177 research outputs found
Subphthalocyaninato boron(III) hydride: synthesis, structure and reactivity
Subphthalocyanine (SubPc) chemistry has been limited so far by their high sensitivity toward strong nucleophiles. In particular, the substitution of the axial chlorine atom by a nucleophilic group in the case of less-reactive SubPcs, such as those bearing electron-withdrawing peripheral substituents, presents some limitations and requires harsh conditions. By taking advantage of the electrophilic character of DIBAL-H, it has been possible to prepare for the first time SubPc-hydride derivatives that exhibit high reactivity as hydroboration reagents of aldehydes. This hydride transfer requires using a typical carbonyl activator (trimethylsilyl triflate) and only one equivalent of aldehyde, affording SubPcs with an axial benzyloxy group in good yield. This transformation has proven to be a useful alternative method for the axial functionalisation of dodecafluoroSubPc, a paradigmatic SubPc derivative, by using electrophiles for the first time. Considering the increasing interest in SubPcs as electron-acceptor semiconductors with remarkable absorption in the visible range to replace fullerene in organic photovoltaic (OPV) devices, it is of the utmost importance to develop new synthetic methodologies for their axial functionalisationFinancial support from Spanish MINECO and MICINN (CTQ2017- 85393-P, PGC2018-094644-B-C21, PDI2019-110091GB-I00) is acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, grant SEV2016-0686). J.L. and L.T. acknowledge MECD, Spain, for a F.P.U. fellowship. I.C. and L.M
Anthracene-Fused Oligo-BODIPYs: a new class of π-extended NIR-absorbing materials
Large π-conjugated systems are key in the
area of molecular materials. Herein, we prepare via AuI
-
catalyzed cyclization a series of fully π-conjugated
anthracene-fused oligo-BODIPYs. Their structural and
optoelectronic properties were studied by several techniques, ranging from X-ray, UV/Vis, and cyclic voltammetry to transient absorption spectroscopy. As a complement, their electronic structures were explored by
means of Density Functional Theory (DFT) calculations.
Depending on the size and shape of the π-conjugated
skeleton, unique features—such as face-to-face
supramolecular organization, NIR absorption and
fluorescence as well as strong electron accepting character—were noted. All in all, the aforementioned features
render them valuable for technological applicationsments
We gratefully acknowledge financial support from the
Spanish MICINN through Projects PID2020-116490GB-I00
(Porphyrinoids) and TED2021-131255B-C43 (PERSOLAR). We also thank financial support to the Comunidad
de Madrid (MAD2D-CM) and MICINN through project
“Materiales disruptivos bidimensionales (2D)” within the
Plan de recuperación, transformación y resiliencia (Materiales avanzados). IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of
Excellence in R&D (MINECO, Grant SEV2016-0686). J.L.
acknowledges MECD, Spain, for a F.P.U. fellowship. European Commission under the Marie Sklodowska-Curie
Action Cofund 2015 (EU project 713366-InterTalentum) is
acknowledged for the support for G.D.S. Generous allocation of computational time from the Centro de Computación
Científica UAM is gratefully acknowledged. Work in
Erlangen was supported by the Deutsche Forschungsgemeinschaft (DFG) through SFB 953 project B10 and the
Bavarian Collaborative Research Project “Solar Technologies go Hybrid” (SolTech
A novel electron Donor-Acceptor Carbazole-Zn(II)Phthalocyanine – Perfluorinated Subphthalocyanine Conjugate: synthesis, characterization, and photoinduced electron-transfer
Porphyrinoids are considered perfect candidates for the preparation of model electron donor-acceptor (D-A) systems as they
enable fast and efficient photoinduced electron transfer. Herein,
we report on the synthesis and photophysical characterization
of a ZnPc SubPc conjugate covalently connected through a
short-range alkyne spacer. We designed and prepared the
conjugate, which comprise, on the one hand, a perfluorinated
SubPc with strong electron acceptor character and, on the
other, a Pc peripherally functionalized with carbazoles with
strong electron donor character. Photoinduced electron transfer
events are in-depth analyzed by several techniques, including
steady-state absorption, time-resolved emission and transient
absorption measurements on different time scales. Our studies
confirm a full charge separation occurring from a photoexcited
charge transfer state68.
