CO oxidation reactions on 3-d single metal atom catalysts/MgO(100).

The present work deals with a comprehensive computational theoretical study of the molecular CO and O2 adsorption on 3d single atoms (M/MgO(100)). The study is based on the chemical elements of the 3d row, as they represent an economic advantage compared with the so-called noble metals. The present study has been performed employing density functional theory calculations. Through the representation of the metastable states, we perform a synergetic analysis of the CO oxidation reaction to find trends that suggest the possible use of new candidates such as Ni/MgO(100) or Cu/MgO(100) single-atom catalysts, for this type of redox reaction. We found that Ni and Cu produce energetically viable CO to CO2 reactions. Ni and Cu atoms show the greatest diffusion barrier and are the best candidates due to their low sintering capability. The energetic and electronic properties of the single Cu and Ni atoms on MgO (100) give them the best characteristics to help in the CO oxidation process.

Role of bimetallic Au-Ir subnanometer clusters mediating O2 adsorption and dissociation on anatase TiO2 (101).

A comprehensive computational study on the oxygen molecule (O2) adsorption and activation on bimetallic Au-Ir subnanometer clusters supported on TiO2(101)- up to five atoms in size-is performed. A global optimization density functional theory-based basin-hopping algorithm is used to determine putative global minima configurations of both mono- and bimetallic clusters supported on the metal oxide surface for all sizes and compositions. Our results indicate a strong cluster-oxide interaction for monometallic Ir clusters with calculated adsorption energy (Eads) values ranging from -3.11 to -5.91 eV. Similar values are calculated for bimetallic Au-Ir clusters (-3.21 up to -5.69 eV). However, weaker Eads values are calculated for Au clusters (ranging from -0.66 to -2.07 eV). As a general trend, we demonstrate that for supported Au-Ir clusters on TiO2(101), those Ir atoms preferentially occupy cluster-oxide interface positions while acting as anchor sites for the Au atoms. The overall geometric arrangements of the putative global minima configurations define O2 adsorption and dissociation, particularly involving the monometallic Au5 and Ir5 as well as the bimetallic Au2Ir3 and Au3Ir2 supported clusters. Spontaneous O2 dissociation is observed on both Ir5 and on the Ir-metallic part of Au3Ir2 and Au2Ir3 supported clusters. This is in sharp contrast with supported Au5, where a large activation energy is needed (1.90 eV). Interestingly, for Au5, we observe that molecular O2 adsorption is favorable at the cluster/oxide interface, followed by a smaller dissociation barrier (0.71 eV). From a single cluster catalysis point of view, our results have strong implications in the ongoing understanding of oxide supported bimetallic while providing a useful first insight into the continuous in silico design of novel subnanometer catalysts.

Beneficial effects of manually assisted chiropractic adjusting instrument in a rabbit model of osteoarthritis.

Osteoarthritis (OA) is a degenerative disease characterized by injury of all joint tissues. Our previous study showed that in experimental osteoporosis, chiropractic manipulation (CM) exerts protective effects on bone. We here assessed whether CM might ameliorate OA by improving subchondral bone sclerosis, cartilage integrity and synovitis. Male New-Zealand rabbits underwent knee surgery to induce OA by anterior cruciate ligament injury. CM was performed using the chiropractic instrument ActivatorV 3 times/week for 8 weeks as follows: force 2 setting was applied to the tibial tubercle of the rabbit right hind limb (TM-OA), whereas the corresponding left hind limb received a false manipulation (FM-OA) consisting of ActivatorV firing in the air and slightly touching the tibial tubercle. After sacrifice, subchondral bone integrity was assessed in the tibiae by microCT and histology. Cartilage damage and synovitis were estimated by Mankin's and Krenn's scores, respectively, and histological techniques. Bone mineral density and content in both cortical and trabecular compartments of subchondral bone decreased in OA rabbits compared to controls, but partially reversed in the TM-OA group. Trabecular bone parameters in the latter group also showed a significant improvement compared to FM-OA group. Moreover RANKL, OPG, ALP and TRAP protein expression in subchondral bone significantly decreased in TM-OA rabbits with respect to FM-OA group. CM was associated with lower Mankin's and Krenn's scores and macrophage infiltrate together with a decreased protein expression of pro-inflammatory, fibrotic and angiogenic factors, in TM-OA rabbits with respect to FM-OA. Our results suggest that CM may mitigate OA progression by improving subchondral bone as well as cartilage and synovial membrane status.

