Profluorescent nitroxides as sensitive probes of oxidative change and free radical reactions

This paper presents a review on the use of tethered nitroxide–fluorophore molecules as probes of oxidative change and free radical generation and reaction. The proximity of the nitroxide free radical to the fluorophore suppresses the normal fluorescence emission process. Nitroxide free radical scavenging, metabolism or redox chemistry return the system to its natural fluorescent state and so these tethered nitroxide–fluorophore molecules are described as being profluorescent. A survey of profluorescent nitroxides found in the literature is provided as well as background on the mechanism of action and applications of these compounds as fluorometric probes within the fields of biological, materials and environmental sciences.

Polycarbonate based nonchemically amplified photoresists for extreme ultraviolet lithography

Some initial EUVL patterning results for polycarbonate based non-chemically amplified resists are presented. Without full optimization the developer a resolution of 60 nm line spaces could be obtained. With slight overexposure (1.4 × E0) 43.5 nm lines at a half pitch of 50 nm could be printed. At 2x E0 a 28.6 nm lines at a half pitch of 50 nm could be obtained with a LER that was just above expected for mask roughness. Upon being irradiated with EUV photons, these polymers undergo chain scission with the loss of carbon dioxide and carbon monoxide. The remaining photoproducts appear to be non-volatile under standard EUV irradiation conditions, but do exhibit increased solubility in developer compared to the unirradiated polymer. The sensitivity of the polymers to EUV light is related to their oxygen content and ways to increase the sensitivity of the polymers to 10 mJ cm-2 is discussed.

N-Aryl stilbazolium dyes as sensitizers for solar cells

Eight new N-arylstilbazolium chromophores with electron donating –NR2 (R = Me or Ph) substituents have been synthesized via Knoevenagel condensations and isolated as their PF6− salts. These compounds have been characterized by using various techniques including 1H NMR and IR spectroscopies and electrospray mass spectrometry. UV–vis absorption spectra recorded in acetonitrile are dominated by intense, low energy π → π* intramolecular charge-transfer (ICT) bands, and replacing Me with Ph increases the ICT energies. Cyclic voltammetric studies show irreversible reduction processes, together with oxidation waves that are irreversible for R = Me, but reversible for R = Ph. Single crystal X-ray structures have been determined for three of the methyl ester-substituted stilbazolium salts and for the Cl− salts of their picolinium precursors. Time-dependent density functional theory calculations afford reasonable predictions of ICT energies, but greater rigour is necessary for –NPh2 derivatives. The four new acid-functionalized dyes give moderate sensitization efficiencies (ca. 0.2%) when using TiO2-based photoanodes, with relatively higher values for R = Ph vs Me, while larger efficiencies (up to 0.8%) are achieved with ZnO substrates.

Mechanism of interaction of hydrocalumites (Ca/Al-LDH) with methyl orange and acidic scarlet GR

The development of new materials for water purification is of universal importance. Among these types of materials are layered double hydroxides (LDHs). Non-ionic materials pose a significant problem as pollutants. The interaction of methyl orange (MO) and acidic scarlet GR (GR) adsorption on hydrocalumite (Ca/Al-LDH-Cl) were studied by X-ray diffraction (XRD), infrared spectroscopy (MIR), scanning electron microscope (SEM) and near-infrared spectroscopy (NIR). The XRD results revealed that the basal spacing of Ca/Al-LDH-MO was expanded to 2.45 nm, and the MO molecules were intercalated with a inter-penetrating bilayer model in the gallery of LDH, with 49o tilting angle. Yet Ca/Al-LDH-GR was kept the same d-value as Ca/Al-LDH-Cl. The NIR spectrum for Ca/Al-LDH-MO showed a prominent band around 5994 cm-1, assigned to the combination result of the N-H stretching vibrations, which was considered as a mark to assess MO- ion intercalation into Ca/Al-LDH-Cl interlayers. From SEM images, the particle morphology of Ca/Al-LDH-MO mainly changed to irregular platelets, with a “honey-comb” like structure. Yet the Ca/Al-LDH-GR maintained regular hexagons platelets, which was similar to that of Ca/Al-LDH-Cl. All results indicated that MO- ion was intercalated into Ca/Al-LDH-Cl interlayers, and acidic scarlet GR was only adsorped upon Ca/Al-LDH-Cl surfaces.

