Intermolecular Proton-Coupled Electron Transfer Reactivity from a Persistent Charge-Transfer State for Reductive Photoelectrocatalysis.

Interest in applying proton-coupled electron transfer (PCET) reagents in reductive electro- and photocatalysis requires strategies that mitigate the competing hydrogen evolution reaction. Photoexcitation of a PCET donor to a charge-separated state (CSS) can produce a powerful H-atom donor capable of being electrochemically recycled at a comparatively anodic potential corresponding to its ground state. However, the challenge is designing a mediator with a sufficiently long-lived excited state for bimolecular reactivity. Here, we describe a powerful ferrocene-derived photoelectrochemical PCET mediator exhibiting an unusually long-lived CSS (τ ∼ 0.9 µs). In addition to detailed photophysical studies, proof-of-concept stoichiometric and catalytic proton-coupled reductive transformations are presented, which illustrate the promise of this approach.

Low-Valent Metal Ions as MOF Pillars: A New Route Toward Stable and Multifunctional MOFs.

PCM-102 is a new organophosphine metal-organic framework (MOF) featuring diphosphine pockets that consist of pairs of offset trans-oriented P(III) donors. Postsynthetic addition of M(I) salts (M = Cu, Ag, Au) to PCM-102 induces single-crystal to single-crystal transformations and the formation of trans-[P2M]+ solid-state complexes (where P = framework-based triarylphosphines). While the unmetalated PCM-102 has low porosity, the addition of secondary Lewis acids to install rigid P-M-P pillars is shown to dramatically increase both stability and selective gas uptake properties, with N2 Brunauer-Emmett-Teller surface areas >1500 m2 g-1. The Ag(I) analogue can also be obtained via a simple, one-pot peri-synthetic route and is an ideal sacrificial precursor for materials with mixed bimetallic MA/MB pillars via postsynthetic, solvent-assisted metal exchange. Notably, the M-PCM-102 family of MOFs contain periodic trans-[P2M]+ sites that are free of counter anions, unlike traditional analogous molecular complexes, since the precursor PCM-102 MOF is monoanionic, enabling access to charge-neutral metal-pillared materials. Four M-PCM-102 materials were evaluated for the separation of C2 hydrocarbons. The separation performance was found to be tunable based on the metal(s) incorporated, and density functional theory was employed to elucidate the nature of the unusual observed sorption preference, C2H2 > C2H6 > C2H4.

Acute and Chronic Altitude-Induced Cognitive Dysfunction in Children and Adolescents.

OBJECTIVE: To assess whether exposure to high altitude induces cognitive dysfunction in young healthy European children and adolescents during acute, short-term exposure to an altitude of 3450 m and in an age-matched European population permanently living at this altitude. STUDY DESIGN: We tested executive function (inhibition, shifting, and working memory), memory (verbal, short-term visuospatial, and verbal episodic memory), and speed processing ability in: (1) 48 healthy nonacclimatized European children and adolescents, 24 hours after arrival at high altitude and 3 months after return to low altitude; (2) 21 matched European subjects permanently living at high altitude; and (3) a matched control group tested twice at low altitude. RESULTS: Short-term hypoxia significantly impaired all but 2 (visuospatial memory and processing speed) of the neuropsychological abilities that were tested. These impairments were even more severe in the children permanently living at high altitude. Three months after return to low altitude, the neuropsychological performances significantly improved and were comparable with those observed in the control group tested only at low altitude. CONCLUSIONS: Acute short-term exposure to an altitude at which major tourist destinations are located induces marked executive and memory deficits in healthy children. These deficits are equally marked or more severe in children permanently living at high altitude and are expected to impair their learning abilities.

Elevation of Pulmonary Artery Pressure in Newborns from High-Altitude Pregnancies Complicated by Preeclampsia.

