Device physics of polymer:fullerene bulk heterojunction solar cells

Plastic solar cells bear the potential for large-scale power generation based on materials that provide the possibility of flexible, lightweight, inexpensive, efficient solar cells. Since the discovery of the photoinduced electron transfer from a conjugated polymer to fullerene molecules, followed by the introduction of the bulk heterojunction (BHJ) concept, this material combination has been extensively studied in organic solar cells, leading to several breakthroughs in efficiency, with a power conversion efficiency approaching 5 %. This article reviews the processes and limitations that govern device operation of polymer.-fullerene BHJ solar cells, with respect to the charge-carrier transport and photogeneration mechanism. The transport of electrons/holes in the blend is a crucial parameter and must be controlled (e.g., by controlling the nanoscale morphology) and enhanced in order to allow fabrication of thicker films to maximize the absorption, without significant recombination losses. Concomitantly, a balanced transport of electrons and holes in the blend is needed to suppress the build-up of the space-charge that will significantly reduce the power conversion efficiency. Dissociation of electron-hole pairs at the donor/acceptor interface is an important process that limits the charge generation efficiency under normal operation condition. Based on these findings, there is a compromise between charge generation (light absorption) and open-circuit voltage (V-oc) when attempting to reduce the bandgap of the polymer (or fullerene). Therefore, an increase in V-oc of polymer.-fullerene cells, for example by raising the lowest unoccupied molecular orbital level of the fullerene, will benefit cell performance as both fill factor and short-circuit current increase simultaneously

Device operation of conjugated polymer/zinc oxide bulk heterojunction solar cells

Solar cells based on a poly (p-phenylene vinylene) (PPV) derivative and zinc oxide nanoparticles can reach a power conversion efficiency of 1.6%. The transport of electrons and holes in these promising devices is characterized and it is found that the electron mobility is equal to 2.8 x 10(-9) m(2) V-1 s(-1), whereas the hole mobility amounts to 5.5 x 10(-10) m(2) V-1 s(-1). By modeling the current-voltage characteristics under illumination it is found that the performance of PPV/zinc oxide solar cells is limited by the charge-carrier mobilities. Subsequently, how to further improve the efficiency is discussed

MODELING SEASONAL WINE GRAPE DEVELOPMENT USING A MIXTURE TECHNIQUE

Biological growth data typically display an increasing sigmoidal pattern over time. Grape development is no exception and shows a similar general trend. A detailed examination of the growth process in grapes, however, reveals a few systematic deviations from this pattern. Specifically, grape development is often characterized by localized areas of growth plateaus leading to an overall growth pattern referred to as a double sigmoidal curve. Capturing and characterizing these local changes in growth is important as they represent important phases in grape development such as veraison. This paper utilizes a model adapted from the technique of mixture models to estimate the growth curve of grapes. The resulting model provides a more accurate description of the growth process and has parameter estimates directly related to the various phases of grape development. The model is demonstrated using data collected from an experimental trellis tension monitoring system in the Chardonnay grape varietie

Rest Pain and Movement-Evoked Pain as Unique Constructs in Hip and Knee Replacements

OBJECTIVE: There is limited information about the extent to which the association between preoperative and chronic postoperative pain is mediated via pain‐on‐movement or pain‐at‐rest. We explored these associations in patients undergoing total hip replacement (THR) and total knee replacement (TKR). METHODS: A total of 322 and 316 patients receiving THR and TKR, respectively, were recruited into a single‐center UK cohort (Arthroplasty Pain Experience) study. Preoperative, acute postoperative, and 12‐month pain severity was measured using self‐reported pain instruments. The association between preoperative/acute pain and chronic postoperative pain was investigated using structural equation modeling (SEM). RESULTS: Patients with high levels of preoperative pain were more likely to report chronic pain after THR (β = 0.195, P = 0.02) and TKR (β = 0.749, P < 0.0001). Acute postoperative pain‐on‐movement was not associated with chronic pain after TKR or THR after adjusting for preoperative pain; however, acute pain‐at‐rest was associated with chronic pain after THR (β = 0.20, P < 0.0002) but not TKR after adjusting for preoperative pain. Analysis of pain‐at‐rest and pain‐on‐movement highlighted differences between THR and TKR patients. Chronic pain‐at‐rest after THR was weakly associated with pain‐at‐rest during the preoperative (β = 0.11, P = 0.068) and acute postoperative period (β = 0.21, P < 0.0001). In contrast, chronic pain‐on‐movement after TKR was strongly associated with the severity of pain‐on‐movement during the preoperative period (β = 0.51, P = 0.001). CONCLUSION: SEM illustrated the different patterns of association between measures of pain over time in patients undergoing THR and TKR for osteoarthritis. These findings highlight the importance of future work that explores the mechanisms underlying pain‐on‐movement and pain‐at‐rest

Trajectories of Pain and Function after Primary Hip and Knee Arthroplasty:The ADAPT Cohort Study

