A Color Indicator Based on 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium Bromide (MTT) and a Biodegradable Poly(ester amide) for Detecting Bacterial Contamination.

Bacterial contamination is a hazard in many industries, including food, pharmaceuticals, and healthcare. The availability of a rapid and simple method for detecting this type of contamination in sterile areas enables immediate intervention to avoid or reduce detrimental effects. Among these methods, colorimetric indicators are becoming increasingly popular due to their affordability, ease of use, and quick visual interpretation of the signal. In this article, a bacterial contamination indicator system was designed by incorporating MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) into an electrospun PADAS matrix, which is a biodegradable poly(ester amide) synthesized from L-alanine, 1,12-dodecanediol, and sebacic acid. Uniaxial stress testing, thermogravimetric analysis and scanning electron microscopy were used to examine the mechanical properties, thermal stability, and morphology of the mats, respectively. The capacity for bacterial detection was not only analyzed with agar and broth assays but also by replicating important environmental conditions. Among the MTT concentrations tested in this study (0.2%, 2%, and 5%), it was found that only with a 2% MTT content the designed system produced a color response visible to the naked eye with optimal intensity, a sensitivity limit of 104 CFU/mL, and 86% cell viability, which showed the great potential for its use to detect bacterial contamination. In summary, by means of the process described in this work, it was possible to obtain a simple, low-cost and fast-response bacterial contamination indicator that can be used in mask filters, air filters, or protective clothing.

Nylons with Applications in Energy Generators, 3D Printing and Biomedicine.

Linear polyamides, known as nylons, are a class of synthetic polymers with a wide range of applications due to their outstanding properties, such as chemical and thermal resistance or mechanical strength. These polymers have been used in various fields: from common and domestic applications, such as socks and fishing nets, to industrial gears or water purification membranes. By their durability, flexibility and wear resistance, nylons are now being used in addictive manufacturing technology as a good material choice to produce sophisticated devices with precise and complex geometric shapes. Furthermore, the emergence of triboelectric nanogenerators and the development of biomaterials have highlighted the versatility and utility of these materials. Due to their ability to enhance triboelectric performance and the range of applications, nylons show a potential use as tribo-positive materials. Because of the easy control of their shape, they can be subsequently integrated into nanogenerators. The use of nylons has also extended into the field of biomaterials, where their biocompatibility, mechanical strength and versatility have paved the way for groundbreaking advances in medical devices as dental implants, catheters and non-absorbable surgical sutures. By means of 3D bioprinting, nylons have been used to develop scaffolds, joint implants and drug carriers with tailored properties for various biomedical applications. The present paper aims to collect evidence of these recently specific applications of nylons by reviewing the literature produced in recent decades, with a special focus on the newer technologies in the field of energy harvesting and biomedicine.

Unlocking the potential of Opuntia species mucilage in chemistry.

Herein, we describe a detailed protocol to extract the mucilage from different species of the genus Opuntia spp. (i.e., Opuntia Ficus (OFi), Opuntia Dillenii (ODi) and Opuntia Robusta (ORo)). The extracted mucilage was characterized by NMR, FTIR-ATR, HPLC, and TGA. OFi was found to have the highest phenolic content, 7.84 ± 1.93 mg catechol/g mucilage. The mucilage from the three species were characterized by having a high content of monosaccharides, being mannose and glucose the most abundant components (ca. 48-73 % and 23-35 %, respectively). In the context of biomass revalorization, the mucilage was proven to serve as a reducing and stabilizing agent in the synthesis of gold nanoparticles (AuNP/mucilage). The synthesis was optimized with a mucilage concentration of 2 mg/mL using 12.5 µL of KAuCl4 and was carried out at 80 °C for 90 min. This protocol afforded spherical nanoparticles with an average size of 9.7 ± 4.0 nm that were stable for at least 14 days, as demonstrated by TEM. Synthesized AuNP/mucilage was evaluated as a plasmonic catalyst for the reduction of 4-nitrophenol as model reaction, showing a considerable enhancement in its kapp of 97 % under white light and a decrease of 24.8 % in its activation energy.

Performance-Enhancing Materials in Medical Gloves.