We hypothesized that fetal exposure to the oxidative stress induced by the combined challenge of preeclampsia (PE) and high altitude would induce a significant impairment in the development of pulmonary circulation. We conducted a prospective study in La Paz (Bolivia, mean altitude 3625 m) in which newborns from singleton pregnancies with and without PE were compared (PE group n = 69, control n = 70). We conducted an echocardiographic study in these infants at the median age of two days. The percentage of cesarean deliveries and small for gestational age (SGA) infants was significantly higher in the PE group. Heart rate, respiratory rate, and oxygen saturation did not vary significantly between groups. Estimated pulmonary arterial pressure and pulmonary vascular resistance were 30% higher in newborns exposed to PE and high altitude compared with those exposed only to high altitude. We also detected signs of right ventricular hypertrophy in infants subjected to both exposures. In conclusion, this study provides evidence that the combination of PE and pregnancy at high altitude induces subclinical alterations in the pulmonary circulation of the newborn. Follow-up of this cohort may provide us with valuable information on the potential increased susceptibility to developing pulmonary hypertension or other pulmonary and cardiovascular disorders.

Hierarchical nanosheets built from superatomic clusters: properties, exfoliation and single-crystal-to-single-crystal intercalation.

Tuning the properties of atomic crystals in the two-dimensional (2D) limit is synthetically challenging, but critical to unlock their potential in fundamental research and nanotechnology alike. 2D crystals assembled using superatomic blocks could provide a route to encrypt desirable functionality, yet strategies to link the inorganic blocks together in predetermined dimensionality or symmetry are scarce. Here, we describe the synthesis of anisotropic van der Waals crystalline frameworks using the designer superatomic nanocluster Co3(py)3Co6Se8L6 (py = pyridine, L = Ph2PN(Tol)), and ditopic linkers. Post-synthetically, the 3D crystals can be mechanically exfoliated into ultrathin flakes (8 to 60 nm), or intercalated with the redox-active guest tetracyanoethylene in a single-crystal-to-single-crystal transformation. Extensive characterization, including by single crystal X-ray diffraction, reveals how intrinsic features of the nanocluster, such as its structure, chirality, redox-activity and magnetic profile, predetermine key properties of the emerging 2D structures. Within the nanosheets, the strict and unusual stereoselectivity of the nanocluster's Co edges for the low symmetry (α,α,ß) isomer gives rise to in-plane structural anisotropy, while the helically chiral nanoclusters self-organize into alternating Δ- and Λ-homochiral rows. The nanocluster's high-spin Co edges, and its rich redox profile make the nanosheets both magnetically and electrochemically active, as revealed by solid state magnetic and cyclic voltammetry studies. The length and flexibility of the ditopic linker was varied, and found to have a secondary effect on the structure and stacking of the nanosheets within the 3D crystals. With these results we introduce a deterministic and versatile synthetic entry to programmable functionality and symmetry in 2D superatomic crystals.

Husbands' perceptions of wives' adjustment to breast cancer: the impact on wives' mood.

Married women's adjustment to breast cancer is positively influenced by their husbands' emotional support and by both spouses' active coping strategies. However, little is known about how women's adjustment is related to their husbands' perceptions of their psychosocial impairment. The current study examined the relationships among wives' coping strategies, the extent of congruence between wives' and husbands' perceptions of wives' adjustment, and wives' mood disturbance in 45 women with Stage I or II breast cancer and their husbands. Mediational analyses demonstrated that discrepancies between husbands' perceptions of wives' adjustment and wives' perceptions of their own adjustment mediated the relationship between wives' use of avoidant coping strategies and wives' mood disturbance. The findings suggest that husbands' over- or under-estimation of wives' adjustment may have a negative impact on wives' mood. Implications for future research are discussed.

Change in "resolved plans" and "suicidal ideation" factors of suicidality after participation in an intensive outpatient treatment program.

BACKGROUND: This study aims to investigate factors related to suicide in a unique clinical population with more chronic psychopathology than many outpatient samples. METHOD: One hundred and five adult outpatients were included in the current study. We predicted that higher scores on the resolved plans and preparation (RPP) factor of the Beck Suicide Scale [Beck, A.T., Kovacs, M., Weissman, M., (1979). Assessment of suicidal intention: The scale for suicidal ideation. Journal of Consulting and Clinical Psychology 47, 343-352] would predict multiple attempter status even after accounting for co-morbid diagnoses and suicidal ideation (SI) factor scores. Additionally, we predicted that the scores on the RPP factor would decrease less over time than scores on the SI factor. RESULTS AND CONCLUSIONS: Results were consistent with both hypotheses, suggesting that RPP factor scores were uniquely predictive of status as a multiple attempter and were more stable over time. LIMITATIONS: Mental health diagnoses were rendered without the use of a structured interview and therefore no reliability data were collected.