Acknowledgements
Financial support from Spanish MINECO (PID2020-116490GB I00,
Porphyrinoids) is acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of
Excellence in R&D (MINECO, Grant SEV2016-0686). J.L. acknowledges MECD, Spain, for a F.P.U. fellowship. Kuwait Foundation for
the Advancement of Science (KFAS) and the RSP unit general
facilities of the Faculty of Science GFS (GS 01/01, GS 02/01, GS
03/01, GS 01/03, GS 01/05) is acknowledged. Work in Erlangen
was supported by the Deutsche Forschungsgemeinschaft (DFG)
through SFB 953 project B10 and the Bavarian Collaborative
Research Project “Solar Technologies go Hybrid" (SolTech
Application of MIR spectroscopy to the evaluation of chemical composition and quality parameters of foal meat: a preliminary study
The aim of this work was to study the potential of mid-infrared spectroscopy to evaluate the chemical composition and quality parameters of foal meat according to differences based on slaughter ages and finishing diets. In addition, the wavelength ranges which contribute to this meat quality differentiation were also determined. Important characteristics as moisture and total lipid content were well predicted using Mid-Infrared Spectroscopy (MIR) with Rv2 values of 82% and 66%, respectively. Regarding fatty acids, the best models were obtained for arachidonic, vaccenic, docosapentaenoic acid (DPA), and docosahexaenoic acid (DHA) with Rv2 values over 65%. Quality parameters, as instrumental colour and texture and sensory attributes did not reach high prediction coefficients (R2). With the spectra data of the region 2198–1118 cm-1, samples were accurately classified according to slaughter age (78%) and finishing diet (72%). This preliminary research shows the potential of MIR spectroscopy as an alternative tool to traditional meat chemical composition methods. Finally, the wavelength range of the spectrum from 2198 to 1118 cm-1 showed good results for classification purposes.This research was funded by INIA Instituto Nacional de Investigación y Tecnología Agraria y Alimentaria, grant number RTA 2012-00090-C03-01 and by the Spanish Ministerio de Ciencia, Innovación y Universidades, Project RTI2018-094475-B-I00 (MCIU/AEI/FEDER, UE)
State selective electron injection in non-aggregated titanium phthalocyanine sensitised nanocrystalline TiO2 films
We describe a novel titanium phthalocyanine that shows no aggregation when anchored to nanocrystalline TiO2 films through its axial carboxylated ligand without the use of co-adsorbents; state selective electron injection into the TiO2 is demonstrated, resulting in efficient photocurrent generation in dye sensitised photoelectrochemical solar cells.Palomares Gil, Emilio J, [email protected]
Papel de la calidad de la grasa de la dieta sobre los niveles postprandiales de secretina, colecistoquinina y polipéptido pancreático en humanos
The effects of adaptation to two diets differing in the type of dietary fat on the circulating levels of secretin, cholecystokinin, and pancreatic polypeptide, were investigated in humans. A relationship with the results concerning gastric acid secretion and gastrin release previously described by us, was also examined. The study in volved 18 cholecystectomized subjects previously submitted to a 30-day adaptation period to diets containing olive (group O) or sunflower oil (group S) as the main fat source. During the experimental period, physiological stimulation was achieved by ingestion of 200 mL oleic acid- (group O) or linoleic acid enriched (group S) liquid mixed meals. Food ingestion did not induce no significant changes in plasma secretin concentration in any of the groups, and no signijicant differences were observed between them for basal and postprandial situations. Plasma cholecystokinin le veIs were signijicantly higher in group O throughout the 30-120 min postprandial periodo The type of dietary fat affected the pancreatic polypeptide response to food, since values in group O were significantly higher than in group S at any point during the postprandial period, thus, despite of significant release in both grollps after the meal. lt is suggested that endogenous cholecystokinin may be responsible for the attenuated gastric acid secretory response and the suppression of serum gastrin previously observed in the subjects of group O, through a somatostatin-mediated (paracrine) or peptide YY-mediated (endocrine) mechanism. Secretin does not seem to be in volved in the fat-induced inhibition of human gastric acid secretion, and a role for pancreatic polypeptide is doubtful.Los efectos de la adaptación a dos dietas que diferían en el tipo de grasa, sobre los niveles circulantes de secretina, colecistoquinina y polipéptido