Coordinatively unsaturated ruthenium complexes as efficient alkyne-azide cycloaddition catalysts

The performance of 16-electron ruthenium complexes with the general formula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or OCH2CF3) was explored in azide−alkyne cycloaddition reactions that afford the 1,2,3- triazole products. The scope of the Cp*Ru(PiPr3)Cl precatalyst was investigated for terminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic studies were conducted and revealed a number of proposed intermediates. Cp*Ru- (PiPr3)(η2-HCCPh)Cl was observed and characterized by 1H, 13C, and 31P NMR at temperatures between 273 and 213 K. A rare example of N,N-κ2-phosphazide complex, Cp*Ru(κ2-iPr3PN3Bn)Cl, was fully characterized, and a single-crystal X-ray diffraction structure was obtained. DFT calculations describe a complete map of the catalytic reactivity with phenylacetylene and/or benzylazide.Publisher PDFPeer reviewe

MR Spectroscopic Imaging of Peripheral Zone in Prostate Cancer Using a 3T MRI Scanner: Endorectal versus External Phased Array Coils.

Magnetic resonance spectroscopic imaging (MRSI) detects alterations in major prostate metabolites, such as citrate (Cit), creatine (Cr), and choline (Ch). We evaluated the sensitivity and accuracy of three-dimensional MRSI of prostate using an endorectal compared to an external phased array "receive" coil on a 3T MRI scanner. Eighteen patients with prostate cancer (PCa) who underwent endorectal MR imaging and proton (1H) MRSI were included in this study. Immediately after the endorectal MRSI scan, the PCa patients were scanned with the external phased array coil. The endorectal coil-detected metabolite ratio [(Ch+Cr)/Cit] was significantly higher in cancer locations (1.667 ± 0.663) compared to non-cancer locations (0.978 ± 0.420) (P < 0.001). Similarly, for the external phased array, the ratio was significantly higher in cancer locations (1.070 ± 0.525) compared to non-cancer locations (0.521 ± 0.310) (P < 0.001). The sensitivity and accuracy of cancer detection were 81% and 78% using the endorectal 'receive' coil, and 69% and 75%, respectively using the external phased array 'receive' coil

Verbal Fluency Predicts Mortality in Alzheimer Disease

OBJECTIVES: To assess the predictive value of neuropsychologic profiles, at diagnosis, for mortality in incident Alzheimer disease (AD). BACKGROUND: Rate of AD progression varies significantly across individuals for reasons that are not well understood. Several studies have linked rapid decline with disproportionately impaired executive functioning, presumably reflecting greater impairment of frontal networks. To the extent that differential neuropsychologic profiles reflect various neuropathologic presentations of AD, such profiles may inform survival estimates early in the disease. METHODS: Five neuropsychologic indices were used to characterize performance in 161 individuals at diagnosis of AD during a 15-year, longitudinal, primarily community-based study. RESULTS: Fifty-two percent of participants reached the mortality end point with a median survival of 5.52 years (95% confidence interval, 4.41-6.63). Cox proportional hazards analyses indicated that older age at diagnosis was associated with higher risk of mortality (risk ratios, 1.08; 95% confidence interval, 1.04-1.12) whereas Hispanic ethnicity predicted lower mortality [0.22 (0.09-0.55)]. Controlling for these 2 demographic variables, higher verbal fluency scores at diagnosis predicted lower mortality [0.69 (0.49-0.96)]. CONCLUSIONS: Disproportionate impairment of both category and letter fluency at the earliest stages of AD predicts mortality. The prognostic value of these tests may derive from their general psychometric properties, or may reflect the measures' sensitivity to an early or critical level of compromise to frontal networks

Rate of Memory Decline in AD Is Related to Education and Occupation: Cognitive Reserve?

