Investigation of zinc polycarboxylate cement used in dental treatments in terms of retrospective dosimeter.

Zinc polycarboxylate cement is one of the few dental materials that demonstrate true adhesion to tooth structure. It is suitable for use in living organisms without causing harm. Its strong adhesion to teeth and low level of irritancy are two important parameters for the dental applications. In this study, the dosimetry properties of zinc polycarboxylate cement using thermoluminescence (TL) method were investigated and determined the effectiveness of its use as a good dosimeter. According to the results of this study, the sample shows a good TL properties with three main peaks found around 140°C, 220°C and 330°C. It has a wide linear dose response between 72 Gy and 2.3 kGy and good reusability of the TL peak found at 330°C. Unfortunately, the TL peak intensity values are rapidly faded within a short waiting time interval. Zinc polycarboxylate cement, which is frequently used in dental crowns, can be used as a retrospective dosimeter for measuring the amount of radiation in space studies and nuclear accidents due to its wide linear dose-response curve in the high dose region.

Construction of Polycarbonates with Pendant Multifunctional Groups via a One-Step CO2/ Diepoxide Copolymerization Approach.

A "one-step" strategy has been demonstrated for the tunable synthesis of multifunctional aliphatic polycarbonates (APCs) with ethylene oxide (EO), ethylene carbonate (EC), and cyclohexene oxide (CHO) side groups by the copolymerization of 4-vinyl-1-cyclohexene diepoxide with carbon dioxide under an aminotriphenolate iron/PPNBz (PPN = bis(triphenylphosphine)-iminium, Bz = benzoate) binary catalyst. By adjusting the PPNBz-to-iron complex ratio and incorporating auxiliary solvents, the content of functional side groups can be tuned within the ranges of 53-75% for EO, 18-47% for EC, and <1-7% for CHO. The yield and molecular weight distribution of the resulting multifunctional APCs are affected by the viscosity of the polymerization system. The use of tetrahydrofuran as an auxiliary solvent enables the preparation of narrow-distribution polycarbonates at high conversion. This work presents a novel perspective for the preparation of tailorable multifunctional APCs.

Reductive depolymerization of polyesters and polycarbonates with hydroboranes by using a lanthanum(III) tris(amide) catalyst.

The homogeneous reductive depolymerization of polyesters and polycarbonates with hydroboranes is achieved with the use of an f-metal complex catalyst. These polymeric materials are transformed into their value-added alcohol equivalents. Catalysis proceeds readily, under mild conditions, with La[N(SiMe3)2]3 (1 mol%) and pinacolborane (HBpin) and shows high selectivity towards alcohols and diols, after hydrolysis.

Synthesis and Characterization of Novel Radiopaque Polycarbonate.

Polymeric materials implanted in the human body are usually invisible under X-ray, and the mixing of heavy metal salts into polymeric materials by physical compounding often poses compatibility problems. A new iodine-containing cyclic carbonate monomer, 4-iodo-N-(2-oxo-1,3-dioxan-5-yl)benzamide (IBTMC), is synthesized, which has a degradable carbonate group as its basic structural unit and iodine atoms attached to the side chain in the form of covalent bonds. The ring-opening polymerization of IBTMC is achieved at room temperature under the catalysis of the solid superbase 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). The structure and X-ray developing ability of the synthesized polycarbonate are characterized by 1 H-NMR, X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS), Gel Permeation Chromatography (GPC), and micro-computed tomography (Micro-CT). The iodine atoms remain bound to the polymer as covalent bonds after a series of reactions and exhibit a high level of X-ray opacity. In vitro degradation experiments of the polymer prove that the polymer is degradable.

Elucidating the anticancer activities of guanidinium-functionalized amphiphilic random copolymers by varying the structure and composition in the hydrophobic monomer.