O2 activation by AuAg clusters on a defective (100)MgO surface.

In the present work, we discuss the electronic properties of supported dispersed bimetallic clusters with respect to their size, geometry, and Aun/Agm (n + m = 6) composition. We have studied with supercell-density functional theory calculations the role of the charge transfer from the MgO defective support toward the cluster in the activation of O2 by AunAgm clusters. We first considered gas-phase clusters with different atomic compositions; then, we deposited all of them on a pristine (100)MgO surface and finally on a more realistic (100)MgO F-center. We performed a global and unrestricted search of the (cluster + surface) geometry. The Mexican enhanced genetic algorithm has been used to exhaustively explore the potential energy surface. Our results show that O2 activation depends on the Aun/Agm ratio. It has been found that both metals involved play different and important roles toward (a) the actual O2 dissociation and (b) weakening of the oxygen-cluster bond, which, in turn, may promote the possibility of a catalytic process to take place, such as the oxidation process of CO and NOx among others.

Fontan procedure: imaging of normal post-surgical anatomy and the spectrum of cardiac and extracardiac complications.

Univentricular congenital heart diseases include a range of entities that result in a functionally single ventricular chamber. Although the only curative therapy is cardiac transplantation, there are several palliative surgical techniques that prevent ventricular volume overload, diverting part or all the systemic venous circulation into the pulmonary arteries. The modern Fontan procedure, which consists of anastomosing both the superior (SVC) and inferior vena cava (IVC) to the right pulmonary artery (RPA), is nowadays the last step before transplantation. The importance of imaging in these entities lies not only in the understanding of the new circuit established after surgical correction, but also in the early detection of the wide spectrum of cardiac and extracardiac complications that can occur due to the new physiological condition. Due to the increased survival of these patients, long-term complications are becoming more common. The main cardiac complications are atrial enlargement, ventricular dysfunction, and stenosis or thrombosis of the conduit. Pulmonary artery stenosis, pulmonary arteriovenous fistulae (PAVF), systemic-pulmonary veno venous shunts (VVS), hepatic congestion, cardiac cirrhosis, and protein-losing enteropathy are potential extracardiac complications.

Estudio cuantitativo y socioeconómico de los espectáculos taurinos populares en la Región de Murcia / Quantitative and socioeconomic study of the bullfighting traditional in the Region Murcia (Spain)

