ABSTRACT Soft photonic materials capable of maintaining optical functionality under large mechanical deformation are highly desirable for wearable photonics, flexible sensors, optical and mechanically adaptive photonic systems. Here, we report highly stretchable luminescent elastomers based on the thermoplastic copolymer PEBAX 2533 incorporating a europium β‐diketonate complex. The transparent films combine intense europium emission with exceptional mechanical flexibility, displaying elongation at break exceeding 1200%, while maintaining high optical transparency in the visible range. The elastomers exhibit intense red luminescence with absolute quantum yields of 0.61. Under mechanical deformation, the 5 D 0 → 7 F 0 transition shows a strain‐dependent spectral shift and intensity modulation, enabling optical strain readout with sensitivities of –1.6 ± 0.2 cm −1 ·ε −1 and −0.44 ± 0.04 ε −1 , respectively. The luminescence spectra also display a thermal dependence, characterized by a blue shift and intensity decrease of the Eu 3+ emission with a temperature sensitivity of 0.08 ± 0.01 cm −1 ·°C −1 over the investigated temperature range. The coexistence of large deformability, high transparency, efficient Eu 3+ emission, and two independently calibrated optical responses establishes Eu‐doped elastomers as a versatile soft photonic platform for multimodal optical transduction, highlighting their potential for flexible sensing technologies in which mechanical and thermal perturbations are optically encoded within the same material platform.
Developing flexible luminescent materials through immobilizing lanthanide ion complexes in plasticized carboxymethylcellulose (CMC) films presents a significant challenge. This study focused on the synthesis of CMC films incorporating [Eu(tta)3(H2O)2] and [Tb(acac)3(H2O)3] complexes, with varying amounts of glycerol as a plasticizer, using casting technique deposition. The resulting films exhibited amorphous characteristics and thermal stability up to approximately 245 degrees C. Photoluminescence studies revealed that films containing the Eu3+ complex displayed intense emission in the red region (614 nm) when excited at 352 nm, attributed to the antenna effect. Notably, the CMC_Eu_20.0 GLY film, with the highest concentration of plasticizer, showed significant enhancements in experimental lifetime (0.69 ms) and quantum efficiency (39 % q (5D0)) compared to the pristine complex (0.22 ms and 24 %, respectively). Films containing the Tb3+ complex, when excited at 300 nm, exhibited strong emission in the green region at 546 nm. An increase in excited lifetime was observed with increasing glycerol content, reaching a maximum of 1.50 ms at 15 % glycerol concentration. The mechanical properties of the films were significantly influenced by plasticizer content. The addition of 20 % glycerol resulted in a substantial increase in elongation at break from 8.9 % to 39.5 %. However, it also led to increased flexibility and reduced traction resistance, as evidenced by the decrease in Young's modulus from 3.4 to 1.5 MPa and breaking stress from 12.4 to 5.6 MPa. Interestingly, the incorporation of lanthanide complexes did not significantly affect the mechanical properties of the films. This finding suggests that luminescent properties can be tailored independently of the mechanical characteristics, offering versatility in material design for various applications.
The design of multifunctional nanostructured materials with potential for both diagnostic and therapeutic use, the so-called theranostic platforms, is a promising strategy in cancer research. In this study, we report the fabrication and physicochemical characterization of Langmuir and Langmuir-Blodgett (LB) films composed of a triacylated uridine derivative (PNM2), previously described as a prodrug with anticancer potential, and the europium complex Eu-(tta)3(H2O)2, known for its luminescent and structural probe properties. Langmuir monolayers at the air-water interface exhibited high rigidity for PNM2, which was modulated upon incorporation of the europium complex. Surface pressure-area isotherms, surface potential data, and dilatational rheology confirmed a transition toward a more fluid-like yet stable film. PM-IRRAS and Brewster angle microscopy indicated uniform molecular organization and specific interactions between Eu3 + and the carbonyl groups of PNM2. Upon transfer to solid substrates, LB films preserved this organization and exhibited strong photoluminescence, with emission spectra confirming efficient energy transfer via the antenna effect. Lifetime and quantum efficiency measurements revealed reduced water coordination and enhanced radiative decay. These results demonstrate that PNM2-Eu-(tta)3(H2O)2 films are structurally robust and optically responsive systems, offering a promising foundation for the development of biofunctional interfaces with potential theranostic applications, including cancer sensing and localized drug delivery.
