Embedded bleeding detector into a PMMA applicator for electron intraoperative radiotherapy.

PURPOSE: The aim of this work is to present a ready to industrialize low-cost and easy-to-install bleeding detector for use in intraoperative electron radiation therapy (IOERT). The detector works in stand-alone mode and is embedded into a translucent polymethylmethacrylate (PMMA) applicator avoiding any contact with the patient, which represent a novelty compared to previous designs. The use of this detector will prevent dose misadministration during irradiation in the event of accumulation of fluids in the applicator. METHODS: The detector is based on capacitive sensor and wireless power-supply electronics. Both sensor and electronics have been embedded in the applicator, so that any contact with the patient would be avoided. Since access to the tumor can be done through different trajectories, the detector has been calibrated for different tilting angles. RESULTS: The result of the calibration provides us with a fit curve that allows the interpolation of the results at any angle. Comparison of estimated fluid height vs real height gives an error of 1 mm for tilting angles less than 10° and 2 mm for tilting angles greater than 15°. This accuracy is better than the one required by clinic. CONCLUSIONS: The performance of the bleeding detector was evaluated in situ. No interference was observed between the detector and the beam. In addition, a user-friendly mobile application has been developed to help the surgical team making decisions before and during irradiation. The measurement provided by the mobile application was stable during the irradiation process.

Ongoing Evolution in the Genus Crocus: Diversity of Flowering Strategies on the Way to Hysteranthy.

Species of the genus Crocus are found over a wide range of climatic areas. In natural habitats, these geophytes diverge in the flowering strategies. This variability was assessed by analyzing the flowering traits of the Spanish collection of wild crocuses, preserved in the Bank of Plant Germplasm of Cuenca. Plants of the seven Spanish species were analyzed both in their natural environments (58 native populations) and in common garden experiments (112 accessions). Differences among species observed in the native habitats were maintained under uniform environmental conditions, suggesting a genetic basis for flowering mechanisms. Two eco-morphological types, autumn- and spring-flowering species, share similar patterns of floral induction and differentiation period in summer. The optimal temperature for this process was 23 °C for both types. Unlike Irano-Turanian crocuses, spring-flowering Spanish species do not require low winter temperatures for flower elongation. Hysteranthous crocuses flower in autumn prior to leaf elongation. We conclude that the variability in flowering traits in crocuses is related to the genetic and environmental regulation of flower primordia differentiation and elongation prior to emergence above the soil surface. The elucidation of the physiological differences between eco-morphological types of crocuses: synanthous with cold requirements and synanthous and hysteranthous without cold requirements, unlocks a new approach to the flowering evolution of geophytes in Mediterranean regions. Crocus species can serve both as a new model in the study of the molecular basis of hysteranthy and for the purposes of developing the molecular markers for desirable flowering traits.

Phantom development for daily checks in electron intraoperative radiotherapy with a mobile linac.

PURPOSE: IORT with mobile linear accelerators is a well-established modality where the dose rate and, therefore, the dose per pulse are very high. The constancy of the dosimetric parameters of the accelerator has to be checked daily. The aim of this work is to develop a phantom with embedded detectors to improve both accuracy and efficiency in the daily test of an IORT linac at the surgery room. METHODS: The developed phantom is manufactured with transparent polymethyl methacrylate (PMMA), allocating 6 parallel-plate chambers: a central one to evaluate the on-axis beam output, another on-axis one placed at a fixed depth under the previous one to evaluate the energy constancy and four off-axis chambers to evaluate the flatness and symmetry. To analyse the readings a specific application has been developed. RESULTS: For all chambers and energies, the mean saturation and polarization corrections were smaller than 0.7%. The beam is monitored at different levels of the clinical beam. Output, energy constancy and flatness correlate very well with the correspondent values with the complete applicator. During the first six months of clinical use the beam dosimetric parameters showed excellent stability. CONCLUSIONS: A phantom has been developed with embedded parallel plate chambers attached to the upper applicator part of an IORT linac. The phantom allows a very efficient setup reducing the time to check the parameters. It provides complete dosimetric information (output, energy and flatness) with just one shot and using ionization chambers with minimum saturation effect, as this highly pulsed beam requires.