Borderline personality disorder: a comparison between children and adults.

Recently, more empirical studies have been devoted to the investigation of borderline personality disorder (BPD) in children and adolescents. Against this background, the purpose of the current review is to compare research findings on diagnostic-related phenomena in child and adolescent samples with those in adult samples to establish the utility of the BPD construct in childhood and adolescence. A search of relevant publications reported in Pubmed and PsycInfo from 1940 (the first clinical descriptions of BPD in childhood) to 2006 was carried out. A total of 58 studies were included. The review of the adult literature was not exhaustive but relied on excellent existing and comprehensive reviews of the adult literature carried out in the past 5 years. Although significant differences seem to exist between juveniles and adults in diagnostic-related phenomena associated with BPD, these can be explained by the principle of heterotypic continuity in development. Moreover, enough overlap between juvenile and adult BPD has been observed to warrant further empirical investigation into the construct of juvenile BPD. Specific areas for future research in juvenile BPD suggested by this review include studies of comorbidity, measure development, and the use of neurobiological measures such as functional neuroimaging.

Sleep-Disordered Breathing and Vascular Function in Patients With Chronic Mountain Sickness and Healthy High-Altitude Dwellers.

BACKGROUND: Chronic mountain sickness (CMS) is often associated with vascular dysfunction, but the underlying mechanism is unknown. Sleep-disordered breathing (SDB) frequently occurs at high altitude. At low altitude, SDB causes vascular dysfunction. Moreover, in SDB, transient elevations of right-sided cardiac pressure may cause right-to-left shunting in the presence of a patent foramen ovale (PFO) and, in turn, further aggravate hypoxemia and pulmonary hypertension. We speculated that SDB and nocturnal hypoxemia are more pronounced in patients with CMS compared with healthy high-altitude dwellers, and are related to vascular dysfunction. METHODS: We performed overnight sleep recordings, and measured systemic and pulmonary artery pressure in 23 patients with CMS (mean ± SD age, 52.8 ± 9.8 y) and 12 healthy control subjects (47.8 ± 7.8 y) at 3,600 m. In a subgroup of 15 subjects with SDB, we assessed the presence of a PFO with transesophageal echocardiography. RESULTS: The major new findings were that in patients with CMS, (1) SDB and nocturnal hypoxemia was more severe (P < .01) than in control subjects (apnea-hypopnea index [AHI], 38.9 ± 25.5 vs 14.3 ± 7.8 number of events per hour [nb/h]; arterial oxygen saturation, 80.2% ± 3.6% vs 86.8% ± 1.7%, CMS vs control group), and (2) AHI was directly correlated with systemic blood pressure (r = 0.5216; P = .001) and pulmonary artery pressure (r = 0.4497; P = .024). PFO was associated with more severe SDB (AHI, 48.8 ± 24.7 vs 14.8 ± 7.3 nb/h; P = .013, PFO vs no PFO) and hypoxemia. CONCLUSIONS: SDB and nocturnal hypoxemia are more severe in patients with CMS than in control subjects and are associated with systemic and pulmonary vascular dysfunction. The presence of a PFO appeared to further aggravate SDB. Closure of the PFO may improve SDB, hypoxemia, and vascular dysfunction in patients with CMS. TRIAL REGISTRY: ClinicalTrials.gov; No.: NCT01182792; URL: www.clinicaltrials.gov.

Exaggerated pulmonary hypertension and right ventricular dysfunction in high-altitude dwellers with patent foramen ovale.

BACKGROUND: There is considerable interindividual variability in pulmonary artery pressure among high-altitude (HA) dwellers, but the underlying mechanism is not known. At low altitude, a patent foramen ovale (PFO) is present in about 25% of the general population. Its prevalence is increased in clinical conditions associated with pulmonary hypertension and arterial hypoxemia, and it is thought to aggravate these problems. METHODS: We searched for a PFO (transesophageal echocardiography) in healthy HA dwellers (n = 22) and patients with chronic mountain sickness (n = 35) at 3,600 m above sea level and studied its effects (transthoracic echocardiography) on right ventricular (RV) function, pulmonary artery pressure, and vascular resistance at rest and during mild exercise (50 W), an intervention designed to further increase pulmonary artery pressure. RESULTS: The prevalence of PFO (32%) was similar to that reported in low-altitude populations and was not different in participants with and without chronic mountain sickness. Its presence was associated with RV enlargement at rest and an exaggerated increase in right-ventricular-to-right-atrial pressure gradient (25 ± 7 mm Hg vs 15 ± 9 mm Hg, P < .001) and a blunted increase in fractional area change of the right ventricle (3% [-1%, 5%] vs 7% [3%, 16%], P = .008) during mild exercise. CONCLUSIONS: These findings show, we believe for the first time, that although the prevalence of PFO is not increased in HA dwellers, its presence appears to facilitate pulmonary vasoconstriction and RV dysfunction during a mild physical effort frequently associated with daily activity. TRIAL REGISTRY: ClinicalTrials.gov; No.: NCT01182792; URL: www.clinicaltrials.gov.

