Nickel(II) complexes of bidentate N-N′ ligands containing mixed pyrazole, pyrimidine and pyridine aromatic rings as catalysts for ethylene polymerisation

This work describes the synthesis and characterisation of Ni(II) complexes of the following neutral bidentate nitrogen ligands containing pyrazole (pz), pyrimidine (pm) and pyridine (py) aromatic rings: 2-pyrazol-1-yl-pyrimidine (pzpm), 2-(4-methyl-pyrazol-1-yl)-pyrimidine (4-Mepzpm), 2-(4-bromo-pyrazol-1-yl)-pyrimidine (4-Brpzpm), 2-(3,5-dimethyl-pyrazol-1-yl)-pyrimidine (pz*pm), 2-pyrazol-1-yl-pyridine (pzpy) and bis(3,5-dimethylpyrazol-1-yl)phenylmethane (bpz*mph). The complexes [NiBr2(pzpm)] (1), [NiBr2(4-Mepzpm)] (2), [NiBr2(4-Brpzpm)] (3), [NiBr2(pz*pm)] (4), [NiBr2(pzpy)] (5) and [NiBr2(bpz*mph)] (6) were tested as catalysts for ethylene polymerisation, in the presence of the cocatalysts methylaluminoxane (MAO) or diethylaluminium chloride (AlEt2Cl), the catalyst systems 1-3/MAO showing moderate to high activities up to the temperature of 20 °C only in the presence of MAO, whereas 4-6/MAO revealed to be inactive. Other related Pd(II) complexes, already reported in previous works, such as [PdClMe(pzpm)], [PdClMe(pz*pm)], [PdClMe(pzpy)] and [PdClMe(bpz*mph)], also showed to be inactive in the polymerisation of ethylene, when activated by MAO or AlEt2Cl. Selected samples of polyethylene products were characterised by GPC/SEC, 1H and 13C NMR and DSC, showing to be low molecular weight polymers with Mn values ranging from ca. 550 to 1500 g mol−1 and unusually low dispersities of 1.2–1.7, with total branching degrees generally varying between 2 and 12%, melting temperatures from 40 to 120 °C and crystallinities from 40 to 70%.

A multi-criteria decision support system for a routing problem in waste collection

Autor proof

Continuous monitoring of concrete mechanical properties since an early age to support construction phasing

The assessment of concrete mechanical properties during construction of concrete structures is of paramount importance for many intrinsic operations. However many of the available non-destructive methods for mechanical properties have limitations for use in construction sites. One of such methodologies is EMM-ARM, which is a variant of classic resonant frequency methods. This paper aims to demonstrate the efforts towards in-situ applicability of EMMARM, as to provide real-time information about concrete mechanical properties such as E-modulus and compressive strength. To achieve the aforementioned objective, a set of adaptations to the method have been successfully implemented and tested: (i) the reduction of the beam span; (ii) the use of a different mould material and (iii) a new support system for the beams. Based on these adaptations, a reusable mould was designed to enable easier systematic use of EMMARM. A pilot test was successfully performed under in-situ conditions during a bridge construction.

A decision support system for a waste collection vehicle routing problem

The selective collection of municipal solid waste for recycling is a very complex and expensive process, where a major issue is to perform cost-efficient waste collection routes. Despite the abundance of commercially available software for fleet management, they often lack the capability to deal properly with sequencing problems and dynamic revision of plans and schedules during process execution. Our approach to achieve better solutions for the waste collection process is to model it as a vehicle routing problem, more specifically as a team orienteering problem where capacity constraints on the vehicles are considered, as well as time windows for the waste collection points and for the vehicles. The final model is called capacitated team orienteering problem with double time windows (CTOPdTW).We developed a genetic algorithm to solve routing problems in waste collection modelled as a CTOPdTW. The results achieved suggest possible reductions of logistic costs in selective waste collection.

The effect of secular trends in the classroom furniture mismatch: support for continuous update of school furniture standards

In order to create safer schools, the Chilean authorities published a Standard regarding school furniture dimensions. The aims of this study are twofold: to verify the existence of positive secular trend within the Chilean student population and to evaluate the potential mismatch between the anthropometric characteristics and the school furniture dimensions defined by the mentioned standard. The sample consists of 3078 subjects. Eight anthropometric measures were gathered, together with six furniture dimensions from the mentioned standard. There is an average increase for some dimensions within the Chilean student population over the past two decades. Accordingly, almost 18% of the students will find the seat height to be too high. Seat depth will be considered as being too shallow for 42.8% of the students. It can be concluded that the Chilean student population has increased in stature, which supports the need to revise and update the data from the mentioned Standard. Practitioner Summary: Positive secular trend resulted in high levels of mismatch if furniture is selected according to the current Chilean Standard which uses data collected more than 20 years ago. This study shows that school furniture standards need to be updated over time.