Perylenediimides as more than just non-fullerene acceptors: versatile components in organic, hybrid and perovskite solar cells.

Recent reviews have highlighted the use of perylenediimides (PDIs) as non-fullerene acceptors in bulk-heterojunction organic photovoltaic devices. This review is focused on the advances in the incorporation of PDIs as photoactive components in different solar cell devices. An impressive number of perylenediimides have been incorporated into p-n organic solar cells, as non-fullerene acceptors in bulk heterojunction solar cells, as photosensitisers in dye-sensitised solar cells, in perovskite solar cells, and also as interlayers acting as either electron- or hole-transporting materials. All of this has led to devices with outstanding photovoltaic performance and these are described in this review.

Improving bleeding detector features for electron intraoperative radiotherapy.

PURPOSE: The aim of this work is to improve the potential bleeding detection during intraoperative radiotherapy with linac polymethyl methacrylate applicators (PMMA), based on one previously developed. The improvements carried out have been focused on: i) minimizing the impact of the detector on the visual through the plastic applicators and ii) avoiding the asymmetry in the detection capability when the applicator is tilted. METHODS: Simulations have been made to select the geometry that provides a reduced visual impact on the applicator as well as allowing an independent response with the tilting angle of the applicator. A low-noise circuit for signal conditioning has been developed. Measurements have been made on three setups: 10 cm, 7 cm and 4 cm applicator diameters, 0° and 45° tilted. RESULTS: The detector has a visibility through the applicator greater than 50%. Due to the geometry, optimal detection is ensured regardless of its orientation when the applicator is tilted. It is possible to detect the presence of fluid well below the typical perturbing fluid depth established by the clinic (1-1.5 cm). CONCLUSIONS: The detector can distinguish the presence of around 0.5 cm of fluid depth while showing a high visual field through the PMMA applicators and providing a measure that does not depend on the detector orientation when the applicator is tilted. The prototype is ready for its industrialization by embedding it into the applicator for clinical use. The detector would have a significant impact on both the quality assurance and the outcome of the treatment.

Directly Linked Zinc Phthalocyanine-Perylenediimide Dyads and a Triad for Ultrafast Charge Separation.

Directly linked to promote strong intramolecular interactions, donor-acceptor dyads and a donor-acceptor-donor triad featuring zinc phthalocyanine (ZnPc) as electron donor and perylenediimide (PDI) as electron acceptor have been synthesized and characterized. Owing to complementary absorption features of the entities, improved light absorption was witnessed in these conjugates. The optimized geometry and electronic structures showed the majority of the highest occupied molecular orbital (HOMO) on the ZnPc entity, whereas the lowest unoccupied molecular orbital (LUMO) was on the PDI entity, suggesting that the charge-separated states would be ZnPc+ -PDI. - . The electrochemical and free-energy calculations suggested exothermic energy and/or electron transfer processes via the singlet states of PDI or ZnPc entities depending on the excitation wavelength of the laser used. The measured rates using femtosecond pump-probe spectroscopy coupled with global analysis of transient data revealed ultrafast energy transfer from 1 PDI* to ZnPc followed by charge separation. However, when ZnPc was selectively excited, only electron transfer was witnessed wherein the time constants for forward and reverse electron transfer processes followed Marcus predictions. The absorption in a wide section of the solar spectrum and the ultrafast charge separation suggest the usefulness of these systems as good photosynthetic models.

Detector for monitoring potential bleeding during electron intraoperative radiotherapy.

