tensile and compression strength of FPUF6 demonstrated a 52% and 130% increment, respectively. The superior dual metal catalytical charring-forming effect and physical barrier effect of ZIF-8@Ti3C2Tx were achieved. In summary, a simple and reliable strategy for preparing flame-retardant FPUF with reinforced mechanical and fire safety properties was provided.

Cationic Alternating Polypeptide Fixed on Polyurethane at Multiple Sites for Excellent Antibacterial and Antifouling Properties.

Bacterial infection and blockage are severe problems for polyurethane (PU) catheters and there is an urgent demand for surface-functionalized polyurethane. Herein, a cationic alternating copolymer comprising allyl-substituted ornithine and glycine (allyl-substituted poly(Orn-alter-Gly)) with abundant carbon-carbon double bond functional groups (C═C) is designed. Polyurethane is prepared with a large quantity of C═C groups (PU-D), and different amounts of allyl-substituted poly(Orn-alter-Gly) are grafted onto the PU-D surface (PU-D-2%AMPs and PU-D-20%AMPs) via the C═C functional groups. The chemical structures of the allyl-substituted poly(Orn-alter-Gly) and polyurethane samples (PU, PU-D, PU-D-2%AMPs, and PU-D-20%AMPs) are characterized and the results reveal that allyl-substituted poly(Orn-alter-Gly) is decorated on the polyurethane. PU-D-20%AMPs shows excellent antibacterial activity against Escherichia coli, Enterococcus faecalis, and Staphylococcus aureus because of the high surface potential caused by cationic allyl-substituted poly(Orn-alter-Gly), and it also exhibits excellent long-term antibacterial activity and antibiofilm properties. PU-D-20%AMPs also has excellent antifouling properties because the cationic copolymer is fixed at multiple reactive sites, thus avoiding the formation of movable long chain brush. A strong surface hydration barrier is also formed to prevent adsorption of proteins and ions, and in vivo experiments reveal excellent biocompatibility. This flexible strategy to prepare dual-functional polyurethane surfaces with antibacterial and antifouling properties has large potential in biomedical implants.

Superhydrophilic Polyurethane/Polydopamine Nanofibrous Materials Enhancing Cell Adhesion for Application in Tissue Engineering.

The use of nanofibrous materials in the field of tissue engineering requires a fast, efficient, scalable production method and excellent wettability of the obtained materials, leading to enhanced cell adhesion. We proposed the production method of superhydrophilic nanofibrous materials in a two-step process. The process is designed to increase the wettability of resulting scaffolds and to enhance the rate of fibroblast cell adhesion. Polyurethane (PU) nanofibrous material was produced in the solution blow spinning process. Then the PU fibers surface was modified by dopamine polymerization in water solution. Two variants of the modification were examined: dopamine polymerization under atmospheric oxygen (V-I) and using sodium periodate as an oxidative agent (V-II). Hydrophobic PU materials after the treatment became highly hydrophilic, regardless of the modification variant. This effect originates from polydopamine (PDA) coating properties and nanoscale surface structures. The modification improved the mechanical properties of the materials. Materials obtained in the V-II process exhibit superior properties over those from the V-I, and require shorter modification time (less than 30 min). Modifications significantly improved fibroblasts adhesion. The cells spread after 2 h on both PDA-modified PU nanofibrous materials, which was not observed for unmodified PU. Proposed technology could be beneficial in applications like scaffolds for tissue engineering.

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.

Microplastics affect sedimentary microbial communities and nitrogen cycling.

Microplastics are ubiquitous in estuarine, coastal, and deep sea sediments. The impacts of microplastics on sedimentary microbial ecosystems and biogeochemical carbon and nitrogen cycles, however, have not been well reported. To evaluate if microplastics influence the composition and function of sedimentary microbial communities, we conducted a microcosm experiment using salt marsh sediment amended with polyethylene (PE), polyvinyl chloride (PVC), polyurethane foam (PUF) or polylactic acid (PLA) microplastics. We report that the presence of microplastics alters sediment microbial community composition and nitrogen cycling processes. Compared to control sediments without microplastic, PUF- and PLA-amended sediments promote nitrification and denitrification, while PVC amendment inhibits both processes. These results indicate that nitrogen cycling processes in sediments can be significantly affected by different microplastics, which may serve as organic carbon substrates for microbial communities. Considering this evidence and increasing microplastic pollution, the impact of plastics on global ecosystems and biogeochemical cycling merits critical investigation.

A New Nanocomposite Copolymer Based On Functionalised Graphene Oxide for Development of Heart Valves.

