3,694 research outputs found
Comparing molecular photofragmentation dynamics in the gas and liquid phases
No full textThis article explores the extent to which insights gleaned from detailed studies of molecular photodissociations in the gas phase (i.e. under isolated molecule conditions) can inform our understanding of the corresponding photofragmentation processes in solution. Systems selected for comparison include a thiophenol (p-methylthiophenol), a thioanisole (p-methylthioanisole) and phenol, in vacuum and in cyclohexane solution. UV excitation in the gas phase results in RX-Y (X = O, S; Y = H, CH3) bond fission in all cases, but over timescales that vary by similar to 4 orders of magnitude - all of which behaviours can be rationalised on the basis of the relevant bound and dissociative excited state potential energy surfaces (PESs) accessed by UV photoexcitation, and of the conical intersections that facilitate radiationless transfer between these PESs. Time-resolved UV pump-broadband UV/visible probe and/or UV pump-broadband IR probe studies of the corresponding systems in cyclohexane solution reveal additional processes that are unique to the condensed phase. Thus, for example, the data clearly reveal evidence of (i) vibrational relaxation of the photoexcited molecules prior to their dissociation and of the radical fragments formed upon X-Y bond fission, and (ii) geminate recombination of the RX and Y products (leading to reformation of the ground state parent and/or isomeric adducts). Nonetheless, the data also show that, in each case, the characteristics (and the timescale) of the initial bond fission process that occurs under isolated molecule conditions are barely changed by the presence of a weakly interacting solvent like cyclohexane. These condensed phase studies are then extended to an ether analogue of phenol (allyl phenyl ether), wherein UV photo-induced RO-allyl bond fission constitutes the first step of a photo-Claisen rearrangement.</p
Wavelength tunable 10-GHz 3-ps pulse source using a dispersion decreasing fiber-based nonlinear optical loop mirror
No full textWe experimentally demonstrate the use of a dispersion decreasing fiber (DDF)-based nonlinear optical loop mirror (NOLM) for the generation of wavelength tunable soliton-like pulses at a repetition rate of 10 GHz. We compress ~12 ps Gaussian pulses from an electro-absorption modulator (EAM) (followed by 125 m of DCF for preliminary linear dispersion compensation) into 3 ps pedestal-free pulses using both high-order soliton compression and nonlinear switching effects within an 8.5 km DDF-based loop mirror. The output pulses from the DDF-based NOLM show considerable pedestal reduction compared to those obtained by directly compressing the EAM seed pulses via a single passage through the DDF. Wavelength tuning of the compressed pulses over a ~15 nm bandwidth (from 1541 to 1556 nm) is demonstrated without a significant increase in pulse duration or degradation in pulse quality
Player agency in interactive narrative: audience, actor & author
No full textThe question motivating this review paper is, how can
computer-based interactive narrative be used as a constructivist learn-
ing activity? The paper proposes that player agency can be used to
link interactive narrative to learner agency in constructivist theory,
and to classify approaches to interactive narrative. The traditional
question driving research in interactive narrative is, ‘how can an in-
teractive narrative deal with a high degree of player agency, while
maintaining a coherent and well-formed narrative?’ This question
derives from an Aristotelian approach to interactive narrative that,
as the question shows, is inherently antagonistic to player agency.
Within this approach, player agency must be restricted and manip-
ulated to maintain the narrative. Two alternative approaches based
on Brecht’s Epic Theatre and Boal’s Theatre of the Oppressed are
reviewed. If a Boalian approach to interactive narrative is taken the
conflict between narrative and player agency dissolves. The question
that emerges from this approach is quite different from the traditional
question above, and presents a more useful approach to applying in-
teractive narrative as a constructivist learning activity
A review of X-ray laser development at Rutherford Appleton Laboratory
No full textRecent experiments undertaken at the Rutherford Appleton Laboratory to produce X-ray lasing over the 5-30 nm wavelength range are reviewed. The efficiency of lasing is optimized when the main pumping pulse interacts with a preformed plasma. Experiments using double 75-ps pulses and picosecond pulses superimposed on 300-ps background pulses are described. The use of travelling wave pumping with the approximately picosecond pulse experiments is necessary as the gain duration becomes comparable to the time for the X-ray laser pulse to propagate along the target length. Results from a model taking account of laser saturation and deviations from the speed of light c of the travelling wave and X-ray laser group velocity are presented. We show that X-ray laser pulses as short as 2-3 ps can be produced with optical pumping pulses of approximate to1-ps
Charisma and Spirituality in the Early Church: A Study of Messalianism and Pseudo-Macarius
