Efficient, Scalable, and Solvent-free Mechanochemical Synthesis of the OLED Material Alq(3) (q=8-Hydroxyquinolinate)

The aluminum complex Alq(3) (q = 8-hydroxyquinolinate), which has important applications in organic light-emitting diode materials, is shown to be readily synthesized as a pure phase under solvent-free mechanochemical conditions from Al(OAc)(2)OH and 8-hydroxyquinoline by ball milling. The initial product of the mechanochemical synthesis is a novel acetic acid solvate of Alq(3), and the alpha polymorph of Alq(3) is obtained on subsequent heating/desolvation of this phase. The structure of the mechanochemically prepared acetic acid solvate of Alq(3) has been determined directly from powder X-ray diffraction data and is shown to be a different polymorph from the corresponding acetic acid solvate prepared by solution-state crystallization of Alq(3) from acetic acid. Significantly, the mechanochemical synthesis of Alq(3) is shown to be fully scalable across two orders of magnitude from 0.5 to 50 g scale. The Alq(3) sample obtained from the solvent-free mechanochemical synthesis is analytically pure and exhibits identical photoluminescence behavior to that of a sample prepared by the conventional synthetic route.

Mineralogical Characteristics and Transformations during Long-Term Operation of a Zerovalent Iron Reactive Barrier

Design and operation of Fe⁰ permeable reactive barriers (PRBs) can be improved by understanding the long-term mineralogical transformations that occur within PRBs. Changes in mineral precipitates, cementation, and corrosion of Fe⁰ filings within an in situ pilot-scale PRB were examined after the first 30 months of operation and compared with results of a previous study of the PRB conducted 15 months earlier using X-ray diffraction and scanning electron microscopy employing energy dispersive X-ray and backscatter electron analyses. Iron (oxy)hydroxides, aragonite, and maghemite and/or magnetite occurred throughout the cores collected 30 mo after installation. Goethite, lepidocrocite, mackinawite, aragonite, calcite, and siderite were associated with oxidized and cemented areas, while green rusts were detected in more reduced zones. Basic differences from our last detailed investigation include (i) mackinawite crystallized from amorphous FeS, (ii) aragonite transformed into calcite, (iii) akaganeite transformed to goethite and lepidocrocite, (iv) iron (oxy)hydroxides and calcium and iron carbonate minerals increased, (v) cementation was greater in the more recent study, and (vi) oxidation, corrosion, and disintegration of Fe⁰ filings were greater, especially in cemented areas, in the more recent study. If the degree of corrosion and cementation that was observed from 15 to 30 mo after installation continues, certain portions of the PRB (i.e., up-gradient entrance of the ground water to the Fe⁰ section of the PRB) may last less than five more years, thus reducing the effectiveness of the PRB to mitigate contaminants.

Playing free: an ethnography of Brazilian free improvisers

In this article I investigate the practice of free music improvisation in Brazil. The reflections and findings presented here are derived from research conducted as part of a four months Higher Education Academy (HEA, UK) Fellowship, carried out between February and June 2014. The aim was to enquire whether or how the practice of free improvisation is taught in the Brazilian higher education system.
As part of this ethnographic study visits to the following universities were scheduled:
The Federal University of Rio de Janeiro - UFRJ
The Universidade Federal do Estado do Rio de Janeiro (UNIRIO)
The University of São Paulo - USP
The Federal University of Minas Gerais – UFMG
The Federal University of Bahia – UFBA.
The Federal University of Rio Grande do Norte in Natal (UFRN) and
The ELM, the Escola Livre de Música in Unicamp.

I discuss here some general background thinking to the research process, specifically recalling the work of French composer and educator Alain Savouret. I proceed to examine the improvisational spirit, the improvisatory worldmaking approach (the ‘jeitinho brasileiro’) that is often considered to be integral to the Brazilian way of life. In the final part of the article I discuss applied ethnographic methodologies, including the design of questions that were used for over 50 video interviews with Brazilian musicians during the research. I conclude with a final reflection on the video interviews with a specific focus on whether free improvisation can be taught, and the importance of listening in the context of free improvisation practices.