pancreático fueron investigados en humanos. También fue examinada la relación, previamente descrita por nosotros, con los resultados que concernían a la secreción de ácido gástrico y la liberación de gastrina. El estudio incluyó a 18 sujetos colecistectomizados previamente sometidos a un período de adaptación de 30 días a dietas que contenían aceite de oliva (grupo O) o de girasol (grupo G) como fuente de grasa principal. Durante el periodo experimental, la estimulación fisiológica se consiguió mediante la ingestión de 200 mi de ácido oleico (grupo O) o aceite de girasol (grupo S) mezclados con la comida. La ingestión de la dieta no indujo cambios significativos sobre la concentración en plasma de secretina en ninguno de los dos grupos, tampoco fueron observadas diferencias significativas entre dicha concentración plasmática en situaciones basal y postprandial. Los niveles plasmáticos de colecistoquinina fueron significativamente mayores en el grupo O durante un periodo postprandial de 30-120 minutos. El tipo de grasa de la dieta afectó a la respuesta del polipéptido pancreático a la comida, los valores en el grupo O fueron significativamente mayores a los del grupo S en cualquier punto durante el período postprandial, a pesar de la significativa liberación en ambos grupos tras la comida. Se sugirió que la colecistoquinina endógena podría ser responsable de la atenuación de la repuesta secetora de ácido gástrico y de la supresión de la serina sérica previamente observada en los sujetos del grupo O, a través dee un mecanismo mediado por somatostatina (paracrino) o por péptido YY (endocrino). La secretina no parece estar implicada en la inhibición inducida por la grasa de la secreción gástrica en humanos, y es dudoso el papel atribuido al polipéptido pancreático
Situación sanitaria del cultivo de la soja en el Noroeste Argentino en la campaña 2013/2014
El personal de la Sección Fitopatología de la Estación Experimental Agroindustrial Obispo Colombres (EEAOC) realiza anualmente una prospección de las enfermedades que afectan al cultivo de la soja en la provincia de Tucumán y sus zonas de influencia. Durantela campaña 2013/2014, se realizaron recorridosquincenales y semanales durante los estadios vegetativos y reproductivos del cultivo, respectivamente. Las localidades evaluadas en la provincia de Tucumán fueron: La Cruz, Villa Benjamín Aráoz y Puesto del Medio,pertenecientes al departamento Burruyacú, y la localidad de San Agustín ubicada en el departamento Cruz Alta. En la provincia de Salta se evaluó la localidad Gral. Mosconi, del dpto. San Martín. Se determinó la incidencia (porcentaje de plantas enfermas con respecto al total de las plantas) y severidad (porcentaje de superficie foliar afectada) de las principales enfermedades.Entre las enfermedades foliares que afectaron al cultivo de la soja en esta campaña 2013/2014 y en las diferentes localidades evaluadas, se destacaron: la mancha marrón,causada por Septoria glycines; la roya de la soja, causada por Phakopsora pachyrhizi; la pústula bacteriana,originada por Xanthomonas axonopodis pv. glycines;tizón de la hoja por Cercospora kikuchii y mancha anillada,causada por Corynespora cassiicola.En los meses de febrero a marzo, se observaron casos de muerte de plantas en rodales, causada por hongos del suelo (Rhizoctonia solani y Fusarium spp.). También se observó la presencia de podredumbre carbonosa de la soja (Macrophomina phaseolina) con valores de incidenciabajos, generalmente de un 3% a un 5%, y de hasta un 10% en Villa Benjamín Aráoz. También se detectaron plantas enfermas por Sclerotinia sclerotiorum, con niveles de incidencia muy bajos (del 1% al 3%) en las distintas localidades evaluadas de la provincia de Tucumán.Fil: de Lisi, Vicente. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; ArgentinaFil: Reznikov, Sebastian. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Tecnología Agroindustrial del Noroeste Argentino; Argentina; ArgentinaFil: Claps, María Paula. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Tecnología Agroindustrial del Noroeste Argentino; Argentina; ArgentinaFil: Bernal, María de Lourdes. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Tecnología Agroindustrial del Noroeste Argentino; Argentina; ArgentinaFil: Díaz, Federico. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; ArgentinaFil: Villafañe, Pedro. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; ArgentinaFil: Aguaysol, Natalia C.. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; ArgentinaFil: Martínez Monteros, M. José. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; ArgentinaFil: González, Victoria. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; ArgentinaFil: Ploper, Leonardo Daniel. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Tecnología Agroindustrial del Noroeste Argentino; Argentina; Argentin
