Mid- and near-infrared spectroscopic investigation of homogeneous cation distribution in MgxZnyAl(x+y)/2-layered double hydroxide (LDH)

In this report, a detailed FTIR fitting analysis was used to recognize Mg, Zn and Al homogeneous distribution in MgxZnyAl(x+y)/2-Layered double hydroxide (LDH) hydroxyl layer. In detail, OH-Mg2Al:OH-Mg3 ratios decreased from 95.2:4.8 (MIR) and 94.2:5.8 (NIR) to 58.9:41.1 (MIR) and 61.8:38.2 (NIR), when Mg:Al increased from 2.2:1.0 to 4.1:1.0 in MgAl-LDHs. These fitting results were similar with theoretical calculations of 94.3:5.7 and 59.0:41.0. In a further analysis of MgxZnyAl(x+y)/2-LDHs, OH bonded Zn2Mg, Zn2Al, MgZnAl, Mg2Al and Mg2Zn peaks were identified at 3420, 3430, 3445–3450, 3454 and 3545 cm-1, respectively. With the decrease of Mg:Zn from 3:1 to 1:3, metal-hydroxyl bands changed from OH-Mg2Al and MgZnAl (with a ratio of 49.4:50.6) to OH-MgZnAl and Zn2Al (with a ratio of 55.0:45.0). They were also similar with theoretical calculations of 47.6:52.4 and 54.6:45.4. As a result, these results show that there is an ordered cation distribution in MgxZnyAl(x+y)/2-LDH, and FTIR is feasible in recognizing this structure.

Spatiotemporal model or time series model for assessing city-wide temperature effects on mortality?

Most studies examining the temperature–mortality association in a city used temperatures from one site or the average from a network of sites. This may cause measurement error as temperature varies across a city due to effects such as urban heat islands. We examined whether spatiotemporal models using spatially resolved temperatures produced different associations between temperature and mortality compared with time series models that used non-spatial temperatures. We obtained daily mortality data in 163 areas across Brisbane city, Australia from 2000 to 2004. We used ordinary kriging to interpolate spatial temperature variation across the city based on 19 monitoring sites. We used a spatiotemporal model to examine the impact of spatially resolved temperatures on mortality. Also, we used a time series model to examine non-spatial temperatures using a single site and the average temperature from three sites. We used squared Pearson scaled residuals to compare model fit. We found that kriged temperatures were consistent with observed temperatures. Spatiotemporal models using kriged temperature data yielded slightly better model fit than time series models using a single site or the average of three sites' data. Despite this better fit, spatiotemporal and time series models produced similar associations between temperature and mortality. In conclusion, time series models using non-spatial temperatures were equally good at estimating the city-wide association between temperature and mortality as spatiotemporal models.

Sunshine, rainfall, humidity and child pneumonia in the tropics : time-series analyses

Few studies have formally examined the relationship between meteorological factors and the incidence of child pneumonia in the tropics, despite the fact that most child pneumonia deaths occur there. We examined the association between four meteorological exposures (rainy days, sunshine, relative humidity, temperature) and the incidence of clinical pneumonia in young children in the Philippines using three time-series methods: correlation of seasonal patterns, distributed lag regression, and case-crossover. Lack of sunshine was most strongly associated with pneumonia in both lagged regression [overall relative risk over the following 60 days for a 1-h increase in sunshine per day was 0·67 (95% confidence interval (CI) 0·51–0·87)] and case-crossover analysis [odds ratio for a 1-h increase in mean daily sunshine 8–14 days earlier was 0·95 (95% CI 0·91–1·00)]. This association is well known in temperate settings but has not been noted previously in the tropics. Further research to assess causality is needed.