Rationale: Use of traditional anticancer chemotherapeutics has been hindered by the multifactorial nature of multi-drug resistance (MDR) development and metastasis. Recently, cationic polycarbonates were reported as novel unconventional anticancer agents that mitigated MDR and inhibited metastasis. The aim of this study is to explore structure-anticancer activity relationship. Specifically, a series of cationic guanidinium-based random copolymers of varying hydrophobicity was synthesized with a narrow polydispersity (Ð = 1.12-1.27) via organocatalytic ring-opening polymerization (OROP) of functional cyclic carbonate monomers, and evaluated for anticancer activity, killing kinetics, degradability and functional mechanism. Methods: Linear, branched and aromatic hydrophobic side chain units, such as ethyl, benzyl, butyl, isobutyl and hexyl moieties were explored as comonomer units for modulating anticancer activity. As hydrophobicity/hydrophilicity balance of the polymers determines their anticancer efficacy, the feed ratio between the two monomers was varied to tune their hydrophobicity. Results: Notably, incorporating the hexyl moiety greatly enhanced anticancer efficiency and killing kinetics on cancer cells. Degradation studies showed that the polymers degraded completely within 4-6 days. Flow cytometry and lactate dehydrogenase (LDH) release analyses demonstrated that anticancer mechanism of the copolymers containing a hydrophobic co-monomer was concentration dependent, apoptosis at IC50, and both apoptosis and necrosis at 2 × IC50. In contrast, the homopolymer without a hydrophobic comonomer killed cancer cells predominantly via apoptotic mechanism. Conclusion: The hydrophobicity of the polymers played an important role in anticancer efficacy, killing kinetics and anticancer mechanism. This study provides valuable insights into designing novel anticancer agents utilizing polymers.

Nonwoven Releasing Propolis as a Potential New Wound Healing Method-A Review.

Wound healing poses a serious therapeutic problem. Methods which accelerate tissue regeneration and minimize or eliminate complications are constantly being sought. This paper is aimed at evaluation of the potential use of biodegradable polymer nonwovens releasing propolis as wound healing dressings, based on the literature data. Propolis is honeybee product with antioxidant, antibacterial, antifungal, anticancer, anti-inflammatory, analgesic, and regenerative properties. Controlled release of this substance throughout the healing should promote healing process, reduce the risk of wound infection, and improve aesthetic effect. The use of biodegradable aliphatic polyesters and polyester carbonates as a propolis carrier eliminates the problem of local drug administration and dressing changes. Well-known degradation processes and kinetics of the active substance release allows the selection of the material composition appropriate to the therapy. The electrospinning method allows the production of nonwovens that protect the wound against mechanical damage. Moreover, this processing technique enables adjusting product properties by modifying the production parameters. It can be concluded that biodegradable polymer dressings, releasing a propolis, may find potential application in the treatment of complicated wounds, as they may increase the effectiveness of treatment, as well as improve the patient's life quality.

Wearable Collector for Noninvasive Sampling of SARS-CoV-2 from Exhaled Breath for Rapid Detection.

Airborne transmission of exhaled virus can rapidly spread, thereby increasing disease progression from local incidents to pandemics. Due to the COVID-19 pandemic, states and local governments have enforced the use of protective masks in public and work areas to minimize the disease spread. Here, we have leveraged the function of protective face coverings toward COVID-19 diagnosis. We developed a user-friendly, affordable, and wearable collector. This noninvasive platform is integrated into protective masks toward collecting airborne virus in the exhaled breath over the wearing period. A viral sample was sprayed into the collector to model airborne dispersion, and then the enriched pathogen was extracted from the collector for further analytical evaluation. To validate this design, qualitative colorimetric loop-mediated isothermal amplification, quantitative reverse transcription polymerase chain reaction, and antibody-based dot blot assays were performed to detect the presence of SARS-CoV-2. We envision that this platform will facilitate sampling of current SARS-CoV-2 and is potentially broadly applicable to other airborne diseases for future emerging pandemics.

4D polycarbonates via stereolithography as scaffolds for soft tissue repair.

3D printing has emerged as one of the most promising tools to overcome the processing and morphological limitations of traditional tissue engineering scaffold design. However, there is a need for improved minimally invasive, void-filling materials to provide mechanical support, biocompatibility, and surface erosion characteristics to ensure consistent tissue support during the healing process. Herein, soft, elastomeric aliphatic polycarbonate-based materials were designed to undergo photopolymerization into supportive soft tissue engineering scaffolds. The 4D nature of the printed scaffolds is manifested in their shape memory properties, which allows them to fill model soft tissue voids without deforming the surrounding material. In vivo, adipocyte lobules were found to infiltrate the surface-eroding scaffold within 2 months, and neovascularization was observed over the same time. Notably, reduced collagen capsule thickness indicates that these scaffolds are highly promising for adipose tissue engineering and repair.