Medical gloves, along with masks and gowns, serve as the initial line of defense against potentially infectious microorganisms and hazardous substances in the health sector. During the COVID-19 pandemic, medical gloves played a significant role, as they were widely utilized throughout society in daily activities as a preventive measure. These products demonstrated their value as important personal protection equipment (PPE) and reaffirmed their relevance as infection prevention tools. This review describes the evolution of medical gloves since the discovery of vulcanization by Charles Goodyear in 1839, which fostered the development of this industry. Regarding the current market, a comparison of the main properties, benefits, and drawbacks of the most widespread types of sanitary gloves is presented. The most common gloves are produced from natural rubber (NR), polyisoprene (IR), acrylonitrile butadiene rubber (NBR), polychloroprene (CR), polyethylene (PE), and poly(vinyl chloride) (PVC). Furthermore, the environmental impacts of the conventional natural rubber glove manufacturing process and mitigation strategies, such as bioremediation and rubber recycling, are addressed. In order to create new medical gloves with improved properties, several biopolymers (e.g., poly(vinyl alcohol) and starch) and additives such as biodegradable fillers (e.g., cellulose and chitin), reinforcing fillers (e.g., silica and cellulose nanocrystals), and antimicrobial agents (e.g., biguanides and quaternary ammonium salts) have been evaluated. This paper covers these performance-enhancing materials and describes different innovative prototypes of gloves and coatings designed with them.

Novel Biobased Epoxy Thermosets and Coatings from Poly(limonene carbonate) Oxide and Synthetic Hardeners.

In the area of coating development, it is extremely difficult to find a substitute for bisphenol A diglycidyl ether (DGEBA), the classical petroleum-based raw material used for the formulation of epoxy thermosets. This epoxy resin offers fast curing reaction with several hardeners and the best thermal and chemical resistance properties for applications in coatings and adhesive technologies. In this work, a new biobased epoxy, derived from poly(limonene carbonate) oxide (PLCO), was combined with polyetheramine and polyamineamide curing agents, offering a spectrum of thermal and mechanical properties, superior to DGEBA-based thermosets. The best formulation was found to be a combination of PLCO and a commercial curing agent (Jeffamine) in a stoichiometric 1:1 ratio. Although PLCO is a solid due to its high molecular weight, it was possible to create a two-component partially biobased epoxy paint without the need of volatile organic compounds (i.e., solvent-free formulation), intended for use in coating technology to partially replace DGEBA-based thermosets.

SEOM-GEMCAD-TTD Clinical Guideline for the diagnosis and treatment of esophageal cancer (2021).

Esophageal cancer is an aggressive tumor, and is the sixth-leading cause of death from cancer. Incidence is rising in Spain, particularly among men. Two main pathological different subtypes have been described: squamous cell carcinoma and adenocarcinoma. Growing evidence of their epidemiology and molecular differences explains their different response to novel treatments, and they are therefore likely to be treated as two separate entities in the near future. The best results are obtained with a multidisciplinary therapeutic strategy, and the introduction of immunotherapy is a promising new approach that will improve prognosis. In these guidelines, we review the evidence for the different methods of diagnosis and therapeutic strategies that form the basis of our standard of care.

Efficient One-Pot Preparation of Thermoresponsive Polyurethanes with Lower Critical Solution Temperatures.

This work reports a simple and scalable strategy to prepare a series of thermoresponsive polyurethanes synthesized via copolymerization of dicyclohexyl diisocyanate with glycerol ethoxylate in a single one-pot system. These polyurethanes exhibit lower critical solution temperatures (LCST) at 57 °C. The LCST of synthesized polyurethane was determined from Dynamic Scanning Calorimetry and UV-vis measurements. Both the LCST and Tg of synthesized polyurethane was tuned by varying the ratio between hard segment (dicyclohexyl diisocyanate) and soft segment (glycerol ethoxylate). Thus, Tg values could be tuned from -54.6 °C to -19.9 °C for samples with different flexibility. The swelling and deswelling studies were done at room temperature and above the LCST respectively. The results showed that the swelling ratio increases with the increase of soft segment (glycerol ethoxylate) in synthesized polyurethanes. Furthermore, the mechanical properties of the membrane were studied by universal tensile testing measurements. Specifically, stress at break values varied from 0.35±0.07 MPa to 0.91±0.15 MPa for the tested membranes, whereas elongation at break data ranged from 101.9±20.9 % to 192.4±24.4 %, and Young's modulus varied from 0.35±0.03 MPa to 1.85±0.19 MPa. Tensile strength of the films increased with the increase of the hard segment and elongation at break decreased.

