Melt electrospinning of poly(epsilon-caprolactone) scaffolds: Phenomenological observations associated with collection and direct writing

Melt electrospinning and its additive manufacturing analogue, melt electrospinning writing (MEW), are two processes which can produce porous materials for applications where solvent toxicity and accumulation in solution electrospinning are problematic. This study explores the melt electrospinning of poly(ε-caprolactone) (PCL) scaffolds, specifically for applications in tissue engineering. The research described here aims to inform researchers interested in melt electrospinning about technical aspects of the process. This includes rapid fiber characterization using glass microscope slides, allowing influential processing parameters on fiber morphology to be assessed, as well as observed fiber collection phenomena on different collector substrates. The distribution and alignment of melt electrospun PCL fibers can be controlled to a certain degree using patterned collectors to create large numbers of scaffolds with shaped macroporous architectures. However, the buildup of residual charge in the collected fibers limits the achievable thickness of the porous template through such scaffolds. One challenge identified for MEW is the ability to control charge buildup so that fibers can be placed accurately in close proximity, and in many centimeter heights. The scale and size of scaffolds produced using MEW, however, indicate that this emerging process will fill a technological niche in biofabrication.

The exhaustive reduction of formylporphyrins to methylporphyrins using dimethylformamide/water as reductant under microwave irradiation

The reduction of meso-formyl derivatives of 5,15-diaryl- and 5,10,15-triphenylporphyrin (and their nickel(II) complexes) to the corresponding meso-methyl porphyrins is achieved in high yield by microwave heating of the substrate in dimethylformamide (DMF) in the presence of acids such as trifluoroacetic acid, or even just with added water. The reactions are complete in less than 30 min at 250 °C. The reaction is strongly suppressed in very dry DMF in the absence of added acid. The meso-hydroxymethyl porphyrins are also reduced to the methyl derivatives, suggesting the primary alcohols may be intermediates in the exhaustive reduction. UV-visible spectra taken at intervals during reaction at 240 °C indicated that at least one other intermediate is present, but it was not identified. In d7-DMF, the methylporphyrin isolated was mainly Por-CD2H, showing that both of the added hydrogens arise from the solvent, and not from the added water or acid.

Changing travel patterns and journeys to health services in Great Britain 1985-2012: An examination health service utilisation using the National Travel Survey

Background This paper examines changing patterns in the utilisation and geographic access to health services in Great Britain using National Travel Survey data (1985-2012). The National Travel Survey (NTS) is a series of household surveys designed to provide data on personal travel and monitor changes in travel behaviour over time. The utilisation rate was derived using the proportion of journeys made to access health services. Geographic access was analysed by separating the concept into its accessibility and mobility dimensions. Methods Variables from the PSU, households, and individuals datasets were used as explanatory variables. Whereas, variables extracted from the journeys dataset were used as dependent variables to identify patterns of utilisation i.e. the proportion of journeys made by different groups to access health facilities in a particular journey distance or time band or by mode of transport; and geographic access to health services. A binary logistic regression analysis was conducted to identify the utilisation rate over the different time periods between different groups. This analysis shows the Odds Ratios (ORs) for different groups making a trip to utilise health services compared to their respective counterparts. Linear multiple regression analyses were conducted to then identify patterns of change in the accessibility and mobility level. Results Analysis of the data has shown that that journey distances to health facilities were signi fi cantly shorter and also gradually reduced over the period in question for Londoners, females, those without a car or on low incomes, and older people. Although rates of utilisation of health services we re Oral Abstracts / Journal of Transport & Health 2 (2015) S5 – S63 S43 signi fi cantly lower because of longer journey times. These fi ndings indicate that the rate of utilisation of health services largely depends on mobility level although previous research studies have traditionally overlooked the mobility dimension. Conclusions This fi nding, therefore, suggests the need to improve geographic access to services together with an enhanced mobility option for disadvantaged groups in order for them to have improved levels of access to health facilities. This research has also found that the volume of car trips to health services also increased steadily over the period 1985-2012 while all other modes accounted for a smaller number of trips. However, it is dif fi cult to conclude from this research whether this increase in the volume of car trips was due to a lack of alternative transport or due to an increase in the level of car-ownership.