Preliminary hemocompatibility assessment of an innovative material for blood contacting surfaces.

Over the years, several devices have been created (and the development of many others is currently in progress) to be in permanent contact with blood: mechanical circulatory supports represent an example thereof. The hemocompatibility of these devices largely depends on the chemical composition of blood-contacting components. In the present work, an innovative material (hybrid membrane) is proposed to fabricate the inner surfaces of a pulsatile ventricular chamber: it has been obtained by coupling a synthetic polymer (e.g., commercial polycarbonate urethane) with decellularized porcine pericardium. The hemocompatibility of the innovative material has been preliminarily assessed by measuring its capacity to promote thrombin generation and induce platelet activation. Our results demonstrated the blood compatibility of the proposed hybrid membrane.

Spatially resolved analysis of Pseudomonas aeruginosa biofilm proteomes measured by laser ablation sample transfer.

Heterogeneity in the distribution of nutrients and oxygen gradients during biofilm growth gives rise to changes in phenotype. There has been long term interest in identifying spatial differences during biofilm development including clues that identify chemical heterogeneity. Laser ablation sample transfer (LAST) allows site-specific sampling combined with label free proteomics to distinguish radially and axially resolved proteomes for Pseudomonas aeruginosa biofilms. Specifically, differential protein abundances on oxic vs. anoxic regions of a biofilm were observed by combining LAST with bottom up proteomics. This study reveals a more active metabolism in the anoxic region of the biofilm with respect to the oxic region for this clinical strain of P. aeruginosa, despite this organism being considered an aerobe by nature. Protein abundance data related to cellular acclimations to chemical gradients include identification of glucose catabolizing proteins, high abundance of proteins from arginine and polyamine metabolism, and proteins that could also support virulence and environmental stress mediation in the anoxic region. Finally, the LAST methodology requires only a few mm2 of biofilm area to identify hundreds of proteins.

Rapid and simple single-chamber nucleic acid detection system prepared through nature-inspired surface engineering.

Background: Nucleic acid (NA)-based diagnostics enable a rapid response to various diseases, but current techniques often require multiple labor-intensive steps, which is a major obstacle to successful translation to a clinical setting. Methods: We report on a surface-engineered single-chamber device for NA extraction and in situ amplification without sample transfer. Our system has two reaction sites: a NA extraction chamber whose surface is patterned with micropillars and a reaction chamber filled with reagents for in situ polymerase-based NA amplification. These two sites are integrated in a single microfluidic device; we applied plastic injection molding for cost-effective, mass-production of the designed device. The micropillars were chemically activated via a nature-inspired silica coating to possess a specific affinity to NA. Results: As a proof-of-concept, a colorimetric pH indicator was coupled to the on-chip analysis of NA for the rapid and convenient detection of pathogens. The NA enrichment efficiency was dependent on the lysate incubation time, as diffusion controls the NA contact with the engineered surface. We could detect down to 1×103 CFU by the naked eye within one hour of the total assay time. Conclusion: We anticipate that the surface engineering technique for NA enrichment could be easily integrated as a part of various types of microfluidic chips for rapid and convenient nucleic acid-based diagnostics.

Separation performance of the copolymer and homopolymer of aliphatic polycarbonate diols as the stationary phases for capillary gas chromatography.

This work presents the investigation of two aliphatic polycarbonate diols (CAPC and HAPC) as the stationary phases for capillary gas chromatography (GC). The CAPC and HAPC capillary columns showed moderate polarity and high column efficiency of 3704 - 4545 plates/m measured by n-octanol and naphthalene at 120 °C. It was found that despite their similar chemical compositions, CAPC and HAPC differ largely in their selectivity towards the isomers of alkanes, methylpyridines and xylenes. As demonstrated, the CAPC column exhibits advantageous comprehensive performance over the HAPC column and the commercial PEG column. Particularly, the CAPC column exhibits higher resolving performance towards the isomers indicated above and the Grob mixture than the HAPC column. Also, it shows distinct advantages over the PEG column in separating the Grob mixture, the isomers of diethylbenzenes and cymenes, and practical analysis of chemical products and the essential oil from the leaves of Rhododendron dauricum L. Additionally, the CAPC column has excellent repeatability and reproducibility on analyte retention times with the relative standard deviation (RSD) values in the range of 0.05% - 0.08% for run-to-run, 0.12% - 0.19% for day-to-day and 2.6% - 4.9% for column-to-column, respectively. Its applications to purity test of chemical products and GC-MS analysis of the essential oil demonstrate its promising future for practical GC analyses.

