Surface functionalized spherical nanoparticles: an optical assessment of local chirality

Electromagnetic radiation propagating through any molecular system typically experiences a characteristic change in its polarization state as a result of light-matter interaction. Circularly polarized light is commonly absorbed or scattered to an extent that is sensitive to the incident circularity, when it traverses a medium whose constituents are chiral. This research assesses specific modifications to the properties of circularly polarized light that arise on passage through a system of surface-functionalized spherical nanoparticles, through the influence of chiral molecules on their surfaces. Non-functionalized nanospheres of atomic constitution are usually inherently achiral, but can exhibit local chirality associated with such surface-bound chromophores. The principal result of this investigation is the quantification of functionally conferred nanoparticle chirality, manifest through optical measurements such as circularly polarized emission. The relative position of chiral chromophores fixed to a nanoparticle sphere are first determined by means of spherical coverage co-ordinate analysis. The total electromagnetic field received by a spatially fixed, remote detector is then determined. It is shown that bound chromophores will accommodate both electric and magnetic dipole transition moments, whose scalar product represents the physical and mathematical origin of chiral properties identified in the detected signal. The analysis concludes with discussion of the magnitude of circular differential optical effects, and their potential significance for the characterization of surface-functionalized nanoparticles

London force and energy transportation between interfacial surfaces

With appropriately selected optical frequencies, pulses of radiation propagating through a system of chemically distinct and organized components can produce areas of spatially selective excitation. This paper focuses on a system in which there are two absorptive components, each one represented by surface adsorbates arrayed on a pair of juxtaposed interfaces. The adsorbates are chosen to be chemically distinct from the material of the underlying surface. On promotion of any adsorbate molecule to an electronic excited state, its local electronic environment is duly modified, and its London interaction with nearest neighbor molecules becomes accommodated to the new potential energy landscape. If the absorbed energy then transfers to a neighboring adsorbate of another species, so that the latter acquires the excitation, the local electronic environment changes and compensating motion can be expected to occur. Physically, this is achieved through a mechanism of photon absorption and emission by molecular pairs, and by the engagement of resonance transfer of energy between them. This paper presents a detailed analysis of the possibility of optically effecting such modifications to the London force between neutral adsorbates, based on quantum electrodynamics (QED). Thus, a precise link is established between the transfer of excitation and ensuing mechanical effects

On the interactions between molecules in an off-resonant laser beam:Evaluating the response to energy migration and optically induced pair forces

Electronically excited molecules interact with their neighbors differently from their ground-state counterparts. Any migration of the excitation between molecules can modify intermolecular forces, reflecting changes to a local potential energy landscape. It emerges that throughput off-resonant radiation can also produce significant additional effects. The context for the present analysis of the mechanisms is a range of chemical and physical processes that fundamentally depend on intermolecular interactions resulting from second and fourth-order electric-dipole couplings. The most familiar are static dipole-dipole interactions, resonance energy transfer (both second-order interactions), and dispersion forces (fourth order). For neighboring molecules subjected to off-resonant light, additional forms of intermolecular interaction arise in the fourth order, including radiation-induced energy transfer and optical binding. Here, in a quantum electrodynamical formulation, these phenomena are cast in a unified description that establishes their inter-relationship and connectivity at a fundamental level. Theory is then developed for systems in which the interplay of these forms of interaction can be readily identified and analyzed in terms of dynamical behavior. The results are potentially significant in Förster measurements of conformational change and in the operation of microelectromechanical and nanoelectromechanical devices. © 2009 American Institute of Physics

(Re)conceptualising coach education and development: towards a rhizomatic approach

To ensure sport coaches across all domains deliver ethical practices, appropriately educating the coaching workforce is of paramount importance. Yet, coach education programmes have been heavily critiqued for failing to enhance coaches’ knowledge and practice. In recognising the sociocultural nature of coach learning, researchers have drawn upon prominent social theorists such as Bourdieu, Foucault, and Bernstein amongst others to critically analyse coach education provision. However, the notion of rhizomatic learning, derived from the philosophy of Deleuze and Guattari, has yet to be applied to coach education research, despite its ability to disrupt normalised and linear education systems. Consequently, the aim of this new horizons paper is to introduce rhizomatic learning as a possible framework for (re)conceptualising coach education and development. The intention of this paper is to put Deleuze and Guattari’s concepts “to work” to help theorise how social actors and coaching discourses function to produce learning and practice

