How mobile are dye adsorbates and acetonitrile molecules on the surface of TiO2 nanoparticles? A quasi-elastic neutron scattering study

Motions of molecules adsorbed to surfaces may control the rate of charge transport within monolayers in systems such as dye sensitized solar cells. We used quasi-elastic neutron scattering (QENS) to evaluate the possible dynamics of two small dye moieties, isonicotinic acid (INA) and bis-isonicotinic acid (BINA), attached to TiO2 nanoparticles via carboxylate groups. The scattering data indicate that moieties are immobile and do not rotate around the anchoring groups on timescales between around 10 ps and a few ns (corresponding to the instrumental range). This gives an upper limit for the rate at which conformational fluctuations can assist charge transport between anchored molecules. Our observations suggest that if the conformation of larger dye molecules varies with time, it does so on longer timescales and/or in parts of the molecule which are not directly connected to the anchoring group. The QENS measurements also indicate that several layers of acetonitrile solvent molecules are immobilized at the interface with the TiO2 on the measurement time scale, in reasonable agreement with recent classical molecular dynamics results

On the measurement of frequency and of its sample variance with high-resolution counters

A frequency counter measures the input frequency $\bar{\nu}$ averaged over a suitable time $\tau$, versus the reference clock. High resolution is achieved by interpolating the clock signal. Further increased resolution is obtained by averaging multiple frequency measurements highly overlapped. In the presence of additive white noise or white phase noise, the square uncertainty improves from $\smash{\sigma^2_\nu\propto1/\tau^2}$ to $\smash{\sigma^2_\nu\propto1/\tau^3}$. Surprisingly, when a file of contiguous data is fed into the formula of the two-sample (Allan) variance $\smash{\sigma^2_y(\tau)=\mathbb{E}\{\frac12(\bar{y}_{k+1}-\bar{y}_k) ^2\}}$ of the fractional frequency fluctuation $y$, the result is the \emph{modified} Allan variance mod $\sigma^2_y(\tau)$. But if a sufficient number of contiguous measures are averaged in order to get a longer $\tau$ and the data are fed into the same formula, the results is the (non-modified) Allan variance. Of course interpretation mistakes are around the corner if the counter internal process is not well understood.Comment: 14 pages, 5 figures, 1 table, 18 reference

Question design in nurse-led and GP-led telephone triage for same-day appointment requests: a comparative investigation

Objective: To compare doctors’ and nurses’ communication with patients in primary care telephone triage consultations. Design: Qualitative comparative study of content and form of questions in 51 telephone triage encounters between practitioners (general practitioners (GPs)=29; nurses=22) and patients requesting a same-day appointment in primary care. Audio-recordings of nurse-led calls were synchronised with video recordings of nurse's use of computer decision support software (CDSS) during triage. Setting: 2 GP practices in Devon and Warwickshire, UK. Participants: 4 GPs and 29 patients; and 4 nurses and 22 patients requesting a same-day face-to-face appointment with a GP. Main outcome measure: Form and content of practitioner-initiated questions and patient responses during clinical assessment. Results: A total of 484 question–response sequences were coded (160 GP; 324 N). Despite average call lengths being similar (GP=4 min, 37 s, (SD=1 min, 26 s); N=4 min, 39 s, (SD=2 min, 22 s)), GPs and nurses differed in the average number (GP=5.51, (SD=4.66); N=14.72, (SD=6.42)), content and form of questions asked. A higher frequency of questioning in nurse-led triage was found to be due to nurses’ use of CDSS to guide telephone triage. 89% of nurse questions were oriented to asking patients about their reported symptoms or to wider-information gathering, compared to 54% of GP questions. 43% of GP questions involved eliciting patient concerns or expectations, and obtaining details of medical history, compared to 11% of nurse questions. Nurses using CDSS frequently delivered questions designed as declarative statements requesting confirmation and which typically preferred a ‘no problem’ response. In contrast, GPs asked a higher proportion of interrogative questions designed to request information. Conclusions: Nurses and GPs emphasise different aspects of the clinical assessment process during telephone triage. These different styles of triage have implications for the type of information available following nurse-led or doctor-led triage, and for how patients experience triage

Self-referential cognition and empathy in autism.

