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1.
Article in English | MEDLINE | ID: mdl-34064938

ABSTRACT

Spain experienced a second wave of the COVID-19 pandemic in autumn 2020, which has been approached with different measures by regional authorities. We analyze the presence of convergence in the cumulative incidence for 14 days (CI14) in provinces and self-governing cities. The Phillips-Sul methodology was used to study the grouping of behavior between provinces, and an ordered logit model was estimated to understand the forces that drive creating the different convergence clubs. We reject the presence of a single pattern of behavior in the evolution of the CI14 across territories. Four statistically different convergence clubs and an additional province (Madrid) with divergent behavior are observed. Provinces with developed agricultural and industrial economic sectors, high mobility, and a high proportion of Central and South American immigrants had the highest level of CI14. We show that the transmission of the virus is not homogeneous in the Spanish national territory. Our results are helpful for identifying differences in determinants that could explain the pandemic's evolution and for formulating hypotheses about the effectiveness of implemented measures.


Subject(s)
COVID-19 , Pandemics , Cities , Humans , SARS-CoV-2 , Spain/epidemiology
2.
Spectrochim Acta A Mol Biomol Spectrosc ; 239: 118498, 2020 Oct 05.
Article in English | MEDLINE | ID: mdl-32470814

ABSTRACT

Tamoxifen is one of the most frequently used drugs for the treatment of estrogen receptor positive breast cancer, which is the most prevalent form of hormone dependent breast cancer. A few years ago, we developed a fluorescent derivative of tamoxifen formed by the covalent binding of tamoxifen to a common dye biomarker. The new compound, known as FLTX1, showed the pharmacological activity of the tamoxifen moiety and efficient fluorescence properties, which could be used synergistically to improve the effect of the drug. In this paper, we demonstrate that irradiation at the absorption band of FLTX1 can result in fluorescence resonance energy transfer to photosensitizers such as Rose Bengal and Merocyanine 540, activating the production of reactive oxygen species (ROS). Indeed, the generation of ROS was demonstrated using a colorimetric assay. Since FLTX1 mostly binds estrogen-receptor overexpressing cancer cells, the results obtained are very promising and suggest a new therapeutic strategy combining chemo- and photodynamic therapies.


Subject(s)
Breast Neoplasms , Pharmaceutical Preparations , Photochemotherapy , Breast Neoplasms/drug therapy , Cell Line, Tumor , Fluorescence Resonance Energy Transfer , Humans
3.
Opt Express ; 24(13): 14383-92, 2016 Jun 27.
Article in English | MEDLINE | ID: mdl-27410592

ABSTRACT

A compact and portable optofluidic microresonator has been fabricated and characterized. It is based on a Fabry-Perot microcavity consisting essentially of two tailored dichroic Bragg mirrors prepared by reactive magnetron sputtering deposition. The microresonator has been filled with an ethanol solution of Nile-Blue dye. Infrared laser emission has been measured with a pump threshold as low as 0.12 MW/cm2 and an external energy conversion efficiency of 41%. The application of the device as a temperature and a chemical sensor is demonstrated. Small temperature variations as well as small amount of water concentrations in the liquid laser medium are detected as a shift of the resonant laser modes.

4.
Rev. calid. asist ; 29(4): 220-228, jul.-ago. 2014.
Article in Spanish | IBECS | ID: ibc-126922

ABSTRACT

Objetivo. Estimar la frecuencia de prácticas inefectivas en la atención primaria (AP) en función de la opinión de profesionales clínicos, así como valorar la importancia, consecuencias y factores que pueden estar contribuyendo a su mantenimiento. Material y métodos. Encuesta de opinión online a una muestra de conveniencia de 575 profesionales de la AP seleccionados a partir de artículos publicados en los últimos años de las revistas Atención Primaria y Semergen. Resultados. Respondieron 212 encuestados (37%). Para el 70,6% (IC 95%: 64,5-73,7) el problema de las prácticas inefectivas resultó frecuente o muy frecuente en AP y la importancia fue valorada con una puntuación media de 7,3 (DE = 1,8) sobre 10. Las principales consecuencias de las prácticas inefectivas fueron poner en peligro la sostenibilidad del sistema (48,1%; IC 95%: 41,2-54,9) y el daño a los pacientes (32,1%; IC 95%: 25,7-38,5). Contribuyeron a su mantenimiento los propios pacientes (28%; IC 95%: 22,6-35,0), la carga de trabajo (26,4%; IC 95%: 20,3-32,5) y la falta de formación continuada (19,3%; IC 95%: 13,9-24,7). Los procesos clínicos con mayor grado de utilización inadecuada fueron la prescripción de antibióticos en determinadas infecciones, la periodicidad del cribado del cáncer de cérvix, el control farmacológico de la diabetes tipo 2, la utilización de psicofármacos en ancianos y el uso de analgésicos en pacientes con hipertensión o insuficiencia renal. Conclusiones. La utilización de intervenciones inefectivas en AP fue apreciada como un problema muy relevante que afectaría a muchos pacientes, pondría en peligro la sostenibilidad del sistema y causaría daño a los pacientes (AU)


