‘Click’ functionalised polymer resins : a new approach to the synthesis of surface attached bipyridinium and naphthalene diimide [2]rotaxanes

Herein we describe the design and synthesis of a series of solid-tethered [2]rotaxanes utilising crown ether-naphthalene diimide or crown ether- bipyridinium host guest interactions. TentaGel polystyrene resins were initially modified in a two-stage procedure to azide functionalised beads before the target supramolecular architectures were attached using a copper catalysed “click” procedure. The final assembly was examined using IR spectroscopy and gel-phase 1H High Resolution Magic Angle Spinning (HR MAS) NMR spectroscopy. The HR MAS technique enabled a direct comparison between the solid-tethered architectures and the synthesis and characterisation of analogous solution-based [2]rotaxanes to be made.

An MMP13-selective inhibitor delays primary tumor growth and the onset of tumor-associated osteolytic lesions in experimental models of breast cancer

We investigated the effects of the matrix metalloproteinase 13 (MMP13)-selective inhibitor, 5-(4-{4-[4-(4-fluorophenyl)-1,3-oxazol-2-yl]phenoxy}phenoxy)-5-(2-methoxyethyl) pyrimidine-2,4,6(1H,3H,5H)-trione (Cmpd-1), on the primary tumor growth and breast cancer-associated bone remodeling using xenograft and syngeneic mouse models. We used human breast cancer MDA-MB-231 cells inoculated into the mammary fat pad and left ventricle of BALB/c Nu/Nu mice, respectively, and spontaneously metastasizing 4T1.2-Luc mouse mammary cells inoculated into mammary fat pad of BALB/c mice. In a prevention setting, treatment with Cmpd-1 markedly delayed the growth of primary tumors in both models, and reduced the onset and severity of osteolytic lesions in the MDA-MB-231 intracardiac model. Intervention treatment with Cmpd-1 on established MDA-MB-231 primary tumors also significantly inhibited subsequent growth. In contrast, no effects of Cmpd-1 were observed on soft organ metastatic burden following intracardiac or mammary fat pad inoculations of MDA-MB-231 and 4T1.2-Luc cells respectively. MMP13 immunostaining of clinical primary breast tumors and experimental mice tumors revealed intra-tumoral and stromal expression in most tumors, and vasculature expression in all. MMP13 was also detected in osteoblasts in clinical samples of breast-to-bone metastases. The data suggest that MMP13-selective inhibitors, which lack musculoskeletal side effects, may have therapeutic potential both in primary breast cancer and cancer-induced bone osteolysis.

Survival models of community tenure and length of hospital stay for the seriously mentally ill : a 10-year perspective

Objective: To examine the effects of personal and community characteristics, specifically race and rurality, on lengths of state psychiatric hospital and community stays using maximum likelihood survival analysis with a special emphasis on change over a ten year period of time. Data Sources: We used the administrative data of the Virginia Department of Mental Health, Mental Retardation, and Substance Abuse Services (DMHMRSAS) from 1982-1991 and the Area Resources File (ARF). Given these two sources, we constructed a history file for each individual who entered the state psychiatric system over the ten year period. Histories included demographic, treatment, and community characteristics. Study Design: We used a longitudinal, population-based design with maximum likelihood estimation of survival models. We presented a random effects model with unobserved heterogeneity that was independent of observed covariates. The key dependent variables were lengths of inpatient stay and subsequent length of community stay. Explanatory variables measured personal, diagnostic, and community characteristics, as well as controls for calendar time. Data Collection: This study used secondary, administrative, and health planning data. Principal Findings: African-American clients leave the community more quickly than whites. After controlling for other characteristics, however, race does not affect hospital length of stay. Rurality does not affect length of community stays once other personal and community characteristics are controlled for. However, people from rural areas have longer hospital stays even after controlling for personal and community characteristics. The effects of time are significantly smaller than expected. Diagnostic composition effects and a decrease in the rate of first inpatient admissions explain part of this reduced impact of time. We also find strong evidence for the existence of unobserved heterogeneity in both types of stays and adjust for this in our final models. Conclusions: Our results show that information on client characteristics available from inpatient stay records is useful in predicting not only the length of inpatient stay but also the length of the subsequent community stay. This information can be used to target increased discharge planning for those at risk of more rapid readmission to inpatient care. Correlation across observed and unobserved factors affecting length of stay has significant effects on the measurement of relationships between individual factors and lengths of stay. Thus, it is important to control for both observed and unobserved factors in estimation.