PURPOSE: The aim of this work is to develop a bleeding detector integrated into the acrylic circular applicators for specific mobile linacs. Thus, a bleeding detector has been developed based on a capacitive sensor to be used with plastic applicators, as in the case of LIAC HWL from Sordina IORT Technologies SpA. According to the clinical impact, we have selected 0.5 cm as the minimum depth of fluid that should be detected. METHODS: An experiment was developed using water-simulating blood. Two setups were considered: non-beveled applicators with 7 cm and 10 cm diameter. Measurements were done for applicators 0° and 45° tilted, both with respect to the horizontal surface, in order to mimic the worst clinical scenario according to the irradiation gantry and applicator bevel angle. The behavior of the detector under irradiation was analyzed and the impact of the stray radiation on the detector was also evaluated. RESULTS: The detector was able to distinguish the presence of liquid at a minimum height of 0.5 cm. A linear behavior was obtained for both setups. We have also verified that the LIAC HWL radiation does not affect the measurements nor does the detector interfere with the stray radiation. The bleeding detector is a quasi-digital capacitive sensor with low-cost, high linearity, and easy to install. CONCLUSIONS: With this detector it is possible to perform a continuous monitoring of the liquid measurements even during the irradiation phase. Thus, it can operate not only as a pre-treatment detector but also as a continuous one.

Solvent-Free Off-On Detection of the Improvised Explosive Triacetone Triperoxide (TATP) with Fluorogenic Materials.

A fluorogenic perylenediimide-functionalized polyacrylate capable of generating color and fluorescence changes in the presence of triacetone triperoxide TATP), an improvised explosive used in terrorist attacks, under solvent-free, solid-state conditions has been developed. The material works by accumulating volatile TATP until it reaches a threshold; therefore, triggering colorimetric and fluorescent responses.

Direct alkylthio-functionalization of unsubstituted perylenediimides.

Herein, we report a simple fluoride-mediated reaction for the direct mono- and dialkylthio-functionalization of unsubstituted perylenediimides (PDIs) under very mild conditions. The aromatic substitution reaction offers the possibility to introduce primary, secondary and, even, tertiary alkanethiols either on the 1- or on the 1,6-bay positions of unsubstituted PDIs. 1,6-DialkylthioPDIs show that absorption and fluorescence spectra shifted to the red when compared with the unsubstituted PDI, with Stokes shifts around 70-80 nm.

Near-Infrared Photoelectrochemical Conversion via Photoinduced Charge Separation in Supramolecular Complexes of Anionic Phthalocyanines with Li(+)@C60.

Two phthalocyanines possessing carboxylate groups ((TBA)4H2Pc·1 and (TBA)4H2Pc·2) form 1:2 supramolecular complexes with lithium cation-encapsulated C60 (Li(+)@C60) [H2Pc·1(4-)/(Li(+)@C60)2 and H2Pc·2(4-)/(Li(+)@C60)2] in a polar mixed solvent. From the UV-vis spectral changes, the binding constants (K) were estimated as ca. 10(12) M(-2). Upon the photoexcitation of constructed supramolecular complexes, photoinduced electron transfer occurred to form the charge-separated (CS) state. The lifetime of the CS state was determined to be 1.2 ms for H2Pc·2(4-)/(Li(+)@C60)2, which is the longest CS lifetime among the porphyrinoid/fullerene supramolecular complexes. H2Pc·1(4-)/(Li(+)@C60)2 also afforded the long-lived CS state of 1.0 ms. The spin state of the long-lived CS states was determined to be a triplet, as indicated by the EPR signal at g = 4. The reorganization energy (λ) and the electronic coupling term were determined to be λ = 1.70 eV, V = 0.15 cm(-1) from the temperature dependence of the rate constant for the charge recombination of the CS state of H2Pc·1(4-)/(Li(+)@C60)2. The energy of the CS state (0.49 eV) is much smaller than the reorganization energy, indicating that the back-electron-transfer process is located in the Marcus normal region. The small electronic coupling term results from the spin-forbidden back electron transfer due to the triplet CS state. Supramolecular complexes of anionic zinc phthalocyanines with Li(+)@C60 were also prepared and investigated. The ZnPc·4(4-)/Li(+)@C60 supramolecular nanoclusters were assembled on the optically transparent electrode (OTE) of nanostructured SnO2 (OTE/SnO2) to construct the dye-sensitized solar cell. The IPCE (incident photon-to-photocurrent efficiency) values of OTE/SnO2/(ZnPc·4(4-)/Li(+)@C60)n were much higher than the sum of the two IPCE values of the individual systems OTE/SnO2/(Li(+)@C60)n and OTE/SnO2/(ZnPc·4(4-))n, covering the near-infrared region.