A proactive intelligent decision support system for predicting the popularity of online news

"Lecture notes in computer science series, ISSN 0302-9743, vol. 9273"

Process simulation support in BPM tools: The case of BPMN

Due to the increasing acceptance of BPM, nowadays BPM tools are extensively used in organizations. Core to BPM are the process modeling languages, of which BPMN is the one that has been receiving most attention these days. Once a business process is described using BPMN, one can use a process simulation approach in order to find its optimized form. In this context, the simulation of business processes, such as those defined in BPMN, appears as an obvious way of improving processes. This paper analyzes the business process modeling and simulation areas, identifying the elements that must be present in the BPMN language in order to allow processes described in BPMN to be simulated. During this analysis a set of existing BPM tools, which support BPMN, are compared regarding their limitations in terms of simulation support.

Intelligent decision support to predict patient barotrauma risk in intensive care units

The occurrence of Barotrauma is identified as a major concern for health professionals, since it can be fatal for patients. In order to support the decision process and to predict the risk of occurring barotrauma Data Mining models were induced. Based on this principle, the present study addresses the Data Mining process aiming to provide hourly probability of a patient has Barotrauma. The process of discovering implicit knowledge in data collected from Intensive Care Units patientswas achieved through the standard process Cross Industry Standard Process for Data Mining. With the goal of making predictions according to the classification approach they several DM techniques were selected: Decision Trees, Naive Bayes and Support Vector Machine. The study was focused on identifying the validity and viability to predict a composite variable. To predict the Barotrauma two classes were created: “risk” and “no risk”. Such target come from combining two variables: Plateau Pressure and PCO2. The best models presented a sensitivity between 96.19% and 100%. In terms of accuracy the values varied between 87.5% and 100%. This study and the achieved results demonstrated the feasibility of predicting the risk of a patient having Barotrauma by presenting the probability associated.

Methodology for real-time adaptation of tunnels support using the observational method

The observational method in tunnel engineering allows the evaluation in real time of the actual conditions of the ground and to take measures if its behavior deviates considerably from predictions. However, it lacks a consistent and structured methodology to use the monitoring data to adapt the support system in real time. The definition of limit criteria above which adaptation is required are not defined and complex inverse analysis procedures (Rechea et al. 2008, Levasseur et al. 2010, Zentar et al. 2001, Lecampion et al. 2002, Finno and Calvello 2005, Goh 1999, Cui and Pan 2012, Deng et al. 2010, Mathew and Lehane 2013, Sharifzadeh et al. 2012, 2013) may be needed to consistently analyze the problem. In this paper a methodology for the real time adaptation of the support systems during tunneling is presented. In a first step limit criteria for displacements and stresses are proposed. The methodology uses graphics that are constructed during the project stage based on parametric calculations to assist in the process and when these graphics are not available, since it is not possible to predict every possible scenario, inverse analysis calculations are carried out. The methodology is applied to the “Bois de Peu” tunnel which is composed by two tubes with over 500 m long. High uncertainty levels existed concerning the heterogeneity of the soil and consequently in the geomechanical design parameters. The methodology was applied in four sections and the results focus on two of them. It is shown that the methodology has potential to be applied in real cases contributing for a consistent approach of a real time adaptation of the support system and highlight the importance of the existence of good quality and specific monitoring data to improve the inverse analysis procedure.

Effect of NaCl additive on solute-solvent interactions in aqueous polyethylene glycol-sodium sulfate two-phase systems

Abstract Partition behavior of eight small organic compounds and six proteins was examined in poly(ethylene glycol)-8000-sodium sulfate aqueous two-phase systems containing 0.215 M NaCl and 0.5 M osmolyte (sorbitol, sucrose, TMAO) and poly(ethylene glycol)-10000-sodium sulfate-0.215 M NaCl system, all in 0.01 M sodium phosphate buffer, pH 6.8. The differences between the solvent properties of the coexisting phases (solvent dipolarity/polarizability, hydrogen bond donor acidity, and hydrogen bond acceptor basicity) were characterized with solvatochromic dyes using the solvatochromic comparison method. Differences between the electrostatic properties of the phases were determined by analysis of partitioning of sodium salts of dinitrophenylated (DNP-) amino acids with aliphatic alkyl side-chain. The partition coefficients of all compounds examined (including proteins) were described in terms of solute-solvent interactions. The results obtained in the study show that solute-solvent interactions of nonionic organic compounds and proteins in polyethylene glycol-sodium sulfate aqueous two-phase system change in the presence of NaCl additive.