Chloramphenicol loaded polylactide melt electrospun scaffolds for biomedical applications.

Melt electrospinning of polylactide (PLA) loaded with chloramphenicol (CAM) has been performed and characteristics of fibers, physical properties of scaffolds, CAM release behavior, antibacterial properties and biocompatibility have been evaluated. The interest of CAM loaded samples is nowadays enhanced for biomedical applications since this antibiotic has been demonstrated to be efficient for the treatment of cancer. Melt electrospinning has been selected as an ideal preparation process because it avoids the use of toxic solvents which are harmful to the environment and could be problematic for biomedical applications. The electrospinning process rendered fibers with a relatively large diameter (between 20 µm and 40 µm depending on the load) and minimum polymer degradation. Characteristics of melt electrospun scaffolds were also compared with those prepared by solution electrospinning. Differences consisted in a more sustained release and a higher biocompatibility for the melt processed samples. Bactericide effect was evaluated as an evidence of the maintenance of the CAM bioactivity after melt processing at high temperature and the slower release caused by the relatively high diameter of the constitutive fibers. Since pure CAM showed thermal degradation at temperatures relatively close to the PLA melting temperature, a complete analysis of the degradation process of pure CAM as well as of PLA samples loaded with CAM was performed. The Invariant Kinetic Parameters method allowed determining an initial decomposition step that followed an autoaccelatory Avrami model, and then an autocatalytic decomposition reaction took place for conversions higher than 50%. Dispersion in the PLA matrix enhances the thermal stability of the antibiotic, with an onset temperature of degradation that was higher by 16 °C in the melt-electrospun fibers than in the liquid state of pure CAM.

Biobased Terpene Derivatives: Stiff and Biocompatible Compounds to Tune Biodegradability and Properties of Poly(butylene succinate).

Different copolymers incorporating terpene oxide units (e.g., limonene oxide) have been evaluated considering thermal properties, degradability, and biocompatibility. Thus, polycarbonates and polyesters derived from aromatic, monocyclic and bicyclic anhydrides have been considered. Furthermore, ring substitution with myrcene terpene has been evaluated. All polymers were amorphous when evaluated directly from synthesis. However, spherulites could be observed after the slow evaporation of diluted chloroform solutions of polylimonene carbonate, with all isopropene units possessing an R configuration. This feature was surprising considering the reported information that suggested only the racemic polymer was able to crystallize. All polymers were thermally stable and showed a dependence of the maximum degradation rate temperature (from 242 °C to 342 °C) with the type of terpene oxide. The graduation of glass transition temperatures (from 44 °C to 172 °C) was also observed, being higher than those corresponding to the unsubstituted polymers. The chain stiffness of the studied polymers hindered both hydrolytic and enzymatic degradation while a higher rate was detected when an oxidative medium was assayed (e.g., weight losses around 12% after 21 days of exposure). All samples were biocompatible according to the adhesion and proliferation tests performed with fibroblast cells. Hydrophobic and mechanically consistent films (i.e., contact angles between 90° and 110°) were obtained after the evaporation of chloroform from the solutions, having different ratios of the studied biobased polyterpenes and poly(butylene succinate) (PBS). The blend films were comparable in tensile modulus and tensile strength with the pure PBS (e.g., values of 330 MPa and 7 MPa were determined for samples incorporating 30 wt.% of poly(PA-LO), the copolyester derived from limonene oxide and phthalic anhydride. Blends were degradable, biocompatible and appropriate to produce oriented-pore and random-pore scaffolds via a thermally-induced phase separation (TIPS) method and using 1,4-dioxane as solvent. The best results were attained with the blend composed of 70 wt.% PBS and 30 wt.% poly(PA-LO). In summary, the studied biobased terpene derivatives showed promising properties to be used in a blended form for biomedical applications such as scaffolds for tissue engineering.