Polymeric heart valves seem to be an attractive alternative to mechanical and biological prostheses as they are more durable, due to the superior properties of novel polymers, and have the biocompatibility and hemodynamics comparable to tissue substitutes. This study reports a comprehensive assessment of a nanocomposite based on the functionalised graphene oxide and poly(carbonate-urea)urethane with the trade name "Hastalex" in comparison with GORE-TEX, a commercial polymer routinely used for cardiovascular medical devices. Experimental data have proved that GORE-TEX has a 2.5-fold (longitudinal direction) and 3.5-fold (transverse direction) lower ultimate tensile strength in comparison with Hastalex (p < 0.05). The contact angles of Hastalex surfaces (85.2 ± 1.1°) significantly (p < 0.05) are lower than those of GORE-TEX (127.1 ± 6.8°). The highest number of viable cells Ea.hy 926 is on the Hastalex surface exceeding 7.5-fold when compared with the GORE-TEX surface (p < 0.001). The platelet deformation index for GORE-TEX is 2-fold higher than that of Hastalex polymer (p < 0.05). Calcium content is greater for GORE-TEX (8.4 mg/g) in comparison with Hastalex (0.55 mg/g). The results of this study have proven that Hastalex meets the main standards required for manufacturing artificial heart valves and has superior mechanical, hemocompatibility and calcific resistance properties in comparison with GORE-TEX.

Migration studies and toxicity evaluation of cyclic polyesters oligomers from food packaging adhesives.

Multilayer materials used in food packaging are commonly manufactured with a polyurethane adhesive layer in its structure that may contain cyclic esters oligomers as potential migrants. However, little is known about their toxicity. In this work, two cyclic esters of polyurethane are evaluated in migration from 20 multilayer packaging samples. They were composed by adipic acid (AA), diethylene glycol (DEG) and isophthalic acid (IPA) and their structure was AA-DEG and AA-DEG-IPA-DEG. The concentration of these compounds in migration exceeded the maximum level established by Regulation EU/10/2011 (10 ng g-1). Bioaccessibility of both compounds was evaluated by studying gastric and intestinal digestion. The studies showed that the concentration of the compounds decreased during digestion and that their hydrolysed molecules increased. Furthermore, endocrine activity in vitro assays were performed. A weak androgen receptor antagonism was identified, whereas no arylhydrocarbon receptor activity or binding to the thyroid hormone transport protein was found.

Polyurethane foam induces epigenetic modification of mitochondrial DNA during different metamorphic stages of Tenebrio molitor.

The present work investigated the changes in DNA methylation pattern of Tenebrio molitor mitochondria genome at different development stages, which was fed with polyurethane foam as a sole diet. Polyurethane foam could influence the global methylation levels in mitochondria DNA of Tenebrio molitor. Different leves of 5-methylcytosine appeared at CpG and non-CpG sites of Tenebrio molitor mtDNA while they were fed with polyurethane foam: 10 CpG and 49 non-CpG sites at larval stage, 4 CpG and 31 non-CpG sites at pupa stage, 7 CpG and 56 non-CpG sites at adult stage in general. Moreover, we observed the decreased levels of ATP generation with the mitochondria DNA methylation variation. The results demonstrated that mitochondria DNA gene could be methylated in response to environmental pollutants to modulate stage-specific functions. Moreover, mtDNA methylation of polyurethane-foam-feeding Tenebrio molitor existed discrepancy in the developmental stage. The tentative methylation mechanism of mtDNA might be that polyurethane foam induced oxidative stress and increased the permeability of mitochondrial membranes, which resulted in transmethylase entry into mitochondria.

Evaluation of the biocompatibility of resin composite-based dental materials with gingival mesenchymal stromal cells.

Resin composite-based dental materials can leach certain components into the oral environment, causing potentially harmful gingival biological effect. Gingival tissue is a rich source of mesenchymal stem cells (MSCs) that is easily accessible, and can be used as a complementary approach for the investigation of dental material biocompatibility. Using gingival MSCs (gMSCs), the present study aimed to investigate the cytotoxicity of two classes of restorative dental materials (ormocers and resin composites) used to restore class II cavities close to the gingival margin, in addition to analyzing the leached compounds from these resin composite-based materials. Functionality assays (Colony-forming unit, migratory potential, and proliferation assays) and a viability assay (MTT) were employed. Cells' aspect was observed by scanning electron microscopy (SEM). Leached monomers were also quantitated using high-performance liquid chromatography (HPLC). The cytotoxicity of the biomaterials was highlighted by impaired functionality and diminished viability of gMSCs. Despite being variants of the same commercial material, the two ormocers behaved differently one material having a more negative impact on cell functionality than the other. Cells appeared to attach well to all materials. Main monomer molecules were mostly released by the tested materials. For all samples, an increased elution of monomers was recorded in artificial saliva as compared with culture medium. One composite material has released nearly eight times more urethane dimetacrylate in artificial saliva than in culture medium. Significantly lower gMSC viability scores were recorded for all the investigated samples in comparison with the control.

Hybrid and biocompatible cellulose/polyurethane nanocomposites with water-activated shape memory properties.

Water-activated shape memory bacterial cellulose/polyurethane nanocomposites were prepared by the immersion of bacterial cellulose (BC) wet membranes into waterborne polyurethane (WBPU) dispersions for different times. The high affinity between the hydrophilic BC and water stable polyurethane led to the coating and embedding of the BC membrane into the WBPU, facts that were confirmed by FTIR, SEM and mechanical testing of the nanocomposites. The mechanical performance of the nanocomposites resulted enhanced with respect to the neat WBPU, confirming the reinforcing effect of the BC membrane. An improvement of the shape fixity ability and faster recovery process with the presence of BC was observed. In 3 min, the nanocomposite with highest BC content recovered the 92.8 ± 6.3% of the original shape, while the neat WBPU only recovered the 33.4 ± 9.6%. The obtained results indicated that 5 min of impregnation time was enough to obtain nanocomposites with improved mechanical performance and fast shape recovery for potential biomedical applications. The present work provides an approach for developing environmentally friendly and biocompatible BC/polyurethane based materials with enhanced mechanical and shape memory properties.