BACKGROUND: Individuals with autism spectrum conditions (ASC) have profound impairments in the interpersonal social domain, but it is unclear if individuals with ASC also have impairments in the intrapersonal self-referential domain. We aimed to evaluate across several well validated measures in both domains, whether both self-referential cognition and empathy are impaired in ASC and whether these two domains are related to each other. METHODOLOGY/PRINCIPAL FINDINGS: Thirty adults aged 19-45, with Asperger Syndrome or high-functioning autism and 30 age, sex, and IQ matched controls participated in the self-reference effect (SRE) paradigm. In the SRE paradigm, participants judged adjectives in relation to the self, a similar close other, a dissimilar non-close other, or for linguistic content. Recognition memory was later tested. After the SRE paradigm, several other complimentary self-referential cognitive measures were taken. Alexithymia and private self-consciousness were measured via self-report. Self-focused attention was measured on the Self-Focus Sentence Completion task. Empathy was measured with 3 self-report instruments and 1 performance measure of mentalizing (Eyes test). Self-reported autistic traits were also measured with the Autism Spectrum Quotient (AQ). Although individuals with ASC showed a significant SRE in memory, this bias was decreased compared to controls. Individuals with ASC also showed reduced memory for the self and a similar close other and also had concurrent impairments on measures of alexithymia, self-focused attention, and on all 4 empathy measures. Individual differences in self-referential cognition predicted mentalizing ability and self-reported autistic traits. More alexithymia and less self memory was predictive of larger mentalizing impairments and AQ scores regardless of diagnosis. In ASC, more self-focused attention is associated with better mentalizing ability and lower AQ scores, while in controls, more self-focused attention is associated with decreased mentalizing ability and higher AQ scores. Increasing private self-consciousness also predicted better mentalizing ability, but only for individuals with ASC. CONCLUSIONS/SIGNIFICANCE: We conclude that individuals with ASC have broad impairments in both self-referential cognition and empathy. These two domains are also intrinsically linked and support predictions made by simulation theory. Our results also highlight a specific dysfunction in ASC within cortical midlines structures of the brain such as the medial prefrontal cortex

Effects of Extreme Obliquity Variations on the Habitability of Exoplanets

We explore the impact of obliquity variations on planetary habitability in hypothetical systems with high mutual inclination. We show that large amplitude, high frequency obliquity oscillations on Earth-like exoplanets can suppress the ice-albedo feedback, increasing the outer edge of the habitable zone. We restrict our exploration to hypothetical systems consisting of a solar-mass star, an Earth-mass planet at 1 AU, and 1 or 2 larger planets. We verify that these systems are stable for $10^8$ years with N-body simulations, and calculate the obliquity variations induced by the orbital evolution of the Earth-mass planet and a torque from the host star. We run a simplified energy balance model on the terrestrial planet to assess surface temperature and ice coverage on the planet's surface, and we calculate differences in the outer edge of the habitable zone for planets with rapid obliquity variations. For each hypothetical system, we calculate the outer edge of habitability for two conditions: 1) the full evolution of the planetary spin and orbit, and 2) the eccentricity and obliquity fixed at their average values. We recover previous results that higher values of fixed obliquity and eccentricity expand the habitable zone, but also find that obliquity oscillations further expand habitable orbits in all cases. Terrestrial planets near the outer edge of the habitable zone may be more likely to support life in systems that induce rapid obliquity oscillations as opposed to fixed-spin planets. Such planets may be the easiest to directly characterize with space-borne telescopes.Comment: 46 pages, 12 Figures, 5 Table

The use of ICT in the assessment of modern languages: the English context and European viewpoints

The ever increasing explosion of highly attractive multimedia resources on offer has boosted the use of information and communication technology (ICT) in the teaching and learning of modern languages. The use of ICT to assess languages is less frequent, however, although online testing is starting to develop. This paper examines the national context for the assessment of modern foreign language proficiency in England, outlines the kinds of assessment currently available and the development of electronic forms of assessment and compares the above with the survey results of a European Union (EU) funded project on current good practice in online assessment of languages in other European countries. The findings indicate that speaking is inadequately served by online testing as tests currently focus primarily on receptive language skills. The implications for future successful online testing include the incorporation of interactive skills and effective formative feedback

Surprisingly different star-spot distributions on the near equal-mass equal-rotation-rate stars in the M dwarf binary GJ 65 AB

We aim to understand how stellar parameters such as mass and rotation impact the distribution of star-spots on the stellar surface. To this purpose, we have used Doppler imaging to reconstruct the surface brightness distributions of three fully convective M dwarfs with similar rotation rates. We secured high cadence spectral time series observations of the 5.5 au separation binary GJ 65, comprising GJ 65A (M5.5V, Prot = 0.24 d) and GJ 65B (M6V, Prot = 0.23 d). We also present new observations of GJ 791.2A (M4.5V, Prot = 0.31 d). Observations of each star were made on two nights with UVES, covering a wavelength range from 0.64 - 1.03μm. The time series spectra reveal multiple line distortions that we interpret as cool star-spots and which are persistent on both nights suggesting stability on the time-scale of 3 d. Spots are recovered with resolutions down to 8.3° at the equator. The global spot distributions for GJ 791.2A are similar to observations made a year earlier. Similar high latitude and circumpolar spot structure is seen on GJ 791.2A and GJ 65A. However, they are surprisingly absent on GJ 65B, which instead reveals more extensive, larger, spots concentrated at intermediate latitudes. All three stars show small amplitude latitude-dependent rotation that is consistent with solid body rotation. We compare our measurements of differential rotation with previous Doppler imaging studies and discuss the results in the wider context of other observational estimates and recent theoretical predictions