Smart design for a flexible, functionalized and electroresponsive hybrid platform based on poly(3,4-ethylenedioxythiophene) derivatives to improve cell viability.

Development of smart functionalized materials for tissue engineering has attracted significant attention in recent years. In this work we have functionalized a free-standing film of isotactic polypropylene (i-PP), a synthetic polymer that is typically used for biomedical applications (e.g. fabrication of implants), for engineering a 3D all-polymer flexible interface that enhances cell proliferation by a factor of ca. three. A hierarchical construction process consisting of three steps was engineered as follows: (1) functionalization of i-PP by applying a plasma treatment, resulting in i-PPf; (2) i-PPf surface coating with a layer of polyhydroxymethy-3,4-ethylenedioxythiophene nanoparticles (PHMeEDOT NPs) by in situ chemical oxidative polymerization of HMeEDOT; and (3) deposition on the previously activated and PHMeEDOT NPs coated i-PP film (i-PPf/NP) of a graft conjugated copolymer, having a poly(3,4-ethylenedioxythiophene) (PEDOT) backbone, and randomly distributed short poly(ε-caprolactone) (PCL) side chains (PEDOT-g-PCL), as a coating layer of ∼9 µm in thickness. The properties of the resulting bioplatform, which can be defined as a robust macroscopic composite coated with a "molecular composite", were investigated in detail, and both adhesion and proliferation of two human cell lines have been evaluated, as well. The results demonstrate that the incorporation of the PEDOT-g-PCL layer significantly improves cell attachment and cell growth not only when compared to i-PP but also with respect to the same platform coated with only PEDOT, constructed in a similar manner, as a control.

Lycopene and Melatonin: Antioxidant Compounds in Cosmetic Formulations.

BACKGROUND: The use of antioxidants has become a common practice in the development of antiaging cosmetics. OBJECTIVE: The aim of this study was to evaluate the clinical efficacy of cosmetic formulations containing lycopene and melatonin antioxidants. METHOD: Thirty-six healthy women from 32 to 65 years were enrolled in this study. The study was carried out for 10 weeks, 2 preconditioning weeks with a control cream without antioxidants, and 8-week test with creams containing antioxidants in study. A multifunctional skin physiology monitor (Courage & Khazaka electronic GmbH®, Germany) was used to measure skin sebum content, hydration, elasticity, erythema index, and melanin index in 4 different regions of the face. RESULTS: There were significant differences between them.

Microstructural Changes during Degradation of Biobased Poly(4-hydroxybutyrate) Sutures.

Fibers of poly(4-hydroxybutyrate) (P4HB) have been submitted to both hydrolytic and enzymatic degradation media in order to generate samples with different types and degrees of chain breakage. Random chain hydrolysis is clearly enhanced by varying temperatures from 37 to 55 °C and is slightly dependent on the pH of the medium. Enzymatic attack is a surface erosion process with significant solubilization as a consequence of a preferent stepwise degradation. Small angle X-ray diffraction studies revealed a peculiar supramolecular structure with two different types of lamellar stacks. These were caused by the distinct shear stresses that the core and the shell of the fiber suffered during the severe annealing process. External lamellae were characterized by surfaces tilted 45° with respect to the stretching direction and a higher thickness, while the inner lamellae were more imperfect and had their surfaces perpendicularly oriented to the fiber axis. In all cases, WAXD data indicated that the chain molecular axis was aligned with the fiber axis and molecules were arranged according to a single orthorhombic structure. A gradual change of the microstructure was observed as a function of the progress of hydrolysis while changes were not evident under an enzymatic attack. Hydrolysis mainly affected the inner lamellar stacks as revealed by the direct SAXS patterns and the analysis of correlation functions. Both lamellar crystalline and amorphous thicknesses slightly increased as well as the electronic contrast between amorphous and crystalline regions. Thermal treatments of samples exposed to the hydrolytic media revealed microstructural changes caused by degradation, with the inner lamellae being those that melted faster.