Interface control of surface photochemical reactivity in ultrathin epitaxial ferroelectric films

Asymmetrical electrical boundary conditions in (001)-oriented Pb(Zr 0.2TiO0.8)O3 (PZT) epitaxial ultrathin ferroelectric films are exploited to control surface photochemical reactivity determined by the sign of the surface polarization charge. It is shown that the preferential orientation of polarization in the as-grown PZT layer can be manipulated by choosing an appropriate type of bottom electrode material. PZT films deposited on the SrRuO3 electrodes exhibit preferential upward polarization (C) whilst the same films grown on the (La,Sr)CoO 3-electrodes are polarized downward (C-). Photochemical activity of the PZT surfaces with different surface polarization charges has been tested by studying deposition of silver nanoparticles from AgNO3 solution under UV irradiation. PZT surfaces with preferential C orientation possess a more active surface for metal reduction than their C- counterparts, evidenced by large differences in the concentration of deposited silver nanoparticles. This effect is attributed to band bending at the bottom interface which varies depending on the difference in work functions of PZT and electrode materials.

Self-organization in arrays of surface-grown nanoparticles : characterization, control, driving forces

Some important issues related to the self-organization in the arrays of nanoparticles on solid surfaces exposed to the low-temperature plasma are analysed and discussed. The available tools for the characterization of the size and position uniformity in nanoarrays are examined. The technique capable of revealing the realistic adsorbed atom and adsorbed radical capture zone pattern based on the surface physics is indicated as the most promising characterization tool. The processes responsible for the self-organization are analysed, the main driving forces of the self-organization are discussed, and possible ways to control the self-organization by controlling the plasma parameters are introduced. A view on the possible ways to further improve the methods of nanoarray characterization and self-organization is presented as well.

Atmospheric-pressure discharges for the fabrication of surface-based metal nanostructures

Various reactor configurations for generating atmospheric-pressure discharges were tested, and several types of nanostructures, including Mo nanoflakes, were successfully synthesized. Here, we present photographs of the discharges, as well as SEM images of representative nanostructures.

Models of social media adoption in emergency management organisations

Recent natural disasters such as the Haitian earthquake 2011, the South East Queensland floods 2011, the Japanese earthquake and tsunami 2011 and Hurricane Sandy in the United States of America in 2012, have seen social media platforms changing the face of emergency management communications, not only in times of crisis and also during business-as-usual operations. With social media being such an important and powerful communication tool, especially for emergency management organisations, the question arises as to whether the use of social media in these organisations emerged by considered strategic design or more as a reactive response to a new and popular communication channel. This paper provides insight into how the social media function has been positioned, staffed and managed in organisations throughout the world, with a particular focus on how these factors influence the style of communication used on social media platforms. This study has identified that the social media function falls on a continuum between two polarised models, namely the authoritative one-way communication approach and the more interactive approach that seeks to network and engage with the community through multi-way communication. Factors such the size of the organisation; dedicated resourcing of the social media function; organisational culture and mission statement; the presence of a social media champion within the organisation; management style and knowledge about social media play a key role in determining where on the continuum organisations sit in relation to their social media capability. This review, together with a forthcoming survey of Australian emergency management organisations and local governments, will fill a gap in the current body of knowledge about the evolution, positioning and usage of social media in organisations working in the emergency management field in Australia. These findings will be fed back to Industry for potential inclusion in future strategies and practices.

