332 research outputs found

    Dehairing Australian alpaca fibres with a cashmere dehairing machine

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    Many classes of alpaca fibres contain a certain amount of coarse fibres, which are strong and stiff, and cause discomfort to the end users of the alpaca fibre products. It is therefore desirable to separate the coarse fibres from the fine alpaca fibres. This paper reports trial results on alpaca dehairing using a cashmere dehairing machine. The diameters of alpaca fleece, dehaired alpaca fibres and removed alpaca fibres were analysed, and the fibre lengths before and after dehairing have been compared. The results indicate that it is feasible to dehair alpaca fibres using a cashmere dehairing facility. The dehaired alpaca fibres are cleaner, bulkier and softer, with around 1.5 &mu;m reduction in average fibre diameter, but the dehairing process shortens the dehaired fibre length considerably. The dehairing effectiveness of coarse fibre removal using the cashmere dehairing technology has also been discussed in this paper. <br /

    Polarization-controlled optimal scatter suppression in transient absorption spectroscopy

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    Ultrafast transient absorption spectroscopy is a powerful technique to study fast photo-induced processes, such as electron, proton and energy transfer, isomerization and molecular dynamics, in a diverse range of samples, including solid state materials and proteins. Many such experiments suffer from signal distortion by scattered excitation light, in particular close to the excitation (pump) frequency. Scattered light can be effectively suppressed by a polarizer oriented perpendicular to the excitation polarization and positioned behind the sample in the optical path of the probe beam. However, this introduces anisotropic polarization contributions into the recorded signal. We present an approach based on setting specific polarizations of the pump and probe pulses, combined with a polarizer behind the sample. Together, this controls the signal-to-scatter ratio (SSR), while maintaining isotropic signal. We present SSR for the full range of polarizations and analytically derive the optimal configuration at angles of 40.5° between probe and pump and of 66.9° between polarizer and pump polarizations. This improves SSR by 33 52 ≈. (or 3 compared to polarizer parallel to probe). The calculations are validated by transient absorption experiments on the common fluorescent dye Rhodamine B. This approach provides a simple method to considerably improve the SSR in transient absorption spectroscopy

    Energy transfer, excited-state deactivation, and exciplex formation in artificial caroteno-phthalocyanine light-harvesting antennas

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    We present results from transient absorption spectroscopy on a series of artificial light-harvesting dyads made up of a zinc phthalocyanine (Pc) covalently linked to carotenoids with 9, 10, or 11 conjugated carbon-carbon double bonds, referred to as dyads 1, 2, and 3, respectively. We assessed the energy transfer and excited-state deactivation pathways following excitation of the strongly allowed carotenoid 82 state as a function of the conjugation length. The 82 state rapidly relaxes to the S* and Si states. In all systems we detected a new pathway of energy deactivation within the carotenoid manifold in which the S* state acts as an intermediate state in the

    Ultrafast transient absorption spectroscopy: principles and application to photosynthetic systems

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    The photophysical and photochemical reactions, after light absorption by a photosynthetic pigment–protein complex, are among the fastest events in biology, taking place on timescales ranging from tens of femtoseconds to a few nanoseconds. The advent of ultrafast laser systems that produce pulses with femtosecond duration opened up a new area of research and enabled investigation of these photophysical and photochemical reactions in real time. Here, we provide a basic description of the ultrafast transient absorption technique, the laser and wavelength-conversion equipment, the transient absorption setup, and the collection of transient absorption data. Recent applications of ultrafast transient absorption spectroscopy on systems with increasing degree of complexity, from biomimetic light-harvesting systems to natural light-harvesting antennas, are presented. In particular, we will discuss, in this educational review, how a molecular understanding of the light-harvesting and photoprotective functions of carotenoids in photosynthesis is accomplished through the application of ultrafast transient absorption spectroscopy

    Femtosecond Stimulated Raman Study of the Photoactive Flavoprotein AppABLUF

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    Femtosecond stimulated Raman Spectroscopy (FSRS) is applied to study the photocycle of a blue light using flavin (BLUF) domain photoreceptor, AppABLUF. It is shown that FSRS spectra are sensitive to the light adapted state of the protein and probe its excited state dynamics. The dominant contribution to the most sensitive excited state Raman active modes is from flavin ring modes. However, TD-DFT calculations for excited state structures indicate that reproduction and assignment of the experimentally observed spectral shift will require high level calculations on the flavin in its specific protein environment

    Diabetes Mellitus Type 2 as a Risk Factor and Outcome Modifier for Cryptococcosis in HIV Negative, Non-transplant Patients, a Propensity Score Match Analysis