Pt(II) and Pd(II) complexes with a thiazoline derivative ligand: Synthesis, structural characterization, antiproliferative activity and evaluation of pro-apoptotic ability in tumor cell lines HT-29 and U-937.

Eluding apoptosis represents the hallmark of tumoral cell behavior. Cisplatin (CisPt) is a very common chemotherapeutic agent to treat cancer by reestablishing apoptotic mechanisms of cell death. However, certain patients acquire resistance to CisPt as well as suffer nephrotoxicity, neurotoxicity, nausea and vomiting. The synthesis of new Pt(II) compounds represents an alternative to CisPt to avoid resistance and undesirable side effects. Pd(II) could be a Pt(II) surrogate given the similarity of coordination chemistry between them, thus widening the spectra of available anticancer drugs. Herein, we have synthesized and characterized two Pt(II) or Pd(II) complexes with TdTn (2-(3,4-dichlorophenyl)imino-N-(2-thiazolin-2-yl)thiazolidine), a thiazoline derivative ligand, with formula [PtCl2(TdTn)] and [PdCl2(TdTn)]. The potential anticancer ability was evaluated in human colon adenocarcinoma HT-29 and human histiocytic lymphoma U-937 cell lines. To that aim, U-937 and HT-29 cells were treated with TdTn, [PtCl2(TdTn)] and [PdCl2(TdTn)] for 24 h. The microscopy monitoring indicated that TdTn, [PtCl2(TdTn)] and [PdCl2(TdTn)] arrested the cell proliferation of U-937 and HT-29 cells with respect to control, in agreement with MTT (3-[4,5-dimethylthiazole-2-yl]-2,5-diphenyltetrazolium bromide) analysis. Moreover, it is noteworthy that the ligand by its own showed antiproliferative effects in both cell lines. [PtCl2(TdTn)] and [PdCl2(TdTn)] caused caspase-3 activation in U-937 cells, simultaneously with caspase-9 activation due to complexes; however, in HT-29 caspase-3 activation occurred simultaneously with caspase-8 activation induced by the ligand TdTn. Only metal complexes were able to induce ROS (Reactive Oxygen Species) generation in U-937 cells, but not TdTn. In HT-29 cells neither the metal complexes, nor the ligand induced ROS generation.

Incorporation of Chloramphenicol Loaded Hydroxyapatite Nanoparticles into Polylactide.

Chloramphenicol (CAM) has been encapsulated into hydroxyapatite nanoparticles displaying different morphologies and crystallinities. The process was based on typical precipitation of solutions containing phosphate and calcium ions and the addition of CAM once the hydroxyapatite nuclei were formed. This procedure favored a disposition of the drug into the bulk parts of the nanoparticles and led to a fast release in aqueous media. Clear antibacterial activity was derived, being slightly higher for the amorphous samples due to their higher encapsulation efficiency. Polylactide (PLA) microfibers incorporating CAM encapsulated in hydroxyapatite nanoparticles were prepared by the electrospinning technique and under optimized conditions. Drug release experiments demonstrated that only a small percentage of the loaded CAM could be delivered to an aqueous PBS medium. This amount was enough to render an immediate bacteriostatic effect without causing a cytotoxic effect on osteoblast-like, fibroblasts, and epithelial cells. Therefore, the prepared scaffolds were able to retain CAM-loaded nanoparticles, being a reservoir that should allow a prolonged release depending on the polymer degradation rate. The studied system may have promising applications for the treatment of cancer since CAM has been proposed as a new antitumor drug.

Isothermal Crystallization Kinetics of Poly(4-hydroxybutyrate) Biopolymer.