Objective. To estimate the frequency of ineffective practices in Primary Health Care (PHC) based on the opinions of clinical professionals from the sector, and to assess the significance, implications and factors that may be contributing to their continuance. Material and methods. An on line survey of opinion from a convenience sample of 575 professionals who had published articles over the last years in Atención Primaria and Semergen medical journals. Results. A total of 212 professionals replied (37%). For 70.6% (95% confidence interval [CI] 64.5 to 73.3) the problem of ineffective practices is frequent or very frequent in PHC, and rate their importance with an average score of 7.3 (standard deviation [SD] = 1.8) out of 10. The main consequences would be endangering the sustainability of the system (48.1%; 95% CI, 41.2 to 54.9) and harming patients (32.1%; 95% CI, 25.7 to 38.5). These ineffective practices are the result of the behaviour of the patients themselves (28%; 95% CI, 22.6 to 35.0) workload (26.4%; 95% CI, 20.3 to 32.5), and the lack of the continuous education (19.3%; 95% CI, 13.9 to 24.7). Clinical procedures of greatest misuse are the prescribing of antibiotics for certain infections, the frequency of cervical cancer screening, rigorous pharmacological monitoring of type 2 diabetes in patients over 65 years, the use of psychotropic drugs in the elderly, or the use of analgesics in patients with hypertension or renal failure. Conclusions. The use of ineffective procedures in PHC is considered a very important issue that negatively affects many patients and their treatment, and possibly endangering the sustainability of the system and causing harm to patients (AU)


Subject(s)
Humans , Male , Female , Health Services Misuse/statistics & numerical data , Health Services Misuse/trends , Primary Health Care/organization & administration , Primary Health Care/standards , Unnecessary Procedures/methods , Unnecessary Procedures , Practice Patterns, Physicians'/organization & administration , Practice Patterns, Physicians'/standards , Health Services Misuse/prevention & control , Primary Health Care/methods , Primary Health Care/trends , Unnecessary Procedures/standards , Unnecessary Procedures/trends , Practice Patterns, Physicians'/trends , Practice Patterns, Physicians'
5.
Rev Calid Asist ; 29(4): 220-8, 2014.
Article in Spanish | MEDLINE | ID: mdl-24928717

ABSTRACT

OBJECTIVE: To estimate the frequency of ineffective practices in Primary Health Care (PHC) based on the opinions of clinical professionals from the sector, and to assess the significance, implications and factors that may be contributing to their continuance. MATERIAL AND METHODS: An on line survey of opinion from a convenience sample of 575 professionals who had published articles over the last years in Atención Primaria and Semergen medical journals. RESULTS: A total of 212 professionals replied (37%). For 70.6% (95% confidence interval [CI] 64.5 to 73.3) the problem of ineffective practices is frequent or very frequent in PHC, and rate their importance with an average score of 7.3 (standard deviation [SD]=1.8) out of 10. The main consequences would be endangering the sustainability of the system (48.1%; 95% CI, 41.2 to 54.9) and harming patients (32.1%; 95% CI, 25.7 to 38.5). These ineffective practices are the result of the behaviour of the patients themselves (28%; 95% CI, 22.6 to 35.0) workload (26.4%; 95% CI, 20.3 to 32.5), and the lack of the continuous education (19.3%; 95% CI, 13.9 to 24.7). Clinical procedures of greatest misuse are the prescribing of antibiotics for certain infections, the frequency of cervical cancer screening, rigorous pharmacological monitoring of type 2 diabetes in patients over 65 years, the use of psychotropic drugs in the elderly, or the use of analgesics in patients with hypertension or renal failure. CONCLUSIONS: The use of ineffective procedures in PHC is considered a very important issue that negatively affects many patients and their treatment, and possibly endangering the sustainability of the system and causing harm to patients.


