183 research outputs found
Film morphology and photophysics of polyfluorene
Journal ArticleWe have studied the interplay between photophysics and film morphology of poly(9,9-dioctyl)fluorene (PFO) using a variety of optical probes. Upon slowly warming a spin-cast PFO film from 80 to 300 K, a fraction of the sample is transformed into a different solid phase, the ß phase. Absorption and electroabsorption measurements show that the ß phase has more extended conjugation than the glassy phase. As a consequence, excited states of the ß phase are redshifted and have higher polarizability. The photoinduced absorption spectrum of a glassy PFO film is dominated by triplet excitons, whereas both polarons and triplet excitons are seen in a sample containing a fraction of the ß phase. The dependence of the photoinduced absorption and photocurrent upon the excitation wavelength shows that there is a clear link between polaron and triplet photogeneration
Structure, Photophysics and the Order-Disorder Transition to the Beta Phase in Poly(9,9-(di -n,n-octyl)fluorene)
X-ray diffraction, UV-vis absorption and photoluminescence (PL) spectroscopy
have been used to study the well-known order-disorder transition (ODT) to the
beta phase in poly(9,9-(di n,n-octyl)fluorene)) (PF8) thin film samples through
combination of time-dependent and temperature-dependent measurements. The ODT
is well described by a simple Avrami picture of one-dimensional nucleation and
growth but crystallization, on cooling, proceeds only after molecular-level
conformational relaxation to the so called beta phase. Rapid thermal quenching
is employed for PF8 studies of pure alpha phase samples while extended
low-temperature annealing is used for improved beta phase formation. Low
temperature PL studies reveal sharp Franck-Condon type emission bands and, in
the beta phase, two distinguishable vibronic sub-bands with energies of
approximately 199 and 158 meV at 25 K. This improved molecular level structural
order leads to a more complete analysis of the higher-order vibronic bands. A
net Huang-Rhys coupling parameter of just under 0.7 is typically observed but
the relative contributions by the two distinguishable vibronic sub-bands
exhibit an anomalous temperature dependence. The PL studies also identify
strongly correlated behavior between the relative beta phase 0-0 PL peak
position and peak width. This relationship is modeled under the assumption that
emission represents excitons in thermodynamic equilibrium from states at the
bottom of a quasi-one-dimensional exciton band. The crystalline phase, as
observed in annealed thin-film samples, has scattering peaks which are
incompatible with a simple hexagonal packing of the PF8 chains.Comment: Submitted to PRB, 12 files; 1 tex, 1 bbl, 10 eps figure
Large scale numerical investigation of excited states in poly(phenylene)
A density matrix renormalisation group scheme is developed, allowing for the
first time essentially exact numerical solutions for the important excited
states of a realistic semi-empirical model for oligo-phenylenes. By monitoring
the evolution of the energies with chain length and comparing them to the
experimental absorption peaks of oligomers and thin films, we assign the four
characteristic absorption peaks of phenyl-based polymers. We also determine the
position and nature of the nonlinear optical states in this model.Comment: RevTeX, 10 pages, 4 eps figures included using eps
The smfBox is an open-source platform for single-molecule FRET
Single-molecule Förster Resonance Energy Transfer (smFRET) is a powerful technique capable of resolving both relative and absolute distances within and between structurally dynamic biomolecules. High instrument costs, and a lack of open-source hardware and acquisition software have limited smFRET’s broad application by non-specialists. Here, we present the smfBox, a cost-effective confocal smFRET platform, providing detailed build instructions, open-source acquisition software, and full validation, thereby democratising smFRET for the wider scientific community
Multimodal super-resolution optical microscopy using a transition metal-based probe provides unprecedented capabilities for imaging both nucle-ar chromatin and mitochondria
Detailed studies on the live cell uptake properties of a dinuclear membrane permeable permeable RuII cell probe show that, at low concentrations, the complex localizes and images mitochondria. At concentrations above ~20 μM the complex images nuclear DNA. Since the complex is extremely photostable, has a large Stokes shift, and displays intrinsic subcellular targeting, its compatibility with super-resolution techniques was investigated. It was found to be very well suited to image mitochondria and nuclear chromatin in two col-our, 2C-SIM; and STED and 3D-STED both in fixed and live cell. In particular, due to its vastly improved photostability compared to conventional SR probes, it can provide images of nuclear DNA at unprecedented resolution