Thermal properties and crystallization kinetics of poly(4-hydroxybutyrate) (P4HB) have been studied. The polymer shows the typical complex melting behavior associated to different lamellar populations. Annealing processes had great repercussions on properties and the morphology of constitutive lamellae as verified by X-ray scattering data. Kinetics of isothermal crystallization was evaluated by both polarizing optical microscopy (POM) and calorimetric (DSC) measurements, which indicated a single crystallization regime. P4HB rendered banded spherulites with a negative birefringence when crystallized from the melt. Infrared microspectroscopy was applied to determine differences on the molecular orientation inside a specific ring according to the spherulite sectorization or between different rings along a determined spherulitic radius. Primary nucleation was increased during crystallization and when temperature decreased. Similar crystallization parameters were deduced from DSC and POM analyses (e.g., secondary nucleation parameters of 1.69 × 105 K2 and 1.58 × 105 K2, respectively). The effect of a sporadic nucleation was therefore minimized in the experimental crystallization temperature range and a good proportionality between overall crystallization rate (k) and crystal growth rate (G) was inferred. Similar bell-shaped curves were postulated to express the temperature dependence of both k and G rates, corresponding to the maximum of these curves close to a crystallization temperature of 14-15 °C.

Non-Isothermal Crystallization Kinetics of Poly(4-Hydroxybutyrate) Biopolymer.

The non-isothermal crystallization of the biodegradable poly(4-hydroxybutyrate) (P4HB) has been studied by means of differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). In the first case, Avrami, Ozawa, Mo, Cazé, and Friedman methodologies were applied. The isoconversional approach developed by Vyazovkin allowed also the determination of a secondary nucleation parameter of 2.10 × 105 K2 and estimating a temperature close to 10 °C for the maximum crystal growth rate. Similar values (i.e., 2.22 × 105 K2 and 9 °C) were evaluated from non-isothermal Avrami parameters. All experimental data corresponded to a limited region where the polymer crystallized according to a single regime. Negative and ringed spherulites were always obtained from the non-isothermal crystallization of P4HB from the melt. The texture of spherulites was dependent on the crystallization temperature, and specifically, the interring spacing decreased with the decrease of the crystallization temperature (Tc). Synchrotron data indicated that the thickness of the constitutive lamellae varied with the cooling rate, being deduced as a lamellar insertion mechanism that became more relevant when the cooling rate increased. POM non-isothermal measurements were also consistent with a single crystallization regime and provided direct measurements of the crystallization growth rate (G). Analysis of the POM data gave a secondary nucleation constant and a bell-shaped G-Tc dependence that was in relative agreement with DSC analysis. All non-isothermal data were finally compared with information derived from previous isothermal analyses.

Crystalline Structures and Structural Transitions of Copolyamides Derived from 1,4-Diaminobutane and Different Ratios of Glutaric and Azelaic Acids.

Copolyamides derived from even 1,4-butanediamine and different mixtures of odd dicarboxylic acids with a great difference in the number of methylene groups (i.e., glutaric and azelaic acids with 3 and 7 groups, respectively) have been synthesized, characterized and structurally studied. Calorimetric analyses revealed a complex behavior with multiple melting peaks associated to lamellar reordering and the presence of defective crystals. Equilibrium melting temperatures were evaluated and showed a eutectic behavior with composition. Copolymers were able to crystallize even for samples with comonomer percentages close to 50%. Negative and ringed spherulites from the melt state and small lath-like lamellar crystals from dilute solution crystallizations were attained. Furthermore, calorimetric data pointed out the exclusion of the less abundant monomer from the lattice of the predominant structure. All samples at room temperature showed a similar crystalline structure (form I) defined by two predominant reflections at spacings close to 0.430 and 0.380 nm, which has been related for even-odd nylons with a two-hydrogen bonded structure. Real time synchrotron experiments showed that melt crystallized samples have two polymorphic transitions on heating, which were practically reversible and consequently were also detected during cooling from the melt state. Interestingly, a different behavior was detected among solution crystallized samples and specifically the transition to the intermediate structure (form II) was not detected during heating for samples enriched on the azelate component or more precisely when they were exclusively crystallized in the form I.

Tuning the Kinetic Stability of the Amorphous Phase of the Chloramphenicol Antibiotic.