Impact of Free Glasses and a Teacher Incentive on Children's Use of Eyeglasses: A Cluster-Randomized Controlled Trial.

Purpose: To study the effect of free glasses combined with teacher incentives on in-school glasses wear among Chinese urban migrant children. Design: Cluster-randomized controlled trial. Methods: Children with VA <= 6/12 in either eye due to refractive error in 94 randomly-chosen primary schools underwent randomization by school to receive free glasses, education on their use and a teacher incentive (Intervention), or glasses prescriptions only (Control). Intervention group teachers received a tablet computer if >= 80% of children given glasses wore them during un-announced visits 6 weeks and 6 months (main outcome) after intervention. Results: Among 4376 children, 728 (16.7%, mean age 10.9 years, 51.0% boys) met enrollment criteria and were randomly allocated, 358 (49.2%, 47 schools) to Intervention and 370 (50.8%, 47 schools) to Control. Among these, 693 children (95.2%) completed the study and underwent analysis. Spectacle wear was significantly higher at 6 months among Intervention children (Observed [main outcome]: 68.3% versus 23.9%, Adjusted Odds Ratio [OR]=11.5, 95% Confidence Interval [CI] 5.91-22.5, P<0.001; Self-reported: 90.6% versus 32.1%, OR = 43.7, 95% CI = 21.7-88.5, P < 0.001). Other predictors of observed wear at 6 months included baseline spectacle wear (P<0.001), uncorrected VA<6/18 (P=0.01) and parental spectacle wear (P=0.02). The 6-month observed wear rate was only 41% among similar-aged children provided free glasses in our previous trial without teacher incentives. Conclusions: Free spectacles and teacher incentives maintain classroom wear in the large majority of children needing glasses over a school year. Low wear among Control children demonstrates the need for interventions.

Safety of Spectacles for Children's Vision: A Cluster-Randomized Controlled Trial.

Purpose: To study safety of children’s glasses in rural China, where fear that glasses harm vision is an important barrier for families and policy-makers. Design: Exploratory analysis from a cluster-randomized, investigator-masked, controlled trial.Methods: Among primary schools (n=252) in western China, children were randomized by school to one of three interventions: free glasses provided in class, vouchers for free glasses at a local facility or glasses prescriptions only (Control group). The main outcome of this analysis is uncorrected visual acuity after 8 months, adjusted for baseline acuity.Results: Among 19,934 children randomly selected for screening, 5852 myopic (spherical equivalent refractive error <= -0.5 D) eyes of 3001 children (14.7%, mean age 10.5 years) had VA <= 6/12 without glasses correctable to > 6/12 with glasses, and were eligible. Among these, 1903 (32.5%), 1798 (30.7%), and 2151 (36.8%) were randomized to Control, Voucher and Free Glasses respectively. Intention-to-treat analyses were performed on all 1831 (96.2%), 1699 (94.5%), and 2007 (93.3%) eyes of children with follow-up in Control, Voucher and Free Glasses groups. Final visual acuity for eyes of children in the treatment groups (Free Glasses and Voucher) was significantly better than for Control children, adjusting only for baseline visual acuity (difference of 0.023 logMAR units [0.23 vision chart lines, 95% CI: 0.03, 0.43]) or for other baseline factors as well (0.025 logMAR units [0.25 lines, 95% CI 0.04, 0.45]). Conclusion: We found no evidence that spectacles promote decline in uncorrected vision with aging among children.

