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    In vivo photoinduced [4 + 2] dimerization of a neo-clerodane diterpene in Baccharis flabellata. ROS and RNS scavenging abilities

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    Secondary metabolites play a major role in the adaptation of plants to the environment. Furan neo-clerodane diterpenes are characteristic secondary metabolites in Baccharis flabellata Hook. & Arn. var. flabellata. One of the main compounds is the diene ent-15,16-epoxy-19-hydroxy-1,3,13(16),14-clerodatetraen-18-oic acid (DAC). In this work a new dimeric compound (DACD) has been isolated and identified by NMR and MS techniques. The presence of other minor dimers was also observed in the same plant methanolic extracts. Assuming that they may be the products of [4 + 2] condensation of two monomeric moieties, the formation of adducts by photochemical dimerization was checked by inducing the in vitro [4 + 2] cycloaddition of DAC. Moreover, the DAC and DACD accumulation rates in aerial parts of B. flabellata specimens were analyzed monthly during a complete phenological cycle. The accumulation of monomer depends on the plant phonological stage; meanwhile the dimer proportion arises in detriment of the monomer as the solar UV radiation increases. Since plants exposed to strong UV intensities produce radical species, the scavenger properties of these compounds toward reactive nitrogen species (RNS), and reactive oxygen species (ROS), were analyzed. Albeit DAC and DACD show significant superoxide radical scavenger activities, the monomer proved to be more effective than the dimer toward ROS, while DACD was an excellent RNS scavenger.Fil: Funes, Matías Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Tonn, Carlos Eugenio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Kurina Sanz, Marcela Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; Argentin

    Synergism between Terbinafine and a Neo-clerodane Dimer or a Monomer Isolated from Baccharis flabellata against Trichophyton rubrum

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    The new neo-clerodane dimer (DACD) likely formed by a [4+2] photo-cycloaddition between two molecules of ent-15,16-epoxy-19-hydroxy-1,3,13(16),14-clerodatetraen-18-oic acid (DAC), both isolated from Baccharis flabellata Hook et Arn. var. flabellata (Asteraceae), were tested in combination withterbinafine (Terb) against Trichophyton rubrum. The interactions were assessed with different methodologies such as 3D CombiTool software, LoeweCombination Index (CI) and isobolograms. Results showed that the monomer DAC as well as its dimer DACD act synergistically with Terb against T. rubrum.DAC/Terb and DACD/Terb showed eight and twelve synergistic mixtures respectively in the CombiTool graphics thus suggesting that DACD/Terb was moresynergistic with Terb than DAC. These results were corroborated by the CI values and the isobolograms of the detected combinations. DACD/Terb showedmuch lower CIs (0.34-0.47) than DAC/Terb (0.57-1.15) at the different inhibition percentages tested. Concomitantly, DACD/Terb isobolograms were moreconcave than for DAC/Terb at the different inhibition percentages. This is the first report showing antifungal synergistic interactions of neo-clerodanes dimers and add new evidences that neo-clerodanes monomers interact synergistically with Terb against T. rubrum.Fil: Rodriguez, María Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; ArgentinaFil: Butassi, Estefanía. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; ArgentinaFil: Funes, Matías Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Zacchino, Susana Alicia Stella. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentin

    Mechanistic studies of Candida albicans photodynamic inactivation with Porophyllum obscurum hexanic extract and its isolated thiophenic compounds

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    Porophyllum obscurum (Spreng) DC (Asteraceae) hexanic extract (PoHex) from aerial parts has demonstrated antifungal activity under UVA irradiation against Candida spp. isolates from patients with oropharyngeal candidiasis and four thiophenes were isolated as responsible of the activity. In the present work, we studied the photomechanisms whereby PoHex and their thiophenes produce photoinactivation of C. albicans. Reactive Oxygen Species generation by PoHex and thiophenes was evaluated: the production of superoxide anion, employing the NBT reduction assay; hydrogen peroxide, through the formation of a red quinoneimine; and singlet oxygen by using the 1,3-DPBF bleaching method. The action of ROS in fungal cells was investigated by evaluating binding of photosensitizer, leakage, apoptosis and stress sensibility that were performed by following M27-A3 guidelines, in parallel under “light” and “darkness” conditions. Results showed that the photosensitive antifungal activity of PoHex required oxygen and both type I (production of superoxide anion and hydrogen peroxide) and type II (production of singlet oxygen) reactions were involved. In addition, we found that ROS generated by PoHex did not cause release of cytoplasmic components due to membrane damage nor apoptosis of C. albicans. Treatment with PoHex and UVA increased cells sensitivities to osmotic stressors; did not reduce resistance to additional oxidative stress and possibly affected the structure of the cell wall. In addition, 2,2′:5′2″terthiophene, the most active PS present in PoHex and the only one that generate single oxygen, at Minimal Fungicide Concentration, did not cause leakage nor apoptosis and did not increase sensitivities to osmotic and oxidative stressors. Results demonstrated that Photodynamic Inactivation employing PoHex under UVA does represent an alternative for topical antifungal therapy for oropharyngeal candidiasis.Fil: Postigo, Agustina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Orgánica. Área Farmacognosia; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; ArgentinaFil: Cardoso Schiavi, Paulina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Funes, Matías Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Sortino, Maximiliano Andrés. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Orgánica. Área Farmacognosia; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentin

    Going Beyond Counting First Authors in Author Co-citation Analysis

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    The present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed

    Extracts of Trichocline sinuata (Asteraceae) as natural sensitizers in the photodynamic inactivation of Candida albicans

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    Despite significant progress in the development of phototherapy drugs, it is widely recognized that natural products remain the primary source of new photoactive compounds. Exploring uncharted flora in the east-central region of Argentina may offer a vast array of opportunities to isolate new photoactive molecules or plant extracts with high potential for use in antimicrobial photodynamic therapy (aPDT) against Candida albicans. To assess the photofungicidal potential of T. sinuata (“contrayerba”) against C. albicans, the extracts underwent spectroscopic and chromatographic analysis, resulting in the identification of furanocoumarin metabolites with similar spectrophotometric properties in all extracts. The extract profiles were created using UHPLC-DAD, and seven furanocoumarins (FCs) were detected. The highest photoinactivation against C. albicans was observed for dicholormethanic extracts (MFC = 62.5 μg/mL), equal to xanthotoxin employed as a positive control. Furthermore, we determine that photochemical mechanisms dependent on oxygen (type I and type II processes) and mechanisms independent of oxygen (photoadduct formation) are involved in the death of these yeasts. These results support the use of native plants of the east-central region of Argentina as potent sensitizers for aPDT and suggest that they can replace xanthotoxin in treating superficial yeast infections of the skin.Fil: Cardoso Schiavi, Paulina. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Departamento de Farmacia. Area de Farmacognosia; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Svetaz, Laura Andrea. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Orgánica. Área Farmacognosia; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; ArgentinaFil: Petenatti, Elisa Margarita. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; ArgentinaFil: Sortino, Maximiliano Andrés. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Orgánica. Área Farmacognosia; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; ArgentinaFil: Tempesti, Tomas Cristian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Funes, Matías Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; Argentin

    ROS-generating rare-earth coordination networks for photodynamic inactivation of Candida albicans

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    Water–ethanol suspensions of 2D coordination network (CN) based on rare earth elements and mixed ligands were evaluated as reactive oxygen species (ROS) generators under UV light irradiation, in contact with a biomimetic substrate (tryptophan) or an O2( 1 Δg) quencher (1,3-diphenylisobenzofuran; 1,3-DPBF). A combination of bottom-up and top-down strategies was implemented in order to obtain nano-sized CN particles and the subsequent colloidal suspensions were also tested towards photodynamic inactivation of Candida albicans (C. albicans). SEM, TEM, FTIR, and XRD techniques were applied to characterize the solids and ICP-AES was employed to determine the metal content of the colloidal suspensions. Promising results were found indicating that the presence of Tb3+ allows an intersystem crossing suitable for singlet oxygen generation, resulting in the antifungal activity of C. albicans culture upon UV-irradiation.Fil: Godoy, Agustín Alejandro. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Bernini, Maria Celeste. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; ArgentinaFil: Funes, Matías Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis. Universidad Nacional de San Luis. Facultad de Ciencias Físico Matemáticas y Naturales. Instituto Multidisciplinario de Investigaciones Biológicas de San Luis; ArgentinaFil: Sortino, Maximiliano Andrés. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Departamento de Química Orgánica. Área Farmacognosia; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; ArgentinaFil: Collins, Sebastián Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; ArgentinaFil: Narda, Griselda Edith. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; Argentin

    Variations on the Author

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    “Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship

    Photodynamic properties and photoantimicrobial action of electrochemically generated porphyrin polymeric films

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    Spectroscopic and photodynamic properties of polymeric films bearing porphyrin units have been studied in both solution containing photooxidizable substrates and in vitro on Escherichia coli and Candida albicans microorganisms. The films were formed by electrochemical polymerization of 5,10,15,20-tetra(4- N,N-diphenylaminophenyl)porphyrin (H2P-film) and its complex with Pd(ll) (PdP-film) on optically transparent indium tin oxide (ITO) electrodes. Absorption spectroscopic studies show the characteristic Soret and Q bands of the porphyrin in the visible region and a band at ∼350 nm corresponding to the tetraphenylbenzidine units. Upon excitation, the H2P-film exhibits two bands of fluorescence emission from porphyrin, while it is not detected using PdP-film. The singlet molecular oxygen, O2( 1δg), productions of these surfaces were evaluated using 9,10-dimethylanthracene in N,N-dimethylformamide. Also, the photodynamic activity was compared in solutions of l-tryptophan. Under these conditions, oxidation of these substrates takes place indicating an efficient photodynamic action of both polymeric films. In vitro investigations show that these films produce photosensitized inactivation of microbial cells in aqueous suspensions. These films exhibit a photosensitizing activity causing a ∼3 log decrease of coli and ∼2.5 log of C. albicans cellular survival after 30 min of irradiation with visible light. The photodynamic effect of the surfaces was also tested by growth delay experiments. The results indicate that porphyrins immobilized on electropolymeric films are interesting and versatile photodynamic surfaces to inactivate microorganisms in liquid suspensions.Fil: Funes, Matías Daniel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Caminos, Daniel Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Alvarez, María Gabriela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Fungo, Fernando Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Otero, Luis Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Durantini, Edgardo Néstor. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentin

    Appropriate Similarity Measures for Author Cocitation Analysis

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    We provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
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