Objective: To determine whether the rate of decline in performance on a memory test is more rapid in AD patients with higher versus lower educational and occupational attainment. Background: Epidemiologic and imaging studies have suggested that, given comparable clinical severity of dementia, AD pathology is more advanced in patients with higher educational and occupational attainment. Because educational and occupational attainment should not influence the progression of AD pathology, and because severe AD pathology will eventually produce a mortality-causing condition, people with higher attainment might experience clinical AD for a shorter time and have a more rapid clinical progression. Methods: A total of 177 AD patients were tested yearly for up to four study visits with the Selective Reminding Test (a memory test). Analysis of prospective change in the total recall score was performed by applying generalized estimating equations to regression analyses with repeated measures. Results: At the initial visit, scores were comparable in the high- and low-education and the high- and low-occupation groups. Overall, memory scores declined by approximately 1 point yearly (p < 0.01). There was a more rapid decline in memory scores in patients with higher educational (p < 0.057) and higher occupational attainment (p < 0.02). The authors then stratified patients based on their initial memory scores. The more rapid decline in memory scores associated with higher educational and occupational attainment was noted only in the group with low initial scores (p < 0.05 for both). The full group and stratified group analyses were also repeated controlling for other potentially relevant variables including age, gender, race, ethnicity, and the presence of extrapyramidal signs, stroke, or at least one apolipoprotein E-ε4 allele. The results remained unchanged. Conclusions: Memory declined more rapidly in AD patients with higher educational and occupational attainment. This adds support to the idea that the discontinuity between the degree of AD pathology and the observed clinical severity of AD is mediated through some form of reserve

Participation in Clinical Trials and Long-Term Outcomes in Alzheimer's Disease

The objective of this study was to determine whether participation in clinical trials affects long-term outcomes in Alzheimer's disease (AD). Participation in clinical trials for persons with dementia is often justified on the grounds that patients benefit from the medical oversight typical of trials, even when experimental agents do not demonstrate short-term benefits. This claim has not been rigorously assessed. Of 215 community-resident subjects enrolled in a prospective study of outcomes in AD, 101 participated in randomized clinical trials (RCTs) during the first 2 years of follow-up. These subjects were compared with subjects who met eligibility requirements for RCTs but did not participate (N = 57) and with subjects who were ineligible (N = 57), over a total of 3.5 years of follow-up. Survival analyses assessed risk of death, nursing home placement, and incident functional deficit end points, adjusting for baseline differences. Subjects who participated in RCTs were younger and more highly educated. Mortality, risk of hospitalization, number of medical examinations conducted by study physicians, and onset of severe functional deficit did not differ between the groups, but risk of nursing home admission was significantly lower among RCT participants compared with eligible nonparticipants and ineligible subjects (16.8% versus 36.8% and 31.6%, respectively [p = 0.01]). The difference in risk of nursing home placement may represent a long-term, drug-related benefit to patients, a selection effect (caregivers of patients who participate in RCTs differ from caregivers of patients who do not), or a positive effect on caregivers (greater contact with a medical service may be associated with better care-giving outcomes). Further research is required to assess these effects

Perceptions of Cohesion by Youth Sport Participants

Cohesion is an important small group variable within sport. However, the conceptualization and examination of cohesion have predominately been oriented toward adult populations. The purpose of the current study was to garner an understanding of what cohesion means to youth sport participants. Fifty-six team sport athletes (M age = 15.63 ± 1.01 years) from two secondary schools took part in focus groups designed to understand participants’ perceptions of (a) the definition of cohesion and indicators of cohesive and noncohesive groups and (b) methods used to attempt to develop cohesion in their groups. Overall, the responses to part (a) yielded 10 categories reflecting a group’s task cohesion and 7 categories reflecting a group’s social cohesion. Finally, participants highlighted eight general methods through which their groups developed cohesion. Results are discussed in relation to a current conceptualization of cohesion and affiliation considerations within a youth sport environment

Hepatic encephalopathy: a neurochemical, neuroanatomical, and neuropsychological study.

Hepatic encephalopathy (HE) is normally diagnosed by neuropsychological (NP) tests, which are not very specific and do not reveal the underlying pathology. Magnetic resonance imaging (MRI) and spectroscopy (MRS) of the brain offer alternative and possibly more specific markers for HE. These methods were applied in conjunction with NP testing in order to determine their usefulness in the identification of HE and to understand the pathogenesis of HE more clearly. MR imaging and spectroscopy examinations, in addition to a battery of 15 NP tests, were administered to investigate 31 patients awaiting liver transplantation and 23 healthy controls. MR image intensities from the globus pallidus region were calculated and normalized to those of the thalamus. Absolute concentrations and ratios with respect to creatine (Cr) of several metabolites were computed from MR spectra. The MR data were correlated with the results of NP tests. The patients showed impairment in NP tests of attention and visuospatial and verbal fluency. In T1-weighted MRI, the relative intensity of the globus pallidus with respect to that of the thalamus region was significantly elevated in patients and correlated(negatively) with three NP tests (Hooper, FAS, and Trails B). The absolute concentrations of myo-inositol (mI) and choline (Ch) were significantly reduced in three brain regions. In addition, the absolute concentrations of glutamine (Gln) and combined glutamate and glutamine (Glx) were increased in all three locations, with Gln increase being significant in all areas while that of Glx only in the occipital white matter. In summary, this study partially confirms a hypothesized mechanism of HE pathogenesis, an increased synthesis of glutamine by brain glutamate in astrocytes due to excessive blood ammonia, followed by a compensatory loss of myo-inositol to maintain astrocyte volume homeostasis. It also indicates that the hyperintensity observed in globus pallidus could be used as complementary to the NP test scores in evaluating the mental health of HE patients