In Vivo Degradation Mechanisms of Aliphatic Polycarbonates and Functionalized Aliphatic Polycarbonates.

Aliphatic polycarbonates (APCs) have been studied for decades but have not been as utilized as aliphatic polyesters in biomaterial applications such as drug delivery and tissue engineering. With the recognition that functionalized aliphatic polymers can be readily synthesized, increased attention is being paid to these materials. A frequently provided reason for utilizing these polymers is that they degrade to form diols and carbon dioxide. However, depending on the structure and molecular weight of the APC, degradation may not occur. In this review, the mechanisms by which APCs and functionalized APCs have been found to degrade in vivo are examined with the objective of providing guidance in the continued development of these polymers as biomaterials.

The Localization Behavior of Different CNTs in PC/SAN Blends Containing a Reactive Component.

Co-continuous blend systems of polycarbonate (PC), poly(styrene-co-acrylonitrile) (SAN), commercial non-functionalized multi-walled carbon nanotubes (MWCNTs) or various types of commercial and laboratory functionalized single-walled carbon nanotubes (SWCNTs), and a reactive component (RC, N-phenylmaleimide styrene maleic anhydride copolymer) were melt compounded in one step in a microcompounder. The blend system is immiscible, while the RC is miscible with SAN and contains maleic anhydride groups that have the potential to reactively couple with functional groups on the surface of the nanotubes. The influence of the RC on the localization of MWCNTs and SWCNTs (0.5 wt.%) was investigated by transmission electron microscopy (TEM) and energy-filtered TEM. In PC/SAN blends without RC, MWCNTs are localized in the PC component. In contrast, in PC/SAN-RC, the MWCNTs localize in the SAN-RC component, depending on the RC concentration. By adjusting the MWCNT/RC ratio, the localization of the MWCNTs can be tuned. The SWCNTs behave differently compared to the MWCNTs in PC/SAN-RC blends and their localization occurs either only in the PC or in both blend components, depending on the type of the SWCNTs. CNT defect concentration and surface functionalities seem to be responsible for the localization differences.

The efficiency and mechanism of a new absorption enhancer, malic acid, for enhancing the oral bioavailability of docetaxel.

This study investigated the efficiency and the related mechanisms of a new absorption enhancer, DL-malic acid (MA), on the oral bioavailability of docetaxel (DTX). Polyethylene glycol polycarbonate (PEG-PCL) modified liposomes (PLip) were prepared for DTX, and incorporated into the pH-sensitive microspheres (MS) with sustained release. MA decreased the transepithelial electrical resistance (TEER) across a Caco-2 cell monolayer by 20% and 57% after 2 and 3 h of co-incubation with DTX-PLip and the cells, respectively, indicating that MA could open tight junctions but not instantaneously. After long enough exposure (4 h) of MA to the small intestine of rats, only the absorption rate constant (ka) of DTX-PLip, but not Duopafei®, was increased, which could be related to the intestinal mucosal permeability of DTX. After co-administration in rats, MA significantly enhanced the oral bioavailability of DTX in DTX-PLip-MS from 44.67% to 81.27%, rather than DTX-PLip and Duopafei®, which could be related to the prolonged intestinal retention time of DTX-PLip via the MS and the promoted drug intercellular transport by MA. The absorption-enhancing effects of MA on DTX-PLip-MS were further confirmed by in vivo imaging. The above findings suggest that MA served as a new and efficient absorption enhancer for DTX-PLip-MS.HIGHlIGHTSIn this study, malic acid as a new absorption enhancer for DTX in polymer-liposome (PLip) embedded in pH-sensitive microspheres (MS) was found for the first time.The malic acid could significantly enhance oral bioavailability of DTX in DTX-PLip-MS (from 44.67 % to 81.27%) rather than Duopafei® and DTX-PLip after co-administration.The absorption enhancement may be closely related to the intestinal retention time and mucosal permeability.These findings will provide an important reference for the study of absorption enhancers for promoting intercellular insoluble drug transport.