Subject(s)
Primary Health Care/standards , Adult , Female , Humans , Male , Middle Aged , Practice Patterns, Physicians' , Surveys and Questionnaires , Unnecessary Procedures
6.
Rev. calid. asist ; 28(2): 84-95, mar.-abr. 2013.
Article in Spanish | IBECS | ID: ibc-111295

ABSTRACT

Objetivo. Describir la evolución de la mortalidad reducible por acción de los servicios sanitarios (MRASS) en España y evaluar si las transferencias sanitarias han supuesto algún cambio significativo. Métodos. La MRASS se definió a partir de una lista de causas utilizada en otros estudios. Se analizan tasas de MRASS ajustadas por edad y sexo en los períodos 1999-2001 y 2006-2008, justo antes y 5 años tras culminar el proceso de transferencias. Resultados. La MRASS representó el 24% de las defunciones en personas de 0-74 años. Descendió entre ambos períodos en mayor medida (19,4%) que el resto de causas (14,5%). El grupo de causas que más descendieron fueron: cardiopatía isquémica (28,0%), resto de enfermedades vasculares (26,8%), enfermedades quirúrgicas y errores médico-quirúrgicos (25,9%) y diabetes (22,5%). Aunque existieron diferencias entre comunidades autónomas (CCAA), no se apreció que estas diferencias ni la evolución de la MRASS se relacionaran con las transferencias. Navarra y Madrid presentaron las menores tasas de MRASS y Canarias, Asturias, Andalucía, Ceuta y Melilla, las mayores. Baleares fue la CCAA donde más disminuyó la MRASS. Conclusiones. La MRASS representa una importante proporción de la experiencia de mortalidad de personas de 0-74 años. Ha descendido en todas las CCAA, y aunque hay grandes diferencias entre ellas, no parece que el proceso de transferencias sanitarias influyera en su evolución en el período estudiado. Pese a limitaciones, la MRASS es un indicador que se debe considerar para monitorizar y detectar debilidades en la efectividad de los sistemas asistenciales(AU)


Objective. To describe the evolution of amenable mortality (MRASS) in Spain and to evaluate differences in trend patterns before and after health care services were tranferred to local authorities. Methods. MRASS was defined from a list of causes of death used in other studies. We analyzed the change in sex-age-standardized death rates of MRASS in two periods: 1999-2001 and 2006-2008, just before, and five years after, the health care transfers were completed. Results. MRASS represented 24% of deaths in persons from 0 to 74 years old. MRASS has seen a reduction (19.4%) between the two periods over and above other causes of mortality (14.5%). The group of causes of mortality which showed most reduction: ischemic heart disease (28%), other vascular disease (27%), surgical conditions and surgical-medical errors (26%), and diabetes (22.5%). Although there were differences between the districts, health care transfers have not created significant variations in MRASS. Navarra and Madrid showed lower rates of MRASS, and the Canary Islands, Asturias, Andalusia, Ceuta and Melilla had higher rates. The Balearic Islands showed the greatest reduction in MRASS. Conclusions. MRASS constitutes an important proportion of trends of mortality in persons between 0-74 years. It has declined in all districts. Even though there were large differences between districts, there does not appear to be any direct influence due to health care transfer in amenable mortality trends. In spite of limitations, MRASS is an indicator to be considered when monitoring and detecting weaknesses in the effectiveness of health care systems(AU)


Subject(s)
Humans , Male , Female , Health Services Research , Health Services Research , Health Services Needs and Demand/standards , Patient Transfer/standards , Mortality Registries/standards , Mortality , Cause of Death/trends , Transfer Agreement/legislation & jurisprudence , Transfer Agreement/standards , Mortality/standards , Confidence Intervals
7.
Rev Calid Asist ; 28(2): 84-95, 2013.
Article in Spanish | MEDLINE | ID: mdl-22985844