En este trabajo se han abordado determinados aspectos relacionados con la gran tradición, así como la importancia cuantitativa y socio-económica que presentan los espectáculos taurinos populares (ETP) en diferentes pueblos de la Región de Murcia. Para ello se han contabilizado todos los espectáculos taurinos celebrados incluidos los ETP, desglosados por municipios, que han sido comunicados al Colegio Oficial de Veterinarios en los últimos 8 años (2004-2011). Para realizar el estudio socioeconómico hemos dividió los ETP en dos tipos; encierros previos a la lidia y encierros o suelta de reses sin lidia posterior. Se han realizado encuesta a asistentes, 150 en el primer tipo de ETP en los municipios de Calasparra y Blanca, 200 participantes en el segundo tipo de ETP en los municipios de Moratalla, Caravaca de la Cruz y Cehegín. Igualmente se han realizado 28 encuestas a peñas de las localidades del Noroeste, donde se celebran ETP. Los festejos taurinos se celebran prácticamente en la totalidad de los municipios, en los últimos 8 años en 42 de ellos, lo que representa el 95%. Se ha producido un aumento de los ETP respecto al total de espectáculos taurinos que pasa del 35% al 53% en 2010, aunque nos encontramos por debajo de la media, ya que en España los ETP fueron el 81% del total de festejos taurinos. Respecto a las características de los asistentes a este tipo de espectáculos, son en su mayoría de fuera de la localidad, suelen ser varones en torno a los 40 años, y casados por lo que pueden acudir con la familia, situación que permite una gran actividad en la localidad y favorece el nivel de gasto en la misma. En relación a la afición de los participantes a los asistentes a los encierros previos a la lidia, les interesa en mayor proporción otro tipo de espectáculos taurinos. Otro dato a resaltar es el alto % de la gente que se queda a dormir en el caso de los encierros con toreo un 40% se queda a dormir, frente al 14% en el caso de los encierros y sueltas sin lidia. El nivel de gasto medio por asistente a un encierro con lidia posterior es de 50€/día, el doble del asistente a un encierro y suelta sin lidia que es de 25€/día y fundamentalmente en restauración en ambos casos. Podemos concluir que en la Región de Murcia en los últimos 8 años se han celebrado ETP el 71,1% del total de municipios, lo que avala la tradición de estos festejos. El número de ETP ha ido en aumento hasta 2009, llegando a celebrarse 98 ETP, lo que supuso el 48% del total de espectáculos taurinos. Los asistentes a los ETP son mayoritariamente de fuera de la localidad, varones y en torno a los 40 años, casados que pueden venir con la familia, situación que permite una gran actividad en la localidad y favorece el nivel de gasto en la misma, que es mayor en el caso de haber lidia posterior al encierro (AU)

In this work some aspects related with the great tradition and the quantitative and socioeconomic importance of the bullfighting traditional shows in different towns of the Murcia Region have been treated. To do this have been posted all the bullfights held including the ETP, disaggregated by municipalities, which have been communicated to the official College of veterinarians in the last 8 years (2004-2011). For the socio-economic study, we have divided the ETP into two types; running bulls previous to the bullfighting and running or release of cattle without bullfighting. Survey to 150 attendees in the first type of ETP in Calasparra and Blanca and 200 attendees in the second type of ETP in Caravaca de la Cruz, Moratalla, Cehegín were realized. Also there have been 28 surveys to sentences of the towns in the Northwest, where they are held ETP. Bullfighting practically takes place in all the towns, in the last eight years in 42 of them, which represents the 95% of the towns. The increase of the percentage of bullfighting traditional shows with respect to the total of bullfighting shows from the 35% to the 53% in 2010, although is minor that average because for Spain bullfighting traditional shows represents the 81% of all bullfighting shows. With regard to the characteristics of the audience to this type of shows, are mainly people from other different towns, about 40 years old, and married so they can come with the family that increase the activity in the town and favor the level of expenses there. In connection with the preferences of the audience to running of bulls previous to the bullfighting, they prefer others types of bullfighting. Another datum to take into account is the high percentage of people that stay overnight, in the case of running of bulls previous to the bullfighting is of 40% against the 14% in the case of loosing and running of bulls without subsequent bullfighting. The average level of expenses by attending person to running of bulls previous to the bullfighting is of 50 €/day, the double that an attending person to loosing and running of bulls without subsequent bullfighting that is 25 €/day, mainly in catering in both cases. In conclusion, the 71,1 % of the total of towns in the Murcia Region has been bullfighting traditional in the last eight years. The number of bullfighting traditional increasing until 2009, when took place 98 shows and represent the 48% of total. The audience bullfighting traditional are mainly people from other different towns, male, about 40 years old, and married so they can come with the family that increase the activity in the town and favor the level of expenses there, that is greater in shows with subsequent bullfighting (AU)

Relationship between functional capacity and quality of life in heart transplant patients.