No full textThe thesis is an investigation into the concept of Charisma and Spirituality in the Early Church with particular emphasis upon the writings of Ps-Macarius, and of a group of ascetics known as the Messalians, evident in the late fourth / early fifth centuries. The Macarian writings are
examined to see what they reveal about the experiential pneumatic theology of the Early Church, the relationship between Syrian and Hellenic traditions of Christian Rhetoric, and the relationship between Ps-Macarius and the Cappadocian Circle. The Macarian corpus as a whole is examined to assess its rhetorical influences and style. The rhetoric of the Macarian corpus is seen to illustrate a high degree of sophistication. This study also gives definition to two terms that have become imprecise and diverse in their use: 'enkrateia' (self-control), and
`Syrian Christianity'. By isolating the characteristics of enkratefa the definitive stages of an encratic lifestyle are identified. The breaking down of the term into enkrateia, radical enkrateta and exclusive enkrateta enables a much clearer discussion to take place as to the
nature of the encratic theology of a group or individual. The final element of this study is a consideration of the distinct Macarian imagery that is evident within the corpus. Two images are considered in detail, the 'flight of the soul' and 'sober intoxication'. Overall this study
shows the variety of influences upon Ps-Macarius, and the uniqueness of his expression. The influences upon Ps-Macarius include a context of endemic Syrian spirituality, a radical encratic lifestyle, a Hellenic rhetorical training, and a distinct interpretation of Platonic and Neo-
Platonic images, coupled to the wider Judaic / Mesopotamian influences of his Church. It is shown that Ps-Macarius represents an individual voice that is distinct and recognisable amongst the Fathers of the Church
Nuclear translocation and signalling of L1-CAM in human carcinoma cells requires ADAM10 and presenilin/gamma-secretase activity
No full textL1-CAM (L1 cell-adhesion molecule), or more simply L1, plays an important role in the progression of human carcinoma. Overexpression promotes tumour-cell invasion and motility, growth in nude mice and tumour metastasis. It is feasible that L1-dependent signalling contributes to these effects. However, little is known about its mechanism in tumour cells. We reported previously that L1 is cleaved by ADAM (a disintegrin and metalloprotease) and that the cytoplasmic part is essential for L1 function. Here we analysed more closely the role of proteolytic cleavage in L1-mediated nuclear signalling. Using OVMz carcinoma cells and L1-transfected cells as a model, we found that ADAM10-mediated cleavage of L1 proceeds in lipid raft and non-raft domains. The cleavage product, L1-32, is further processed by PS (presenilin)/gamma-secretase to release L1-ICD, an L1 intracellular domain of 28 kDa. Overexpression of dominantnegative PS1 or use of a specific gamma-secretase inhibitor leads to an accumulation of L1-32. Fluorescence and biochemical analysis revealed a nuclear localization for L1-ICD. Moreover, inhibition of ADAM10 and/or gamma-secretase blocks nuclear translocation of L1-ICD and L1-dependent gene regulation. Overexpression of recombinant L1-ICD mediates gene regulation in a similar manner to full-length L1. Our results establish for the first time that regulated proteolytic processing by ADAM10 and PS/gamma-secretase is essential for the nuclear signalling of L1 in human carcinoma cell lines. Key words: a disintegrin and metalloprotease 10 (ADAM10), L1 cell-adhesion molecule (L1-CAM), nuclear translocation, presenilin (PS)/gamma-secretase activity, raft, signalling
Evidence for resistance of the microenvironment of the primary plastoquinone acceptor (QA−·Fe2+) to mild trypsinization in PS II particles
No full textAbstractMild trypsinization of PS II particles at pH 6.0, which almost completely blocks reoxidation of the primary plastoquinone acceptor, QA−·Fe2+, by endogenous plastoquinone (PQ) as well as by exogenous (p-BQ) quinones, does not affect the shape or the amplitude of the EPR signal attributed to QA−·Fe2+. The effect of DCMU on the EPR signal [(1984) FEBS Lett. 105, 156-162] is completely eliminated in mildly trypsinized PS II particles. The lack of effect of mild trypsin treatment on the QA−·Fe2+ microenvironment is briefly discussed in relation to the functional and structural organization of the PS II acceptor side.Photosystem IISemiquinone-iron complexTrypsinHerbicidePhotosythesi
LinoSPAD2: A 512×1 linear SPAD camera with system-level 135-ps SPTR and a reconfigurable computational engine for time-resolved single-photon imaging