ABSTRACT

OBJECTIVE: To describe the evolution of amenable mortality (MRASS) in Spain and to evaluate differences in trend patterns before and after health care services were transferred to local authorities. METHODS: MRASS was defined from a list of causes of death used in other studies. We analyzed the change in sex-age-standardized death rates of MRASS in two periods: 1999-2001 and 2006-2008, just before, and five years after, the health care transfers were completed. RESULTS: MRASS represented 24% of deaths in persons from 0 to 74 years old. MRASS has seen a reduction (19.4%) between the two periods over and above other causes of mortality (14.5%). The group of causes of mortality which showed most reduction: ischemic heart disease (28%), other vascular disease (27%), surgical conditions and surgical-medical errors (26%), and diabetes (22.5%). Although there were differences between the districts, health care transfers have not created significant variations in MRASS. Navarra and Madrid showed lower rates of MRASS, and the Canary Islands, Asturias, Andalusia, Ceuta and Melilla had higher rates. The Balearic Islands showed the greatest reduction in MRASS. CONCLUSIONS: MRASS constitutes an important proportion of trends of mortality in persons between 0-74 years. It has declined in all districts. Even though there were large differences between districts, there does not appear to be any direct influence due to health care transfer in amenable mortality trends. In spite of limitations, MRASS is an indicator to be considered when monitoring and detecting weaknesses in the effectiveness of health care systems.


Subject(s)
Mortality/trends , National Health Programs/organization & administration , Politics , Preventive Health Services/organization & administration , Quality Indicators, Health Care , Adolescent , Adult , Aged , Cause of Death , Child , Child, Preschool , Female , Humans , Infant , Infant, Newborn , Male , Middle Aged , Program Evaluation , Quality of Health Care , Spain/epidemiology , Young Adult
8.
Meat Sci ; 73(1): 109-15, 2006 May.
Article in English | MEDLINE | ID: mdl-22062060

ABSTRACT

In this study, a total of 163 young-bull carcasses belonging to seven Spanish native beef cattle breeds showing substantial carcass variation were photographed in order to obtain digital assessments of carcass dimensions and profiles. This dataset was then analysed using machine learning (ML) methodologies to ascertain the influence of carcass profiles on the grade obtained using the SEUROP system. To achieve this goal, carcasses were obtained using the same standard feeding regime and classified homogeneous conditions in order to avoid non-linear behaviour in grading performance. Carcass weight affects grading to a large extent and the classification error obtained when this attribute was included in the training sets was consistently lower than when it was not. However, carcass profile information was considered non-relevant by the ML algorithm in earlier stages of the analysis. Furthermore, when carcass weight was taken into account, the ML algorithm used only easy-to-measure attributes to clone the classifiers decisions. Here we confirm the possibility of designing a more objective and easy-to-interpret system to classify the most common types of carcass in the territory of the EU using only a few single attributes that are easily obtained in an industrial environment.

9.
Meat Sci ; 71(3): 514-21, 2005 Nov.
Article in English | MEDLINE | ID: mdl-22060927

ABSTRACT

A total of 159 bulls representing seven Spanish beef breeds were fed with concentrates, managed in the same conditions and slaughtered at two commercial weights (veal and young-bull). Carcasses were measured and classified in order to characterise the carcass variation in the Spanish beef market and to assess the relationship among carcass measurements and grading. Principal Component Analysis clearly separated commercial types regardless the inclusion of the carcass weight in the input data. Within commercial weights the studied breeds clustered into three groups according to muscular development and carcass classification score: high meat producer breeds (Asturiana de los Valles and Rubia Gallega); medium meat producers (Parda Alpina and Pirenaica); and low meat producers (Avileña, Retinta and Morucha). The perimeter and width of the leg (muscular development) besides the length and width of the carcass basically defined these three carcass types. Conformation was an important trait in explaining variation between breeds because its values were positively correlated with muscular development and carcass compactness.

10.
J Chem Phys ; 120(13): 6180-90, 2004 Apr 01.
Article in English | MEDLINE | ID: mdl-15267504

ABSTRACT

The optically active dopant distribution in a Tm(3+)-Yb(3+) doped silica based glass ceramic sample has been investigated. A systematic analysis of the upconversion fluorescence of the Tm(3+)-Yb(3+) codoped glass and glass ceramic has been performed at room temperature. Tm(3+) and Yb(3+) single doped glass and glass ceramics have also been included in the study. Upon infrared excitation at 790 nm into the (3)H(4) level of the Tm(3+) ions a blue upconversion emission is observed, which is drastically increased in the Yb(3+) codoped samples. A rate equation model confirmed the energy transfer upconversion mechanism. Based on these results, the temporal dynamic curves of the levels involved in the upconversion process, (3)H(4), (2)F(5/2), and (1)G(4) were interpreted in the glass ceramic samples. The contribution of the optically active Tm(3+) and Yb(3+) ions in the crystalline and in the vitreous phase of the glass ceramic was distinguished and the ratio of Tm(3+) ions in the crystalline phase could be quantified for the 1 mol % Tm(3+)-2.5 mol % Yb(3+) glass ceramic. A surprising result was obtained for that concentration: the main contribution to the upconversion emission of the glass ceramic is due to Tm(3+)-Yb(3+) ions in the vitreous phase.