The goal of heart transplantation (HT) is not only to prolong the life of patients with end-stage heart failure, but also to offer them the sort of health they enjoyed before the disease. It is widely known that patients' functional capacity improves after HT but what about their quality of life (QoL)? Do functional capacity and QoL improve simultaneously? In the present study, we compared the progression of effort capacity and QoL in the first 2 years after HT. A prospective longitudinal study was performed in 58 heart transplant recipients (43 males, 15 females, age 51.6 ± 10 years) able to complete an effort test 2, 6, 12, and 24 months after transplantation. The studied variables included the five dimensions of the Euroqol-5D questionnaire (EQ-5D) test: mobility, self-care, daily activities, pain/discomfort, anxiety, and depression; a visual analog scale from 0 to 100; and the results (metabolic equivalent units [METs] and time of exercise) of the effort test at 2, 6, 12, and 24 months after transplantation. Analysis of variance was used to compare these variables at each point. Significance was set at P < .05. Functional capacity, measured by both METs and time of exercise, improved progressively (METs: 2 months: 5.2 ± 1.8, 6 months: 6.6 ± 2.1, 12 months: 7.5 ± 2.2, and 24 months: 8.5 ± 2.3, P < .001). As well, the result of EQ-5D questionare improved in parallel to exercise capacity. However, visual analog scale score did not change significatively during the follow-up (2 months: 78.9.3 ± 16.1, 6 months: 83.8 ± 11.3, 12 months: 83.3 ± 11.1, 24 months: 85.2 ± 14.9; P = .192), reaching a plateau at 6 to 24 months. In conclusion, the improvement in functional capacity shown by heart transplant recipients in the first 2 years after transplantation was not parallel to the feelings of well-being measured by the analog scale of the EQ-5D. Possibly long after transplantation patients will compare themselves to healthy people rather than to their state before HT, resulting in improvements the visual analog scale.

Clinical predictors of immunotolerance in heart transplantation.

BACKGROUND AND AIM: The drugs routinely administered to prevent rejection often cause lethal side effects. Tolerant patients, therefore, should be identified to minimize these problems. The aim of this analysis was to identify clinical variables that may be associated with tolerance. METHODS: We recruited 522 heart transplants (HT), excluding combined procedures, retransplantations, pediatric recipients, and subjects who died in the first year to obtain a cohort of 375 patients. Two groups were distinguished by the presence of echocardiographic, clinical, or pathological evidence of rejection in the first year (15 echocardiograms and 10 protocol biopsies per patient); 99 tolerant patients were compared with 276 nontolerant patients. We analyzed clinical variables related to morbidity and mortality. RESULTS: The univariate analysis showed few differences between the groups. The multivariate analysis showed that only major histocompatibility complex (MHC)-A and MHC-DR matched recipients were significantly associated with tolerance. Thus, the likelihood of tolerance was increased by 1.7- and 2.8-fold if 1 or 2 MHC-I matches were present and by 3.4- and 3.7-fold if 1 or 2 MHC-DR matches were present, respectively survival curves showed significant differences (P=.034). Most deaths in both groups were related to immunosuppressive drugs; among tolerant subjects, deaths were due to infection and neoplasms and among nontolerant patients, deaths were due to chronic rejection, neoplasms, and infection. CONCLUSIONS: The only clinical parameter that can determined whether a HT recipient was tolerant was MHC-A and MHC-DR matching. If there is matching, a reduced immunosuppressive load should be prescribed to prevent drug toxicity.

Lymphomas in heart transplant recipients: do antivirals protect against the neoplastic effect of anti-CD3 monoclonal antibody?

INTRODUCTION AND AIM: After cardiac allograft vasculopathy, tumors are the second leading cause of death among heart transplantation (HT) patients after the first year. Lymphomas are tumors of lymphocytic origin whose development has been associated with the use of anti-CD3 monoclonal antibody (OKT3). Some studies suggest that the use of acyclovir could counteract this effect. Our aim was to investigate the impact of gancyclovir on OKT3 and lymphoma development after HT. MATERIALS AND METHODS: We included all 239 HTs performed in our center from 1989 to 2002. We divided patients into those who received gancyclovir treatment (prophylaxis, pre-emptive therapy, or for cytomegalovirus infection) versus those who did not receive this agent at any time during follow-up (88 vs 151 patients). The statistical methods were Student's t and chi-square tests. RESULTS: There were no differences in the baseline characteristics of the patients--gender, recipient age, etiology leading to HT, diabetes, and dyslipidemia--except for a higher rate of hypertension among the group who did not receive gancyclovir (73.7 vs 60.2%; P=.03). None of the 7 patients who developed lymphomas during the follow-up received gancyclovir (0 vs 4.6%; P=.040). CONCLUSIONS: Antivirals may have a relevant role to neutralize potential neoplastic effects (especially lymphomas) associated with the use of OKT3 induction therapy.

