Effect of extending conjugation via thiophene-based oligomers on the excited state electron transfer rates to ZnO nanocrystals.

Oligothiophene dyes with two to five thiophene units were anchored to oleate-capped, quantum-confined zinc oxide nanocrystals (ZnO NCs) through a cyanoacrylate functional group. While the fluorescence of the bithiophene derivative was too weak for meaningful quenching studies, the fluorescence of the dyes with three, four and five thiophene rings was quenched upon binding to the NCs. Ultrafast pump-probe spectroscopy was used to observe the singlet excited states of the free dyes dissolved in dichloromethane as well as attached to a ZnO NC dispersed in the same solvent. When the dyes were bound to ZnO NCs, ultrafast spectroscopic measurements revealed rapid disappearance of the singlet excited state and appearance of a new transient absorption at higher energy that was assigned to the oxidized dye based on the similar absorption observed upon oxidation of the dye using nitrosonium ion. The appearance lifetimes of the oxidized dyes were assigned to the excited state electron transfer and were 36 ± 2, 22.3 ± 3.9, 26.5 ± 1.5 and 19.4 ± 0.8 ps for bi-, ter-, quarter- and quinquethiophene dyes respectively. Two factors contributed to the similarity in the electron transfer lifetime. First the excited state energies of the dyes were similar, and second, the free energy for electron transfer reaction was sufficiently large to move the event into the energy-independent regime.

Band Gap Tuning of Solution-Processed Ferroelectric Perovskite BiFe1-x Co x O3 Thin Films.

Ferroelectric perovskite oxides are emerging as a promising photoactive layer for photovoltaic applications because of their very high stability and their alternative ferroelectricity-related mechanism for solar energy conversion that could lead to extraordinarily high efficiencies. One of the biggest challenges so far is to reduce their band gap toward the visible region while simultaneously retaining ferroelectricity. To address these two issues, herein an elemental composition engineering of BiFeO3 is performed by substituting Fe by Co cations, as a means to tune the characteristics of the transition metal-oxygen bond. We demonstrate by solution processing the formation of epitaxial, pure phase, and stable BiFe1-x Co x O3 thin films for x ≤ 0.3 and film thickness up to 100 nm. Importantly, the band gap can be tuned from 2.7 to 2.3 eV upon cobalt substitution while simultaneously enhancing ferroelectricity. As a proof of concept, nonoptimized vertical devices have been fabricated and, reassuringly, the electrical photoresponse in the visible region of the Co-substituted phase is improved with respect to the unsubstituted oxide.

Effects of a phosphonate anchoring group on the excited state electron transfer rates from a terthiophene chromophore to a ZnO nanocrystal.

Terthiophene dyes were synthesized having a carboxylate or a phosphonate moiety at the 2-position which serves as an anchoring group to zinc oxide nanocrystals (ZnO NCs). Electronic absorption and fluorescence measurements, combined with reduction potentials, provided estimates of -1.81 and -1.86 V vs. NHE for the excited state reduction potential of the carboxylate and phosphonate, respectively. Static quenching was observed when the dyes were bound to the surface of acetate-capped ZnO NCs having a diameter of 2.8 nm. Stern-Volmer studies conducted at several dye concentrations established that a minor fraction of the adsorbed dye remained unquenched even at 1 : 1 dye to NC ratios. Adsorption isotherm measurements established that the phosphonate binds more strongly than the carboxylate and that saturation coverage was ∼1.2 dyes per nm2 for both dyes. Ultrafast transient absorption spectroscopic experiments were used to probe excited state dynamics. In the presence of ZnO NCs, disappearance of the singlet excited state of the dye corresponded to appearance of the spectroscopic signature of the oxidized dye with a time constant of 1.5 ± 0.1 and 6.1 ± 0.2 ps, respectively, for the carboxylate and phosphonate dye. The difference in the electron transfer rates was attributed to a larger electronic coupling for the dye having the carboxylate anchoring group.

Polymer:Fullerene Bimolecular Crystals for Near-Infrared Spectroscopic Photodetectors.