11.
Rev. ortop. traumatol. (Madr., Ed. impr.) ; 48(1): 17-21, ene. 2004. ilus, tab
Article in Es | IBECS | ID: ibc-29470

ABSTRACT

Objetivos. Comparar retrospectivamente los resultados de las técnicas de Bankart y Boytchev para el tratamiento abierto de la luxación recidivante anterior de hombro. Material y método. Se intervinieron 75 pacientes con luxación recidivante anterior de hombro, 41 mediante la técnica de Bankart utilizando suturas ancladas (grupo A), y 34 mediante la técnica de Boytchev (grupo B).Resultados. Hubo un número significativamente mayor de pacientes con estabilidad normal en el grupo A (p < 0,05), y un número significativamente mayor de pacientes en el grupo B con aprensión cuando se realizó una posición forzada (p < 0,05). El número de pacientes sin limitaciones funcionales fue significativamente mayor en el grupo A (p < 0,05), y el de pacientes con una limitación leve significativamente mayor en el B (p < 0,05). No existieron diferencias significativas en cuanto a la flexión y la rotación interna postoperatorias. Hubo más pacientes con una limitación de la rotación externa en el grupo A, siendo esta diferencia estadísticamente significativa (p < 0,01). La limitación media de la rotación externa fue mayor en el grupo A (6,4o) que en el grupo B (1,9o), siendo esta diferencia estadísticamente significativa (p < 0,01). El resultado global según la escala de Rowe fue mejor en el grupo A, aunque la diferencia no fue estadísticamente significativa. Conclusiones. La técnica de Bankart proporciona una estabilidad y una función más satisfactorias que la de Boytchev, aunque produce una mayor limitación de la rotación externa. (AU)


Subject(s)
Adolescent , Adult , Female , Male , Middle Aged , Humans , Shoulder Dislocation/surgery , Orthopedic Procedures/methods , Recurrence , Retrospective Studies
12.
Gest. hosp. (Ed. impr.) ; 13(4): 131-142, oct. 2002. ilus, tab, graf
Article in Es | IBECS | ID: ibc-20272

ABSTRACT

Objetivo: Diseñar y examinar la fiabilidad de una herramienta para evaluar los resultados y distribuir incentivos entre los servicios del hospital. Material y Métodos: Se definieron de forma explícita las características de la herramienta de evaluación (representatividad, transparencia, claridad, pertinencia, accesibilidad, veracidad, carácter reproducible, sensibilidad, especificidad, estabilidad, eficiencia y aceptación) y se utilizaron dichos criterios para seleccionar indicadores y desarrollar los modelos de evaluación específicos de cada servicio. Para validar el método se midió su precisión (coherencia intra e interobservador, coeficiente de variación y bondad de ajuste a la normal) y su validez de contenido, de construcción y de criterio con respecto a una encuesta de opinión previa entre el equipo directivo (correlación de Pearson e índice Kappa). Resultados: La herramienta desarrollada constaba de 15 modelos de evaluación elaborados a partir de 49 indicadores (31 de actividad, cuatro de costes y 14 de calidad asistencial). Se evaluaron 56 unidades aistenciales, cuya calificación media fue de 73,5 ñ 18,1 puntos, con un mínimo de 29 y un máximo de 100. En Actividad la puntuación media fue de 52,1 ñ 14,7 sobre 70, en Costes de 13,7 ñ 7,4 sobre 20 y en Calidad de 7,6 ñ 2,1 sobre 10. El modelo se ajustaba a una distribución normal, con un CV de 0,25, un error intraobsevador de 0,25 por ciento e interobservador del 0,48 por ciento. La correlación con la opinión del equipo directivo era positiva (r = 0,43 p = 0,004), pero los índices de concordancia kappa eran bajos (0,21). Conclusiones: El método de evaluación probado es preciso, está bien construido y tiene una aparente validez de criterio. Queda ahora por demostrar si sirve para mejorar los resultados y la calidad de la asistencia prestada (AU)