Assessing the short-term effects of heatwaves on mortality and morbidity in Brisbane, Australia : comparison of case-crossover and time series analyses

Background Heat-related impacts may have greater public health implications as climate change continues. It is important to appropriately characterize the relationship between heatwave and health outcomes. However, it is unclear whether a case-crossover design can be effectively used to assess the event- or episode-related health effects. This study examined the association between exposure to heatwaves and mortality and emergency hospital admissions (EHAs) from non-external causes in Brisbane, Australia, using both case-crossover and time series analyses approaches. Methods Poisson generalised additive model (GAM) and time-stratified case-crossover analyses were used to assess the short-term impact of heatwaves on mortality and EHAs. Heatwaves exhibited a significant impact on mortality and EHAs after adjusting for air pollution, day of the week, and season. Results For time-stratified case-crossover analysis, odds ratios of mortality and EHAs during heatwaves were 1.62 (95% confidence interval (CI): 1.36–1.94) and 1.22 (95% CI: 1.14–1.30) at lag 1, respectively. Time series GAM models gave similar results. Relative risks of mortality and EHAs ranged from 1.72 (95% CI: 1.40–2.11) to 1.81 (95% CI: 1.56–2.10) and from 1.14 (95% CI: 1.06–1.23) to 1.28 (95% CI: 1.21–1.36) at lag 1, respectively. The risk estimates gradually attenuated after the lag of one day for both case-crossover and time series analyses. Conclusions The risk estimates from both case-crossover and time series models were consistent and comparable. This finding may have implications for future research on the assessment of event- or episode-related (e.g., heatwave) health effects.

Effects of temperature on mortality in Chiang Mai city, Thailand : a time series study

Background The association between temperature and mortality has been examined mainly in North America and Europe. However, less evidence is available in developing countries, especially in Thailand. In this study, we examined the relationship between temperature and mortality in Chiang Mai city, Thailand, during 1999–2008. Method A time series model was used to examine the effects of temperature on cause-specific mortality (non-external, cardiopulmonary, cardiovascular, and respiratory) and age-specific non-external mortality (<=64, 65–74, 75–84, and > =85 years), while controlling for relative humidity, air pollution, day of the week, season and long-term trend. We used a distributed lag non-linear model to examine the delayed effects of temperature on mortality up to 21 days. Results We found non-linear effects of temperature on all mortality types and age groups. Both hot and cold temperatures resulted in immediate increase in all mortality types and age groups. Generally, the hot effects on all mortality types and age groups were short-term, while the cold effects lasted longer. The relative risk of non-external mortality associated with cold temperature (19.35°C, 1st percentile of temperature) relative to 24.7°C (25th percentile of temperature) was 1.29 (95% confidence interval (CI): 1.16, 1.44) for lags 0–21. The relative risk of non-external mortality associated with high temperature (31.7°C, 99th percentile of temperature) relative to 28°C (75th percentile of temperature) was 1.11 (95% CI: 1.00, 1.24) for lags 0–21. Conclusion This study indicates that exposure to both hot and cold temperatures were related to increased mortality. Both cold and hot effects occurred immediately but cold effects lasted longer than hot effects. This study provides useful data for policy makers to better prepare local responses to manage the impact of hot and cold temperatures on population health.

Higher harmonic large-amplitude fourier transformed alternating current voltammetry : analytical attributes derived from studies of the oxidation of ferrocenemethanol and uric acid at a glassy carbon electrode

An analytical evaluation of the higher ac harmonic components derived from large amplitude Fourier transformed voltammetry is provided for the reversible oxidation of ferrocenemethanol (FcMeOH) and oxidation of uric acid by an EEC mechanism in a pH 7.4 phosphate buffer at a glassy carbon (GC) electrode. The small background current in the analytically optimal fifth harmonic is predominantly attributed to faradaic current associated with the presence of electroactive functional groups on the GC electrode surface, rather than to capacitive current which dominates the background in the dc, and the initial three ac harmonics. The detection limits for the dc and the first to fifth harmonic ac components are 1.9, 5.89, 2.1, 2.5, 0.8, and 0.5 µM for FcMeOH, respectively, using a sine wave modulation of 100 mV at 21.46 Hz and a dc sweep rate of 111.76 mV s−1. Analytical performance then progressively deteriorates in the sixth and higher harmonics. For the determination of uric acid, the capacitive background current was enhanced and the reproducibility lowered by the presence of surface active uric acid, but the rapid overall 2e− rather than 1e– electron transfer process gives rise to a significantly enhanced fifth harmonic faradaic current which enabled a detection limit of 0.3 µM to be achieved which is similar to that reported using chemically modified electrodes. Resolution of overlapping voltammetric signals for a mixture of uric acid and dopamine is also achieved using higher fourth or fifth harmonic components, under very low background current conditions. The use of higher fourth and fifth harmonics exhibiting highly favorable faradaic to background (noise) current ratios should therefore be considered in analytical applications under circumstances where the electron transfer rate is fast.