Psychiatrists' views on pathways to care for people with schizophrenia in Vietnam

Objectives: Research about the outcomes of schizophrenia and the factors that determine them in developing countries is still limited. In this study, we interviewed experienced Vietnamese psychiatrists to examine their perspectives on outcome determinants in their country. The qualitative approach aimed to complement existing epidemiological knowledge and contribute to debate around the hypothesis that recovery is better in developing countries. Methods: Fifteen Vietnamese psychiatrists working in five leading psychiatric facilities participated in semi-structured interviews. Thematic content analysis of their expressed views identified three themes related to important outcome determinants in Vietnam: access to contemporary treatment, established patient-level prognostic indicators, and sociocultural variables. Results: The improving accessibility of modern treatment (including new medications, specialist staff and facilities) and increasing community adoption of a medical perspective on mental illness were seen as factors leading to improved outcomes, particularly in urban areas. However, some psychiatrists also identified the potentially beneficial nature of some aspects of Vietnamese society and culture being eroded by modernization, including traditional family structures, forms of employment and lifestyles. Conclusions: The perspectives of psychiatrists in this study suggest that socioeconomic change may be exerting conflicting influences on the outcomes of schizophrenia in Vietnam and other developing countries. Their views have implications in terms of how adequate treatment and support for people with severe mental illness can be provided in the context of limited resources, staffing and formal treatment options. Further research is needed to establish current recovery rates and prospectively explore the impact of modernization on outcomes.

Reinforcing stigma or delivering a fresh start: Bankruptcy and future engagement in the workforce

In Australia, bankruptcy retains a social stigma, as is often seen as a personal failing, and an indication that the individual cannot be trusted to meet their obligations. Official labelling and informal labelling reinforce this stigmatisation of bankruptcy in employment and business contexts. This occurs through legislation and policy that imposes restrictions on participation in some occupations on the grounds of bankruptcy, and imposes obligations on persons to disclose their bankruptcy to their employer. These restrictions and obligations that are varying in length and extent, both within industries and professions and across industries and professions, and appear to lack a coherent policy justification. Further, informal labelling is facilitated by the law providing for a permanent, publicly accessible record of bankruptcy, and failing to restrict the use of bankruptcy information in employment and business decision-making. This stigmatisation of bankruptcy inhibits the fresh start objective of bankruptcy, and is not supported by a strong correlation between bankruptcy and negative personal or other attributes. This article therefore argues that a review is needed to determine the circumstances in which there is a genuine policy justification for employment restrictions, and the appropriate length and scope of such restrictions. Reform of the Bankruptcy Act should also be considered. Possible areas for law reform including reducing the minimum period of bankruptcy; removing the permanency and/or public accessibility of the bankruptcy record; revising the language used in the Bankruptcy Act; and introducing a prohibition or restriction on the ability of employers to use bankruptcy status in employment decision making. Such changes would promote the fresh start objective of Australia’s bankruptcy system, and increase the likelihood that bankruptcy does not unfairly inhibit an individual’s ability to engage as an economic actor in Australian society and thereby improve their financial well-being.

Saviour Siblings and the Regulation of Assisted Reproductive Technology: Harm, Ethics and Law

Advances in the field of Assisted Reproductive Technology (ART) have been revolutionary. This book focuses on the use of ARTs in the context of families who seek to conceive a matching sibling donor as a source of tissue to treat an existing sick child. Such children have been referred to as ‘saviour siblings’. Considering the legal and regulatory frameworks that impact on the accessibility of this technology in Australia and the UK, the work analyses the ethical and moral issues that arise from the use of the technology for this specific purpose. The author claims the only justification for limiting a family’s reproductive liberty in this context is where the exercise of reproductive decision-making results in harm to others. It is argued that the harm principle is the underlying feature of legislative action in Western democratic society, and as such, this principle provides the grounds upon which a strong and persuasive argument is made for a less-restrictive regulatory approach in the context of ‘saviour siblings’.