Solid-liquid interfacial free energy out of equilibrium

The properties of the interface between solid and melt are key to solidification and melting, as the interfacial free energy introduces a kinetic barrier to phase transitions. This makes solidification happen below the melting temperature, in out-of-equilibrium conditions at which the interfacial free energy is ill defined. Here we draw a connection between the atomistic description of a diffuse solid-liquid interface and its thermodynamic characterization. This framework resolves the ambiguities in defining the solid-liquid interfacial free energy above and below the melting temperature. In addition, we introduce a simulation protocol that allows solid-liquid interfaces to be reversibly created and destroyed at conditions relevant for experiments. We directly evaluate the value of the interfacial free energy away from the melting point for a simple but realistic atomic potential, and find a more complex temperature dependence than the constant positive slope that has been generally assumed based on phenomenological considerations and that has been used to interpret experiments. This methodology could be easily extended to the study of other phase transitions, from condensation to precipitation. Our analysis can help reconcile the textbook picture of classical nucleation theory with the growing body of atomistic studies and mesoscale models of solidification.

Element-Free Galerkin Modelling of Crack Migration in Composite Laminates

The development of a virtual testing environment, as a cost-effective industrial design tool in the design and analysis of composite structures, requires the need to create models efficiently, as well as accelerate the analysis by reducing the number of degrees of freedom, while still satisfying the need for accurately tracking the evolution of a debond, delamination or crack front. The eventual aim is to simulate both damage initiation and propagation in components with realistic geometrical features, where crack propagation paths are not trivial. Meshless approaches, and the Element-Free Galerkin (EFG) method, are particularly suitable for problems involving changes in topology and have been successfully applied to simulate damage in homogeneous materials and concrete. In this work, the method is utilized to model initiation and mixed-mode propagation of cracks in composite laminates, and to simulate experimentally-observed crack migration which is difficult to model using standard finite element analysis. N

Failure-Free Survival and Radiotherapy in Patients With Newly Diagnosed Nonmetastatic Prostate Cancer: Data From Patients in the Control Arm of the STAMPEDE Trial

Importance: The natural history of patients with newly diagnosed high-risk nonmetastatic (M0) prostate cancer receiving hormone therapy (HT) either alone or with standard-of-care radiotherapy (RT) is not well documented. Furthermore, no clinical trial has assessed the role of RT in patients with node-positive (N+) M0 disease. The STAMPEDE Trial includes such individuals, allowing an exploratory multivariate analysis of the impact of radical RT.

Objective: To describe survival and the impact on failure-free survival of RT by nodal involvement in these patients.

Design, Setting, and Participants: Cohort study using data collected for patients allocated to the control arm (standard-of-care only) of the STAMPEDE Trial between October 5, 2005, and May 1, 2014. Outcomes are presented as hazard ratios (HRs) with 95% CIs derived from adjusted Cox models; survival estimates are reported at 2 and 5 years. Participants were high-risk, hormone-naive patients with newly diagnosed M0 prostate cancer starting long-term HT for the first time. Radiotherapy is encouraged in this group, but mandated for patients with node-negative (N0) M0 disease only since November 2011.

Exposures: Long-term HT either alone or with RT, as per local standard. Planned RT use was recorded at entry.

Main Outcomes and Measures: Failure-free survival (FFS) and overall survival.

Results: A total of 721 men with newly diagnosed M0 disease were included: median age at entry, 66 (interquartile range [IQR], 61-72) years, median (IQR) prostate-specific antigen level of 43 (18-88) ng/mL. There were 40 deaths (31 owing to prostate cancer) with 17 months' median follow-up. Two-year survival was 96% (95% CI, 93%-97%) and 2-year FFS, 77% (95% CI, 73%-81%). Median (IQR) FFS was 63 (26 to not reached) months. Time to FFS was worse in patients with N+ disease (HR, 2.02 [95% CI, 1.46-2.81]) than in those with N0 disease. Failure-free survival outcomes favored planned use of RT for patients with both N0M0 (HR, 0.33 [95% CI, 0.18-0.61]) and N+M0 disease (HR, 0.48 [95% CI, 0.29-0.79]).

Conclusions and Relevance: Survival for men entering the cohort with high-risk M0 disease was higher than anticipated at study inception. These nonrandomized data were consistent with previous trials that support routine use of RT with HT in patients with N0M0 disease. Additionally, the data suggest that the benefits of RT extend to men with N+M0 disease.

Trial Registration: clinicaltrials.gov Identifier: NCT00268476; ISRCTN78818544.

