Ultrafast dynamics of photoinduced charge separation in cyanine- and polymer-based organic photovoltaic systems

Organic photovoltaics (OPV) have the potential to provide low-cost solar-to-electricity converting devices. Improving such devices requires a deeper understanding of the ultrafast photoinduced processes occurring after light absorption. We have performed femtosecond (fs) transient absorption spectroscopy, as well as time-resolved electroabsorption (Stark effect) on model OPV systems to follow electron and hole transfer dynamics, as well as charge carrier motion in the active layer to the electrodes. Solid-state cyanine borate (Cy3-B) films undergo intra-ion pair reductive quenching on the picosecond (ps) timescale. We have found that when intermixing Cy3-B with a fullerene acceptor (PCBM), photoexcitation leads to the appearance of oxidized Cy3 in less than 70 fs. We correlated the rate and yield of Cy3 oxidation to the PCBM loading. We then investigated a cyanine Cy3-P in a bilayer geometry with fullerene C60. In this case, ultrafast electron transfer in less than 100 fs is followed by slower dissociation of interfacial charge transfer states in the presence of an electric field. A photoinduced Stark effect observed in neat C60 enabled to identify an initially delocalized excited state, which localizes in 360 fs. Lastly, we analyzed how microstructural changes in polymer pBTTT:PCBM blends impact free charge carrier formation and motion. We identified that the intermixed phase efficiently produces charge carriers within 100 fs, and that pure fullerene and pBTTT domains attract the charge carriers separating them further apart. This is ascribed to an energy cascade toward the neat domains. This thesis reveals ultrafast charge transfer at donor-acceptor interfaces in such OPV systems by means of fs transient absorption spectroscopy. Results emphasize that a second step is needed for charge separation in order to successfully compete with charge pair recombination in these systems. An electric field applied can act as a driving force to dissociate interfacial charge transfer states. Pure donor or acceptor domains attract holes or electrons, respectively, and reduce geminate charge recombination in blends. These second steps in charge separation were derived from photoinduced electroabsorption dynamics in transient absorption measurements, as well as time-resolved electroabsorption based on the Stark effect

Viewing oxidative stress through the lens of oxidative signalling rather than damage

Concepts of the roles of reactive oxygen species (ROS) in plants and animals have shifted in recent years from focusing on oxidative damage effects to the current view of ROS as universal signalling metabolites. Rather than having two opposing activities, i.e. damage and signalling, the emerging concept is that all types of oxidative modification/damage are involved in signalling, not least in the induction of repair processes. Examining the multifaceted roles of ROS as crucial cellular signals, we highlight as an example the loss of PSII function called photoinhibition, where photo-protection has classically been conflated with oxidative damage

Current Challenges for the Early Detection of Alzheimer's Disease: Brain Imaging and CSF Studies

The development of prevention therapies for Alzheimer's disease (AD) would greatly benefit from biomarkers that are sensitive to the subtle brain changes that occur in the preclinical stage of the disease. Reductions in the cerebral metabolic rate of glucose (CMRglc), a measure of neuronal function, have proven to be a promising tool in the early diagnosis of AD. In vivo brain 2-[18F]fluoro-2-Deoxy-D-glucose-positron emission tomography (FDG-PET) imaging demonstrates consistent and progressive CMRglc reductions in AD patients, the extent and topography of which correlate with symptom severity. There is increasing evidence that hypometabolism appears during the preclinical stages of AD and can predict decline years before the onset of symptoms. This review will give an overview of FDG-PET results in individuals at risk for developing dementia, including: presymptomatic individuals carrying mutations responsible for early-onset familial AD; patients with Mild Cognitive Impairment (MCI), often a prodrome to late-onset sporadic AD; non-demented carriers of the Apolipoprotein E (ApoE) ε4 allele, a strong genetic risk factor for late-onset AD; cognitively normal subjects with a family history of AD; subjects with subjective memory complaints; and normal elderly followed longitudinally until they expressed the clinical symptoms and received post-mortem confirmation of AD. Finally, we will discuss the potential to combine different PET tracers and CSF markers of pathology to improve the early detection of AD

Dolichol: A Component of the Cellular Antioxidant Machinery

Dolichol, an end product of the mevalonate pathway, has been proposed a biomarker of aging, but its biological role, not to mention its catabolism, has not been fully understood. UV-B radiation was used to induce oxidative stress in isolated rat hepatocytes by the collagenase method. Effects on dolichol, phospholipids-bound polyunsaturated fatty acids (PL PUFA) and known lipid soluble antioxidants [coenzyme Q (CoQ) and α-tocopherol] were studied. The increase in oxidative stress was detected by a probe sensitive to reactive oxygen species (ROS). Peroxidation of lipids was assessed by measuring the release of thiobarbituric acid reactive substances (TBARS). Dolichol, CoQ and α-tocopherol were assessed by high-pressure liquid chromatography (HPLC), PL PUFA by gas-liquid chromatography (GC). UV-B radiation caused an immediate increase in ROS as well as lipid peroxidation and a simultaneous decrease in the levels of dolichol and lipid soluble antioxidants. Decrease in dolichol paralleled changes in CoQ levels and was smaller than that in α-tocopherol. The addition of mevinolin, a competitive inhibitor of the enzyme 3-hydroxy-3-methylglutaryl CoA reductase (HMG-CoAR), magnified the loss of dolichol and was associated with an increase in TBARS production. Changes in PL PUFA were minor. These findings highlight that oxidative stress has very early and similar effects on dolichol and lipid soluble antioxidants. Lower levels of dolichol are associated with enhanced peroxidation of lipids, which suggest that dolichol may have a protective role in the antioxidant machinery of cell membranes and perhaps be a key to understanding some adverse effects of statin therapy