Victim and offender accounts of interpersonal conflict: autobiographical narratives of forgiveness and unforgiveness.

Participants wrote 2 narratives that described an incident in which they angered or hurt someone (offender) or in which someone angered or hurt them (victim) and the offense was forgiven or not forgiven. Victims portrayed the offense as continuing (open), and offenders portrayed the offense as over (closed). Forgiveness narratives portrayed offenses as closed and with positive outcomes; however, for some victims, forgiveness coincided with continued anger, suggesting incomplete forgiveness. Dispositional empathy was associated with more benign interpretations of offenses, and situational empathy (e.g., for the offender) was associated with victims' forgiveness. In contrast, offenders' empathy for victims was associated with less self-forgiveness. Thus, both victim or offender role and forgiveness must be considered to understand narratives of interpersonal offenses.

Frenectomía: abordaje transdisciplinario / Frenectomy: transdisciplinary approach

El propósito de este trabajo es presentar un protocolo de atención de frenectomía para una atención temprana de las alteraciones de la lengua en niños. El enfoque transdisciplinario involucra la participación en conjunto de dos o más profesionales en un mismo espacio terapéutico, enriqueciendo el abordaje. Requiere del compromiso de todos los profesionales, incluidos los cuidadores. En la práctica clínica, observamos la necesidad de contar con fonoaudiólogas y odontopediatras que conjuntamente realicen la detección de alteraciones en las funciones del sistema estomatognático. De esta manera, se realiza el abordaje eficiente de la frenectomía, considerando los procedimientos pre y posquirúrgicos. El propósito de este artículo es proponer un protocolo del área para la atención en la fase prequirúrgico y posquirúrgico de la cirugía del frenillo lingual en pacientes odontopediátricos. (AU)

The purpose of this paper is to present a frenectomy care protocol for early attention to language disorders in children. The transdisciplinary approach involves the joint participation of two or more professionals in the same therapeutic space, enriching the approach. It requires the commitment of all professionals, including caregivers. In clinical practice, we observed the need to have phonoaudiologists and pediatric dentists jointly perform the detection of alterations in the functions of the Stomatognathic System. In this way, an efficient approach to frenectomy is carried out, considering pre and post surgical procedures. The purpose of this article is to propose an area protocol for care in the pre-surgical and post-surgical phase of lingual frenulum surgery in odonto-pediatric patients. (AU)

Attribution of blame, self-forgiving attitude and psychological adjustment in women with breast cancer.

The purpose of this study was to examine relationships among self-blame for developing breast cancer, a self-forgiving attitude, mood, and quality of life among women with breast cancer. In this cross-sectional study, 123 women with Stages 0-III breast cancer completed questionnaires measuring demographic and medical characteristics, self-blame, self-forgiveness, mood, and quality of life. Women who blamed themselves reported more mood disturbance (p

Association of spirituality and sobriety during a behavioral spirituality intervention for Twelve Step (TS) recovery.

Twelve-Step (TS) recovery utilizes spirituality to promote sobriety, yet there are no proven programs designed to facilitate spiritual involvement. We developed a seven-week behavioral spirituality intervention titled "Knowing Your Higher Power" for implementation along with usual TS care. Twenty-six participants from a recovery center enrolled. We assessed behavior at baseline, 7-week, and 12-week follow-up. The sample showed significant increase in spiritual involvement and beliefs over the 12-week measurement period and a significantly greater spirituality score in those maintaining total sobriety compared to those that relapsed. These findings encourage a controlled trial to determine if this work has efficacy for practitioners in substance abuse treatment.