A molecular theory for two-photon and three-photon fluorescence polarization

In the analysis of molecular structure and local order in heterogeneous samples, multiphoton excitation of fluorescence affords chemically specific information and high-resolution imaging. This report presents the results of an investigation that secures a detailed theoretical representation of the fluorescence polarization produced by one-, two-, and three-photon excitations, with orientational averaging procedures being deployed to deliver the fully disordered limits. The equations determining multiphoton fluorescence response prove to be expressible in a relatively simple, generic form, and graphs exhibit the functional form of the multiphoton fluorescence polarization. Amongst other features, the results lead to the identification of a condition under which the fluorescence produced through the concerted absorption of any number of photons becomes completely unpolarized. It is also shown that the angular variation of fluorescence intensities is reliable indicator of orientational disorder

Signatures of material and optical chirality:Origins and measures

Chirality in materials and light is of abiding interest across a broad range of scientific disciplines. This article discusses present and emerging issues in relation to molecular and optical chirality, also including some important developments in chiral metamaterials. Quantifying the chirality of matter or light leads to issues concerning the most appropriate measures, such as a helicity parameter for specific chiral chromophores and technical measures of light chirality. An optical helicity and chirality density depend on a difference between the numbers of left- and right-handed photons in a beam. In connection with circularly polarized luminescence, adoption of the Stokes parameter to spontaneous emission from chiral molecules invites critical attention. Modern spectroscopic techniques are often based on the different response arising from left-handed circularly polarized light compared to right-handed light. This dissimilarity can be exploited as a foundation for the separation of chiral molecules, promising new avenues of application

Compliance With Protocols for Prevention of Neonatal Group B Streptococcal Sepsis: Practicalities and Limitations

Objective: To compare two protocols for intrapartum antibiotic prophylaxis (IAP) against neonatal group B streptococcal (GBS) sepsis, with respect to staff compliance, in a prospective cohort study in the obstetric units of a community hospital (A) and a university teaching hospital (B). Methods: Cohorts comprised about 500 women attending antenatal clinics at each hospital (total 1096). Women identified as GBS carriers at 26–32 weeks'gestation and those who had intrapartum clinical risk factors (CRF) were eligible for IAP. Compliance was defined as the proportion of women eligible for IAP who received it according to protocol–as determined by audit of case records–and compared between hospitals and according to indication. Results: Overall, 39% of women were eligible for IAP. Indications were GBS carriage alone (21%), CRF alone (13% ) and both (5% ). Compliance was similar for GBS carriers at both hospitals: 78% at Hospital A and 76% at Hospital B. However, because of the poor predictive value of screening before 32 weeks, only 65%of intrapartum GBS carriers actually received IAP. For women with CRF only, compliance was significantly lower at Hospital B than Hospital A (56 vs. 75%; p= 0.03). Conclusions: According to currently recommended protocols, about one-third of healthy women are eligible for intrapartum antibiotics to prevent neonatal GBS sepsis. In practice, antibiotics are often used inefficiently because of poor compliance with protocols and poor predictive values of selection criteria. Better implementation strategies should improve compliance, but GBS vaccines are needed to replace prophylactic antibiotic use, with its associated disadvantages

Lifestyle Sports and Physical Education Teachers’ Professional Development in the United Kingdom: A Qualitative Survey Analysis

Lifestyle sports can contribute to national sport and physical activity agendas. However, schools in the United Kingdom (UK) have generally resisted the implementation of such activities within the physical education (PE) curriculum. This may stem from PE teachers’ limited knowledge and restricted engagement with lifestyle sports continuing professional development (CPD), coupled with the dominance of traditional team sports within the PE curriculum. Consequently, the aim of this research was to explore the opportunities and challenges PE teachers in the UK encounter when delivering lifestyle sports, in addition to understanding their current professional development needs to enhance their practice. Data were collected via an online qualitative survey involving 53 UK-based PE teachers. Following a reflexive thematic analysis process, three themes were developed: (1) PE teachers’ understanding, conceptualisation, and delivery of lifestyle sports; (2) challenges to delivering lifestyle sports within the PE curriculum; and (3) the learning needs and CPD preferences of PE teachers. Findings indicated that the participants possessed diverse conceptualisations of lifestyle sports, while faced with logistical, contextual, and personal factors which impacted their practice. Furthermore, the participants outlined their preferences towards lifestyle sports CPD and the challenges restricting their engagement with learning opportunities. Recommendations for future research are discussed