In this study, we produced hydroxypropyl methylcellulose (HPMC) films containing silver nanoparticles (AgNPs) by a straightforward method for potential wound dressing applications. Polyvinylpyrrolidone (PVP) or polyvinyl alcohol (PVA) was added to these films to improve their mechanical properties. Various compositions of HPMC, PVP/PVA, and AgNPs were tested. The films containing AgNPs exhibited a yellow color, and the confirmation of silver nanoparticles was achieved through UV–Vis analysis. The antimicrobial capacity of HPMC films was assessed against strains of Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, and Candida albicans. Pristine HPMC and HPMC films blended with PVA/PVP displayed no antimicrobial activity, emphasizing the essential role of silver nanoparticles. The films with the highest AgNP content effectively inhibited Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus, surpassing the literature data. Some samples showed moderate inhibitory activity against Candida albicans. These films show potential as wound dressings, attributed to their antimicrobial properties and their convenient removal in the shower or by using a gentle water spray which may lead to reduced discomfort compared to traditional dressings. Further research is required to assess their clinical performance.
In this study, the effect of Eu3+ on the magnetic, optical, and structural behavior of the slow-cooled La0.7Sr0.3MnO3 and La0.4Eu0.3Sr0.3MnO3 manganites was investigated using magnetization measurements as a function of the applied field, X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, FTIR measurements, and photoluminescence tests. The results showed that the addition of Eu3+ decreases the saturation magnetization of the manganite. An additional europium compound was identified after the slow cooling. The photoluminescence properties of this manganite showed to be dependent on the excitation wavelength, being more effective through the charge transfer band which transfers energy from the matrix to the Eu3+ ions. Two-lifetime constants were determined from photoluminescence experiments.
The purpose of this work was to develop a simple method to produce self-supported films composed of hydroxypropyl methylcellulose (HPMC) and polyaniline (PANI) by the direct mixture of aqueous dispersions of both polymers with subsequent drying. The addition of HPMC, a cellulose derivative with an excellent film-forming capacity, was fundamental to overcoming the poor processability of PANI, which impairs its use in many technological applications. All films showed conductivity in the order of 10-2 to 10-3 S cm-1, which is in the range for metals or semiconductors. The typical electroactivity of PANI was also maintained in the hybrid films. The thermal stability and the mechanical properties of the pristine PANI were also improved with the addition of HPMC. Cellulose-containing conducting polymers can be considered a material of the future, with possible applications in several areas, such as smart wallpapers, e-papers, and sensors.
In this study, orodispersible films formed from hydroxypropyl methylcellulose (HPMC) E6 (2, 2.5, and 3%) and plasticizers ((glycerin (Gly), propylene glycol (PP), or polyethylene glycol (PEG)), containing doxazosin mesylate, were prepared by the solvent casting method and characterized. Design of experiments (DoE) was used as a statistical tool to facilitate the interpretation of the experimental data and allow the identification of optimal levels of factors for maximum formulation performance. Differential scanning calorimetry (DSC) curves and X-ray powder diffraction (XRPD) diffractograms showed doxazosin mesylate amorphization, probably due to complexation with the polymer (HPMC E6), and the glass transition temperature of the polymer was reduced by adding a plasticizer. Fourier transformed infrared (FTIR) spectroscopy results showed that the chemical structure of doxazosin mesylate was preserved when introduced into the polymer matrix, and the plasticizers, glycerin and PEG, affected the polymer matrix with high intensity. The addition of plasticizers increased the elongation at break and adhesiveness (Gly > PEG > PP), confirming the greater plasticizer effect of Gly observed in DSC and FTIR studies. Greater transparency was observed for the orodispersible films prepared using PP. The addition of citric acid as a pH modifier was fundamental for the release of doxazosin mesylate, and the desirability formulation had a release profile similar to that of the reference product.
