Solid-state synthesis and characterization of σ-Alkane complexes, [Rh(L2)(η2,η2-C7H12)][BArF4] (L2 = bidentate chelating phosphine)

The use of solid/gas and single-crystal to single-crystal synthetic routes is reported for the synthesis and characterization of a number of σ-alkane complexes: [Rh(R2P(CH2)nPR2)(η2,η2-C7H12)][BArF4]; R = Cy, n = 2; R = iPr, n = 2,3; Ar = 3,5-C6H3(CF3)2. These norbornane adducts are formed by simple hydrogenation of the corresponding norbornadiene precursor in the solid state. For R = Cy (n = 2), the resulting complex is remarkably stable (months at 298 K), allowing for full characterization using single-crystal X-ray diffraction. The solid-state structure shows no disorder, and the structural metrics can be accurately determined, while the 1H chemical shifts of the Rh···H–C motif can be determined using solid-state NMR spectroscopy. DFT calculations show that the bonding between the metal fragment and the alkane can be best characterized as a three-center, two-electron interaction, of which σCH → Rh donation is the major component. The other alkane complexes exhibit solid-state 31P NMR data consistent with their formation, but they are now much less persistent at 298 K and ultimately give the corresponding zwitterions in which [BArF4]− coordinates and NBA is lost. The solid-state structures, as determined by X-ray crystallography, for all these [BArF4]− adducts are reported. DFT calculations suggest that the molecular zwitterions within these structures are all significantly more stable than their corresponding σ-alkane cations, suggesting that the solid-state motif has a strong influence on their observed relative stabilities

Are Menstrual and Nonmenstrual Migraine Attacks Different?

Migraine is the second most common headache condition next to tension-type headache. Up to one fourth of all women have migraine, and 20% of them experience migraine without aura attack in at least two thirds of their menstrual cycles. The current literature is analyzed in response to the question of whether menstrual and nonmenstrual migraine attacks are different. The different studies provide conflicting results, so it is not possible to answer the question firmly. Future studies should be based on the general population. Collection of both prospective and retrospective data is warranted, and headache diagnosis base on interviews by physicians with interest in headache are more precise than lay interviews or questionnaires

Genetics of Menstrual Migraine: The Epidemiological Evidence

Approximately one of every three to five women with migraine without aura experience migraine attacks in relation to menstruation. The International Classification of Headache Disorders, 2nd Edition provides appendix diagnoses for pure and menstrually related migraine without aura that need further validation. Probands with menstrual migraine might have more affected relatives than probands with nonmenstrual migraine. However, precise epidemiological, family, and twin data still are lacking

An ongoing case-control study to evaluate the NHS Bowel Cancer Screening Programme

© 2014 Massat et al.; licensee BioMed Central. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly credited. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated

Human blood PIG-A mutation and micronucleated reticulocyte flow cytometric assays: Method optimization and evaluation of intra- and inter-subject variation.

We previously described flow cytometry-based methods for scoring the incidence of micronucleated reticulocytes (MN-RET) and PIG-A mutant phenotype reticulocytes (MUT RET) in rodent and human blood samples. The current report describes important methodological improvements for human blood analyses, including immunomagnetic enrichment of CD71-positive reticulocytes prior to MN-RET scoring, and procedures for storing frozen blood for later PIG-A analysis. Technical replicate variability in MN-RET and MUT RET frequencies based on blood specimens from 14 subjects, intra-subject variability based on serial blood draws from 6 subjects, and inter-subject variation based on up to 344 subjects age 0 to 73 years were quantified. Inter-subject variation explained most of the variability observed for both endpoints (≥ 77%), with much lower intra-subject and technical replicate variability. The relatively large degree of inter-subject variation is apparent from mean and standard deviation values for MN-RET (0.15 ± 0.10%) and MUT RET (4.7 ± 5.0 per million, after omission of two extreme outliers). The influences of age and sex on inter-subject variation were investigated, and neither factor affected MN-RET whereas both influenced MUT RET frequency. The lowest MUT RET values were observed for subjects < 11 years old, and males had moderately higher frequencies than females. These results indicate that MN-RET and MUT RET are automation-compatible biomarkers of genotoxicity that bridge species of toxicological interest to include human populations. These data will be useful for appropriately designing future human studies that include these biomarkers of genotoxicity, and highlight the need for additional work aimed at identifying the sources of inter-individual variability reported herein

Patient and health service delay in the diagnosis of pulmonary tuberculosis in Ethiopia

BACKGROUND: Delay in the diagnosis of tuberculosis may worsen the disease, increase the risk of death and enhance tuberculosis transmission in the community. This study aims to determine the length of delay between the onset of symptoms and patients first visit to health care (patient delay), and the length of delay between health care visit and the diagnosis of tuberculosis (health service delay). METHODS: A cross sectional survey that included all the public health centres was conducted in Addis Ababa from August 1 to December 31 1998. Patients were interviewed on the same day of diagnosis using structured questionnaire. RESULTS: 700 pulmonary TB patients were studied. The median patient delay was 60 days and mean 78.2 days. There was no significant difference in socio-demographic factors in those who delayed and came earlier among smear positives. However, there was a significant difference in distance from home to health institute and knowledge about TB treatment among the smear negatives. The health service delay was low (median 6 days; mean 9.5 days) delay was significantly lower in smear positives compared to smear negatives. Longer health service delay (delay more than 15 days) was associated with far distance. CONCLUSIONS: The time before diagnosis in TB patients was long and appears to be associated with patient inadequate knowledge of TB treatment and distance to the health centre. Further decentralization of TB services, the use of some components of active case finding, and raising public awareness of the disease to increase service utilization are recommended

Modalidades de pago de los servicios del Reino de Valencia a la Corona (1585-1604) Pagos directos, pagos delegados

Se analiza las relaciones entre la Hacienda Real y la Hacienda de la Diputación del Reino deValencia en la satisfacción de los pagos de los gastos diversos contraídos por parte de la Corona. Una parte importante consistió en operaciones de endoso, por las cuáles el rey trasladaba el pago de una deuda suya a su deudora, la Generalidad del Reino de Valencia, con criterios de eficiencia, para el pronto pago de los acreedores.The relations between the Royal Treasury and the Treasury the Generalitat of the Kingdom of Valencia are analyzed in the satisfaction of the payments of the various expenses incurred by the Cromw. An important part consisted of endorsement operations, for which the king transferred the payment of a debt to his debtor, the Generalitat of the Kingdom of Valencia, with efficiency criteria, for the prompt payment of creditors

New discoveries in the transmission biology of sleeping sickness parasites: applying the basics

The sleeping sickness parasite, Trypanosoma brucei, must differentiate in response to the changing environments that it encounters during its complex life cycle. One developmental form, the bloodstream stumpy stage, plays an important role in infection dynamics and transmission of the parasite. Recent advances have shed light on the molecular mechanisms by which these stumpy forms differentiate as they are transmitted from the mammalian host to the insect vector of sleeping sickness, tsetse flies. These molecular advances now provide improved experimental tools for the study of stumpy formation and function within the mammalian bloodstream. They also offer new routes to therapy via high-throughput screens for agents that accelerate parasite development. Here, we shall discuss the recent advances that have been made and the prospects for future research now available