Infrared thermography is useful for ruling out fractures in paediatric emergencies.

UNLABELLED: Musculoskeletal injuries are a leading cause of paediatric injuries and emergency department visits in Western countries. Diagnosis usually involves radiography, but this exposes children without fractures to unnecessary ionising radiation. We explored whether infrared thermography could provide a viable alternative in trauma cases. We compared radiography and thermal images of 133 children who had been diagnosed with a trauma injury in the emergency unit of a Spanish hospital. As well as the thermal variables in the literature, we introduced a new quantifier variable, the size of the lesion. Decision tree models were built to assess the technique's accuracy in diagnosing whether a bone had been fractured or not. Infrared thermography had a sensitivity of 0.91, a specificity of 0.88 and a negative predictive value of 0.95. The new lesion size variable introduced appeared to be of main importance to the discriminatory power of the method. CONCLUSION: The high negative predictive value of infrared thermography suggests that it is a promising method for ruling out fractures.

Infrared thermal imaging in the diagnosis of musculoskeletal injuries: a systematic review and meta-analysis.

OBJECTIVE: Musculoskeletal injuries occur frequently. Diagnostic tests using ionizing radiation can lead to problems for patients, and infrared thermal imaging could be useful when diagnosing these injuries. CONCLUSION: A systematic review was performed to determine the diagnostic accuracy of infrared thermal imaging in patients with musculoskeletal injuries. A meta-analysis of three studies evaluating stress fractures was performed and found a lack of support for the usefulness of infrared thermal imaging in musculoskeletal injuries diagnosis.

La predicción de la satisfacción con la vida en personas mayores de Angola: El efecto moderador del género / Predicting life satisfaction in Angolan elderly: The moderating effect of gender

Existe abundante investigación que ha estudiado la satisfacción vital en personas mayores y ha encontrado evidencia empírica de sus mejores predictores. Cuando se estudia la satisfacción con la vida de las personas mayores y sus predictores se hallan diferencias en función del género incluyendo, por ejemplo, las interacciones con la viudedad. En este contexto, el presente estudio se ha centrado en los siguientes objetivos: (1) poner a prueba la invarianza en función del género de una medida de satisfacción con la vida, (2) predecir la satisfacción vital usando varias variables relacionadas con el proceso de envejecimiento y (3) poner a prueba el potencial efecto moderador del género en esta predicción. La muestra estaba compuesta por 1003 personas mayores angoleñas. Se probaron varios modelos estructurales MIMIC multi-grupo (hombres vs. mujeres). Por un lado, los resultados mostraron que existe invarianza en función del género para la medida de satisfacción vital. Por otro lado, no se encontró efecto de moderación en las variables relacionadas con el proceso de envejecimiento. En otras palabras, los efectos estimados de las variables psicosociales en la satisfacción con la vida son los mismos en ambos géneros. La discusión relaciona estos resultados con la literatura existente y señala las contribuciones de este estudio

A considerable amount of research has been done to explain life satisfaction in the elderly, and there is growing empirical evidence on the best predictors of life satisfaction. When studying elderly's life satisfaction and its predictors, gender differences have been found in several studies, including significant interactions with widowhood, for example. In this context, the present study aims were: (1) to test for the gender invariance in a life satisfaction measure; (2) to predict life satisfaction using several variables related to the aging process; and (3) to test the potential moderator effects due to gender in this prediction. Participants were 1003 Angolan elderly. Several multi-group (men vs. women) MIMIC structural models were tested. First, results showed that there is gender invariance for the measurement of life satisfaction. Second, results found no moderation effects on key variables of the aging process. In other words, the estimated effects of psychosocial variables on life satisfaction remain the same for both genders. The discussion relates these results to the existing literature and posits the contributions of the study

Water soluble fluorescent-magnetic perylenediimide-containing maghemite-nanoparticles for bimodal MRI/OI imaging.