Abstract The purpose of this work was to develop a simple method to produce self-supported and homogeneous films composed of hydroxypropyl methylcellulose (HPMC) and polyaniline (PANI) by the simple mixture of aqueous solutions of both polymers with subsequent drying. The addition of HPMC, a cellulose derivative with an excellent film-forming capacity, was fundamental to overcoming the poor processability of pristine PANI film, which impairs its use in many technological applications. Despite being an insulating polymer, the addition of HPMC did not significantly decrease the conductivity and all hybrid films showed conductivity in the order of 10− 2 − 10− 3 S cm− 1, which is in the range for metals or semiconductors. The typical electroactivity of PANI was also maintained with the addition of HPMC. Also, as a beneficial, adding HPMC the thermal stability and the mechanical properties of the pristine PANI were improved. Cellulose-containing conducting polymers with electroactive activity can be considered as a material of the future, with possible applications in several areas, such as smart wallpapers, e-papers, and sensors.
This investigation describes the synthesis, characterization, and in vitro cytotoxic evaluation of luminescentsuperparamagnetic iron oxide nanoparticles (SPIONs) functionalized with biomolecules and Eu3+ and Tb3+ complexes. They emerge as strong candidates for a large number of biomedical applications, such as drug delivery for bioapplications in therapy and diagnosis (theranostic). Aiming these applications, magnetite nanoparticles (Fe3O4) functionalized with biocompatible ligands, Chitosan (CS) and Glutathione (GSH) and Eu3+ and Tb3+ beta-Diketonates complexes were synthesized by a one-step procedure and characterized by different experimental techniques. Regarding bioapplication, their cytotoxicity using the cell viability assay of the blood mononuclear cell fraction were performed. The results show that the cytotoxicity depends on the concentration, nature of ligands and complexes. The SPIONs are luminescent with emission in the visible region under ultraviolet excitation and stable in nanoscale in aqueous medium. They are good candidates as nano-luminescent carriers in biomedical applications.
Bacterial nanocellulose (BNC) is a natural biopolymer obtained by gram-negative bacteria by means of a green and inexhaustible biotechnological process using glucose as producing source. BCN hydrogels is formed by cellulose nanofibrils that maintain an open network structure, an ideal matrix to produce new class of organic-inorganic nanocomposites (OIN) for multifunctional applications. The polyoxometalates (POMs) are complex molecules with several metallic ions sharing oxide ions, forming a highly symmetrical metal oxide cluster. Phosphotungstic acid (PWA), H3PW12O40 photoreduction process activated under ultraviolet irradiation, promoting color change. In this work, photochromic organic-inorganic nanocomposites were prepared by soaking phosphotungstic acid (H3PW12O40) in wet BNC membranes mats at room temperature. Semi-transparent and free-standing BNC/PWA nanocomposite with paper-like aspect were obtained. BNC network was able to control, stabilize and disperse PWA particles in a narrow nanometric distribution, and FTIR spectra indicated that the primary Keggin structure was also preserved in the nanocomposites, independently on the PWA content. The nanoparticles present a narrow distribution of around 16 nm, independently on the PWA concentration. BNC/PWA nanocomposites showed reversible photochromic behavior characteristic of the equilibrium between different tungsten oxidation states. PWA reduction (W6+→ W5+) and organic matrix oxidation is proposed to occur through a radical process involving the interaction of one electron from the oxygen atom of the PWA and one hydrogen from BNC matrix. The photochromic effect vanishes almost completely after 5 h. This mechanism is real in the presence of oxygen, however, if the membranes are left in nitrogen or under vacuum the blue color remains longer than 45 days. Photo-electrochemical behavior was studied by spectroelectrochemistry measurements. It is worth noting that all processes were still reversible in the timescale of the experiment and color changes were observed in several cycles.
The production of nanostructured materials for biological and medical applications may be applied toward the conjugation of adequate substances to boost the stimulus response of sensors and diagnostic probes. In this sense, Langmuir-Blodgett films constituted of bioinspired and biomimetic materials have attracted attention because of the ease of manipulation of the molecular architecture. In this paper, we employed a nucleoside-based drug, which was linked with a sterol hydrophobic moiety (3',4'-acetonide-uridine-succinate-cholesterol conjugate) to provide it an amphiphilic character. The drug was spread on the air-water interface, alone or mixed with stearic acid, forming Langmuir monolayers, and the complex Eu(tta)3(H2O)2 was incorporated in the drug-containing monolayer. Interactions at the air-water interface between stearic acid, the drug, and the europium complex were then investigated with tensiometry, surface potential, infrared spectroscopy, and Brewster angle microscopy. The Langmuir films were transferred to solid supports as Langmuir-Blodgett films, which presented luminescent properties that could be tuned according to the molecular architecture. We believe that these results can serve as a novel approach to characterize and assemble materials organized in the molecular scale for medical applications.