Heating mechanism of self-interaction of surface polaritons at n-type semiconductor-metal interface

The influence of electron heating in the high-frequency surface polariton (SP) field on the dispersion properties of the SPs considered is investigated. High frequency SPs propagate at the interface between an n-type semiconductor with finite electron pressure, and a metal. The nonlinear dispersion relation for the SPs is derived and investigated.

Excitation of surface plasmon-polariton waves at a semiconductor-metal interface

The excitation of surface plasmon-polariton waves propagating across an external magnetic field (Voigt geometry) in a semiconductor-metal structure by means of the attenuated total reflection method is investigated. The phase matching conditions for the surface waves excitation in the Kretchmann configuration are derived and analyzed. The effect of different nonlinearities on the excitation of the surface waves is studied as well.

Self-interaction of surface polaritons at the narrow-gap n-type semiconductor metal interface

The non-linear self-interaction of the potential surface polaritons (SP) which is due to the free carriers dispersion law where nonparabolicity is studied. The SP propagate at the interface between n-type semiconductor and a metal. The self interaction of the SP is shown to be different in semiconductors with normal and inverse zone structures. The results of the SP field envelope evolution are given. The obtained nonlinear frequency shift has been compared with shifts which are due to another self-interaction mechanisms. This comparison shows that the nonlinear self-interaction mechanism, which is due to free carriers spectrum nonparabolicity, is especially significant in narrow-gap semiconductor materials.

Dispersion properties of surface waves in a two-layer plasma structure bounded by a metal

The effect of the nonuniformity of the electron density on the dispersion properties of surface waves propagating in a direction transverse to an external magnetic field is studied for the model of a two-layer plasma structure bounded by a metal. It is shown that the spectra of the waves can be effectively controlled by varying the degree of nonuniformity of the density and the dimensions of the layers.

The effect of the nonparabolicity of the free carriers dispersion law on the propagation of surface polaritons in a semiconductor-metal structure

The results of a study on the influence of the nonparabolicity of the free carriers dispersion law on the propagation of surface polaritons (SPs) located near the interface between an n-type semiconductor and a metal arc reported. The semiconductor plasma is assumed to be warm and nonisothermal. The nonparabolicity of the electron dispersion law has two effects. The first one is associated with nonlinear self-interaction of the SPs. The nonlinear dispersion equation and the nonlinear Schrodinger equation for the amplitude of the SP envelope are obtained. The nonlinear evolution of the SP is studied on the base of the above mentioned equations. The second effect results in third harmonics generation. Analysis shows that these third harmonics may appear as a pure surface polariton, a pseudosurface polariton, or a superposition of a volume wave and a SP depending on the wave frequency, electron density and lattice dielectric constant.

Self-modulation of surface waves at a plasma-metal interface

The ponderomotive force effects on surface waves at a plasma-metal interface are studied. The waves propagate across an external magnetic field parallel to the interface. It is shown that the account of the ponderomotive force can lead to the appearance of solitons, which are not possible when the second-harmonic and magnetic nonlinearities are concerned. © 1998 American Institute of Physics.

Heating self-interaction mechanism of surface magnetoplasma waves in plasma-like medium bounded by metal

The influence of electron heating in the high-frequency surface magnetoplasma wave(SM) field on dispersion properties of the considered SM is investigated. High frequency SM propagate at the interface between a plasma like medium with a finite electrons pressure and a metal. The nonlinear dispersion relation for the SM is derived and investigated.

Excitation of surface plasma waves in crossed electric and magnetic fields

The efficiency of the excitation of surface plasma waves in the presence of external, steady crossed magnetic and electric fields is studied analytically and numerically for a geometry in which the waves propagate along the interface between a plasma-like medium and a metal in the direction transverse to both fields. The magnetic and electric fields are assumed to be parallel and transverse to the interface, respectively. The condition for which the drift instability of the surface wave arises is found.