We employ broadband dielectric spectroscopy to study the relaxation dynamics and crystallization kinetics of a broad-spectrum antibiotic, chloramphenicol, in its supercooled liquid form. Two dynamic processes are observed: the structural α relaxation, which becomes kinetically frozen at Tg = 302 ± 1 K, and an intramolecular secondary relaxation. Under isothermal conditions, the supercooled drug displays interconversion between different isomers, followed by recrystallization. Recrystallization follows the Avrami law with Avrami exponent n = 1.3 ± 0.1, consistent with a one-dimensional growth of crystalline platelets, as observed by electron microscopy. Exposure to humid atmosphere and subsequent heating to high temperature is found to degrade the compound. The partially degraded sample displays a much lower tendency to crystallize, likely because the presence of the degradation products results in spatial frustration. This sample exhibits enhanced conductivity and an additional relaxation, intermediate to the ones observed in the pure sample, which likely corresponds to the noncooperative dynamics of the main degradation product. We find that dispersing the antibiotic in polylactic acid results in an amorphous sample, which does not crystallize at room temperature for relatively long times.

Isomeric cationic ionenes as n-dopant agents of poly(3,4-ethylenedioxythiophene) for in situ gelation.

Three isomeric ionene polymers containing 1,4-diazabicyclo[2.2.2]octane (DABCO) and N,N'-(x-phenylene)dibenzamide (x = ortho-/meta-/para-) linkages have been used as dopant agents to produce n-doped poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes by reducing already dedoped conducting polymer (CP) films. This work focuses on the influence of the ionene topology on both the properties of n-doped PEDOT:ionene electrodes and the success of the in situ thermal gelation of the ionene inside the CP matrix. The highest doping level is reached for the para-isomeric ionene-containing electrode, even though the content of ortho- and meta-topomers in the corresponding n-doped PEDOT:ionene electrodes is greater. Thus, many of the incorporated ionene units are not directly interacting with CP chains and, therefore, they do not play an active role as n-dopant agents but they are crucial for the in situ formation of the ionene hydrogels. The effect of the ionene topology is practically non-existent on properties such as the specific capacitance and wettability of PEDOT:ionene films, and it is small but non-negligible on the electrochemical and thermal stability. In contrast, the surface morphology, topography, and distribution of dopant molecules significantly depend on the ionene topology. In situ thermal gelation was successful in PEDOT films n-doped with the ortho- and para-topomers, even though this assembly process was much faster for the former than for the latter. The gelation considerably improved the mechanical response of the electropolymerized PEDOT film, which was practically non-existent before it. Molecular dynamics simulations prove that the strength and abundance of PEDOTionene specific interactions (i.e. π-π stacking, N-HS hydrogen bonds and both N+O and N+S interactions) are higher for the meta-isomeric ionene, for which the in situ gelation was not achieved, than for the ortho- and para-ones.

Reducing Missed Opportunities for Influenza Vaccination in Patients with Rheumatoid Arthritis: Evaluation of a Multisystem Intervention.

OBJECTIVE: To assess a multimodal intervention for reducing missed opportunities for outpatient influenza vaccination in individuals with rheumatoid arthritis (RA). METHODS: Patients with RA were enrolled from a single center and each rheumatology outpatient visit was tracked for missed opportunities for influenza vaccination, defined as a visit in which an unvaccinated patient without contraindications remained unvaccinated or lacked documentation of vaccine recommendation in the electronic medical record (EMR). Providers then received a multimodal intervention consisting of an education session, EMR alerts, and weekly provider-specific e-mail reminders. Missed opportunities before and after the intervention were compared, and the determinants of missed opportunities were analyzed. RESULTS: A total of 228 patients with RA were enrolled (904 preintervention visits) and 197 returned for at least 1 postintervention visit (721 postintervention visits). The preintervention frequency of any missed opportunities for influenza vaccination was 47%. This was reduced to 23% postintervention (p < 0.001). Among those vaccinated, the relative hazard for influenza vaccination post- versus preintervention period was 1.24 (p = 0.038). Younger age, less frequent office visits, higher erythrocyte sedimentation rate, and negative attitudes about vaccines were each independently associated with missed opportunities preintervention. Postintervention, these factors were no longer associated with missed opportunities; however, the intervention was not as effective in non-Hispanic black patients, non-English speakers, those residing outside of the New York City metropolitan area, and those reporting prior adverse reactions to vaccines. CONCLUSION: Improved uptake of influenza vaccination in patients with RA is possible using a multimodal approach. Certain subgroups may need a more potent intervention for equivalent efficacy.