No full textThe LinoSPAD2 camera combines a 512×1 linear single-photon avalanche diode (SPAD) array with an FPGA-based photon-counting and time-stamping platform, to create a reconfigurable sensing system capable of detecting single photons. The read-out is fully parallel, where each SPAD is connected to a different FPGA input. The hardware can be reconfigured to achieve different functionalities, such as photon counters, time-to-digital converter (TDC) arrays and histogramming units. Time stamping is performed by an array of 64 TDCs, with 20 ps resolution (LSB), serving 256 channels by means of 4:1 sharing. At sensor level, the pixel pitch is 26.2 μm with a fill factor of 25.1%. The median dark count rate of each SPAD at room temperature is below 100 cps at 6V excess bias, the single-photon timing resolution (SPTR) of each channel is 50 ps FWHM, and the peak photon detection probability reaches ~50% at 510 nm at the same excess bias. The fill factor can be increased by 2.3× by means of microlenses, with good spatial uniformity and flat spectral response above 400 nm. At system level, the average instrument response function (IRF) is 135 ps FWHM. The LinoSPAD2 camera enables a wide range of time-of-flight and time-resolved applications, including 3D imaging, fluorescence lifetime imaging microscopy (FLIM), heralded spectroscopy, and compressive Raman imaging, to name a few. Thanks to its features, LinoSPAD2 is a novel generation of reconfigurable single-photon image sensors capable of adapting their read-out and processing to match application-specific requirements, and combining SPAD arrays with advanced, massively-parallel computational functionalities. Green Open Access added to TU Delft Institutional Repository ‘You share, we take care!’ – Taverne project https://www.openaccess.nl/en/you-share-we-take-care Otherwise as indicated in the copyright section: the publisher is the copyright holder of this work and the author uses the Dutch legislation to make this work public.QCD/DiCarlo La
Glazing systems with Parallel Slats Transparent Insulation Material (PS-TIM): evaluation of building energy and daylight performance
No full textBeing responsible for a significant proportion of total heat loss in façade dominated buildings, the design and specification of the envelope, particularly the building’s glazing system, is a key factor in determining overall energy consumption. To address this, an innovative double glazed façade system comprising parallel transparent/translucent plastic slats sandwiched between the glass panes to form a Parallel Slat Transparent Insulation Material (PS-TIM) system is proposed as a potential solution. This PS-TIM system reduces heat transfer between the glazing panes whilst maintaining access to solar radiation and daylight.
The presence of the PS-TIM structure significantly affects the thermal and optical performance of the window system in which it is employed. This presents a further significant challenge when trying to predict its performance using dynamic building simulation approaches. Using a typical small office as a case study subject to varying climatic conditions, we investigate the thermal and optical behaviour of a range of PS-TIMs with respect to their daylight and energy performance. We find that when compared to a conventional double glazed system, the application of PS-TIMs can result in a more visually comfortable and uniformly lit environment, which might be desired in an office space, and, in the specific case of the small office under test, can result in a reduction in energy consumption of up to 35.8%. Furthermore, having explored the performance of the system in response to varying climatic conditions, we also present some advice as to how architects and engineers might apply PS-TIMs to window systems or glazed façades
Synthesis and Characterization of PEO-PS-PEO Triblock Copolymer Conjugated with Ni-NTA for Biosensors, 2018
No full textPoly(ethylene oxide)-poly(styrene)-poly(ethylene oxide) triblock copolymer with di-hydroxyl terminated groups (HO-PEO-PS-PEO-OH) was conjugated with nitrilotriacetic acid (NTA) via esterification reaction using N,N'-Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP) and Dimethylformamide (DMF) as a solvent at 80 ?C. The poly(ethylene oxide)-poly(styrene)-poly(ethylene oxide) with NTA end groups (NTA-PEO-PS-PEO-NTA) was characterized and structure confirmed by 1H NMR, 13C NMR, and FT-IR spectroscopies. Thermogravimetric analysis (TGA) was carried out to investigate the thermal stability of the starting triblock copolymer poly(ethylene oxide)-poly(styrene)-poly(ethylene oxide) with di-hydroxyl terminated groups (HO-PEO-PS-PEO-OH) and the conjugated poly(ethylene oxide)-poly(styrene)-poly(ethylene oxide) functional polymer (NTA-PEO-PS-PEO-NTA). Surface morphologies of the (HO-PEO-PS-PEO-OH) and (NTA-PEO-PS-PEO-NTA) were studied by atomic force microscopy. In addition, the size distributions were determined using dynamic light scattering. The thermal behavior of the (HO-PEO-PS-PEO-OH) and (NTA-PEO-PS-PEO-NTA) were examined by differential scanning calorimetry (DSC). DSC thermograms indicate the formation of a two phase polymer matrix. The poly(ethylene oxide)-poly(styrene)-poly(ethylene oxide) with NTA functionalized end groups (NTA-PEO-PS-PEO-NTA) was bound or chelated with Ni(II) metal ion. The binding studies were carried out by ultraviolet-visible (UV-Vis) spectroscopy. The electronic behaviors of PEO-b-PS-b-PEO/ PS/ NTA-PEO-b-PS-b-PEO-NTA with ratio (1/5/1) and PEO-b-PS-b-PEO/ PS/ NTA-PEO-b-PS-b-PEO-NTA-Ni containing 1% of oxidized single-walled carbon nanotubes (SWCNTs) were investigated by IV plots from Kelvin sensing. The IV plots before sensitizing with protein varied from the IV plots after binding with protein indicating that the composites may be used as active components in biosensors. KEYWORDS: Materials Chemistry, Polymer Chemistr
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