Spectroscopic photodetection is a powerful tool in disciplines such as medical diagnosis, industrial process monitoring, or agriculture. However, its application in novel fields, including wearable and biointegrated electronics, is hampered by the use of bulky dispersive optics. Here, solution-processed organic donor-acceptor blends are employed in a resonant optical cavity device architecture for wavelength-tunable photodetection. While conventional photodetectors respond to above-gap excitation, the cavity device exploits weak subgap absorption of intermolecular charge-transfer states of the intercalating poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) bimolecular crystal. This enables a highly wavelength selective, near-infrared photoresponse with a spectral resolution down to 14 nm, as well as dark currents and detectivities comparable with commercial inorganic photodetectors. Based on this concept, a miniaturized spectrophotometer, comprising an array of narrowband cavity photodetectors, is fabricated by using a blade-coated PBTTT:PCBM thin film with a thickness gradient. As an application example, a measurement of the transmittance spectrum of water by this device is demonstrated.

The effect of selective contact electrodes on the interfacial charge recombination kinetics and device efficiency of organic polymer solar cells.

Organic polymer solar cells (OPSCs) have been prepared using TiO(x) metal oxides as selective electrodes for electron collection. The interfacial charge transfer reactions, under working conditions, that limit the energy conversion efficiency of these devices have been measured and compared to the standard OPSC geometry which collects the electrons through a low work function metal contact.

[Spermatic cord leiomyosarcoma. Case report and bibliographic review]. / Leiomiosarcoma de cordón espermático. Aportación de un caso y revisión de la literatura.

OBJECTIVE: To report one new case of paratesticular leiomyosarcoma. METHODS: We describe the case of a 68-year-old male patient consulting for right groin pain over two years with a physical examination corresponding to right inguinal hernia. During surgery for hernia correction a paratesticular mass was discovered. RESULTS: Right radical orchiectomy was performed. After the operation there was a recurrence at the scar which was operated and finally the disease progressed both locally and systemically. CONCLUSIONS: We point out the scarce frequency of this type of tumours. We believe that orchiectomy and excision of the cord is the treatment of choice. The use of adjuvant therapies doesn't influence survival significantly.

Interfacial charge recombination between e(-)-TiO2 and the I(-)/I3(-) electrolyte in ruthenium heteroleptic complexes: dye molecular structure-open circuit voltage relationship.

A series of heteroleptic ruthenium(II) polypyridyl complexes containing phenanthroline ligands have been designed, synthesized, and characterized. The spectroscopic and electrochemical properties of the complexes have been studied in solution and adsorbed onto semiconductor nanocrystalline metal oxide particles. The results show that for two of the ruthenium complexes, bearing electron-donating (-NH2) or electron-withdrawing (-NO2) groups, the presence of the redox-active I(-)/I3(-) electrolyte produces important changes in the interfacial charge transfer processes that limit the device performance. For example, those dyes enhanced the electron recombination reaction between the photoinjected electrons at TiO2 and the oxidized redox electrolyte. In an effort to understand the details of such striking observations, we have monitored the charge transfer reactions taking place at the different interfaces of the devices using time-resolved single photon counting, laser transient spectroscopy, and light-induced photovoltage measurements.

Relación entre la edad del varón y la calidad del estudio seminal. Experiencia en el área sanitaria 14 de la Agencia Valenciana de la Salud / Relationship between male age and semen quality. Experience at the number 14 health-care area of the Valencia health-care agency

Objetivo: El recuento del número de espermatozoides y del número de formas móviles son dos parámetros muy importantes en la medición de la calidad espermática a través del espermiograma. Numerosos factores como la obesidad, el tabaquismo, la contaminación ambiental, el estrés, o la edad, actúan alterando la capacidad de fecundación del semen y por tanto interfieren en la cuantía de estas dos variables. Métodos: Se pretende estudiar la influencia sobre la calidad del semen de la edad. Se estudiaron un total de 156 pacientes. Los integrantes fueron divididos en tres grupos: 20-30 años; 31-40 años; 40-50 años. Se utilizó una cámara Mackler y un microscopio Nickon. Resultados: Se realizó un estudio estadístico no paramétrico (prueba de Kruskall-Wallis) relacionando las variables recuento espermático y movilidad con la edad. Recuento-edad: X2= 8.239 (p = 0.016). Espermatozoides inmóviles-edad: X2= 6.871 (p = 0.032). Espermatozoides móviles-edad: X2=7.378 (p = 0.025). Conclusiones: La edad del paciente está íntimamente relacionada con la disminución del número de espermatozoides, con la disminución del número de formas móviles y con el aumento de las inmóviles (AU)

