Transition of synthetic chromium oxide gel to crystalline chromium oxide : a hot stage Raman spectroscopic study

Chromium oxide gel material was synthesised and appeared to be X-ray amorphous. The changes in the structure of the synthetic chromium oxide gel were investigated using hot-stage Raman spectroscopy based upon the results of thermogravimetric analysis. The thermally decomposed product of the synthetic chromium oxide gel in nitrogen atmosphere was confirmed to be crystalline Cr2O3 as determined by the hot-stage Raman spectra. Two bands were observed at 849 and 735 cm-1 in the Raman spectrum at 25 °C, which were attributed to the symmetric stretching modes of O-CrIII-OH and O-CrIII-O. With temperature increase, the intensity of the band at 849 cm-1 decreased, while the band at 735 cm-1 increased. These changes in intensity are attributed to the loss of OH groups and formation of O-CrIII-O units in the structure. A strongly hydrogen bonded water H-O-H bending band was found at 1704 cm-1 in the Raman spectrum of the chromium oxide gel, however this band shifted to around 1590 cm-1 due to destruction of the hydrogen bonds upon thermal treatment. Six new Raman bands were observed at 578, 540, 513, 390, 342 and 303 cm-1 attributed to the thermal decomposed product Cr2O3. The use of the hot-stage Raman microscope enabled low-temperature phase changes brought about through dehydration and dehydroxylation to be studied.

Limited information estimation and evaluation of DSGE models

We advance the proposition that dynamic stochastic general equilibrium (DSGE) models should not only be estimated and evaluated with full information methods. These require that the complete system of equations be specified properly. Some limited information analysis, which focuses upon specific equations, is therefore likely to be a useful complement to full system analysis. Two major problems occur when implementing limited information methods. These are the presence of forward-looking expectations in the system as well as unobservable non-stationary variables. We present methods for dealing with both of these difficulties, and illustrate the interaction between full and limited information methods using a well-known model.

An enhanced explicit rate algorithm for ABR traffic control in ATM networks

A high performance, low computational complexity rate-based flow control algorithm which can avoid congestion and achieve fairness is important to ATM available bit rate service. The explicit rate allocation algorithm proposed by Kalampoukas et al. is designed to achieve max–min fairness in ATM networks. It has several attractive features, such as a fixed computational complexity of O(1) and the guaranteed convergence to max–min fairness. In this paper, certain drawbacks of the algorithm, such as the severe overload of an outgoing link during transient period and the non-conforming use of the current cell rate field in a resource management cell, have been identified and analysed; a new algorithm which overcomes these drawbacks is proposed. The proposed algorithm simplifies the rate computation as well. Compared with Kalampoukas's algorithm, it has better performance in terms of congestion avoidance and smoothness of rate allocation.

Ovine bone and marrow derived progenitor cells : isolation, characterization, and osteogenic potential

Recently, research has focused on bone marrow derived multipotent mesenchymal precursor cells (MPC) for their potential clinical use in bone engineering. Prior to clinical application, MPC-based treatment concepts need to be evaluated in preclinical, immunocompetent, large animal models. Sheep in particular are considered a valid model for orthopaedic and trauma related research. However, ovine MPC and their osteogenic potential remain poorly characterized. In the present study, ex vivo expanded MPC isolated from ovine bone marrow proliferated at a higher rate than osteoblasts (OB) derived from tibial compact bone as assessed using standard 2D culture. MPC expressed the respective phenotypic profile typical for different mesenchymal cell populations (CD14-/CD31-/CD45- /CD29+/CD44+/CD166+) and showed a multilineage differentiation potential. When compared to OB, MPC had a higher mineralization potential under standard osteogenic culture conditions and expressed typical markers such as osteocalcin, osteonectin and type I collagen at the mRNA and protein level. After 4 weeks in 3D culture, MPC constructs demonstrated higher cell density and mineralization, whilst cell viability on the scaffolds was assessed >90%. Cells displayed a spindle-like morphology and formed an interconnected network. Implanted subcutaneously into NOD/SCID mice on type I collagen coated polycaprolactone-tricalciumphosphate (mPCL-TCP) scaffolds, MPC presented a higher developmental potential than osteoblasts. In summary, this study provides a detailed in vitro characterisation of ovine MPC from a bone engineering perspective and suggests that MPC provide promising means for future bone disease related treatment applications.