Spousal support and satisfaction with healthcare services as moderators between psychological morbidity and adherence to diet in Type 2 Diabetes patients

Objectives: This study analyzed the moderating role of partners’ support and satisfaction with healthcare services in the relationship between psychological morbidity and adherence to diet in patients with type 2 diabetes (T2DM). Methods: Participants were 387 recently diagnosed T2DM patients that answered the following instruments: Revised Summary of Diabetes Self- Care Activities Measure, Hospital Anxiety and Depression Scales, Multidimensional Diabetes Questionnaire and Patient Satisfaction Questionnaire. Results: Partners’ positive and negative support moderated the relationship between psychological morbidity and adherence to diet. Satisfaction with healthcare services also moderated the relationship between psychological morbidity and adherence to diet. Conclusions: Intervention programs to promote adherence to diet in patients with type 2 diabetes should focus on partners’ support and patient satisfaction with healthcare services.

Repository power: how repositories can support Open Access mandates

Many funding agencies have Open Access mandates in place, but how often are scientific publications as outputs linked to funding details? The benefits of linking funding information to publications as part of the deposit workflow can assist in adhering to Open Access mandates. This paper examines how OpenAIRE – Open Access Infrastructure for Research in Europe – can ease monitoring Open Access and reporting processes for funders, and presents some results and opportunities. It also outlines how it relies on cleaned and curated repository content, a vital cog in the ever turning wheel of the global scholarly landscape, and the benefits it brings.

Electrosynthesis of heterocyclic compounds by radical cyclization in environmentally friendly media

We investigated the reductive intramolecular cyclization of bromopropargyl ethers derivatives, catalyzed by electrogenerated (1,4,8,11-tetramethyl-1,4,8,11-tetraaza-cyclotetradecane)nickel(I), [Ni(tmc)]+ as the catalysts in N,N,N-trimethyl-N-(2- hydroxyethyl)ammonium bis(trifluoromethylsulfonyl)imide,[N1 1 1 2(OH)][NTf2] and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C2mim][NTf2] by cyclic voltammetry and controlled-potential electrolysis. The results show that the reaction leads to the formation of the expected cyclic compounds, which are important intermediates in the synthesis of natural products with possible biological activities.

Silicon nanowire arrays coupled with cobalt phosphide spheres as low-cost photocathodes for efficient solar hydrogen evolution

We demonstrate the first example of silicon nanowire array photocathodes coupled with hollow spheres of the emerging earth-abundant cobalt phosphide catalysts. Compared to bare silicon nanowire arrays, the hybrid electrodes exhibit significantly improved photoelectrochemical performance toward the solar-driven H2 evolution reaction.

Effect of chitosan-Aloe vera coating on postharvest quality of blueberry (Vaccinium corymbosum) fruit

The present study was carried out to evaluate the effect of chitosan-based edible coatings with Aloe vera extract on the postharvest blueberry fruit quality during storage at 5 °C. Firstly, A. vera fractions (pulp and liquid) were extracted from leaves and evaluated in terms of antifungal and antioxidant capacities. The choice of the most adequate chitosan and A. vera fraction concentrations to be incorporated in coating formulation was made based on the wettability of the corresponding coating solutions. Coatings with 0.5% (w/v) chitosan + 0.5% (w/v) glycerol + 0.1% (w/v) Tween 80 + 0.5% (v/v) A. vera liquid fraction presented the best characteristics to uniformly coat blueberry surface. Physico-chemical (i.e., titratable acidity, pH, weight loss) and microbiological analyses of coated blueberries (non-inoculated or artificially inoculated with Botrytis cinerea) were performed during 25 d. Microbiological growth and water loss levels were approximately reduced by 50% and 42%, respectively, in coated blueberries after 25 d compared to uncoated blueberries. After 15 d, weight loss values were 6.2% and 3.7% for uncoated and chitosanA. vera coated blueberries, respectively. Uncoated fruits presented mold contamination after 2 d of storage (2.0 ± 0.32 log CFU g1), whilst fruits with chitosan-based coatings with A. vera presented mold contamination only after 9 d of storage (1.3 ± 0.35 log CFU g1). Overall, coatings developed in this study extend blueberries shelf-life for about 5 d, demonstrating for the first time that the combination of chitosan and A. vera liquid fraction as edible coating materials has great potential in expanding the shelf-life of fruits.