Tuning intermolecular interactions in di-octyl substituted polyfluorene via hydrostatic pressure
Polyfluorenes (PFs) represent a unique class of poly para-phenylene based
blue-emitting polymers with intriguing structure-property relationships. Slight
variations in the choice of functionalizing side chains result in dramatic
differences in the inter- and intra-chain structures in PFs. We present
photoluminescence (PL) and Raman scattering studies of bulk samples and thin
films of dioctyl-substituted PF (PF8) under hydrostatic pressure. The bulk
sample was further thermally annealed at 1.9 GPa. The PL vibronics of the as-is
sample red-shift at an average rate of 26 meV/GPa. The thermally annealed
sample is characterized by at least two phase transitions at 1.1 GPa and 4.2
GPa, each of which has a different pressure coefficient for PL vibronics. The
Huang-Rhys factor, a measure of the electron-phonon interaction, is found to
increase with increasing pressures signaling a higher geometric relaxation of
the electronic states. The Raman peaks harden with increasing pressures; the
intra-ring C-C stretch frequency at 1600 cm has a pressure coefficient
of 7.2 cm/GPa and exhibits asymmetric line shapes at higher pressures,
characteristic of a strong electron-phonon interaction. The optical properties
of PF8 under high pressure are further contrasted with those of a branched side
chain substituted PF.Comment: 22 pages, 10 figure
Interpopulational variation in costs of reproduction related to pregnancy in a viviparous lizard
APOE ε2 resilience for Alzheimer’s disease is mediated by plasma lipid species: Analysis of three independent cohort studies
Introduction
The apolipoprotein E (APOE) genotype is the strongest genetic risk factor for late-onset Alzheimer\u27s disease. However, its effect on lipid metabolic pathways, and their mediating effect on disease risk, is poorly understood.
Methods
We performed lipidomic analysis on three independent cohorts (the Australian Imaging, Biomarkers and Lifestyle [AIBL] flagship study, n = 1087; the Alzheimer\u27s Disease Neuroimaging Initiative [ADNI] 1 study, n = 819; and the Busselton Health Study [BHS], n = 4384), and we defined associations between APOE ε2 and ε4 and 569 plasma/serum lipid species. Mediation analysis defined the proportion of the treatment effect of the APOE genotype mediated by plasma/serum lipid species.
Results
A total of 237 and 104 lipid species were associated with APOE ε2 and ε4, respectively. Of these 68 (ε2) and 24 (ε4) were associated with prevalent Alzheimer\u27s disease. Individual lipid species or lipidomic models of APOE genotypes mediated up to 30% and 10% of APOE ε2 and ε4 treatment effect, respectively.
Discussion
Plasma lipid species mediate the treatment effect of APOE genotypes on Alzheimer\u27s disease and as such represent a potential therapeutic target
Ras GTPase-like protein MglA, a controller of bacterial social-motility in Myxobacteria, has evolved to control bacterial predation by Bdellovibrio
Bdellovibrio bacteriovorus invade Gram-negative bacteria in a predatory process requiring Type IV pili (T4P) at a single invasive pole, and also glide on surfaces to locate prey. Ras-like G-protein MglA, working with MglB and RomR in the deltaproteobacterium Myxococcus xanthus, regulates adventurous gliding and T4P-mediated social motility at both M. xanthus cell poles. Our bioinformatic analyses suggested that the GTPase activating protein (GAP)-encoding gene mglB was lost in Bdellovibrio, but critical residues for MglABd GTP-binding are conserved. Deletion of mglABd abolished prey-invasion, but not gliding, and reduced T4P formation. MglABd interacted with a previously uncharacterised tetratricopeptide repeat (TPR) domain protein Bd2492, which we show localises at the single invasive pole and is required for predation. Bd2492 and RomR also interacted with cyclic-di-GMP-binding receptor CdgA, required for rapid prey-invasion. Bd2492, RomRBd and CdgA localize to the invasive pole and may facilitate MglA-docking. Bd2492 was encoded from an operon encoding a TamAB-like secretion system. The TamA protein and RomR were found, by gene deletion tests, to be essential for viability in both predatory and non-predatory modes. Control proteins, which regulate bipolar T4P-mediated social motility in swarming groups of deltaproteobacteria, have adapted in evolution to regulate the anti-social process of unipolar prey-invasion in the “lone-hunter” Bdellovibrio. Thus GTP-binding proteins and cyclic-di-GMP inputs combine at a regulatory hub, turning on prey-invasion and allowing invasion and killing of bacterial pathogens and consequent predatory growth of Bdellovibrio
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