Effect of providing free glasses on children's educational outcomes in China: cluster randomized controlled trial

Objective: To assess the effect of provision of free glasses on academic performance in rural Chinese children with myopia. Design: Cluster randomized, investigator masked, controlled trial.Setting 252 primary schools in two prefectures in western China, 2012-13. Participants: 3177 of 19 934 children in fourth and fifth grades (mean age 10.5 years) with visual acuity <6/12 in either eye without glasses correctable to >6/12 with glasses. 3052 (96.0%) completed the study.Interventions Children were randomized by school (84 schools per arm) to one of three interventions at the beginning of the school year: prescription for glasses only (control group), vouchers for free glasses at a local facility, or free glasses provided in class. Main outcome measures: Spectacle wear at endline examination and end of year score on a specially designed mathematics test, adjusted for baseline score and expressed in standard deviations. Results: Among 3177 eligible children, 1036 (32.6%) were randomized to control, 988 (31.1%) to vouchers, and 1153 (36.3%) to free glasses in class. All eligible children would benefit from glasses, but only 15% wore them at baseline. At closeout glasses wear was 41% (observed) and 68% (self reported) in the free glasses group, and 26% (observed) and 37% (self reported) in the controls. Effect on test score was 0.11 SD (95% confidence interval 0.01 to 0.21) when the free glasses group was compared with the control group. The adjusted effect of providing free glasses (0.10, 0.002 to 0.19) was greater than parental education (0.03, −0.04 to 0.09) or family wealth (0.01, −0.06 to 0.08). This difference between groups was significant, but was smaller than the prespecified 0.20 SD difference that the study was powered to detect. Conclusions: The provision of free glasses to Chinese children with myopia improves children’s performance on mathematics testing to a statistically significant degree, despite imperfect compliance, although the observed difference between groups was smaller than the study was originally designed to detect. Myopia is common and rarely corrected in this setting. Trial Registration: Current Controlled Trials ISRCTN03252665.

A evolução do equipamento de salvamento aquático em contexto operacional : o design simbiótico como ferramenta na redução do stress e facilitador da tarefa

Tese de doutoramento, Belas-Artes (Design de Equipamento), Universidade de Lisboa, Faculdade de Belas-Artes, 2014

Mix design process of polyester polymer mortars modified with recycled GFRP waste materials

In this study, the effect of incorporation of recycled glass fibre reinforced plastics (GFRP) waste materials, obtained by means of shredding and milling processes, on mechanical behaviour of polyester polymer mortars (PM) was assessed. For this purpose, different contents of GFRP recyclates, between 4% up to 12% in weight, were incorporated into polyester PM materials as sand aggregates and filler replacements. The effect of the addition of a silane coupling agent to resin binder was also evaluated. Applied waste material was proceeding from the shredding of the leftovers resultant from the cutting and assembly processes of GFRP pultrusion profiles. Currently, these leftovers as well as non-conform products and scrap resulting from pultrusion manufacturing process are landfilled, with additional costs to producers and suppliers. Hence, besides the evident environmental benefits, a viable and feasible solution for these wastes would also conduct to significant economic advantages. Design of experiments and data treatment were accomplish by means of full factorial design approach and analysis of variance ANOVA. Experimental results were promising toward the recyclability of GFRP waste materials as partial replacement of aggregates and reinforcement for PM materials, with significant improvements on mechanical properties of resultant mortars with regards to waste-free formulations.

Direct-search penalty/barrier methods

In Nonlinear Optimization Penalty and Barrier Methods are normally used to solve Constrained Problems. There are several Penalty/Barrier Methods and they are used in several areas from Engineering to Economy, through Biology, Chemistry, Physics among others. In these areas it often appears Optimization Problems in which the involved functions (objective and constraints) are non-smooth and/or their derivatives are not know. In this work some Penalty/Barrier functions are tested and compared, using in the internal process, Derivative-free, namely Direct Search, methods. This work is a part of a bigger project involving the development of an Application Programming Interface, that implements several Optimization Methods, to be used in applications that need to solve constrained and/or unconstrained Nonlinear Optimization Problems. Besides the use of it in applied mathematics research it is also to be used in engineering software packages.