An on-surface reaction confined within a porous molecular template

On-surface reactions based on metal-catalysed Ullmann coupling have been successfully employed to synthesise a wide variety of covalently coupled structures. Substrate chemistry and topology are both known to effect the progression of an on-surface reaction; offering routes to control efficiency and selectivity. Here, we detail ultra-high vacuum scanning probe microscopy experiments showing that templating a catalytically active surface, via a supramolecular template, influences the reaction pathway of an onsurface Ullmann-type coupling reaction by inhibiting one potential intermediate structure and stabilising another

Efficacy of Budesonide Orodispersible Tablets as Induction Therapy for Eosinophilic Esophagitis in a Randomized Placebo-Controlled Trial.

BACKGROUND & AIMS: Swallowed topical-acting corticosteroids are recommended as first-line therapy for eosinophilic esophagitis (EoE). Asthma medications not optimized for esophageal delivery are sometimes effective, although given off-label. We performed a randomized, placebo-controlled trial to assess the effectiveness and tolerability of a budesonide orodispersible tablet (BOT), which allows the drug to be delivered to the esophagus in adults with active EoE. METHODS: We performed a double-blind, parallel study of 88 adults with active EoE in Europe. Patients were randomly assigned to groups that received BOT (1 mg twice daily; n = 59) or placebo (n = 29) for 6 weeks. The primary end point was complete remission, based on clinical and histologic factors, including dysphagia and odynophagia severity ≤2 on a scale of 0-10 on each of the 7 days before the end of the double-blind phase and a peak eosinophil count <5 eosinophils/high power field. Patients who did not achieve complete remission at the end of the 6-week double-blind phase were offered 6 weeks of open-label treatment with BOT (1 mg twice daily). RESULTS: At 6 weeks, 58% of patients given BOT were in complete remission compared with no patients given placebo (P < .0001). The secondary end point of histologic remission was achieved by 93% of patients given BOT vs no patients given placebo (P < .0001). After 12 weeks, 85% of patients had achieved remission. Six-week and 12-week BOT administration were safe and well tolerated; 5% of patients who received BOT developed symptomatic, mild candida, which was easily treated with an oral antifungal agent. CONCLUSIONS: In a randomized trial of adults with active EoE, we found that budesonide oral tablets were significantly more effective than placebo in inducing clinical and histologic remission. Eudra-CT number 2014-001485-99; ClinicalTrials.gov ID NCT02434029

Interacting contributions of different departments to brand success

Adopting a grounded theory perspective, this research investigates the roles and interactions between marketing, customer services and human resources (HR) in driving success in UK financial services brands. CEOs/MDs, Directors of Marketing, HR and Customer Services, their line reports, front line staff and their agencies from 2 successful and 4 less successful financial services corporations participated in depth interviews for this project. Marketing strategically defining the brand, HR aligning policies behind the brand and customer services staff being brand exemplars enhances brand success. Organizations should abhor power struggles as no one department is critical -- rather working together is key. The brand fulcrum model helps managers and researchers appreciate the harmonious activities of brand guardians (marketing), brand enablers (HR) and promise delivers (customer services). Favoring one department shifts the brand center of gravity resulting in an unstable state, which more equitable responsibility allocation resolves.Brand Services HR Customer services Marketing

Fonds Louis Bertrand. Fonds numérisé. Correspondance de Louis Bertrand. [Carte de visite de Louise Fayard]

Numérisation effectuée à partir d'un document original : LBC0570.Appartient à l'ensemble documentaire : 3M000Appartient à l'ensemble documentaire : 3M007Fayard, Louise née Pattin (1880-1972).Bertrand, Louis (1866-1941).Paris (France).Lieu de copie : Paris (52 rue de la Faisanderie

Fonds Louis Bertrand. Fonds numérisé. Correspondance de Louis Bertrand. [Carte autographe de Louise Fayard à Louis Bertrand]

Numérisation effectuée à partir d'un document original : LBC0523.Appartient à l'ensemble documentaire : 3M000Appartient à l'ensemble documentaire : 3M007Fayard, Louise née Pattin (1880-1972).Bertrand, Louis (1866-1941).Pinterville (Eure, France).Lieu de copie : Environs de Louviers (Pinterville, le Parc

Fonds Louis Bertrand. Fonds numérisé. Correspondance de Louis Bertrand. [Lettre autographe de Louise Fayard à Louis Bertrand]

Numérisation effectuée à partir d'un document original : LBC0518.Appartient à l'ensemble documentaire : 3M000Appartient à l'ensemble documentaire : 3M007Fayard, Louise née Pattin (1880-1972).Bertrand, Louis (1866-1941).Paris (France).Lieu de copie : Pari