Energetics of rare earth manganese perovskites A1-xA ' xMnO3 (A = La, Nd, Y and A ' = Sr, La) systems

High temperature reaction calorimetry using molten lead berate as solvent has been used to study the thermochemistry of NdMnO3, YMnO3, La1-xSrxMnO3 (with 0 < x < 0.5), and Ln(0.5)Ca(0.5)MnO(3) (with Ln = La, Nd, Y), The enthalpies of formation of these multicomponent oxides from their binary constituents have been calculated from the measured enthalpy of drop solution, The energetic stability of the perovskite depends on the size of the A cation, The enthalpy of formation of YMnO3 (smallest A cation) is more endothermic than those of NdMnO3 and LaMnO3. The energetics of the perovskite also depends on the oxidation state of the B site's ions. In the La1-xSrxMnO3 system, the energetic stability of the structure increases with the Mn4+/Mn3+ ratio, The new values of the enthalpies of oxidations, with reliable standard entropies, were used to plot the phase stability diagram of the lanthanum-manganese-oxygen system in the temperature range 300-1100 K, The LaMnO3/MnO phase boundary evaluated in this study agrees with the one published by Atsumi et nl. calculated from thermogravimetric and conductivity measurements.

Support services for higher degree research students: A survey of three Australian universities

A survey was conducted across three Australian universities to identify the types and format of support services available for higher degree research (HDR, or MA and Ph.D.) students. The services were classified with regards to availability, location and accessibility. A comparative tool was developed to help institutions categorise their services in terms of academic, administrative, social and settlement, language and miscellaneous (other) supports. All three universities showed similarities in the type of academic support services offered, while differing in social and settlement and language support services in terms of the location and the level of accessibility of these services. The study also examined the specific support services available for culturally and linguistically diverse (CALD) students. The three universities differed in their emphases in catering to CALD needs, with their allocation of resources reflecting these differences. The organisation of these services within the universities was further assessed to determine possible factors that may influence the effective delivery of these services, by considering HDR and CALD student specific issues. The findings and tools developed by this study may be useful to HDR supervisors and university administrators in identifying key support services to better improve outcomes for the HDR students and universities.

Determination of refractive and volatile elements in sediment using laser ablation inductively coupled plasma mass spectrometry

Wet-milling protocol was employed to produce pressed powder tablets with excellent cohesion and homogeneity suitable for laser ablation (LA) analysis of volatile and refractive elements in sediment. The influence of sample preparation on analytical performance was also investigated, including sample homogeneity, accuracy and limit of detection. Milling in volatile solvent for 40 min ensured sample is well mixed and could reasonably recover both volatile (Hg) and refractive (Zr) elements. With the exception of Cr (−52%) and Nb (+26%) major, minor and trace elements in STSD-1 and MESS-3 could be analysed within ±20% of the certified values. Comparison of the method with total digestion method using HF was tested by analysing 10 different sediment samples. The laser method recovers significantly higher amounts of analytes such as Ag, Cd, Sn and Sn than the total digestion method making it a more robust method for elements across the periodic table. LA-ICP-MS also eliminates the interferences from chemical reagents as well as the health and safety risks associated with digestion processes. Therefore, it can be considered as an enhanced method for the analysis of heterogeneous matrices such as river sediments.

Temperature dependent vibrational lifetimes in supercritical fluids near the critical point

Vibrational relaxation measurements on the CO asymmetric stretching mode (similar to 1980 cm(-1)) of tungsten hexacarbonyl (W(CO)(6)) as a function of temperature at constant density in several supercritical solvents in the vicinity of the critical point are presented. In supercritical ethane, at the critical density, there is a region above the critical temperature (Tc) in which the lifetime increases with increasing temperature. When the temperature is raised sufficiently (similar to T-c + 70 degrees C), the lifetime decreases with further increase in temperature. A recent hydrodynamic/thermodynamic theory of vibrational relaxation in supercritical fluids reproduces this behavior semiquantitatively. The temperature dependent data for fixed densities somewhat above and below the critical density is in better agreement with the theory. In fluoroform solvent at the critical density, the vibrational lifetime also initially increases with increasing temperature. However, in supercritical CO2 at the critical density, the temperature dependent vibrational lifetime decreases approximately linearly with temperature beginning almost immediately above T-c. The theory does not reproduce this behavior. A comparison between the absolute lifetimes in the three solvents and the temperature trends is made.

Preparation of lamellar and hexagonal forms of mesoporous silica and zirconiaby the neutral amine route: lamellar-hexagonal transformation in the solid state

The chain length of the surfactant and the solvent composition are two of the factors that determine whether the lamellar or the hexagonal form of mesoporous SiO2 (or ZrO2) is formed by the neutral amine route; a lamellar-hexagonal transformation occurs on removal of the amine from the former.