Subject(s)
Humans , Hospital Departments , Hospital Departments/economics
13.
J Am Chem Soc ; 123(48): 11925-32, 2001 Dec 05.
Article in English | MEDLINE | ID: mdl-11724599

ABSTRACT

The substitution of a terminal hydride ligand in the complexes [Ir(2)(mu-H)(mu-Pz)(2)H(3)(L)P(i)Pr(3))(2)] (L = NCCH(3) (1) or pyrazole (3)) by chloride provokes a significant change in the lability of the L ligand, despite the fact that the substituted hydride and the L ligand lie in opposite extremes of the diiridium(III) complexes. Detailed structural studies of complex 3 and its chloro-trihydride analogue [Ir(2)(mu-H)(mu-Pz)(2)H(2)Cl(HPz)(P(i)Pr(3))(2)] (4) have shown that this behavior is a consequence of the transmission of ligand trans effects from one extreme of the molecule to the other, with the participation of the bridging hydride. Extended Hückel calculations on model diiridium complexes have suggested that such trans effect transmissions are due to the formation of molecular orbitals of sigma symmetry extended along the backbones of the complexes. This is also an expected feature for metal-metal bonded complexes. The feasibility of the transmission of ligand trans effects and trans influences through metal-metal bonds and its relevance to the understanding of both the reactivity and structures of metal-metal bonded dinuclear compounds have been substantiated through structural studies and selected reactions of the diiridium(II) complexes [Ir(2)(mu-1,8-(NH)(2)naphth)I(CH(3))(CO)(2)(P(i)Pr(3))(2)] (isomers 6 and 7) and their cationic derivatives [Ir(2)(mu-1,8-(NH)(2)naphth)(CH(3))(CO)(2)(P(i)Pr(3))(2)](CF(3)SO(3)) (isomers 8 and 9).

14.
Inorg Chem ; 40(18): 4785-92, 2001 Aug 27.
Article in English | MEDLINE | ID: mdl-11511230

ABSTRACT

The tetranuclear complexes [M4(mu-PyS2)2(diolefin)4] [PyS2 = 2,6-pyridinedithiolate; M = Rh, diolefin = cod (1,5-cyclooctadiene) (1), tfbb (tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene) (2); M = Ir, diolefin = cod (3), tfbb (4)] exhibit two one-electron oxidations at a platinum disk electrode in dichloromethane at potentials accessible by chemical reagents. The rhodium tetranuclear complexes were selectively oxidized to the monocationic complexes [Rh4(mu-PyS2)2(diolefin)4](+) (1(+), 2(+)) by mild one-electron oxidants such as [Cp2Fe](+) or [N(C6H4Br-4)3](+) and isolated as the PF6(-), BF4(-), and ClO4(-) salts. Silver salts behave as noninnocent one-electron oxidants for the reactions with the rhodium complexes 1 and 2 since they give sparingly soluble coordination polymers. The complex [Ir4(mu-PyS2)2(cod)4](+) (3(+)) was obtained as the tetrafluoroborate salt by reaction of 3 with 1 molar equiv of AgBF4, but the related complex 4(+) could not be isolated from the chemical oxidation of [Ir4(mu-PyS2)2(tfbb)4] (4) with AgBF4. Oxidation of 3 and 4 with 2 molar equiv of common silver salts resulted in the fragmentation of the complexes to give the diamagnetic triiridium cations [Ir3(mu-PyS2)2(diolefin)3](+). The molecular structure of [Ir3(mu-PyS2)2(cod)3]BF4, determined by X-ray diffraction methods, showed the three metal atoms within an angular arrangement. Both 2,6-pyridinedithiolate tridentate ligands bridge two metal-metal bonded d(7) centers in pseudo octahedral environments and one d(8) square-planar iridium center. An interpretation of the EPR spectra of the 63-electron mixed-valence paramagnetic tetranuclear complexes suggests that the unpaired electron is delocalized over two of the metal atoms in the complexes 1(+)-3(+).