Falls in Parkinson's disease : kinematic evidence for impaired head and trunk control

Changes in stride characteristics and gait rhythmicity characterize gait in Parkinson's disease and are widely believed to contribute to falls in this population. However, few studies have examined gait in PD patients who fall. This study reports on the complexities of walking in PD patients who reported falling during a 12-month follow-up. Forty-nine patients clinically diagnosed with idiopathic PD and 34 controls had their gait assessed using three-dimensional motion analysis. Of the PD patients, 32 (65%) reported at least one fall during the follow-up compared with 17 (50%) controls. The results showed that PD patients had increased stride timing variability, reduced arm swing and walked with a more stooped posture than controls. Additionally, PD fallers took shorter strides, walked slower, spent more time in double-support, had poorer gait stability ratios and did not project their center of mass as far forward of their base of support when compared with controls. These stride changes were accompanied by a reduced range of angular motion for the hip and knee joints. Relative to walking velocity, PD fallers had increased mediolateral head motion compared with PD nonfallers and controls. Therefore, head motion could exceed “normal” limits, if patients increased their walking speed to match healthy individuals. This could be a limiting factor for improving gait in PD and emphasizes the importance of clinically assessing gait to facilitate the early identification of PD patients with a higher risk of falling.

Melt electrospinning of polycaprolactone and its blends with poly(ethylene glycol)

Melt electrospinning is one aspect of electrospinning with relatively little published literature, although the technique avoids solvent accumulation and/or toxicity which is favoured in certain applications. In the study reported, we melt-electrospun blends of poly(ε-caprolactone) (PCL) and an amphiphilic diblock copolymer consisting of poly(ethylene glycol) and PCL segments (PEG-block-PCL). A custom-made electrospinning apparatus was built and various combinations of instrument parameters such as voltage and polymer feeding rate were investigated. Pure PEG-block-PCL copolymer melt electrospinning did not result in consistent and uniform fibres due to the low molecular weight, while blends of PCL and PEG-block-PCL, for some parameter combinations and certain weight ratios of the two components, were able to produce continuous fibres significantly thinner (average diameter of ca 2 µm) compared to pure PCL. The PCL fibres obtained had average diameters ranging from 6 to 33 µm and meshes were uniform for the lowest voltage employed while mesh uniformity decreased when the voltage was increased. This approach shows that PCL and blends of PEG-block-PCL and PCL can be readily processed by melt electrospinning to obtain fibrous meshes with varied average diameters and morphologies that are of interest for tissue engineering purposes. Copyright © 2010 Society of Chemical Industry

Melt electrospinning

Melt electrospinning is relatively under-investigated compared to solution electrospinning but provides opportunities in numerous areas, in which solvent accumulation or toxicity are a concern. These applications are diverse, and provide a broad set of challenges to researchers involved in electrospinning. In this context, melt electrospinning provides an alternative approach that bypasses some challenges to solution electronspinning, while bringing new issues to the forefront, such as the thermal stability of polymers. This Focus Review describes the literature on melt electrospinning, as well as highlighting areas where both melt and solution are combined, and potentially merge together in the future.

Clinical outcomes in residential care : setting benchmarks for quality

Aim Australian residential aged care does not have a system of quality assessment related to clinical outcomes, or comprehensive quality benchmarking. The Residential Care Quality Assessment was developed to fill this gap; and this paper discusses the process by which preliminary benchmarks representing high and low quality were developed for it. Methods Data were collected from all residents (n = 498) of nine facilities. Numerator–denominator analysis of clinical outcomes occurred at a facility-level, with rank-ordered results circulated to an expert panel. The panel identified threshold scores to indicate excellent and questionable care quality, and refined these through Delphi process. Results Clinical outcomes varied both within and between facilities; agreed thresholds for excellent and poor outcomes were finalised after three Delphi rounds. Conclusion Use of the Residential Care Quality Assessment provides a concrete means of monitoring care quality and allows benchmarking across facilities; its regular use could contribute to improved care outcomes within residential aged care in Australia.

