Ring closure reactions of bicyclic prolinol and prolin ester enantiomers

Starting from the of bicyclic proline ester, ethyl exo-2-azabicyclo[2.2.1]heptane-3-carboxylate (+)-5 several hydantoines and thiohydantoines were prepared by acidic ring closure of the corresponding urea or thiourea derivatives. Enantiomer (-)-5 was reduced to 2-azanorbornylmethanol 12, which was transformed to 5,8-methanooxazolo- and thiazolo[3,4-a] pyridine derivatives. The structures, stereochemistry and relative configurations of the synthesized compounds were proved by NMR

Topological properties of inequality and deprivation in an educational system: Unveiling the key-drivers through complex network analysis

This research conceives an educational system as a complex network to incorporate a rich framework for analyzing topological and statistical proper-ties of inequality and learning deprivation at different levels, as well as to simu-late the structure, stability and fragility of the educational system. The model provides a natural way to represent educational phenomena, allowing to test public policies by computation before being implemented, bringing the oppor-tunity of calibrating control parameters for assessing order parameters over time in multiple territorial scales. This approach provides a set of unique advantages over classical analysis tools because it allows the use of large-scale assessments and other evidences for combining the richness of qualitative analysis with quantitative inferences for measuring inequality gaps. An additional advantage, as shown in our results using real data from a Latin American country, is to provide a solution to con-cerns about the limitations of case studies or isolated statistical approaches.info:eu-repo/semantics/acceptedVersio

Imidotungsten(VI) complexes with chelating amino and imino phenolates

The reaction of WOCl(4) with 2,4-di-tert-butyl-6-((isopropylamino)methyl)phenol followed by the reaction with phenyl isocyanate leads to the formation of imidotungsten(VI) complex [W(NPh)Cl(3)(OC(6)H(3)(CH(2)NH-i-Pr)-2-t-Bu(2)-4,6)] 4 with a chelating aminophenolate ligand. When the same procedure was applied using aminophenols with bulkier substituents in the amino group, the final product was an unexpected Schiff-base complex [W(NPh)Cl(3)(OC(6)H(3)(CH = NPh)-2-t-Bu(2)-4,6)] 5, where the ligand is derived from 2,4-di-tert-butyl-6-((phenylimino)methyl)phenol. Complex 5 is also formed in the thermal degradation of 4. On the whole, 5 appears to be formed by a disproportionation of intermediate compounds, which are analogous to complex 4. The solid-state structures of 4 and 5 have been determined by X-ray crystallography whereas the solution structures were studied by (1)H and (13)C NMR

Illness and injury of travellers abroad : Finnish nationwide data from 2010 to 2012, with incidences in various regions of the world

The number of international tourist arrivals reached 1,000 million in 2012. Assessment of travellers' health problems has relied on proportionate morbidity data. Given the lack of data on number of visitors to each region, incidences have been impossible to calculate. This study, largest yet reporting travellers' health problems, is the first to present incidence of illness and injury. Data on Finnish travellers with health problems abroad during 2010 to 2012 were retrieved from the database of an assistance organisation, SOS International, covering 95% of those requiring aid abroad. The numbers were compared with those of Finnish travellers in the database of the Official Statistics of Finland. The SOS International database included 50,710 cases: infections constituted the most common health problem (60%), followed by injuries (14%), diseases of skin (5%), musculoskeletal system and connective tissue (5%), digestive tract (3%), and vascular system (2%). Gastroenteritis (23%) and respiratory infections (21%) proved the most frequent diagnoses. Overall incidence of illness or injury was high in Africa (97.9/100,000 travel days; 95% Bayesian credible interval (BCI): 53.1-145.5), southern Europe plus the eastern Mediterranean (92.3; 95% BCI: 75.4-110.1) and Asia (65.0; 95% BCI: 41.5-87.9). The data show significant differences between geographical regions, indicating the main risks and thus providing destination-specific tools for travellers' healthcare.Peer reviewe

Functional disability and death wishes in older Europeans: results from the EURODEP concerted action

Functional disability was independently associated with death wishes in older adults. Results can help inform clinicians who care for older persons with functional impairment.</p

Religion as a Cross-cultural Determinant of Depression in Elderly Europeans: Results from the EURODEP Collaboration

Background. The protective effects of religion against late life depression may depend on the broader sociocultural environment. This paper examines whether the prevailing religious climate is related to cross-cultural differences of depression in elderly Europeans. Methods. Two approaches were employed, using data from the EURODEP collaboration. First, associations were studied between church-attendance, religious denomination and depression at the syndrome level for six EURODEP study centres (five countries, N = 8398). Secondly, ecological associations were computed by multi-level analysis between national estimates of religious climate, derived from the European Value Survey and depressive symptoms, for the pooled dataset of 13 EURODEP study centres (11 countries, N = 17739). Results. In the first study, depression rates were lower among regular church-attenders, most prominently among Roman Catholics. In the second study, fewer depressive symptoms were found among the female elderly in countries, generally Roman Catholic, with high rates of regular church-attendance. Higher levels of depressive symptoms were found among the male elderly in Protestant countries. Conclusions. Religious practice is associated with less depression in elderly Europeans, both on the individual and the national level. Religious practice, especially when it is embedded within a traditional value-orientation, may facilitate coping with adversity in later life