Impact of smoking on survival after heart transplantation.

INTRODUCTION: Smoking is an important risk factor in any population group. According to previous studies, having been a smoker before heart transplantation (HT) confers a greater likelihood of developing any type of tumor or other complication after HT. Our objective was to determine the impact of having been a smoker before HT on survival, respiratory complications during the postoperative period, and long-term tumor development. MATERIALS AND METHODS: After excluding combined transplantations, pediatric transplantations, and retransplantations, we retrospectively reviewed 288 HT performed between November 1987 and September 2006. We divided patients into nonsmokers (including those who quit smoking more than 1 year before HT (n = 163), exsmokers for less than 1 year (n = 76), and those who smoked until HT (n = 49). The statistical tests were chi-square, Student t, analysis of variance (ANOVA), and Kaplan-Meier curves. RESULTS: There were more male patients among smokers and exsmokers than nonsmokers (93.9% vs 96.1% vs 82%, respectively; P = .003). There were no differences in baseline characteristics between the groups. Exsmokers remained intubated for a longer time than smokers or nonsmokers (33.4 +/- 44.6 vs 14.2 +/- 7.3 vs 17.9 +/- 19.2, respectively; P = .05). We observed the same trend in recovery unit stay (7.9 +/- 10.5 days vs 4.4 +/- 1.88 days vs 4.84 +/- 3.49 days, respectively; P = .021). The development of any type of tumor was also more frequent among smokers and exsmokers, although not significantly. The survival rate was similar in nonsmokers and exsmokers, although higher than in smokers (89.57 vs 92.11% vs 81.63%, respectively; P = .031). We did not observe differences in the causes of death. CONCLUSIONS: Patients who smoke or have smoked until shortly before HT showed a poorer prognosis and a longer recovery unit stay. There was also a trend to increased tumor development.

Nosocomial infection in the community hospital: severe infection due to Serratia species.

BACKGROUND: Serratia bacteremia is an uncommon illness in hospitalized patients. The aim of this study was to determine how frequently this disease occurs nosocomially and to discover the most common portals of entry and the underlying disorders. METHODS: Fifty-six cases of Serratia bacteremia documented by blood culture (17 cases over a 4-year period in a community hospital in Gainesville, Florida, and 39 cases over a 3-year period in three community hospitals in Dayton, Ohio) were reviewed. Comparison was made with 60 control cases of general bacteremia from three Dayton hospitals. RESULTS: Of the 56 study cases of Serratia bacteremia, 45 (80.4%) were classified as nosocomial, compared with 13 (21.7%) of the controls. Twenty-seven (48.2%) of the 56 Serratia cases occurred in intensive care units. The cases were evenly distributed over the two study periods, and no outbreaks on specific units were noted. The most common portals of entry for Serratia organisms were, in descending order, lung, genitourinary tract, unknown, intravenous line, gastrointestinal tract, and skin. The most common underlying disorder for Serratia bacteremia was malignancy, followed by renal failure (acute or chronic) and diabetes mellitus. Most of the Serratia organisms tested were sensitive to carbenicillin, trimethoprim/sulfamethoxazole, ceftizoxime, ceftriaxone, ceftazidime, cefotetan, aztreonam, ticarcillin/clavulanate, and ciprofloxacin. The organisms were largely resistant to ampicillin, tetracycline, cefazolin, cephalothin, and cefuroxime. Twenty-five percent of the patients with Serratia bacteremia died, compared with 13.6 of the bacteremic controls. CONCLUSION: Serratia bacteremia is often acquired nosocomially. The mortality rate among the study population was surprisingly low for this opportunistic bacteremia, but was higher (though not significantly so) than that of the controls.