This article describes the synthesis, characterization, in vitro cytotoxic and genotoxicity evaluation of chitosan-iron oxide nanoparticles (Fe3O4-CS) as vehicles for ibuprofen (IBU) molecule. Magnetite (Fe3O4) nanoparticles were synthesized by co-precipitation of iron salts and coated with chitosan, leading to the formation of Fe3O4-CS hybrid nanoparticles, and then IBU was adsorbed on the surface of the modified nanoparticles. The physicochemical, morphological, and magnetic properties of the nanoparticles were determined by X-ray powder diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy and SQUID magnetic measurements. The nanoparticles have shown stability in aqueous medium presenting an average hydrodynamic size of 36 ± 9 nm for Fe3O4-CS, and 132 ± 1 nm for Fe3O4-CS-IBU. The cytotoxicity of nanoparticles using the cell viability of the blood mononuclear cell fraction and the analysis of gene expression of the repair genes hMSH2, hMSH6 and NF-kB were performed to evaluate their applicability as drug carriers. The results showed that Fe3O4-CS nanoparticles are suitable candidates as magnetic vehicles for ibuprofen in biomedical applications.
One of the main approaches toward obtaining efficient up converting materials with practical applications involves the development of composites with synergism between components. Herein, we reported an optical temperature sensing using up-conversion fluorescence emission at 530 and 550 nm in the Er3+/Yb3+-co-doped NaYF4 nanoparticles and SBA-15/NaYF4:Yb,Er composites excited at 976 nm. Nanoparticles and composites were prepared and investigated by X-ray diffractometry, N2 adsorption–desorption isotherms, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and up-conversion photoluminescence. Spherical like NaYF4:Yb,Er nanoparticles exhibited a mixture of hexagonal and cubic phases, while the rare earth ions incorporated inside of SBA-15 mesopores crystallized in a cubic phase. Optical thermometry property was investigated in the temperature range from 30 to 90 °C, and a maximum absolute sensitivity were 0.03/°C and 0.38/°C for nanoparticles and composites, respectively. The lower temperature range makes the composites with potential for application in biological systems.
Incorporation of enzymes in matrices as nanostructured films is a strategy to achieve molecular architectures able to enhance the efficiency of sensors and optoelectronic devices. In this present work, urease was inserted in the aqueous subphase of a di-ureasil hybrid compound (DUPTS) assembled as a Langmuir monolayer. Phosphotungstic acid (PWA) was introduced in the aqueous subphase in order to stabilize DUPTS by means of electrostatic interactions. Incorporation of urease in the Langmuir film could be attested with surface pressure and surface potential-area isotherms, rheological measurements, polarization modulation infrared reflection-absorption spectroscopy, and Brewster angle microscopy. The monolayers were transferred to solid supports as Langmuir-Blodgett films and characterized with infrared and fluorescence spectroscopies, proving not only the co-transfer of urease to the solid support, but also the conservation of part of its secondary structure. The enzyme activity could be detected towards urea hydrolysis enabling the urease/PWA/DUPTS supramolecular system to be employed for sensors as well as for other optoelectronic devices.
The incorporation of polyoxometalates in suitable matrices has been a main effort to produce transparent photochromic materials. Polymeric films based on high transparent polymethylmethacrylate (PMMA) containing phosphotungstic acid (PWA) have been obtained by casting and also by inkjet printing. In this investigation, polymeric PMMA matrix containing PWA were developed in an appropriate ratio of CH2Cl2/THF solvents to provide suitable transparent solution. PMMA/PWA composites obtained by casting were characterized by IR-ATR, Raman, XRD, TG/DTG, UV-Vis. Inkjet printing solution were characterized by surface tension (ST), viscosity and contact angle (CA) on glass substrate and films by optical microscopy. Infrared-ATR and Raman spectroscopies showed that the polyoxometalate structure was preserved in the polymeric matrix and the interaction between them occurred due to electrostatic forces. XRD indicated that PMMA and photochromic films were amorphous and display thermal stability up to 300 degrees C. Upon the UV irradiation, transparent films become blue and the photobleaching process were performed as a function of the temperature in a presence of air. These high transparent and photosensitive photochromic films present potential application as coating by casting and miniatured devices by inkjet printing.