Self-forgiveness, spirituality, and psychological adjustment in women with breast cancer.

We evaluated whether a self-forgiving attitude and spirituality were related to psychological adjustment among 81 women being treated for breast cancer at a medical oncology clinic in a county general hospital. Both a self-forgiving attitude and spirituality were unique predictors of less mood disturbance and better quality of life (p's < 0.001). These results are consistent with previous research that has demonstrated a positive relationship between spirituality and well-being. The findings also suggest that self-forgiveness should be explored experimentally to determine whether it can protect against the psychological effects of breast cancer-related stress. Interventions targeting these characteristics could improve the quality of life and alleviate stress, especially in women with breast cancer in public sector settings.

Optimism, social support and psychosocial functioning among women with breast cancer.

Personality, psychosocial, demographic and medical variables have been identified as correlates of adjustment to breast cancer and quality of life (QoL). Most studies have examined relationships between personality, social support and adjustment to cancer in predominantly middle-class Caucasian samples, thus limiting the generalizability of their findings. Eighty-one female outpatients at a medical oncology breast clinic in a county general hospital serving primarily indigent Hispanic and African-American patients completed measures assessing demographic and medical information, health-related QoL, cancer-specific distress, mood disturbance, dispositional optimism and satisfaction with social support. Older age, receipt of treatment and greater optimism accounted for 41% of the variance in emotional well-being (p<0.01). Absence of family history of breast cancer, receipt of treatment and optimism accounted for 43% of the variance in functional well-being (p<0.01). Optimism and satisfaction with social support accounted for 43% of the variance in social/family well-being (p<0.01). Absence of treatment (not yet treated) and pessimism accounted for 31% of the variance in cancer-specific distress (p<0.01). Finally, family history of breast cancer and pessimism accounted for 48% of the variance in mood disturbance (p<0.001). Family history of breast cancer and pessimism were related to mood disturbance (p<0.001). No between-group differences were found for race/ethnicity for any of the variables. Encouraging positive expectations and facilitating social support may help women in public sector medical settings cope with the stressful demands of diagnosis and treatment of breast cancer regardless of race/ethnicity.

Medical and psychosocial predictors of delay in seeking medical consultation for breast symptoms in women in a public sector setting.

We examined demographic, medical and psychosocial factors related to delay in seeking medical consultation for breast symptoms. In this cross-sectional survey, 124 women with breast symptoms attending an outpatient breast surgery clinic in a county general hospital completed questionnaires measuring demographic, medical and psychosocial variables. Our outcome variable was delay in seeking medical consultation. Younger age (p

Depressed mood and social support as predictors of quality of life in women receiving home health care.

We examined relationships among depressed mood, social support and quality of life in 58 medically ill low-income women 40 years and older receiving home health care. Analyses showed a negative relationship between depressed mood and quality of life (p's < or = 0.05). Positive relationships were found between number of people available for support and two of three quality of life domains as well as satisfaction with support and all three domains (p's < or = 0.05). Results also provided preliminary support that belonging to a church is related to emotional well-being (p = 0.039) and among those belonging to a church, recent increased activity was related to social/family well-being (p = 0.004). Mediational analyses revealed a cycle of depressed mood, dissatisfaction with social support, and loss of social support providers underlying the poor quality of life of many participants. This highlights the need to address the relationship between depression and social support when treating patients with chronic illness.

Notation systems for transcription: an empirical investigation.

A 21-syllable question posed by Bernard Shaw in a CNN television interview with Margaret Thatcher was presented to 90 participants, either as an audio recording or as a typed transcript or as both. Participants were asked to speak it, as closely as possible, as Shaw had (or, in conditions without the audio recording, as he might have). The typed version was either an ordinary transcript or a transcript in one of three transcription systems used currently in research on spoken discourse, all of which incorporate notations for prosody. Hence, there were nine conditions in all, with five women and five men in each. Contrary to the experimental hypothesis, approximations to Shaw's original temporal measures of performance were not degraded but were instead improved significantly by the addition of a prosodically notated transcript to the audio recording and significantly more in the absence of the audio recording. Presentation of the ordinary transcript alone produced the worst approximation to Shaw's temporal measures. The usefulness, accuracy, and readability of transcripts prepared according to detailed notation systems are discussed.