Investigation of mediated oxidation of ascorbic acid by ferrocenemethanol using large-amplitude fourier transformed ac voltammetry under quasi-reversible electron-transfer conditions at an indium tin oxide electrode

The ability of the technique of large-amplitude Fourier transformed (FT) ac voltammetry to facilitate the quantitative evaluation of electrode processes involving electron transfer and catalytically coupled chemical reactions has been evaluated. Predictions derived on the basis of detailed simulations imply that the rate of electron transfer is crucial, as confirmed by studies on the ferrocenemethanol (FcMeOH)-mediated electrocatalytic oxidation of ascorbic acid. Thus, at glassy carbon, gold, and boron-doped diamond electrodes, the introduction of the coupled electrocatalytic reaction, while producing significantly enhanced dc currents, does not affect the ac harmonics. This outcome is as expected if the FcMeOH (0/+) process remains fully reversible in the presence of ascorbic acid. In contrast, the ac harmonic components available from FT-ac voltammetry are predicted to be highly sensitive to the homogeneous kinetics when an electrocatalytic reaction is coupled to a quasi-reversible electron-transfer process. The required quasi-reversible scenario is available at an indium tin oxide electrode. Consequently, reversible potential, heterogeneous charge-transfer rate constant, and charge-transfer coefficient values of 0.19 V vs Ag/AgCl, 0.006 cm s (-1) and 0.55, respectively, along with a second-order homogeneous chemical rate constant of 2500 M (-1) s (-1) for the rate-determining step in the catalytic reaction were determined by comparison of simulated responses and experimental voltammograms derived from the dc and first to fourth ac harmonic components generated at an indium tin oxide electrode. The theoretical concepts derived for large-amplitude FT ac voltammetry are believed to be applicable to a wide range of important solution-based mediated electrocatalytic reactions.

Probing second harmonic components of pH-sensitive Redox processes in a mesoporous TiO2-Nafion film electrode with Fourier-transformed large-amplitude sinusoidally modulated voltammetry

Electrochemical processes in mesoporous TiO2-Nafion thin films deposited on indium tin oxide (ITO) electrodes are inherently complex and affected by capacitance, Ohmic iR-drop, RC-time constant phenomena, and by potential and pH-dependent conductivity. In this study, large-amplitude sinusoidally modulated voltammetry (LASMV) is employed to provide access to almost purely Faradaic-based current data from second harmonic components, as well as capacitance and potential domain information from the fundamental harmonic for mesoporous TiO2-Nafion film electrodes. The LASMV response has been investigated with and without an immobilized one-electron redox system, ferrocenylmethyltrimethylammonium+. Results clearly demonstrate that the electron transfer associated with the immobilized ferrocene derivative follows two independent pathways i) electron hopping within the Nafion network and ii) conduction through the TiO2 backbone. The pH effect on the voltammetric response for the TiO2 reduction pathway (ii) can be clearly identified in the 2nd harmonic LASMV response with the diffusion controlled ferrocene response (i) acting as a pH independent reference. Application of second harmonic data derived from LASMV measurement, because of the minimal contribution from capacitance currents, may lead to reference-free pH sensing with systems like that found for ferrocene derivatives.