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    Cryptococcosis is an opportunistic fungal infection of worldwide distribution with significant associated morbidity and mortality. HIV, organ transplantation, malignancy, cirrhosis, sarcoidosis, and immunosuppressive medications are established risk factors for cryptococcosis. Type 2 diabetes mellitus (DM2) has been hypothesized as a risk factor and an outcome modifier for cryptococcosis. We aimed to compare outcomes among HIV-negative, non-transplant (NHNT) patients with and without DM2. We queried a global research network to identify NHNT patients (n = 3280). We performed a propensity score-matched (PSM) analysis comparing clinical outcomes among cryptococcosis patients by DM status. We also characterize adults with cryptococcosis and DM2 as the only risk factor. After PSM, NHNT patients with DM2 were more likely to develop cognitive dysfunction [9% vs. 6%, OR 1.6; 95% CI (1.1–2.3); P = 0.01] but had similar mortality, hospitalization, ICU, and stroke risk after acquiring cryptococcosis when compared to NHNT patients without DM2. Pulmonary cryptococcosis was the most common site of infection. Among 44 cryptococcosis patients with DM2 as the only identifiable risk factor for disease, the annual incidence of cryptococcosis was 0.001%, with a prevalence of 0.002%. DM2 is associated with increased cognitive dysfunction risk in NHNT patients with cryptococcosis. It is rare for DM2 to be the only identified risk factor for developing cryptococcosis. Kidney disease, hyperglycemia, and immune dysfunction can increase the risk of cryptococcosis in patients with DM2

    Excitons in a Photosynthetic Light-Harvesting System: A Combined Molecular Dynamics/Quantum Chemistry and Polaron Model Study

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    The dynamics of pigment-pigment and pigment-protein interactions in light-harvesting complexes is studied with a novel approach which combines molecular dynamics (MD) simulations with quantum chemistry (QC) calculations. The MD simulations of an LH-II complex, solvated and embedded in a lipid bilayer at physiological conditions (with total system size of 87,055 atoms) revealed a pathway of a water molecule into the B800 binding site, as well as increased dimerization within the B850 BChl ring, as compared to the dimerization found for the crystal structure. The fluctuations of pigment (B850 BChl) excitation energies, as a function of time, were determined via ab initio QC calculations based on the geometries that emerged from the MD simulations. From the results of these calculations we constructed a time-dependent Hamiltonian of the B850 exciton system from which we determined the linear absorption spectrum. Finally, a polaron model is introduced to describe quantum mechanically both the excitonic and vibrational (phonon) degrees of freedom. The exciton-phonon coupling that enters into the polaron model, and the corresponding phonon spectral function are derived from the MD/QC simulations. It is demonstrated that, in the framework of the polaron model, the absorption spectrum of the B850 excitons can be calculated from the autocorrelation function of the excitation energies of individual BChls, which is readily available from the combined MD/QC simulations. The obtained result is in good agreement with the experimentally measured absorption spectrum.Comment: REVTeX3.1, 23 pages, 13 (EPS) figures included. A high quality PDF file of the paper is available at http://www.ks.uiuc.edu/Publications/Papers/PDF/DAMJ2001/DAMJ2001.pd

    BLUF Domain Function Does Not Require a Metastable Radical Intermediate State

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    BLUF (blue light using flavin) domain proteins are an important family of blue light-sensing proteins which control a wide variety of functions in cells. The primary light-activated step in the BLUF domain is not yet established. A number of experimental and theoretical studies points to a role for photoinduced electron transfer (PET) between a highly conserved tyrosine and the flavin chromophore to form a radical intermediate state. Here we investigate the role of PET in three different BLUF proteins, using ultrafast broadband transient infrared spectroscopy. We characterize and identify infrared active marker modes for excited and ground state species and use them to record photochemical dynamics in the proteins. We also generate mutants which unambiguously show PET and, through isotope labeling of the protein and the chromophore, are able to assign modes characteristic of both flavin and protein radical states. We find that these radical intermediates are not observed in two of the three BLUF domains studied, casting doubt on the importance of the formation of a population of radical intermediates in the BLUF photocycle. Further, unnatural amino acid mutagenesis is used to replace the conserved tyrosine with fluorotyrosines, thus modifying the driving force for the proposed electron transfer reaction; the rate changes observed are also not consistent with a PET mechanism. Thus, while intermediates of PET reactions can be observed in BLUF proteins they are not correlated with photoactivity, suggesting that radical intermediates are not central to their operation. Alternative nonradical pathways including a keto–enol tautomerization induced by electronic excitation of the flavin ring are considered

    Personality predicts the vibrancy of colour imagery: The case of synaesthesia

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    In this study we show that personality traits predict the physical qualities of mentally generated colours, using the case of synaesthesia. Developmental grapheme-colour synaesthetes have the automatic lifelong association of colours paired to letters or digits. Although these colours are internal mental constructs, they can be measured along physical dimensions such as saturation and luminance. The personality of synaesthetes can also be quantified using self-report questionnaires relating, for example, to the five major traits of Conscientiousness, Extraversion, Agreeableness, Neuroticism, and Openness to experience. In this paper, we bring together both types of quality by examining whether the personality of individual synaesthetes predicts their synaesthetic colours. Twenty grapheme-colour synaesthetes were tested with the Big Five Inventory (BFI) personality questionnaire. Their synaesthesia was also tested in terms of consistency and average colour saturation and luminance. Two major results were found: although personality did not influence the overall robustness (i.e., consistency) of synaesthesia, it predicted the nature of synaesthetes’ colours: the trait of Openness was positively correlated with the saturation of synaesthetic colours. Our study provides evidence that personality and internal perception are intertwined, and suggests future avenues of research for investigating the associations between the two
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