Disposable immunosensor using a simple method for oriented antibody immobilization for label-free real-time detection of an oxidative stress biomarker implicated in cancer diseases

This work proposes a novel approach for a suitable orientation of antibodies (Ab) on an immunosensing platform, applied here to the determination of 8-hydroxy-2′-deoxyguanosine (8OHdG), a biomarker of oxidative stress that has been associated to chronic diseases, such as cancer. The anti-8OHdG was bound to an amine modified gold support through its Fc region after activation of its carboxylic functions. Non-oriented approaches of Ab binding to the platform were tested in parallel, in order to show that the presented methodology favored Ab/Ag affinity and immunodetection of the antigen. The immunosensor design was evaluated by quartz-crystal microbalance with dissipation, atomic force microscopy, electrochemical impedance spectroscopy (EIS) and square-wave voltammetry. EIS was also a suitable technique to follow the analytical behavior of the device against 8OHdG. The affinity binding between 8OHdG and the antibody immobilized in the gold modified platform increased the charge transfer resistance across the electrochemical set-up. The observed behavior was linear from 0.02 to 7.0 ng/mL of 8OHdG concentrations. The interference from glucose, urea and creatinine was found negligible. An attempt of application to synthetic samples was also successfully conducted. Overall, the presented approach enabled the production of suitably oriented Abs over a gold platform by means of a much simpler process than other oriented-Ab binding approaches described in the literature, as far as we know, and was successful in terms of analytical features and sample application.

Adaptive Penalty and Barrier function based on Fuzzy Logic

Optimization methods have been used in many areas of knowledge, such as Engineering, Statistics, Chemistry, among others, to solve optimization problems. In many cases it is not possible to use derivative methods, due to the characteristics of the problem to be solved and/or its constraints, for example if the involved functions are non-smooth and/or their derivatives are not know. To solve this type of problems a Java based API has been implemented, which includes only derivative-free optimization methods, and that can be used to solve both constrained and unconstrained problems. For solving constrained problems, the classic Penalty and Barrier functions were included in the API. In this paper a new approach to Penalty and Barrier functions, based on Fuzzy Logic, is proposed. Two penalty functions, that impose a progressive penalization to solutions that violate the constraints, are discussed. The implemented functions impose a low penalization when the violation of the constraints is low and a heavy penalty when the violation is high. Numerical results, obtained using twenty-eight test problems, comparing the proposed Fuzzy Logic based functions to six of the classic Penalty and Barrier functions are presented. Considering the achieved results, it can be concluded that the proposed penalty functions besides being very robust also have a very good performance.

Armourstone revetments : will standard design criteria prevent failure? /

Bank stabilization structures are used to prevent the loss of valuable land within the urban environment and the decision for the type of structure used depends on the properties of the stream. In the urban areas of Southern Ontario there is a preference for the use of armourstone blocks as bank stabilization. The armourstone revetment is a free standing stone structure with large blocks of stone layered vertically and offset from one another. During fieldwork at Forty Mile Creek in Grimsby, Ontario armourstone failure was identified by the removal of two stones within one column from the wall. Since the footer stones were still in place, toe scour was eliminated as a cause of failure. Through theoretical, field, and experimental work the process of suction has been identified as a mode of failure for the armourstone wall and the process of suction works similarly to quarrying large blocks of rock off bedrock streambeds. The theory of lateral suction has previously not been taken into consideration for the design of these walls. The physical and hydraulic evidence found in the field and studied during experimental work indicate that the armourstone wall is vulnerable to the process of suction. The forces exerted by the flow and the resistance of the block determine the stability of the armourstone block within the wall. The design of the armourstone wall, high surface velocities, and short pulses of faster flowing water within the profile could contribute to armourstone failure by providing the forces needed for suction to occur, therefore adjustments to the design of the wall should be made in order to limit the effect.