Exploiting the facile oxidation of evaporated gold films to drive electroless silver deposition for the creation of bimetallic Au/Ag surfaces

Gold is often considered as an inert material but it has been unequivocally demonstrated that it possesses unique electronic, optical, catalytic and electrocatalytic properties when in a nanostructured form.[1] For the latter the electrochemical behaviour of gold in aqueous media has been widely studied on a plethora of gold samples, including bulk polycrystalline and single-crystal electrodes, nanoparticles, evaporated films as well as electrodeposited nanostructures, particles and thin films.[1b, 2] It is now well-established that the electrochemical behaviour of gold is not as simple as an extended double-layer charging region followed by a monolayer oxide-formation/-removal process. In fact the so-called double-layer region of gold is significantly more complicated and has been investigated with a variety of electrochemical and surface science techniques. Burke and others[3] have demonstrated that significant processes due to the oxidation of low lattice stabilised atoms or clusters of atoms occur in this region at thermally and electrochemically treated electrodes which were confirmed later by Bond[4] to be Faradaic in nature via large-amplitude Fourier transformed ac voltammetric experiments. Supporting evidence for the oxidation of gold in the double-layer region was provided by Bard,[5] who used a surface interrogation mode of scanning electrochemical microscopy to quantify the extent of this process that forms incipient oxides on the surface. These were estimated to be as high as 20% of a monolayer. This correlated with contact electrode resistance measurements,[6] capacitance measurements[7] and also electroreflection techniques...

Surgical resection for non-small cell lung cancer : clinical features and outcomes for a consecutive series at an Irish tertiary referral centre

Background: Few patients diagnosed with lung cancer are still alive 5 years after diagnosis. The aim of the current study was to conduct a 10-year review of a consecutive series of patients undergoing curative-intent surgical resection at the largest tertiary referral centre to identify prognostic factors. Methods: Case records of all patients operated on for lung cancer between 1998 and 2008 were reviewed. The clinical features and outcomes of all patients with non-small cell lung cancer (NSCLC) stage I-IV were recorded. Results: A total of 654 patients underwent surgical resection with curative intent during the study period. Median overall survival for the entire cohort was 37 months. The median age at operation was 66 years, with males accounting for 62.7 %. Squamous cell type was the most common histological subtype, and lobectomies were performed in 76.5 % of surgical resections. Pneumonectomy rates decreased significantly in the latter half of the study (25 vs. 16.3 %), while sub-anatomical resection more than doubled (2 vs. 5 %) (p < 0.005). Clinico-pathological characteristics associated with improved survival by univariate analysis include younger age, female sex, smaller tumour size, smoking status, lobectomy, lower T and N status and less advanced pathological stage. Age, gender, smoking status and tumour size, as well as T and N descriptors have emerged as independent prognostic factors by multivariate analysis. Conclusion: We identified several factors that predicted outcome for NSCLC patients undergoing curative-intent surgical resection. Survival rates in our series are comparable to those reported from other thoracic surgery centres. © 2012 Royal Academy of Medicine in Ireland.

Made by motion, Series one

“Made by Motion” is a collaboration between digital artist Paul Van Opdenbosch and performer and choreographer Elise May; a series of studies on captured motion data used to generating experimental visual forms that reverberate in space and time. The project investigates the invisible forces generated by and influencing the movement of a dancer. Along with how the forces can be captured and applied to generating visual outcomes that surpass simple data visualisation, projecting the intent of the performer’s movements. The source or ‘seed’ comes from using an Xsens MVN - Inertial Motion Capture system to capture spontaneous dance movements, with the visual generation conducted through a customised dynamics simulation. In this first series the visual investigation focused on manipulating the movement date at the instance of capture, capture been the recording of three-dimensional movement as ‘seen’ by the hardware and ‘understood’ through the calibration of software. By repositioning the capture hardware on the body we can effectively change how the same sequence of movements is ‘seen’ by the motion capture system thus generating a different visual result from effetely identical movement. The outcomes from the experiments clearly demonstrates the effectiveness of using motion capture hardware as a creative tool to manipulate the perception of the capture subject, in this case been a sequence of dance movements. The creative work exhibited is a cross-section of the experiments conducted in practice with the first animated work (Movement A - Control) using the motion capture hardware in its default ‘normal’ configuration. Following this is the lower body moved to the upper body (Lb-Ub), right arm moved onto the left arm (Ra-La), right leg moved onto the left leg (Rl-Ll) and finally the left leg moved onto a object that is then held in the left hand (Ll-Pf (Lh)).