Dussertite BaFe3+3(AsO4)2(OH)5 : a Raman spectroscopic study of a hydroxy-arsenate mineral

The mineral dussertite, a hydroxy-arsenate mineral of formula BaFe3+3(AsO4)2(OH)5, has been studied by Raman complimented with infrared spectroscopy. The spectra of three minerals from different origins were investigated and proved quite similar, although some minor differences were observed. In the Raman spectra of Czech dussertite, four bands are observed in the 800 to 950 cm-1 region. The bands are assigned as follows: the band at 902 cm-1 is assigned to the (AsO4)3- ν3 antisymmetric stretching mode, at 870 cm-1 to the (AsO4)3- ν1 symmetric stretching mode, and both at 859 cm-1 and 825 cm-1 to the As-OM2+/3+ stretching modes/and or hydroxyls bending modes. Raman bands at 372 and 409 cm-1 are attributed to the ν2 (AsO4)3- bending mode and the two bands at 429 and 474 cm-1 are assigned to the ν4 (AsO4)3- bending mode. An intense band at 3446 cm-1 in the infrared spectrum and a complex set of bands centred upon 3453 cm-1 in the Raman spectrum are attributed to the stretching vibrations of the hydrogen bonded (OH)- units and/or water units in the mineral structure. The broad infrared band at 3223 cm-1 is assigned to the vibrations of hydrogen bonded water molecules. Raman spectroscopy identified Raman bands attributable to (AsO4)3- and (AsO3OH)2- units.

Rumination, post-traumatic growth, and distress : structural equation modelling with cancer survivors

Objective Theoretical models of post-traumatic growth (PTG) have been derived in the general trauma literature to describe the post-trauma experience that facilitates the perception of positive life changes. To develop a statistical model identifying factors that are associated with PTG, structural equation modelling (SEM) was used in the current study to assess the relationships between perception of diagnosis severity, rumination, social support, distress, and PTG. Method A statistical model of PTG was tested in a sample of participants diagnosed with a variety of cancers (N=313). Results An initial principal components analysis of the measure used to assess rumination revealed three components: intrusive rumination, deliberate rumination of benefits, and life purpose rumination. SEM results indicated that the model fit the data well and that 30% of the variance in PTG was explained by the variables. Trauma severity was directly related to distress, but not to PTG. Deliberately ruminating on benefits and social support were directly related to PTG. Life purpose rumination and intrusive rumination were associated with distress. Conclusions The model showed that in addition to having unique correlating factors, distress was not related to PTG, thereby providing support for the notion that these are discrete constructs in the post-diagnosis experience. The statistical model provides support that post-diagnosis experience is simultaneously shaped by positive and negative life changes and that one or the other outcome may be prevalent or may occur concurrently. As such, an implication for practice is the need for supportive care that is holistic in nature.

Longitudinal investigation of wandering behavior in department of veterans affairs nursing home care units

Objectives To explore the extent of and factors associated with male residents who change wandering status post nursing home admission. Design Longitudinal design with secondary data analyses. Admissions over a 4-year period were examined using repeat assessments with the Minimum Data Set (MDS) to formulate a model understanding the development of wandering behavior. Setting One hundred thirty-four Veterans Administration (VA) nursing homes throughout the United States. Participants: Included 6673 residents admitted to VA nursing homes between October 2000 and October 2004. Measurements MDS variables (cognitive impairment, mood, behavior problems, activities of daily living and wandering) included ratings recorded at residents’ admission to the nursing home and a minimum of two other time points at quarterly intervals. Results The majority (86%) of the sample were classified as non wanderers at admission and most of these (94%) remained non wanderers until discharge or the end of the study. Fifty one per cent of the wanderers changed status to non wanderers with 6% of these residents fluctuating in status more than two times. Admission variables associated with an increased risk of changing status from non-wandering to wandering included older age, greater cognitive impairment, more socially inappropriate behavior, resisting care, easier distractibility, and needing less help with personal hygiene. Requiring assistance with locomotion and having three or more medical comorbidities were associated with a decreased chance of changing from non-wandering to wandering status. Conclusion A resident’s change from non-wandering to wandering status may reflect an undetected medical event that affects cognition, but spares mobility.

