Identification of key functionalization species in the Cp*Ir(III)-catalyzed-ortho halogenation of benzamides.

Cp*Ir(iii) complexes have been shown to be effective for the halogenation of N,N-diisopropylbenzamides with N-halosuccinimide as a suitable halogen source. The optimized conditions for the iodination reaction consist of 0.5 mol% [Cp*IrCl2]2 in 1,2-dichloroethane at 60 °C for 1 h to form a variety of iodinated benzamides in high yields. Increasing the catalyst loading to 6 mol% and the time to 4 h enabled the bromination reaction of the same substrates. Reactivity was not observed for the chlorination of these substrates. A variety of functional groups on the para-position of the benzamide were well tolerated. Kinetic studies showed the reaction dependence is first order in iridium, positive order in benzamide, and zero order in N-iodosuccinimide. A KIE of 2.5 was obtained from an independent H/D kinetic isotope effect study. Computational studies (DFT-BP3PW91) indicate that a CMD mechanism is more likely than an oxidative addition pathway for the C-H bond activation step. The calculated functionalization step involves an Ir(v) species that is the result of oxidative addition of acetate hypoiodite that is generated in situ from N-iodosuccinimide and acetic acid.

Relative efficiency of Gafchromic EBT3 and MD-V3 films exposed to low-energy photons and its influence on the energy dependence.

Energy-dependence of Gafchromic films exposed to low-energy photons has been reported to be a function of absorbed-dose. However, these studies are based on a relative-response, R, which considers the absorbed-dose in water and not within the film sensitive-volume. This work investigated the relative-efficiency, REfilm, (ratio of absorbed-dose required to produce the same net optical density (netOD) by 60Co gamma and by x-ray) of Gafchromic EBT3 and MD-V3 films exposed to five x-ray beams from 20 kV to 160 kV and 60Co gamma rays. A factor that accounts for the energy-dependence, fx,Q,med, based on REfilm, phantom-material and depth at which the films are placed during irradiation was used to remove the influence of absorbed dose. Values of REfilm indicated that the absorbed dose from 60Co gamma rays needs to be 4 and 3 times larger than those from 20 kV x-rays to produce the same netOD within the EBT3 and MD-V3 sensitive volumes, respectively. Thus, saturation could help explain why Gafchromic films show under-response to very low doses from low-energy photon beams, regardless of film model. Furthermore, REfilm, was found to be nearly independent of netOD and colour-channels. Consequently, fx,Q,med is independent of the absorbed dose and colour-channels. In contrast, besides the variation with the photon energy, fx,Q,med varied with film model, depth and phantom material used during the irradiation. Thus, the results suggest that fx,Q,med is a more reliable wide-ranging parameter for evaluating the degree of energy-dependence of the film rather than the relative-response method commonly considered.

Diet quality of adolescents with eating disorders.

Purpose To compare the nutritional intake of adolescents with eating disorders (EDs) to recommended Daily Values of macronutrients and micronutrients, using the Nutrition Data Systems for Research (NDSR); to determine if nutritional content varied among the different sub-types of EDs; and to use the Healthy Eating Index 2010 (HEI-2010) as a measurement of diet quality in this population. Methods Forty-six adolescents referred to an ED Program were recruited for inclusion in this study. A detailed 24-h dietary recall from each participant was obtained and a detailed nutritional analysis was generated, allowing for calculation of the HEI-2010. Descriptive statistics were calculated to determine baseline characteristics of the study population and to determine associations and differences between ED subtypes. Results Average daily caloric intake was below recommended values in the study population. Despite this, the distribution of macronutrients was within the ranges recommended for older children and adolescents by the Dietary Guidelines for Americans, 2010. Micronutrient content varied considerably. The study population had a mean HEI-2010 score of 60.1, falling within the "needs improvement" category. A majority of the participants had insufficient caloric intake for the HEI to be applicable. Conclusion Results suggest that adolescents with EDs have a surprisingly normal distribution of macronutrient intake. Although using a diet quality assessment tool such as the HEI-2010 has been helpful in analyzing overall diet quality in the general population, the restrictive caloric intake which characterizes the ED population prevents the utility of such a guide for most patients with EDs.

Thoracic endometriosis: first reported case in Puerto Rico and review of literature.

Endometriosis is defined as the presence of endometrial tissue in extra uterine sites. It affects 5-15% of females during their reproductive years. Thoracic endometriosis syndrome is characterized by the presence of functional endometrial tissue within the pleura, the lung parenchyma or the airway. The overall prevalence of this condition is unknown due to a lack of epidemiological studies, variety of symptoms, signs and locations. We present the first reported case of recurrent catamenial pneumothorax in Puerto Rico and a review of recent literature.