The protein shell of apoferritin-encapsulated maghemite nanoparticles was functionalized with two different red-emitting perylenediimide fluorophores (PDI). One glycosacharide-PDI complex has been synthesized for the first time to be labeled to apoferritin-encapsulated maghemite nanoparticles. Bifunctionality of maghemite@perylenediimide was demonstrated by both magnetic-core and fluorescent-labeled shell properties. SQUID measurements confirmed superparamagnetic behavior above 35K. Fluorescence of perylenediimides is retained once attached to the magnetic nanoparticle. Moreover, fluorescence microscopy showed that one of these fluorescent-magnetic nanoparticles was specifically internalized in bifidobacteria without affecting cell viability. These results revealed that the dual-modal imaging probes of maghemite@perylenediimide nanoparticles have the potential to be used as optical/MR dual imaging agents.

A water-soluble perylene dye functionalised with a 17ß-estradiol: a new fluorescent tool for steroid hormones.

We have successfully been able to synthesise a specific estrogen receptor-directed biolabel based on a fluorescent water-soluble perylenebisimide, thus offering great potential for determining the presence of estrogen receptors in any kind of cell. Moreover, this synthetic strategy allows the preparation of other conjugates involved in the study of any kind of receptor, simply by selecting the appropriate agonist or antagonist.

Characterization and polymerization of thienylphenyl and selenylphenyl amines and their interaction with CdSe quantum dots.

Hybrid quantum-dot-sensitized solar cells show promising novel optoelectronic properties. An adequate design of such cells requires a deep understanding of the characteristics of each component, including their interactions. In this context, the electrochemical properties of two different hole-transporting materials (HTMs) and their chemical interactions with trioctylphosphine-capped CdSe quantum dots are investigated to evaluate their potential use in hybrid quantum-dot-sensitized solar cells. Tris[4-(thien-2-yl)phenyl]amine (TTPA) and tris[4-(selen-2-yl)phenyl]amine (TSePA) are studied in the solid state as thin films deposited on a conducting substrate. Spectroelectrochemical studies evidence both solid-state electropolymerization and doping. Upon addition of TSePA or partially polymerized TTPA to a colloidal solution of trioctylphosphine-capped CdSe quantum dots, the steady-state photoluminescence is quenched. This suggests that the quantum dots and the HTM strongly interact, probably through an excited-state charge-transfer mechanism. The combination of all these pieces of information indicates that polymerized TTPA and TSePA are potential candidates as HTMs for hybrid quantum-dot-sensitized solar cells.

Alkoxy-styryl DCDHF fluorophores.

A photostable dicyanomethylenedihydrofuran fluorophore which contains electron-donating alkoxy groups is described. This chromophore is highly environmentally-sensitive, which is a remarkable property for a fluorescent reporter. Its light excitation also enables, in low viscous solvents, the formation of dark states whose radical or triplet nature is ruled out.

Fluoride-triggered indium-mediated synthesis of (hetero)biaryls.

A simple method for the preparation of triorganoindium reagents under mild conditions based in indium-silicon exchange is described.

Indium-mediated synthesis of heterobiaryls.

The palladium-mediated coupling reaction between triorganoindium reagents and organic electrophiles is extended to the synthesis of heteroaromatic compounds. Both electron-rich and electron-poor heterocycles can act as the organic electrophile or as the organoindium derivative.

Bond dissociation energies for radical dimers derived from highly stabilized carbon-centered radicals.

[reaction: see text] The temperature dependence of the dissociation of dimers formed from highly stabilized carbon-centered radicals has been examined. Analysis of the data yields the bond dissociation energy (BDE) for the central head-to-head C-C bond in these compounds. For example, for the dimer derived from 3-phenyl-2-coumaranone, BDE is 23.6 kcal/mol and the C-C bond length 1.596 A, a rather long value for a sigma bond.