Disparities in survival among women with invasive cervical cancer

Abstract

N‐Chlorination reactions of alkyl‐, cycloalkyl‐, heterocyclic, and aromatic amines by HOCl have been investigated in the gas and aqueous phase. Density functional (B3LYP), double hybrid (B2PLYPD), and composite theoretical model (G3B3) have been used to assess steric, electronic, and solvent effects on the reactivity of different families of amines toward HOCl. When solvent effects are included by using CPCM/UAHF model, all computational methods predict the same order of reactivity within each group of amines. In agreement with experimental data, heterocyclic amines have the highest reactivity, with energy barriers calculated between 160 and 225 kJ mol−1 (B2PLYPD/AUG‐cc‐pVTZ//B3LYP/6‐31G(d) level). The substituted anilines are the least reactive species, with energy barriers calculated as high as 300 kJ mol−1. Two different reaction mechanisms of N‐chlorination have been considered in the gas phase: the one which includes the transition state TSa with cyclic arrangement of four atoms (N, Cl, O, and H) involved in an intramolecular rearrangement, and the second in which the hydrogen‐bridged structure TSb is characterized with the linear NClO moiety. The former is energetically more feasible (ca. 120 kJ mol−1) for alkyl‐, cycloalkyl‐, and heterocyclic amines, whereas the latter is operative in the case of aromatic amines. If two water molecules are explicitly included in the calculations, the rate‐determining transition state TSw has been located for N‐chlorination of all amines under study. It is characterized by eight‐membered ring geometry in which water molecules assist the simultaneous transfer of the three hydrogen atoms coupled with the NCl bond formation. To reproduce the experimentally observed trends in reactivity of amines, the inclusion of bulk and specific solvent effects is mandatory. Steric effects have been found to govern the reactivity of alkylamines, that is, more bulkier amines react slower with HOCl. It has been found that electronic structure parameters (HOMO–LUMO gap, natural bond orbital occupancy, and NPA charge on N atom) can be successfully used as descriptors for the reactivity of heterocyclic and aromatic amines. These results indicate the predictive power of our computational approach, which can be applied to calculate nucleophilic reactivities of more complex structures of environmentally or biologically relevant amines. © 2012 Wiley Periodicals, Inc.

Breast cancer care in the Canada and the United States: Ecological comparisons of extremely impoverished and affluent urban neighborhoods

“…Moreover, household incomes typically differed by less than $3000 in such, respective, extremely poor urban neighborhoods of America and Canada. Perhaps not surprisingly, very extreme affluence was a bit more prevalent in the California sample, but on both sides of the border, this study's definition seemed to converge quite closely with contemporary definitions of extreme affluence (e.g., less than 5% poor or typical incomes of $75,000 to $100,000 or more; Barrett et al, 2008;Brookfield et al, 2009;Henry et al, 2009;Lee and Marlay, 2007). 2.1.2.…”

The Need for Societal Investment to Improve Cervical Cancer Outcomes in Nigeria: A commentary

“…Leaving individuals to bear the cost for such lifesaving preventive and therapeutic services, implicitly limits the utilization of cervical cancer services which could contribute to the late presentation in advanced stages with dismal survival probability. Even in developed societies were treatment facilities are available, cost related factors, health insurance, low levels of health literacy, lack of social support and transportation barriers have limiting effects on patients receiving care in a timely fashion 4,[13][14][15][16][17] . It is therefore imperative to look closely at the options for improving cervical cancer health outcomes in Nigeria and similar settings in Africa in the perspective of societal rather than individual investments.…”

Iatrogenic Menopause After Treatment for Cervical Cancer

“…Failure to engage with a structured screening programme has been indentified as one of the major risk factors for developing a malignancy and this raises the concern that this population of women may continue this behavioural pattern after their diagnosis, being less likely to comply with treatment for their premature menopause. The reasons for such behaviour will of course be multi-factorial however it is known that the majority of women who develop a cervical cancer belong to the most deprived socioeconomic quintile [31], which raises the possibility that a lack of health education is a significant contributing factor. Social isolation and factors that result in a lack of engagement with health care, either due to alcohol abuse or a language barrier, have been shown to be associated with emergency routes of presentation for cervical cancer and advanced disease at diagnosis [32].…”