Influence of Surface Chemistry on Ibuprofen Adsorption and Confinement in Mesoporous Silicon Microparticles

The effect of adsorption and confinement on ibuprofen was studied by immersion loading the molecules into porous silicon (PSi) microparticles. The PSi micro particles were modified into thermally oxidized PSi (TOPSi) and thermally hydrocarbonized PSi (THCPSi) to evaluate the effects of the loading solvent and the surface chemistry on the obtainable drug payloads. The payloads, location, and the molecular state of the adsorbed drug were evaluated using thermal analysis. The results showed that after the adsorption of similar to 800 mg/cm(3) (w(drug)/v(pores)) of drug into the mesopores, depending on the solvent used in the immersion, the drug began to rapidly recrystallize on the external surface of the particles. Moderate concentrations, however, enabled payloads of 800-850 mg/cm(3) without excessive surface crystallization, and thus, there was no need for rinsing the samples to remove the externally crystallized portion. The results showed that the confined ibuprofen forms nanocrystals inside of the mesopores after approximately 200 mg/cm(3) payloads were obtained, accounting for half of the adsorbed drug amount. The presence of both crystalline and noncrystalline phases was further characterized using variable temperature solid-state nuclear magnetic resonance (NMR) measurements. The interactions between the drug molecules and the pore walls of TOPSi and THCPSi were observed using Fourier transform infrared and H-1 NMR spectroscopies, and the hydrogen bonding between the silanol groups of TOPSi and the adsorbed ibuprofen was confirmed, but having only limited effect on the overall state of the confined drug. In vitro drug permeation studies in Caco-2 and Caco-2/HT29 cocultures showed that the adsorption onto hydrophilic or hydrophobic PSi microparticles had no significant effects on the ibuprofen permeation, whether the drug was partially nanocrystalline or completely in a liquidlike state

Carbonic anhydrase XII is a marker of good prognosis in invasive breast carcinoma

Hypoxia and pH influence gene expression in tumours, and it is becoming increasingly clear that the pattern of genes expressed by a tumour determines its growth and survival characteristics. Hypoxia-inducible factor-1 (HIF-1) is a key mediator of the cellular response to hypoxia and high HIF-1 expression has been identified as a poor prognostic factor in tumours. Recently, we identified the tumour-associated carbonic anhydrases (CA), CA9 and CA12 as hypoxia-inducible in tumour cell lines. Furthermore, we identified CA IX to be a poor prognostic factor in breast cancer. The aim of this study was to assess the prognostic significance of CA XII. CA XII expression was studied by immunohistochemistry in a series of 103 cases of invasive breast cancer and any association with recognised prognostic factors or relation with the outcome was examined. CA XII expression was present in 77 out of 103 (75%) cases and was associated with lower grade (P=0.001), positive estrogen receptor status (P&lt;0.001), and negative epidermal growth factor receptor status (P&lt;0.001). Furthermore, although CA XII expression was associated with an absence of necrosis (P&lt;0.001), expression of CA XII in some high-grade tumours was induced in regions directly adjacent to morphological necrosis. Additionally, using univariate analysis, CA XII positive tumours were associated with a lower relapse rate (P=0.04) and a better overall survival (P=0.01). In conclusion, CA XII expression is influenced both by factors related to differentiation and hypoxia in breast cancer in vivo and CA XII expression is associated with a better prognosis in an unselected series of invasive breast carcinoma patients

Expression of a novel carbonic anhydrase, CA XIII, in normal and neoplastic colorectal mucosa

BACKGROUND: Carbonic anhydrase (CA) isozymes may have an important role in cancer development. Some isozymes control pH homeostasis in tumors that appears to modulate the behaviour of cancer cells. CA XIII is the newest member of the CA gene family. It is a cytosolic isozyme which is expressed in a number of normal tissues. The present study was designed to investigate CA XIII expression in prospectively collected colorectal tumor samples. METHODS: Both neoplastic and normal tissue specimens were obtained from the same patients. The analyses were performed using CA XIII-specific antibodies and an immunohistochemical staining method. For comparison, the tissue sections were immunostained for other cytosolic isozymes, CA I and II. RESULTS: The results indicated that the expression of CA XIII is down-regulated in tumor cells compared to the normal tissue. The lowest signal was detected in carcinoma samples. This pattern of expression was quite parallel for CA I and II. CONCLUSION: The down-regulation of cytosolic CA I, II and XIII in colorectal cancer may result from reduced levels of a common transcription factor or loss of closely linked CA1, CA2 and CA13 alleles on chromosome 8. Their possible role as tumor suppressors should be further evaluated