BACKGROUND AND PURPOSE:Pain and function improve dramatically in the first three months after hip and knee arthroplasty but the trajectory after three months is less well described. It is also unclear how pre-operative pain and function influence short- and long-term recovery. We explored the trajectory of change in function and pain until and beyond 3-months post-operatively and the influence of pre-operative self-reported symptoms. METHODS:The study was a prospective cohort study of 164 patients undergoing primary hip (n = 80) or knee (n = 84) arthroplasty in the United Kingdom. Self-reported measures of pain and function using the Western Ontario and McMaster Universities Osteoarthritis index were collected pre-operatively and at 3 and 12 months post-operatively. Hip and knee arthroplasties were analysed separately, and patients were split into two groups: those with high or low symptoms pre-operatively. Multilevel regression models were used for each outcome (pain and function), and the trajectories of change were charted (0-3 months and 3-12 months). RESULTS:Hip: Most improvement occurred within the first 3 months following hip surgery and patients with worse pre-operative scores had greater changes. The mean changes observed between 3 and twelve months were statistically insignificant. One year after surgery, patients with worse pre-operative scores had post-operative outcomes similar to those observed among patients with less severe pre-operative symptoms. Knee: Most improvement occurred in the first 3 months following knee surgery with no significant change thereafter. Despite greater mean change during the first three months, patients with worse pre-operative scores had not 'caught-up' with those with less severe pre-operative symptoms 12 months after their surgery. CONCLUSION:Most symptomatic improvement occurred within the first 3 months after surgery with no significant change between 3-12 months. Further investigations are now required to determine if patients with severe symptoms at the time of their knee arthroplasty have a different pre-surgical history than those with less severe symptoms and if they could benefit from earlier surgical intervention and tailored rehabilitation to achieve better post-operative patient-reported outcomes

Resolving the Hard X-ray Emission of GX 5-1 with INTEGRAL

We present the study of one year of INTEGRAL data on the neutron star low mass X-ray binary GX 5-1. Thanks to the excellent angular resolution and sensitivity of INTEGRAL, we are able to obtain a high quality spectrum of GX 5-1 from ~5 keV to ~100 keV, for the first time without contamination from the nearby black hole candidate GRS 1758-258 above 20 keV. During our observations, GX 5-1 is mostly found in the horizontal and normal branch of its hardness intensity diagram. A clear hard X-ray emission is observed above ~30 keV which exceeds the exponential cut-off spectrum expected from lower energies. This spectral flattening may have the same origin of the hard components observed in other Z sources as it shares the property of being characteristic to the horizontal branch. The hard excess is explained by introducing Compton up-scattering of soft photons from the neutron star surface due to a thin hot plasma expected in the boundary layer. The spectral changes of GX 5-1 downward along the "Z" pattern in the hardness intensity diagram can be well described in terms of monotonical decrease of the neutron star surface temperature. This may be a consequence of the gradual expansion of the boundary layer as the mass accretion rate increases.Comment: 10 pages, 17 figures, accepted for publication in A&

Measurement properties of the EQ-5D across four major geriatric conditions: Findings from TOPICS-MDS

Background: As populations age, chronic geriatric conditions linked to progressive organ failure jeopardize health-related quality of life (HRQoL). Thus, this research assessed the validity and applicability of the EQ-5D (a common HRQoL instrument) across four major chronic geriatric conditions: hearing issues, joint damage, urinary incontinence, or dizziness with falls. Methods: The study sample comprised 25,637 community-dwelling persons aged 65 years and older residing in the Netherlands (Data source: TOPICS-MDS, www.topics-mds.eu ). Floor and ceiling effects were examined. To assess convergent validity, random effects meta-correlations (Spearman's rho) were derived between individual EQ-5D domains and related survey items. To further examine construct validity, the association between sociodemographic characteristics and EQ-5D summary scores were assessed using linear mixed models. Outcomes were compared to the overall study population as well as a 'healthy' subgroup reporting no major chronic conditions. Results: Whereas ceiling effects were observed in the overall study population and the 'healthy' subgroup, such was not the case in the geriatric condition subgroups. The majority of hypotheses regarding correlations between survey items and sociodemographic associations were supported. EQ-5D summary scores were lower in respondents who were older, female, widowed/single, lower educated, and living alone. Increasing co-morbidity had a clear negative effect on EQ-5D scores. Conclusion: This study supported the construct validity of the EQ-5D across four major geriatric conditions. For older persons who are generally healthy, i.e. reporting few to no chronic conditions, the EQ-5D confers poor discriminative ability due to ceiling effects. Although the overall dataset initially suggested poor discriminative ability for the EQ-5D, such was not the case within subgroups presenting with major geriatric conditions

Synthesis and In Vitro (Anticancer) Evaluation of eta(6)-Arene Ruthenium Complexes Bearing Stannyl Ligands