Comparison of Kenz Lifecorder EX and ActiGraph accelerometers in 10-yr-old children

A new accelerometer, the Kenz Lifecorder EX (LC; Suzuken Co. Ltd, Nagoya, Japan), offers promise as a feasible monitor alternative to the commonly used Actigraph (AG: Actigraph LLC, Fort Walton Beach, FL). Purpose: This study compared the LC and AG accelerometers and the Yamax SW-200 pedometer (DW) under free-living conditions with regard to children's steps taken and time in light-intensity physical activity (PA) and moderate to vigorous PA (MVPA). Methods: Participants (N = 31, age = 10.2 ± 0.4 yr) wore LC, AG, and DW monitors from arrival at school (7:45 a.m.) until they went to bed. Time in light and MVPA intensities were calculated using two separate intensity classifications for the LC (LC_4 and LC_5) and four classifications for the AG (AG_Treuth, AG_Puyau, AG_Trost, and AG_Freedson). Both accelerometers provided steps as outputs. DW steps were self-recorded. Repeated-measures ANOVA was used to assess overlapping monitor outputs. Results: There was no difference between DW and LC steps (Δ = 200 steps), but a nonsignificant trend was observed in the pairwise comparison between DW and AG steps (Δ = 1001 steps, P = 0.058). AG detected significantly greater steps than the LC (Δ = 801 steps, P = 0.001). Estimates of light-intensity activity minutes ranged from a low of 75.6 ± 18.4 min (LC_4) to a high of 309 ± 69.2 min (AG_Treuth). Estimates of MVPA minutes ranged from a low of 25.9 ± 9.4 min (LC_5) to a high of 112.2 ± 34.5 min (AG_Freedson). No significant differences in MVPA were seen between LC_5 and AG_Treuth (Δ = 4.9 min) or AG_Puyau (Δ = 1.7 min). Conclusion: The LC detected a comparable number of steps as the DW but significantly fewer steps than the AG in children. Current results indicate that the LC_5 and either AG_Treuth or AG_Puyau intensity derivations provide similar mean estimates of time in MVPA during-free living activity in 10-yr-old children.

Motivational Interviewing (MINT) improves Continuous Positive Airway Pressure (CPAP) acceptance and adherence : a randomised controlled trial

Objective: Adherence to Continuous Positive Airway Pressure Therapy (CPAP) for Obstructive Sleep Apnoea (OSA) is poor. We assessed the effectiveness of a motivational interviewing intervention (MINT) in addition to best practice standard care to improve acceptance and adherence to CPAP therapy in people with a new diagnosis of OSA. Method: 106 Australian adults (69% male) with a new diagnosis of obstructive sleep apnoea and clinical recommendation for CPAP treatment were recruited from a tertiary sleep disorders centre. Participants were randomly assigned to receive either three sessions of a motivational interviewing intervention ‘MINT’ (n=53; mean age=55.4 years), or no intervention ‘Control’ (n=53; mean age=57.74). The primary outcome was the difference between the groups in objective CPAP adherence at 1 month, 2 months, 3 months and 12 months follow-up. Results: Fifty (94%) participants in the MINT group and 50 (94%) of participants in the control group met all inclusion and exclusion criteria and were included in the primary analysis. The hours of CPAP use per night in the MINT group at 3 months was 4.63 hours and 3.16 hours in the control group (p=0.005). This represents almost 50% better adherence in the MINT group relative to the control group. Patients in the MINT group were substantially more likely to accept CPAP treatment. Conclusions: MINT is a brief, manualized, effective intervention which improves CPAP acceptance and objective adherence rates as compared to standard care alone.

Exploring Rhythmic Automata

The use of Cellular Automata (CA) for musical purposes has a rich history. In general the mapping of CA states to note-level music representations has focused on pitch mapping and downplayed rhythm. This paper reports experiments in the application of one-dimensional cellular automata to the generation and evolution of rhythmic patterns. A selection of CA tendencies are identified that can be used as compositional tools to control the rhythmic coherence of monophonic passages and the polyphonic texture of musical works in broad-brush, rather than precisely deterministic, ways. This will provide the composer and researcher with a clearer understanding of the useful application of CAs for generative music.

Raman spectroscopy of the multi-anion mineral schlossmacherite (H3O,Ca)Al3(AsO4,PO4,SO4)2(OH)6

The mineral schlossmacherite (H3O,Ca)Al3(AsO4,PO4,SO4)2(OH)6 , a multi-cation-multi-anion mineral of the beudantite mineral subgroup has been characterised by Raman spectroscopy. The mineral and related minerals functions as a heavy metal collector and is often amorphous or poorly crystalline, such that XRD identification is difficult. The Raman spectra are dominated by an intense band at 864 cm-1, assigned to the symmetric stretching mode of the AsO43- anion. Raman bands at 809 and 819 cm-1 are assigned to the antisymmetric stretching mode of AsO43- . The sulphate anion is characterised by bands at 1000 cm-1 (ν1), and at 1031, 1082 and 1139 cm-1 (ν3). Two sets of bands in the OH stretching region are observed: firstly between 2800 and 3000 cm-1 with bands observed at 2850, 2868, 2918 cm-1 and secondly between 3300 and 3600 with bands observed at 3363, 3382, 3410, 3449 and 3537 cm-1. These bands enabled the calculation of hydrogen bond distances and show a wide range of H-bond distances.