Red de seguimiento y coordinación del Máster en Ciencia de Materiales
El Máster en Ciencia de Materiales se imparte en la Facultad de Ciencias de la Universidad de Alicante, consta de 60 créditos ECTS que se cursan durante 1 año académico. El máster está implantado desde el curso 2010-2011 por lo que durante el actual curso 2014-2015 tendremos la quinta promoción de egresados. La red docente está formada por la comisión académica del Máster en Ciencia de Materiales. Esta comisión (profesorado, alumno y personal de administración y servicios) lleva realizando un seguimiento de la titulación durante los 4 cursos anteriores. Por tanto la red tiene como objetivo principal el seguimiento, coordinación, evaluación y mejora de la planificación realizada con las experiencias recogidas a lo largo de estos años. Además, se realizará un estudio de los diferentes indicadores de calidad que utilizan las agencias de acreditación puesto que este año el Máster se someterá a la renovación de la acreditación
A multiparameter flow cytometry immunophenotypic algorithm for the identification of newly diagnosed symptomatic myeloma with an MGUS-like signature and long-term disease control
GEM (Grupo Español de MM)/PETHEMA (Programa para el Estudio de la Terapéutica en Hemopatías Malignas) cooperative study group: et al.Achieving complete remission (CR) in multiple myeloma (MM) translates into extended survival, but two subgroups of patients fall outside this paradigm: cases with unsustained CR, and patients that do not achieve CR but return into a monoclonal gammopathy of undetermined significance (MGUS)-like status with long-term survival. Here, we describe a novel automated flow cytometric classification focused on the analysis of the plasma-cell compartment to identify among newly diagnosed symptomatic MM patients (N=698) cases with a baseline MGUS-like profile, by comparing them to MGUS (N=497) patients and validating the classification model in 114 smoldering MM patients. Overall, 59 symptomatic MM patients (8%) showed an MGUS-like profile. Despite achieving similar CR rates after high-dose therapy/autologous stem cell transplantation vs other MM patients, MGUS-like cases had unprecedented longer time-to-progression (TTP) and overall survival (OS; ∼60% at 10 years; P<0.001). Importantly, MGUS-like MM patients failing to achieve CR showed similar TTP (P=0.81) and OS (P=0.24) vs cases attaining CR. This automated classification also identified MGUS patients with shorter TTP (P=0.001, hazard ratio: 5.53) and ultra-high-risk smoldering MM (median TTP, 15 months). In summary, we have developed a biomarker that identifies a subset of symptomatic MM patients with an occult MGUS-like signature and an excellent outcome, independently of the depth of response.Peer Reviewe
Development of an activity disease score in patients with uveitis (UVEDAI)
To develop a disease activity index for patients with uveitis (UVEDAI) encompassing the relevant domains of disease activity considered important among experts in this field. The steps for designing UVEDAI were: (a) Defining the construct and establishing the domains through a formal judgment of experts, (b) A two-round Delphi study with a panel of 15 experts to determine the relevant items, (c) Selection of items: A logistic regression model was developed that set ocular inflammatory activity as the dependent variable. The construct "uveitis inflammatory activity" was defined as any intraocular inflammation that included external structures (cornea) in addition to uvea. Seven domains and 15 items were identified: best-corrected visual acuity, inflammation of the anterior chamber (anterior chamber cells, hypopyon, the presence of fibrin, active posterior keratic precipitates and iris nodules), intraocular pressure, inflammation of the vitreous cavity (vitreous haze, snowballs and snowbanks), central macular edema, inflammation of the posterior pole (the presence and number of choroidal/retinal lesions, vascular inflammation and papillitis), and global assessment from both (patient and physician). From all the variables studied in the multivariate model, anterior chamber cell grade, vitreous haze, central macular edema, inflammatory vessel sheathing, papillitis, choroidal/retinal lesions and patient evaluation were included in UVEDAI. UVEDAI is an index designed to assess the global ocular inflammatory activity in patients with uveitis. It might prove worthwhile to motorize the activity of this extraarticular manifestation of some rheumatic diseases
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