Treatment of the known half-sandwich complexes of the type [(eta(6)-C6H6)RuCl2(P(OR)(3))] (R = Me or Ph) with SnCl2 yielded three new half-sandwich ruthenium complexes (C1-C3): [(eta(6)-C6H6)RuCl(SnCl3)(P(OMe)(3))] (C1), [(eta(6)-C6H6)RuCl(SnCl3)(P(OPh)(3))] (C2) and the bis-stannyl complex [(eta(6)-C6H6)Ru(SnCl3)(2)(P(OMe)(3))] (C3) by facile insertion of SnCl2 into the Ru-Cl bonds. Treatment of the known complexes [(eta(6)-C6H6)RuCl(SnCl3)(PPh3)] and [(eta(6)-C6H6)RuCl2(PPh3)] with 4-dimethylaminopyridine (DAMP) and ammonium tetrafluoroborate afforded the complex salts: [(eta(6)-C6H6)Ru(SnCl3)(PPh3)(DAMP)]+BF4- (C4) and [(eta(6)-C6H6)RuCl(PPh3)(DAMP)]+BF4- (C5) respectively. Complexes C1-C5 have been fully characterized by spectroscopic means (IR, UV-vis, multinuclear NMR, ESI-MS) and their thermal behaviour elucidated by thermal gravimetric analysis (TGA). Structural characterization by single crystal X-ray crystallography of the novel complex C2 and [(eta(6)-C6H6)RuCl2(P(OPh)(3))], the latter having escaped elucidation by this method, is also reported. Finally, the cytotoxicity of the complexes was determined on the A2780 (human ovarian cancer), A2780cisR (human ovarian cis-platin-resistant cancer), and the HEK293 (human embryonic kidney) cell lines and discussed, and an attempt is made to elucidate the effect of the stannyl ligand on cytotoxicity

Echocardiographic Assessment of Embryonic and Fetal Mouse Heart Development: A Focus on Haemodynamics and Morphology

Background. Heart development is a complex process, and abnormal development may result in congenital heart disease (CHD). Currently, studies on animal models mainly focus on cardiac morphology and the availability of hemodynamic data, especially of the right heart half, is limited. Here we aimed to assess the morphological and hemodynamic parameters of normal developing mouse embryos/fetuses by using a high-frequency ultrasound system. Methods. A timed breeding program was initiated with a WT mouse line (Swiss/129Sv background). All recordings were performed transabdominally, in isoflurane sedated pregnant mice, in hearts of sequential developmental stages: 12.5, 14.5, and 17.5 days after conception (n=105). Results. Along development the heart rate increased significantly from 125 ± 9.5 to 219 ± 8.3 beats per minute. Reliable flow measurements could be performed across the developing mitral and tricuspid valves and outflow tract. M-mode measurements could be obtained of all cardiac compartments. An overall increase of cardiac systolic and diastolic function with embryonic/fetal development was observed. Conclusion. High-frequency echocardiography is a promising and useful imaging modality for structural and hemodynamic analysis of embryonic/fetal mouse hearts

Clinical Course of TGA After Arterial Switch Operation in the Current Era

Background: The number of patients with an arterial switch operation (ASO) for transposition of the great arteries (TGA) is steadily growing; limited information is available regarding the clinical course in the current era. Objectives: The purpose was to describe clinical outcome late after ASO in a national cohort, including survival, rates of (re-)interventions, and clinical events. Methods: A total of 1,061 TGA-ASO patients (median age 10.7 years [IQR: 2.0-18.2 years]) from a nationwide prospective registry with a median follow-up of 8.0 years (IQR: 5.4-8.8 years) were included. Using an analysis with age as the primary time scale, cumulative incidence of survival, (re)interventions, and clinical events were determined. Results: At the age of 35 years, late survival was 93% (95% CI: 88%-98%). The cumulative re-intervention rate at the right ventricular outflow tract and pulmonary branches was 36% (95% CI: 31%-41%). Other cumulative re-intervention rates at 35 years were on the left ventricular outflow tract (neo-aortic root and valve) 16% (95% CI: 10%-22%), aortic arch 9% (95% CI: 5%-13%), and coronary arteries 3% (95% CI: 1%-6%). Furthermore, 11% (95% CI: 6-16%) of the patients required electrophysiological interventions. Clinical events, including heart failure, endocarditis, and myocardial infarction occurred in 8% (95% CI: 5%-11%). Independent risk factors for any (re-)intervention were TGA morphological subtype (Taussig-Bing double outlet right ventricle [HR: 4.9, 95% CI: 2.9-8.1]) and previous pulmonary artery banding (HR: 1.6, 95% CI: 1.0-2.2). Conclusions: TGA-ASO patients have an excellent survival. However, their clinical course is characterized by an ongoing need for (re-)interventions, especially on the right ventricular outflow tract and the left ventricular outflow tract indicating a strict lifelong surveillance, also in adulthood.</p