Objectives: Spermatic count and number of mobile forms are two very important parameters for the measurement of spermatic quality by means of sperm analysis. Numerous factors such as obesity, smoking, environment contamination, stress, or age act modifying the sperm fecundation capacity, therefore they interfere in the numbers of this two variables. Methods: We aim to study the influence of age on semen quality. We studied 156 patients. They were divided into three groups: 20-30 years; 31-40 years; and 40-50 years. A Mackler's camera and a Nikon microscope were used for evaluation. Results: Nonparametric statistical study was performed establishing the relationship between sperm count and mobility and age. Age-count: X2: 8.239 (p = 0.016). Non mobile spermatozoids-age: X2 = 6.871 (p = 0.032). Mobile spermatozoids-age: X2 = 7.378 (p = 0.025). Conclusions: The age of the patient is intimately related to a decrease of the number of spermatozoids, with the decrease of the number of mobile forms and the increase of the non mobile (AU)

[Brucellar orchitis. Case report and bibliographic review]. / Orquitis brucelar. A propósito de un nuevo caso y revisión de la literatura.

OBJECTIVE: We report one case of unilateral epididymo-orchitis secondary to Brucella and perform a bibliographic review. METHODS: We report the case of a 5 1-year-old male with fever, predominantly in the evening hours, over one month associated with a subacute inflammatory process on the right testicle and osteoarticular pain on the left ribs. RESULTS: Treatment was performed with rifampicin 600 mg/day for 45 days and doxicilin 100 mg/12 hours for 45 days. CONCLUSIONS: The brucellar etiology should be taken into consideration in front of an epididymo- orchitis with torpid outcome, mainly in areas of endemic Brucella and patients that have had contact with cattle or non controlled milk derivatives. We emphasize that contact could have been several months before the appearance of clinical epididymoorchitis.

[Inverted papilloma. Report of two cases and bibliographic review]. / Papiloma invertido. Aportación de dos casos y revisión de la literatura.

OBJECTIVE: Inverted papilloma is a rare polypoid lesion of the urothelium, known as a different entity since 1963. Not many more than 100 cases have been published. Although its malignant potential is still unknown, several scientific publications have noted it. METHODS: We report to cases of inverted papilloma and perform a detailed bibliographic review. RESULTS: Both patients were diagnosed by the Pathology Department and entered periodic follow-up visits, being free of recurrence at 24 and 18 months respectively. CONCLUSIONS: The possibility that inverted papilloma is a lesion with malignant potential should be considered in every case, and we suggest that patients with this diagnosis should enter a follow-up protocol like any bladder neoplasia.

[Bladder leiomyoma. Report of two new cases and bibliographic review]. / Leiomioma vesical. A propósito de dos nuevos casos y revisión de la literatura.

OBJECTIVE: Primary mesothelial tumors of the bladder are rare entities, being leiomyoma the most frequent of them. It may grow without any clinical symptoms or with very unspecific ones. METHODS: We report two cases of bladder leiomyoma in 2 patients, and performed a bibliographic review. RESULTS: They were treated by transurethral resection, with an excellent outcome, without incidences over five years of follow-up. CONCLUSIONS: Surgical treatment continues to be the best solution; it is easy to perform and has a very limited number of complications. Prognosis is good in any case and progression is anecdotic.