Public regulatory reform and management earnings forecasts in a low private litigation environment

We examine the impact of continuous disclosure regulatory reform on the likelihood, frequency and qualitative characteristics of management earnings forecasts issued in New Zealand’s low private litigation environment. Using a sample of 720 earnings forecasts issued by 94 firms listed on the New Zealand Exchange before and after the reform (1999–2005), we provide strong evidence of significant changes in forecasting behaviour in the post-reform period. Specifically, firms were more likely to issue earnings forecasts to pre-empt earnings announcements and, in contrast to findings in other legal settings, those earnings forecasts exhibited higher frequency and improved qualitative characteristics (better precision and accuracy). An important implication of our findings is that public regulatory reforms may have a greater benefit in a low private litigation environment and thus add to the global debate about the effectiveness of alternative public regulatory reforms of corporate requirements.

Fixed-wing attitude estimation using temporal tracking of the horizon and optical flow

In this paper, a method has been developed for estimating pitch angle, roll angle and aircraft body rates based on horizon detection and temporal tracking using a forward-looking camera, without assistance from other sensors. Using an image processing front-end, we select several lines in an image that may or may not correspond to the true horizon. The optical flow at each candidate line is calculated, which may be used to measure the body rates of the aircraft. Using an Extended Kalman Filter (EKF), the aircraft state is propagated using a motion model and a candidate horizon line is associated using a statistical test based on the optical flow measurements and the location of the horizon. Once associated, the selected horizon line, along with the associated optical flow, is used as a measurement to the EKF. To test the accuracy of the algorithm, two flights were conducted, one using a highly dynamic Uninhabited Airborne Vehicle (UAV) in clear flight conditions and the other in a human-piloted Cessna 172 in conditions where the horizon was partially obscured by terrain, haze and smoke. The UAV flight resulted in pitch and roll error standard deviations of 0.42◦ and 0.71◦ respectively when compared with a truth attitude source. The Cessna flight resulted in pitch and roll error standard deviations of 1.79◦ and 1.75◦ respectively. The benefits of selecting and tracking the horizon using a motion model and optical flow rather than naively relying on the image processing front-end is also demonstrated.

A Raman spectroscopic study of the antimony mineral klebelsbergite Sb4O4(OH)2(SO4)

Many minerals based upon antimonite and antimonate anions remain to be studied. Most of the bands occur in the low wavenumber region, making infrared spectroscopy difficult to use. This problem can be overcome by using Raman spectroscopy. Raman spectra of the mineral klebelsbergite Sb4O4(OH)2(SO4) were studied, and related to the structure of the mineral. Raman bands observed at 971 cm-1 and a series of overlapping bands are observed at 1029, 1074, 1089, 1139 and 1142 cm-1 are assigned to the SO42- ν1 symmetric and ν3 antisymmetric stretching modes. Two Raman bands are observed at 662 and 723 cm-1 and assigned to the SbO ν3 antisymmetric and ν1 symmetric stretching modes. The intense Raman bands at 581, 604 and 611 cm-1 are assigned to the ν4 SO42- bending modes. Two overlapping bands at 481 and 489 cm-1 are assigned to the ν2 SO42- bending mode. Low intensity bands at 410, 435 and 446 cm-1 may be attributed to OSbO bending modes. The Raman band at 3435 cm-1 is attributed to the OH stretching vibration of the OH units. Multiple Raman bands for both SO42- and SbO stretching vibrations support the concept of the non-equivalence of these units in the klebelsbergite structure. It is proposed that two sulphate anions are distorted to different extents in the klebelsbergite structure.

Effect of pH on the uptake of arsenate and vanadate and the stability of these anions in alkaline solutions – a Raman spectroscopic study

Hydrotalcites have been synthesised using three different pH solutions to assess the effect of pH on the uptake of arsenate and vanadate. The ability of these hydrotalcites to remove vanadate and arsenate from solution has been determined by ICP-OES. Raman spectroscopy is used to monitor changes in the anionic species for hydrotalcites synthesised at different pH values. The results show a reduction in the concentration of arsenate and vanadate anions that are removed in extremely alkaline solutions. Hydrotalcites containing arsenate and vanadate are stable in solutions up to pH 10. Exposure of these hydrotalcites to higher pH values results in the removal of large percentages of arsenate and vanadate from the hydrotalcite interlayer.