Electron tomography of (In,Ga)N insertions in GaN nanocolumns grown on semi-polar (11(2)over-bar2) GaN templates

We present results of scanning transmission electron tomography on GaN/(In,Ga)N/GaN nanocolumns (NCs) that grew uniformly inclined towards the patterned, semi-polar GaN( 112̄ 2 ) substrate surface by molecular beam epitaxy. For the practical realization of the tomographic experiment, the nanocolumn axis has been aligned parallel to the rotation axis of the electron microscope goniometer. The tomographic reconstruction allows for the determination of the three-dimensional indium distribution inside the nanocolumns. This distribution is strongly interrelated with the nanocolumn morphology and faceting. The (In,Ga)N layer thickness and the indium concentration differ between crystallographically equivalent and non-equivalent facets. The largest thickness and the highest indium concentration are found at the nanocolumn apex parallel to the basal planes

Trajectories of Offending from Childhood to Early Adulthood in Girls With and Without Mental Health System Involvement

Criminology literature is overwhelmingly based in studies of males, though studies of gender differences or of females are rapidly accumulating. Rates of psychiatric disorder are typically higher in females involved with justice systems compared to males. However, the juvenile or criminal justice involvement of girls in mental health systems, or with serious mental health conditions is greatly understudied. Identifying their arrest risk onset, peak, and offset provides practitioners information about when to intervene and with whom. The goal of the present study is to describe within-individual longitudinal arrest patterns from ages 8-24 in this population, and determine whether their arrest patterns differ from general offender females in ways that have practice implications. Methods: Using statewide administrative data from the Massachusetts Department of Mental Health (DMH) and Massachusetts’ juvenile and criminal courts, a database was constructed that contained juvenile and criminal arrest histories to age 25 for females born 1976-79. DMH females were adolescent service users (n=738), Non-DMH females had no DMH database records (n=34,436). Massachusetts Census 2000 provided the size of the general female population. Developmental trajectory modeling was used to group individuals’ patterns of offending over time (trajectories) into “clusters” of those whose trajectories are similar, and describe trajectories. Trajectory comparison methods minimized the greater Non-DMH cohort size. Results: DMH females were far more likely to be arrested by age 25 than Non-DMH females (46% vs. 22%) and to be arrested at multiple ages (28% vs. 7%). Analyses revealed eight justice system trajectories among those with multiple ages of arrest. Trajectories varied on level of involvement and timing of onset/offset/peaks. Non-DMH females comprised at least 93% of each trajectory cluster, though several clusters showed significant over- or under-representation of DMH females. Conclusions: Concern about justice system involvement of female youths in intensive MH services is justified. Among girls with multiple ages with arrest, differences in criminal careers between the mental health and non mental health system users was minimal. Implications of trajectory findings for timing and type of intervention will be presented

Network robustness and fragility: Percolation on random graphs

Recent work on the internet, social networks, and the power grid has addressed the resilience of these networks to either random or targeted deletion of network nodes. Such deletions include, for example, the failure of internet routers or power transmission lines. Percolation models on random graphs provide a simple representation of this process, but have typically been limited to graphs with Poisson degree distribution at their vertices. Such graphs are quite unlike real world networks, which often possess power-law or other highly skewed degree distributions. In this paper we study percolation on graphs with completely general degree distribution, giving exact solutions for a variety of cases, including site percolation, bond percolation, and models in which occupation probabilities depend on vertex degree. We discuss the application of our theory to the understanding of network resilience.Comment: 4 pages, 2 figure