Fluoride release from two types of fluoride-containing orthodontic adhesives: Conventional versus resin-modified glass ionomer cements-An in vitro study.

INTRODUCTION: Development of white spot lesions (WSLs) during orthodontic treatment is a common risk factor. Fixation of the orthodontic appliances with glass ionomer cements could reduce the prevalence of WSL's due to their fluoride release capacities. The purpose of this study was to evaluate differences of fluoride release properties from resin-modified and conventional glass ionomer cements (GICs). METHODS: The resin-modified GICs Fuji ORTHO LC (GC Orthodontics), Meron Plus QM (VOCO), as well as the conventional GICs Fuji ORTHO (GC Orthodontics), Meron (VOCO) and Ketac Cem Easymix (3M ESPE) were tested in this study. The different types of GICs were applied to hydroxyapatite discs according to the manufacturer's instructions and stored in a solution of TISAB III (Total Ionic Strength Adjustment Buffer III) and fluoride-free water at 37°C. Fluoride measurements were made after 5 minutes, 2 hours, 24 hours, 14 days, 28 days, 2 months, 3 months and 6 months. One factor analysis of variance (ANOVA) was used for the overall comparison of the cumulative fluoride release (from measurement times of 5 minutes to 6 months) between the different materials with the overall level of significance set to 0.05. Tukey's post hoc test was used for post hoc pairwise comparisons in the cumulative fluoride release between the different materials. RESULTS: The cumulative fluoride release (mean ± sd) in descending order was: Fuji ORTHO LC (221.7 ± 10.29 ppm), Fuji ORTHO (191.5 ± 15.03 ppm), Meron Plus QM (173.0 ± 5.89 ppm), Meron (161.3 ± 7.84 ppm) and Ketac Cem Easymix (154.6 ± 6.09 ppm) within 6 months. Analysis of variance detected a significant difference in the cumulative fluoride release between at least two of the materials (rounded p-value < 0.001). Pairwise analysis with Tukey's post hoc test showed a significant difference in the cumulative fluoride release for all the comparisons except M and MPQM (p = 0.061) and KCE and M (p = 0.517). CONCLUSION: Fluoride ions were released cumulatively over the entire test period for all products. When comparing the two products from the same company (Fuji ORTHO LC vs. Fuji ORTHO from GC Orthodontics Europe GmbH and Meron Plus QM vs. Meron from VOCO GmbH, Mannheim, Germany), it can be said that the resin-modified GICs have a higher release than conventional GICs. The highest individual fluoride release of all GICs was at 24 hours. A general statement, whether resin-modified or conventional GICs have a higher release of fluoride cannot be made.

In Vivo Degradation Mechanism and Biocompatibility of a Biodegradable Aliphatic Polycarbonate: Poly(Trimethylene Carbonate-co-5-Hydroxy Trimethylene Carbonate).

A recently developed viscous liquid aliphatic polycarbonate, poly(trimethylene carbonate-co-5-hydroxy trimethylene carbonate), has advantageous properties for the delivery of acid-sensitive drugs such as proteins and peptides. This copolymer degrades in vitro via an alkaline-catalyzed intramolecular cyclization reaction yielding oligo (trimethylene carbonate), glycerol, and carbon dioxide, but its in vivo degradation mechanisms are presently unknown. The in vivo degradation mechanism and tissue response to this copolymer were investigated following subcutaneous implantation in Wistar rats. The molecular weight and composition of the copolymer varied in the same manner following subcutaneous implantation as observed in vitro. These findings suggest that the copolymer also degraded in vivo principally via intramolecular cyclization. The tissue response in terms of the inflammatory zone cell density, fibrous capsule thickness, and macrophage response was intermediate to that of two clinically used biodegradable sutures, Vicryl and Monocryl, indicating that the copolymer can be considered biotolerable. Collectively, the data show that further development of this copolymer as a drug delivery material is warranted.

Tyrosine-derived polycarbonate nerve guidance tubes elicit proregenerative extracellular matrix deposition when used to bridge segmental nerve defects in swine.

