pH-induced changes in the fabrication of multilayers of poly(acrylic acid) and chitosan: fabrication, properties, and tests as a drug storage and delivery system

Multilayers of poly(acrylic acid), PAA, and chitosan, CHI, have been built by the layer-by-layer (LbL) method from aqueous solutions at different pH values and analyzed by the dissipative quartz crystal microbalance (D-QCM) and ellipsometry. The results showed that under all of the assembly conditions considered the growth of the films is nonlinear. The thickness of the PAA layers increases as the pH of the assembling solutions decreases, whereas the adsorption of CHI is almost unaffected by the pH conditions. The comparison of the thickness obtained by D-QCM and by ellipsometry has allowed us to calculate the water content of the films, showing that the multilayers are highly hydrated, with an average water content higher than 20%. The analysis of D-QCM data has provided high-frequency values of the complex shear modulus that are in the megapascal range and shows a transition from mainly viscous to mainly elastic behavior for the added PAA layers, depending on the pH. The monomer surface density in each layer (obtained from the combination of ellipsometry and differential refractive index measurements) indicated that the monomer density depends on the assembly conditions. It was found that the adsorption kinetics is a bimodal process, with characteristic times that depend on the number and nature of the layers. Finally, the possibility of using of these multilayers as a drug storage and delivery system has been evaluated.     

Calorimetry of Portland cement with metakaolins, quartz and gypsum additions

In this work two aluminic pozzolans (metakaolins) and a non-pozzolan were added to two Portland cements with very different mineral composition, to determine the effect on the rate of heat release and the mechanisms involved. The main analytical techniques deployed were: conduction calorimetry, pozzolanicity and XRD. The results showed that the two metakaolins induced stimulation of the hydration reactions due to the generation of pozzolanic activity at very early stage, because of their reactive alumina, Al₂O₃^r− contents, mainly. Such stimulation was found to be more specific than generic for more intense C₃A hydration than C₃S, at least at very early on into the reaction, and more so when 7.0% SO₃ was added, and for this reason, such stimulation is described as ‘indirect’ to differentiate it from the ‘direct’ variety. As a result of both stimulations, the heat of hydration released is easy to assimilate to a Synergistic Calorific Effect.     

Solving the deterministic and stochastic uncapacitated facility location problem: from a heuristic to a simheuristic

The uncapacitated facility location problem (UFLP) is a popular combinatorial optimization problem with practical applications in different areas, from logistics to telecommunication networks. While most of the existing work in the literature focuses on minimizing total cost for the deterministic version of the problem, some degree of uncertainty (e.g., in the customers’ demands or in the service costs) should be expected in real-life applications. Accordingly, this paper proposes a simheuristic algorithm for solving the stochastic UFLP (SUFLP), where optimization goals other than the minimum expected cost can be considered. The development of this simheuristic is structured in three stages: (i) first, an extremely fast savings-based heuristic is introduced; (ii) next, the heuristic is integrated into a metaheuristic framework, and the resulting algorithm is tested against the optimal values for the UFLP; and (iii) finally, the algorithm is extended by integrating it with simulation techniques, and the resulting simheuristic is employed to solve the SUFLP. Some numerical experiments contribute to illustrate the potential uses of each of these solving methods, depending on the version of the problem (deterministic or stochastic) as well as on whether or not a real-time solution is required.     

Preclinical Investigation of Methylene Blue-mediated Antimicrobial Photodynamic Therapy on Leishmania Parasites Using Real-Time Bioluminescence

Cutaneous leishmaniasis (CL) is a neglected disease that promotes destructive lesions. Difficulties in treatment are related to accessibility of drugs, resistance and toxicity. Antimicrobial photodynamic therapy (APDT) has been emerging as a promising treatment for CL. In this work, we evaluated methylene blue (MB)-mediated APDT (MB-APDT) on Leishmania amazonensis in vitro and in vivo by bioluminescence technique. In vitro, MB-APDT was performed using a red LED (λ = 660 ± 11 nm, 100 mW cm⁻²) and MB (100 µm ) at different light doses. In vivo, mice were infected and 4 weeks later, randomly divided into three groups: control, APDT 1 (single session) and APDT 2 (two sessions of MB-APDT). MB was used at 100 µm and energy dose was established at 150 J cm⁻². Parasite burden, lesion size and pain were evaluated weekly for 4 weeks. In vitro, lethal dose for 90% parasite inactivation was achieved at 48.8 J cm⁻². In vivo, although APDT 1 and APDT 2 groups have showed similar parasite burden after 4 weeks, two sessions were clinically better, especially considering the inflammatory process associated to CL. Our findings reinforce MB-APDT as a cost-effective treatment to combat CL.     