Orquitis brucelar. A propósito de un nuevo caso y revisión de la literatura / Brucellar orchitis. Case report and bibliographic review

OBJETIVO: Presentamos un caso de orquiepididimitis aguda unilateral secundaria a infección por Brucella y revisamos la literatura al respecto. MÉTODOS: Presentamos el caso de un varón de 51 años con fiebre de predominio vespertino de un mes de evolución asociado a proceso inflamatorio subagudo en teste derecho y dolor osteoarticular costal izquierdo. RESULTADOS: Se trata mediante Rifampicina a una dosis de 600 mg./día durante 45 días y Doxiclina 100 mg. cada 12 horas durante 45 días. CONCLUSIONES: Se debe tener en cuenta la etiología brucelósica ante orquiepididimitis de evolución tórpida, especialmente en áreas donde la Brucella pueda ser endémica y en personas que hayan tenido contacto con ganado o derivados de la leche no sujetos a control. Destacar que el contacto puede haber sido incluso varios meses antes de la clínica de orquiepididimitis

OBJECTIVE: We report one case of unilateral epididymo-orchitis secondary to Brucella and perform a bibliographic review. METHODS: We report the case of a 51-year-old male with fever, predominantly in the evening hours, over one month associated with a subacute inflammatory process on the right testicle and osteoarticular pain on the left ribs. RESULTS: Treatment was performed with rifampicin 600 mg/day for 45 days and doxicilin 100 mg/12 hours for 45 days. CONCLUSIONS: The brucellar etiology should be taken into consideration in front of an epididymo- orchitis with torpid outcome, mainly in areas of endemic Brucella and patients that have had contact with cattle or non controlled milk derivatives. We emphasize that contact could have been several months before the appearance of clinical epididymo-orchitis

Papiloma invertido. Aportación de dos casos y revisión de la literatura / Inverted papilloma. Report of two cases and bibliographic review

Objetivo: El papiloma invertido es una rara lesión polipoidea del urotelio, conocida como entidad diferente desde 1963, desde cuando escasamente se han publicado más de 100 casos en la literatura. Aunque su potencial maligno es todavía desconocido, existen varias publicaciones científicas en las que se denota. Métodos: Presentamos dos casos de papiloma invertido y hacemos una detallada revisión de la literatura científica al respecto. Resultados: Ambos pacientes fueron diagnosticados por el servicio de Anatomía Patológica de papiloma invertido, siguiendo controles periódicos posteriores y no apareciendo recidivas en ninguno de los dos casos, a los 24 y 18 meses de seguimiento respectivamente. Conclusiones: La posibilidad de que el papiloma invertido sea una lesión con potencial maligno debe ser en todo caso considerada y sugerimos que los pacientes con este diagnóstico sean sometidos a los exámenes urológicos de seguimiento en cualquier neoplasia vesical (AU)

Objective: Inverted papilloma is a rare polypoid lesion of the urothelium, known as a different entity since 1963. Not many more than 100 cases have been published. Although its malignant potential is still unknown, several scientific publications have noted it. Methods: We report to cases of inverted papilloma and perform a detailed bibliographic review. Results: Both patients were diagnosed by the Pathology Department and entered periodic follow-up visits, being free of recurrence at 24 and 18 months respectively. Conclusions: The possibility that inverted papilloma is a lesion with malignant potential should be considered in every case, and we suggest that patients with this diagnosis should enter a follow-up protocol like any bladder neoplasia (AU)

Leiomioma vesical. A propósito de dos casos y revisión de la literatura / Bladder leiomyoma. Report of two new cases and bibliographic review

Objetivo: Los tumores mesoteliales primarios de la vejiga son entidades raras, y de entre ellos el más frecuente es el leiomioma vesical, que puede crecer sin apenas manifestaciones clínicas o muy inespecíficas. Métodos: Presentamos el caso de un leiomioma vesical en dos pacientes y la revisión de la literatura. Resultados: El tratamiento fue mediante una resección transuretral, la evolución excelente y el seguimiento en consultas externas tras más de 5 años sin incidencias. Conclusiones: El abordaje quirúrgico sigue siendo la mejor solución, de fácil ejecución y con un porcentaje escaso de complicaciones. El pronóstico es bueno en cualquier caso y las recidivas son anecdóticas (AU)

Objective: Primary mesothelial tumors of the bladder are rare entities, being leiomyoma the most frequent of them. It may grow without any clinical symptoms or with very unspecific ones. Methods: We report two cases of bladder leiomyoma in 2 patients, and performed a bibliographic review. Results: They were treated by transurethral resection, with an excellent outcome, without incidences over five years of follow-up. Conclusions: Surgical treatment continues to be the best solution; it is easy to perform and has a very limited number of complications. Prognosis is good in any case and progression is anecdotic (AU)