Subject(s)
Chelating Agents/chemistry , Iridium/chemistry , Pyridines/chemistry , Rhodium/chemistry , Crystallography, X-Ray , Electrochemistry , Electron Spin Resonance Spectroscopy , Indicators and Reagents , Magnetics , Oxidation-Reduction , Spectrophotometry, Infrared
15.
Inorg Chem ; 39(21): 4868-78, 2000 Oct 16.
Article in English | MEDLINE | ID: mdl-11196966

ABSTRACT

The course of methyl iodide oxidative addition to various nucleophilic complexes, [Ir2(mu-1,8-(NH)2naphth)(CO)2(PiPr3)2] (1), [IrRh(mu-1,8-(NH)2naphth)(CO)2(PiPr3)2] (2), and [Rh2(mu-1,8-(NH)2naphth)(CO)2(PR3)2] (R = iPr, 3; Ph, 4; p-tolyl, 5; Me, 6), has been investigated. The CH3I addition to complex 1 readily affords the diiridium(II) complex [Ir2(mu-1,8-(NH)2naphth)I(CH3)(CO)2(PiPr3)2] (7), which undergoes slow rearrangement to give a thermodynamically stable stereoisomer, 8. The reaction of the Ir-Rh complex 2 gives the ionic compound [IrRh(mu-1,8-(NH)2naphth)(CH3)(CO)2(PiPr3)2]I (10). The dirhodium compounds, 3-5, undergo one-center additions to yield acyl complexes of the formula (Rh2(mu-1,8-(NH)2naphth)I(COCH3)(CO)(PR3)2] (R = iPr, 12; Ph, 13; p-tolyl, 14). The structure of 12 has been determined by X-ray diffraction. Further reactions of these Rh(III)-Rh(I) acyl derivatives with CH3I are productive only for the p-tolylphosphine derivative, which affords the bis-acyl complex [Rh2(mu-1,8-(NH)2naphth)(CH3CO)2I2(P(p-tolyl)3)2] (15). The reaction of the PMe3 derivative, 6, allows the isolation of the bis-methyl complex [Rh2(mu-1,8-(NH)2naphth)(mu-I)(CH3)2(CO)2(PMe3)2]I (16a), which emanates from a double one-center addition. Upon reaction with methyl triflate, the starting materials, 1, 2, 3, and 6, give the isostructural cationic methyl complexes 9, 11, 17, and 18, respectively. The behavior of these cationic methyl compounds toward CH3I, CH3OSO2CF3, and tetrabutylamonium iodide is consistent with the role of these species as intermediates in the SN2 addition of CH3I. Compounds 18 and 17 react with an excess of methyl triflate to give [Rh2(mu-1,8-(NH)2naphth)(mu-OSO2CF3)(CH3)2(CO)2(PMe3)2][CF3SO3] (19) and [Rh2(mu-1,8-(NH)2naphth)(OSO2CF3)(COCH3)(CH3)(CO)(PiPr3)2][CF3SO3] (20), respectively. Upon treatment with acetonitrile, complexes 17 and 18 give the isostructural cationic acyl complexes [Rh2(mu-1,8-(NH)2naphth)(COCH3)(NCCH3)(CO)(PR3)2][CF3SO3] (R = iPr, 21; Me, 22). A kinetic study of the reaction leading to 21 shows that formation of these complexes involves a slow insertion step followed by the fast coordination of the acetonitrile. The variety of reactions found in this system can be rationalized in terms of three alternative reaction pathways, which are determined by the effectiveness of the interactions between the two metal centers of the dinuclear complex and by the steric constraints due to the phosphine ligands.

20.
Chest ; 91(2): 281-3, 1987 Feb.
Article in English | MEDLINE | ID: mdl-3802947

ABSTRACT

We describe a patient with pulmonary ceroid histiocytosis. Skin pigmentation, chest x-ray film and laboratory findings were normal. Only pulmonary function tests were abnormal (TLC = 63 percent, DLco = 52 percent). Based on these functional data, the patient was submitted to a lung biopsy by thoracotomy. Brown pigmented histiocytes were shown occupying alveolar spaces. Similar brown pigmented hepatocytes were seen in the liver biopsy.


Subject(s)
Ceroid/metabolism , Lung Neoplasms/metabolism , Lymphatic Diseases/metabolism , Pigments, Biological/metabolism , Adult , Bone Marrow/metabolism , Female , Follow-Up Studies , Histiocytes/metabolism , Histocytochemistry , Humans , Liver/metabolism , Lung Neoplasms/drug therapy , Lung Neoplasms/pathology , Lymphatic Diseases/drug therapy , Lymphatic Diseases/pathology , Respiratory Function Tests
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