Promising biomaterials should be tested in appropriate large animal models that recapitulate human inflammatory and regenerative responses. Previous studies have shown tyrosine-derived polycarbonates (TyrPC) are versatile biomaterials with a wide range of applications across multiple disciplines. The library of TyrPC has been well studied and consists of thousands of polymer compositions with tunable mechanical characteristics and degradation and resorption rates that are useful for nerve guidance tubes (NGTs). NGTs made of different TyrPCs have been used in segmental nerve defect models in small animals. The current study is an extension of this work and evaluates NGTs made using two different TyrPC compositions in a 1 cm porcine peripheral nerve repair model. We first evaluated a nondegradable TyrPC formulation, demonstrating proof-of-concept chronic regenerative efficacy up to 6 months with similar nerve/muscle electrophysiology and morphometry to the autograft repair control. Next, we characterized the acute regenerative response using a degradable TyrPC formulation. After 2 weeks in vivo, TyrPC NGT promoted greater deposition of pro-regenerative extracellular matrix (ECM) constituents (in particular collagen I, collagen III, collagen IV, laminin, and fibronectin) compared to commercially available collagen-based NGTs. This corresponded with dense Schwann cell infiltration and axon extension across the lumen. These findings confirmed results reported previously in a mouse model and reveal that TyrPC NGTs were well tolerated in swine and facilitated host axon regeneration and Schwann cell infiltration in the acute phase across segmental defects - likely by eliciting a favorable neurotrophic ECM milieu. This regenerative response ultimately can contribute to functional recovery.

Combating drug-resistant bacterial infection using biodegradable nanoparticles assembled from comb-like polycarbonates grafted with amphiphilic polyquaternium.

Bacterial infection is a serious clinical threat. The misuse of antibiotics has already resulted in the emergence of antibiotic-resistant strains of pathogenic bacteria. Efficient membrane-destructive antibacterial agents are considered as an alternative, promising solution against bacterial infection. Herein, we prepared a new type of comb-like cationic, polyethylene glycol (PEG) block polycarbonates with polyquaternium arms (G-CgQAs). The amphiphilic G-CgQAs could self-assemble into about 60 nm sized nanoparticles (NPs) with positive charges (20~30 mV). G-CgQA-3 NPs with an appropriate hydrophobic-hydrophilic balance in the polyquaternium arms showed antibacterial activity against Gram-negative, Gram-positive, and drug-resistant strains at low concentrations (MIC 64-128 µg mL-1) and low hemolysis (HC50 > 2000 µg mL-1). In vivo anti-infection tests indicated G-CgQA-3 NPs could highly inhibit the growth of vancomycin-resistant bacteria by spraying on wounds. Collectively, G-CgQA NPs hold great promise for the prevention of infection, serving as new antibacterial agents. This study also highlights the significance of a hydrophobic block in positive polyquaternium arms to facilitate the antibacterial activity of cationic, quaternized polymers. The design of comb-like amphiphilic cationic polycarbonates provides a new method for manufacturing antibacterial nano-agents.

Colorimetric detection of residual quaternary ammonium compounds on dry surfaces and prediction of antimicrobial activity using bromophenol blue.

Controlling and monitoring the residual activity of quaternary ammonium compounds (QACs) are critical for maintaining safe yet effective levels of these agents in the environment. This study investigates the utility of bromophenol blue (BPB) as a safe, rapid and user-friendly indicator to detect in situ residual QACs dried on hard, non-porous surfaces, as well a means to assess their antimicrobial efficacy. At pH 7, BPB has a purple colour which turns blue upon its complexation with QACs such as didecyldimethylammonium chloride (DDAC). BPB itself has no antimicrobial properties up to 400 ppm. Within the range of 0-400 ppm, BPB colour change was tied to specific DDAC antimicrobial performances with a detection threshold of 100 ppm. BPB concentration and application volume could be adjusted such that a colour shift from purple to blue correlated with a set percent reduction (>99·9%) in test bacteria (Staphylococcus aureus and Klebsiella aerogenes). The BPB solutions developed in this study yielded similar colour shifts on polycarbonate and stainless steel surfaces and did not cross-react with chemical ingredients commonly found in sanitizers and disinfectant products. Overall, this study suggests that BPB provides a simple solution to safely monitor the post-application level and biocidal activity of residual dried QACs on surfaces.