Solid state lighting (SSL) revolutionized the light sources and displays market. Challenges include the seek for low cost and efficient materials able to emit pure colours (red, green and blue). Herein, we report amine-functionalized organic/inorganic di-ureasil hybrids consisting of a siliceous skeleton and oligopolyether chains, d-U(600), modified by distinct concentration values of a blue emitting uncharged polyfluorene (poly (9,9-dioctylfluorene)-co-phenylene) (PF). Structural and thermal studies reveal that the interaction between the PF and the d-U(600) yield to an enhancement of the PF thermal stability. The optical characterization shows that the emission is strongly dependent on the excitation energy presenting a red-shift as the excitation wavelength increases, enabling a fine tuning of the emission colour coordinates. Under UV excitation, a maximum emission quantum yield value 0.44 +/- 0.04 was attained, which is remarkably higher when compared to the value found for the undoped d-U(600), 0.13 +/- 0.01, an analogous to the value found for the isolated PF, pointing out that the incorporation into the hybrid host did not yield to an emission efficiency quenching. A commercial LED chip emitting at 365 nm was coated by the PF-doped d-U(600) showing a wall-plug efficiency of 0.04% and a luminous efficacy of 0.003 lm.W-1, demonstrating the applicability of these materials as blue-emitting phosphors to be applied in SSL.
Multifunctional composite (MFC) di-ureasil hybrid synthesized by sol gel method containing phosphotungstic acid (PWA) and Eu3+ ions have been successfully incorporated into mesoporous silica (SBA-15) by post-synthesis method. MFC were characterized by Fourier transform-infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), nitrogen adsorption–desorption (NAI), thermogravimetric and differential thermal analysis, transmission electron microscopy (TEM) and also photoluminescence. FTIR showed that both di-ureasil and PWA were incorporated into the mesoporous silica. NAI, TEM and SAXS confirmed the incorporation of the PWA and di-ureasil into the mesoporous of SBA-15. Composites are thermal stable at about 240 °C and photoluminescence has demonstrated that Eu3+ ions were successfully entrapped and occupies local environment with low symmetry.
Objetivos Docentes- Describir las caracteristicas radiologicas de la carcinomatosis peritoneal de origen ovarico, resaltando el papel del radiologo de cara a la planificacion del tratamiento quirurgico.- Revisar la utilidad de las nuevas tecnicas radiologicas disponibles: Tomografia computerizada multidetector (TCMD), Resonancia Magnetica (RM) anatomica y funcional y Tomografia por emision de positrones-TC (PET-TC) en el estudio de la carcinomatosis peritoneal.- Detallar cuales son los ultimos avances quirurgicos y oncologicos y explicar las peculiaridades del seguimiento radiologico de la carcinomatosis peritoneal. Revision del temaEl cancer de ovario tiene la mayor mortalidad de los tumores ginecologicos malignos y se debe a sus caracteristicas tumorales, ya que en la mayoria de los casos el diagnostico se establece en estadios avanzados (III/IV), presentandose en el 70% de los casos con carcinomatosis peritoneal o con metastasis a distancia. (fig. 1)
The search for new molecular architectures to improve the efficiency of sensors and optoelectronic devices is fundamental to enhance the effectiveness of nanostructured materials. In this present work, a di-ureasil hybrid compound (DUPTS) was spread at the air-water interface in order to form Langmuir monolayers. Phosphotungstic acid, H3PW12O40, PWA inserted in the aqueous subphase stabilized the formation of DUPTS as a stable Langmuir film, as showed with surface pressure and surface potential-area isotherms, rheological measurements, polarization modulation reflection-absorption spectroscopy, and Brewster angle microscopy. The monolayers were transferred to solid supports as Langmuir-Blodgett films and presented different patterns of heterogeneity as observed with atomic force microscopy, with the morphology dependent on the presence of PWA and on the kind of solid support surface.