Targeting histone deacetylases for the treatment of disease : Epigenetics Review Series

The 'histone code' is a well-established hypothesis describing the idea that specific patterns of post-translational modifications to histones act like a molecular 'code' recognized and used by non-histone proteins to regulate specific chromatin functions. One modification, which has received significant attention, is that of histone acetylation. The enzymes that regulate this modification are described as lysine acetyltransferases or KATs, and histone deacetylases or HDACs. Due to their conserved catalytic domain HDACs have been actively targeted as a therapeutic target. The pro-inflammatory environment is increasingly being recognized as a critical element for both degenerative diseases and cancer. The present review will discuss the current knowledge surrounding the clinical potential and current development of histone deacetylases for the treatment of diseases for which a pro-inflammatory environment plays important roles, and the molecular mechanisms by which such inhibitors may play important functions in modulating the pro-inflammatory environment. © 2009 Foundation for Cellular and Molecular Medicine/Blackwell Publishing Ltd.

A single institution experience of streptozocin/fluorouracil combination chemotherapy : a case series

Background The combination chemotherapy regimen of streptozocin and 5-fluorouracil (FU/STZ) has been used for the treatment of metastatic neuroendocrine tumours. Aim The aim of this study was to analyse the use of this regimen in a tertiary oncology referral centre over a 10-year period. Method We retrospectively analysed nine cases from February 2000 to May 2010. Patient demographics, chemotherapy schedule, toxicities, progression-free and overall survival were tabulated for each patient. Result The median progression-free survival was 17 months (range 3-48+ months), and overall survival 31 months (range 12-53+ months) with no toxicity related deaths. Conclusion FU/STZ was a well-tolerated regimen that produced significant benefit in the setting of metastatic and progressive disease. Our case series demonstrated comparable progression-free survival and overall survival in relation to randomized controlled studies and previous case series. © Royal Academy of Medicine in Ireland 2011.

Preliminary bond-slip model for CFRP sheets bonded to steel plates

Carbon fiber reinforced polymer (CFRP) sheets have established a strong position as an effective method for innovative structural rehabilitation. However, the use of externally bonded CFRP in the repair and rehabilitation of steel structures is a relatively new technique that has the potential to improve the way structures are repaired. An important step toward understanding bond behaviour is to have an estimation of local bond stress versus slip relationship. The current study aims to establish the bond-slip model for CFRP sheets bonded to steel plate. To obtain the shear stress versus slippage relationship, a series of double strap tension type bond tests were conducted. This paper reports on the findings of the experimental studies. The strain and stress distributions measured in the specimens for two different bond lengths. The results show a preliminary bi-linear bond-slip model may be adopted for CFRP sheet bonded with steel plate.

Treatment rationale study design for the MetLung trial : a randomized, double-blind phase III study of onartuzumab (MetMAb) in combination with erlotinib versus erlotinib alone in patients who have received standard chemotherapy for stage IIIB or IV met-positive non-small-cell lung cancer

We present the treatment rationale and study design of the MetLung phase III study. This study will investigate onartuzumab (MetMAb) in combination with erlotinib compared with erlotinib alone, as second- or third-line treatment, in patients with advanced non-small-cell lung cancer (NSCLC) who are Met-positive by immunohistochemistry. Approximately 490 patients (245 per treatment arm) will receive erlotinib (150 mg oral daily) plus onartuzumab or placebo (15 mg/kg intravenous every 3 weeks) until disease progression, unacceptable toxicity, patient or physician decision to discontinue, or death. The efficacy objectives of this study are to compare overall survival (OS) (primary endpoint), progression-free survival, and response rates between the 2 treatment arms. In addition, safety, quality of life, pharmacokinetics, and translational research will be investigated across treatment arms. If the primary objective (OS) is achieved, this study will provide robust results toward an alternative treatment option for patients with Met-positive second- or third-line NSCLC. © 2012 Elsevier Inc. All Rights Reserved.