Fast physics-chemical characterization of fly ash

This paper analyzes the effect of fly ash chemical character on early Portland cement hydration and the possible adverse effects generated by the addition of gypsum. Behaviour was analyzed for pure Portland cements with varying mineralogical compositions and two types of fly ash, likewise differing in chemical composition, which were previously characterized under sulphate attack as: silicic-ferric-aluminic or aluminic-silicic ash in chemical character, irrespective if they are in nature, siliceous or siliceous and aluminous materials according to the ASTM C 618-94a. The experimental results showed that water demand for paste with a normal consistency increased with the replacement ratio in fly ash with a more aluminic than silicic chemical character, whereas it declined when silicic-ferric-aluminic ash was used. On the other hand, the differences between the total heat of hydration released at the first valley and the second peak also clearly differentiated the two types of ash. While the relative differences increased in the more aluminic than silicic ash, they declined in the more silicic than aluminic. In another vein, the findings indicate that within a comparable Blaine fineness range, the reactive alumina (Al₂O₃^r−) content in pozzolanic additions has a greater effect on mortar strength than the reactive silica (SiO₂^r−) content, at least in early ages up to 28 days. Finally, the adverse effect generated in the presence of excess gypsum is due primarily to the chemical interaction between the gypsum and the C₃A in the Portland cement and the reactive alumina (Al₂O₃^r−) in the fly ash.     

Improving the efficiency of a best-first bottom-up approach for the Constrained 2D Cutting Problem

This work introduces several improvements in the solution of the Constrained 2D Cutting Problem. Such improvements combine the detection of dominated and duplicated cutting patterns with the implementation of parallel approaches for best-first search methods. The analysis of symmetries and dominances among the cutting patterns is able to discard some non-optimal or redundant builds, thus reducing the search space to be explored. The experimental evaluation demonstrates that when the domination/duplication rules are applied to an efficient parallel approach, the obtained reduction in the number of managed nodes involves a noticeable decrease in the computational effort associated with the final search process.     

Calorimetric comparison of portland cements containing silica fume and metakaolin

This new study must be regarded to be a direct outcome of two previous studies published by these same authors, which were conducted to respond to interesting questions brought out about the effect of silica fume, SF and metakaolins, M and MQ, on the heat of hydration of portland cements, PC, with very different C₃A and C₃S contents. The answer to these so interesting questions has been the primary objective of the present research. For this purpose, the same PC, PC1 (14% C₃A) and PC2 (≈0% C₃A), metakaolins, silica fume and blended cements were once again used more 60/40 for sulphate attack, and the same analytical techniques (CC, pozzolanicity and XRD analysis) and parameters determined as well. In this new research, the sulphate attack was determined by two accelerated methods: Le Chatelier-Ansttet and ASTM C 452-68. The experimental results of sulphate attack mainly, have demonstrated definitively that the high, rapid and early pozzolanic activity exhibited by SF also is, as in the case of the two metakaolins, more specific than generic, for it indirectly stimulated greater C₃A than C₃S hydration, but only in the first 16 h monitored in this study. Thereafter it is the contrary, i.e., anti- or contra-specific for the same purpose. And the longer the hydration time, the more anti- or contra-specific it became, since, when exposed to sulphate attack, SF blended cements resisted or even prevented the aggressive attack against PC1 which, with a higher C₃A content than PC2, was the more vulnerable of the two. By contrast, metakaolin MQ not only failed to hinder or prevent the attack, but heightened its effects, rendering it more intense, aggressive and rapid, leading to what could be called a rapid gypsum attack.     