Two-dimensional self-assembly of a symmetry-reduced tricarboxylic acid

Investigations of the self-assembly of simple molecules at the solution/solid interface can provide useful insight into the general principles governing supramolecular chemistry in two dimensions. Here, we report on the assembly of 3,4′,5-biphenyl tricarboxylic acid (H3BHTC), a small hydrogen bonding unit related to the much-studied 1,3,5-benzenetricarboxylic acid (trimesic acid, TMA), which we investigate using scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. STM images show that H3BHTC assembles by itself into an offset zigzag chain structure that maximizes the surface molecular density in favor of maximizing the number density of strong cyclic hydrogen bonds between the carboxylic groups. The offset geometry creates “sticky” pores that promote solvent coadsorption. Adding coronene to the molecular solution produces a transformation to a high-symmetry host–guest lattice stabilized by a dimeric/trimeric hydrogen bonding motif similar to the TMA flower structure. Finally, we show that the H3BHTC lattice firmly immobilizes the guest coronene molecules, allowing for high-resolution imaging of the coronene structure.

First donor-acceptor interaction promoted gelation of organic fluids

In recent years there has been considerable interest in developing new types of gelators of organic solvents.1 Despite the recent advances, a priori design of a gelator for gelling a given solvent has remained a challenging task. Various noncovalent interactions like hydrogen-bonding,2 metal coordination3 etc. have been used as the driving force for the gelation process. A special class of cholesterol-based gelators were reported by Weiss,4 and by Shinkai.5 Gels derived from these molecules have been used for chiral recognition/sensing,6 for studying photo- and metal-responsive functions,7 and as templates to make hollow fiber silica.8 Other types of organogels have been used for designing polymerized 9 and reverse aerogels,10 and in molecular imprinting.11 Hanabusa’s group has recently reported organogels with a bile acid derivative.12 This has prompted us to disclose our results on a novel electron donor–acceptor (EDA) interaction mediated two-component13 gelator system based on the bile acid14 backbone.

Free Energy Gap Dependence of the Electron-Transfer Rate from the Inverted to the Normal Region

numerical study of the free energy gap (FEG) dependence of the electron-transfer rate in polar solvents is presented. This study is based on the generalized multidimensional hybrid model, which not only includes the solvent polarization and the molecular vibration modes, but also the biphasic polar response of the solvent. The free energy gap dependence is found to be sensitive to several factors, including the solvent relaxation rate, the electronic coupling between the surfaces, the frequency of the high-frequency quantum vibrational mode, and the magnitude of the solvent reorganization energy. It is shown that in some cases solvent relaxation can play an important role even in the Marcus normal regime. The minimal hybrid model involves a large number of parameters, giving rise to a diverse non-Marcus FEG behavior which is often determined collectively by these parameters. The model gives the linear free energy gap dependence of the logarithmic rate over a substantial range of FEG, spanning from the normal to the inverted regime. However, even for favorable values of the relevant parameters, a linear free energy gap dependence of the rate could be obtained only over a range of 5000-6000 cm(-1) (compared to the experimentally observed range of 10000 cm(-1) reported by Benniston et al.). The present work suggests several extensions/generalizations of the hybrid model which might be necessary to fully understand the observed free energy gap dependence.

Ultrasonic Degradation of Poly(acrylic acid)

The ultrasonic degradation of poly(acrylic acid), a water-soluble polymer, was studied in the presence of persulfates at different temperatures in binary solvent Mixtures of methanol and water. The degraded samples were analyzed by gel permeation chromatography for the time evolution of the molecular weight distributions. A continuous distribution kinetics model based on midpoint chain scission was developed, and the degradation rate coefficients were determined. The decline in the rate of degradation of poly(acrylic acid) with increasing temperature and with an increment in the methanol content in the binary solvent mixture of methanol and water was attributed to the increased vapor pressure of the solutions. The experimental data showed an augmentation of the degradation rate of the polymer with increasing oxidizing agent (persulfate) concentrations. Different concentrations of three persulfates-potassium persulfate, ammonium persulfate, and sodium persulfate-were used. It was found that the ratio of the polymer degradation rate coefficient to the dissociation rate constant of the persulfate was constant. This implies that the ultrasonic degradation rate of poly(acrylic acid) can be determined a priori in the presence of any initiator.