Evaluation of in vitro cytotoxicity and properties of polydimethylsiloxane-based polyurethane/crystalline nanocellulose bionanocomposites.

Polydimethylsiloxane-based polyurethane (PU)/crystalline nanocellulose (CNC) bionanocomposites were produced via in situ prepolymer approach. Also, hexamethylene diisocyanate as aliphatic diisocyanate monomer and 1,4-butanediol as aliphatic chain extender were used. CNC was incorporated into PU matrix to prepare different PU/CNC bionanocomposites. Effect of CNC content on the properties of the bionanocomposites such as thermal, thermophysical, microstructure, and in vitro cytotoxicity was investigated. According to the results, incorporating CNCs into PU matrix significantly affected the hydrogen bonding between different microstructures of matrix. Adding different amounts of CNCs affected the thermal and thermophysical properties of bionanocomposites. Also, higher amounts of CNCs resulted in lower crystallization of hard segment. Neat PU matrix showed a moderate cytotoxicity behavior against human fibroblast cells. However, incorporating CNCs significantly improved the cytotoxicity behavior of bionanocomposites where by addition of 2 wt % of CNCs, cell viability increased to 90-100%. © 2019 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 107A: 1771-1778, 2019.

Reinforcement of dental resin composite via zirconium hydroxide coating and phosphate ester monomer conditioning of nano-zirconia fillers.

OBJECTIVES: The present study aimed to evaluate effects of conditioning with the phosphate ester monomer 10-methacryloyloxydecyl dihydrogen phosphate (MDP), with and without precoating with zirconium hydroxide for nano-size zirconia fillers, on mechanical properties of dental resin composites. MATERIALS AND METHODS: Nano-zirconia fillers coated with or without zirconium hydroxide [Zr(OH)4] were prepared. Transmission electron microscopy (TEM), Fourier infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) were used to observe the coating and to characterize Zr(OH)4 coating on the zirconia filler surface. Zirconia fillers with or without Zr(OH)4 coating were conditioned with MDP and were subsequently used to prepare experimental resin composites. XPS was used to analyze the Zr-O-P bonds on the filler surface after MDP conditioning. Moreover, three-point bending strength and elastic modulus of prepared resin composites were measured, and Weibull analysis was performed. Resin composites without addition of zirconia fillers and the ones with addition of untreated or silane conditioned-zirconia fillers were set as controls. Cell counting kit (CCK)-8 was used to test cell cytotoxicity of these zirconia fillers-containing experimental resin composites. RESULTS: Nano-zirconia fillers were coated with Zr(OH)4 through chemical deposition. FTIR and XPS analysis confirmed the increase of hydroxyl groups after Zr(OH)4 coating. XPS detected the highest contents of Zr-O-P bonds on MDP-conditioned zirconia fillers with pre-Zr(OH)4 coating, followed by MDP-conditioned zirconia fillers. Resin composite with added MDP-conditioned zirconia fillers with and without Zr(OH)4 coating exhibited greater three-point bending strength, elastic modulus values, and Weibull moduli. According to the cytotoxicity classification, resin composites containing experimental zirconia fillers were considered to have no significant cell cytotoxicity. CONCLUSION: Nano-zirconia fillers conditioned with MDP, with or without precoating with Zr(OH)4, improve the mechanical properties of resin composites, and are potentially safe for clinical use.

The Epidemiology of Breast Implant-Associated Anaplastic Large Cell Lymphoma in Australia and New Zealand Confirms the Highest Risk for Grade 4 Surface Breast Implants.

BACKGROUND: The epidemiology and implant-specific risk for breast implant-associated (BIA) anaplastic large cell lymphoma (ALCL) has been previously reported for Australia and New Zealand. The authors now present updated data and risk assessment since their last report. METHODS: New cases in Australia and New Zealand were identified and analyzed. Updated sales data from three leading breast implant manufacturers (i.e., Mentor, Allergan, and Silimed) were secured to estimate implant-specific risk. RESULTS: A total of 26 new cases of BIA-ALCL were diagnosed between January of 2017 and April of 2018, increasing the total number of confirmed cases in Australia and New Zealand to 81. This represents a 47 percent increase in the number of reported cases over this period. The mean age and time to development remain unchanged. The implant-specific risk has increased for Silimed polyurethane (23.4 times higher) compared with Biocell, which has remained relatively static (16.5 times higher) compared with Siltex implants. CONCLUSIONS: The number of confirmed cases of BIA-ALCL in Australia and New Zealand continues to rise. The implant-specific risk has now changed to reflect a strong link to implant surface area/roughness as a major association with this cancer.