Effects of Tau and Sampling Frequency on the Regularity Analysis of ECG and EEG Signals Using ApEn and SampEn Entropy Estimators

Electrocardiography (ECG) and electroencephalography (EEG) signals provide clinical information relevant to determine a patient’s health status. The nonlinear analysis of ECG and EEG signals allows for discovering characteristics that could not be found with traditional methods based on amplitude and frequency. Approximate entropy (ApEn) and sampling entropy (SampEn) are nonlinear data analysis algorithms that measure the data’s regularity, and these are used to classify different electrophysiological signals as normal or pathological. Entropy calculation requires setting the parameters r (tolerance threshold), m (immersion dimension), and τ (time delay), with the last one being related to how the time series is downsampled. In this study, we showed the dependence of ApEn and SampEn on different values of τ, for ECG and EEG signals with different sampling frequencies (F_s), extracted from a digital repository. We considered four values of F_s (128, 256, 384, and 512 Hz for the ECG signals, and 160, 320, 480, and 640 Hz for the EEG signals) and five values of τ (from 1 to 5). We performed parametric and nonparametric statistical tests to confirm that the groups of normal and pathological ECG and EEG signals were significantly different (p < 0.05) for each F and τ value. The separation between the entropy values of regular and irregular signals was variable, demonstrating the dependence of ApEn and SampEn with F_s and τ. For ECG signals, the separation between the conditions was more robust when using SampEn, the lowest value of F_s, and τ larger than 1. For EEG signals, the separation between the conditions was more robust when using SampEn with large values of F_s and τ larger than 1. Therefore, adjusting τ may be convenient for signals that were acquired with different F_s to ensure a reliable clinical classification. Furthermore, it is useful to set τ to values larger than 1 to reduce the computational cost.     

Fast physics-chemical and calorimetric characterization of natural pozzolans and other aspects

This research reports on the effects of including natural pozzolans in two Portland cements with different mineralogical compositions, with and without excess gypsum at amounts equivalent to 7.0% SO₃. The main analytical techniques used to study these effects were: the amount of water needed to make a paste of normal consistency, the 2-day Frattini pozzolanicity test and conduction calorimetry. The results obtained showed that these natural pozzolans caused contradictory (accelerating and retarding) effects on the rheology of the resulting cements, depending on the mineralogical composition of the respective Portland clinkers as well as the reactive chemical composition of the pozzolans, in particular their reactive alumina content (Al₂O₃ ^r−). The addition of gypsum also caused acceleration and delays in the calorimetric evolution of the resulting pastes, which proved to be heavily dependent upon the more or less aluminic chemical character of the natural pozzolans studied. This, in turn, was conditioned by the higher or lower Al₂O₃ ^r− content (for the SiO₂ ^r− content was of a very similar order of magnitude in all three pozzolans analyzed). The Al₂O₃ ^r− content was likewise responsible for paste behaviour in the afore-mentioned trials and analyses, and the pozzolanic activity exhibited by the compound was found to be more specific than generic, indirectly stimulating C₃A hydration more intensely and rapidly than C₃S hydration in PC1, one of the two Portland cements used. Indeed, when these natural pozzolans exhibited such prior pozzolanic activity in the second cement studied, PC2, the hydration of its 79.5% of C₃S was not indirectly stimulated to the same degree; rather, the contrary effect was observed, i.e., this cement was physically diluted by the three pozzolans. Pozzolan O stimulated hydration directly and non-directly more than indirectly, while pozzolan C acted conversely, and A exhibited varying combinations of the two patterns. The physical state of the reactive alumina, Al₂O₃ ^r−, in these three natural pozzolans, must be more amorphous than vitreous, i.e., resembling metakaolin more than fly ash in this regard. That notwithstanding, the reactive alumina content in each pozzolan must have conditioned the water/cementitious material ratio obtained for the respective blends with both types of Portland cement (a finding that could be used in future for speedy, simple, reliable and economical characterization), as well as their specific pozzolanicity developed and the rate and total heat of hydration generated by such blended cements.