Performance recordivity : studio music in a live context

A broad range of positions is articulated in the academic literature around the relationship between recordings and live performance. Auslander (2008) argues that “live performance ceased long ago to be the primary experience of popular music, with the result that most live performances of popular music now seek to replicate the music on the recording”. Elliott (1995) suggests that “hit songs are often conceived and produced as unambiguous and meticulously recorded performances that their originators often duplicate exactly in live performances”. Wurtzler (1992) argues that “as socially and historically produced, the categories of the live and the recorded are defined in a mutually exclusive relationship, in that the notion of the live is premised on the absence of recording and the defining fact of the recorded is the absence of the live”. Yet many artists perform in ways that fundamentally challenge such positions. Whilst it is common practice for musicians across many musical genres to compose and construct their musical works in the studio such that the recording is, in Auslander’s words, the ‘original performance’, the live version is not simply an attempt to replicate the recorded version. Indeed in some cases, such replication is impossible. There are well known historical examples. Queen, for example, never performed the a cappella sections of Bohemian Rhapsody because it they were too complex to perform live. A 1966 recording of the Beach Boys studio creation Good Vibrations shows them struggling through the song prior to its release. This paper argues that as technology develops, the lines between the recording studio and live performance change and become more blurred. New models for performance emerge. In a 2010 live performance given by Grammy Award winning artist Imogen Heap in New York, the artist undertakes a live, improvised construction of a piece as a performative act. She invites the audience to choose the key for the track and proceeds to layer up the various parts in front of the audience as a live performance act. Her recording process is thus revealed on stage in real time and she performs a process that what would have once been confined to the recording studio. So how do artists bring studio production processes into the live context? What aspects of studio production are now performable and what consistent models can be identified amongst the various approaches now seen? This paper will present an overview of approaches to performative realisations of studio produced tracks and will illuminate some emerging relationships between recorded music and performance across a range of contexts.

Is the mineral borickyite (Ca,Mg)(Fe3+,Al)4(PO4,SO4,CO3)(OH)8•3-7.5H2O the same as delvauxite CaFe3+4(PO4,SO4)2(OH)8•4-6H2O?

The two minerals borickyite and delvauxite CaFe3+4(PO4,SO4)2(OH)8•4-6H2O have the same formula. Are the minerals identical or different? The minerals borickyite and delvauxite have been characterised by Raman spectroscopy. The minerals are related to the minerals diadochite and destinezite. Both minerals are amorphous. Delvauxite appears to vary in crystallinity from amorphous to semi-crystalline. The minerals are often X-ray non-diffracting. The minerals are found in soils and may be described as ‘colloidal’ minerals. Vibrational spectroscopy enables an assessment of the molecular structure of borickyite and delvauxite. Bands are assigned to phosphate and sulphate stretching and bending modes. Multiple water bending and stretching modes imply that non-equivalent water molecules in the structure exist with different hydrogen bond strengths. The two minerals show differing spectra and must be considered as different minerals.

Controlling Minimally-Actuated Vehicles for Applications in Ocean Observation

Establishing a persistent presence in the ocean with an AUV to observe temporal variability of large-scale ocean processes requires a unique sensor platform. In this paper, we propose a strategy that utilizes ocean model predictions to increase the autonomy and control of Lagrangian or profiling floats for precisely this purpose. An A* planner is applied to a local controllability map generated from predictions of ocean currents to compute a path between prescribed waypoints that has the highest likelihood of successful execution. The control to follow the planned path is computed by use of a model predictive controller. This controller is designed to select the best depth for the vehicle to exploit ambient currents to reach the goal waypoint. Mission constraints are employed to simulate a practical data collection mission. Results are presented in simulation for a mission off the coast of Los Angeles, CA USA, and show surprising results in the ability of a Lagrangian float to reach a desired location.

Selling James Bond : product placement in the James Bond films

The character of James Bond for many people is intrinsically linked in their minds with particular brands – Aston Martin, Bollinger, Omega, Smirnoff vodka, and so on. This direct association between character and brand highlights the intrinsic role of product placement in the film industry, and in the James Bond films in particular. Selling James Bond: Product Placement in the James Bond Films provides a comprehensive overview of the history of product placement in the James Bond series – charting the progression of the practice and drawing direct correlations to significant cultural and historical events that impacted upon the number and types of products incorporated into the series. While primarily a financial arrangement, it is also important that the practice of product placement be examined and understood in relation to these cultural contexts, an area of research so far largely ignored by academic study. Through extensive content analysis of the official James Bond film series, as well as utilising directors’ commentary and industry reports, this book illustrates the strong impact specific cultural and historical events have had on the practice of product placement in the series. In doing so, it provides an exciting and in-depth “behind the scenes” look at the James Bond film series, and its complicated and sometimes contentious history of product placement. In the process, it charts the gradual emergence of product placement from the more traditional background shot to becoming so embedded in the actual film narrative that they have become simply yet another method for filmmakers to produce cultural meaning.