Study of condition-dependent decomposition reactions; Part I. The thermal behaviour and decomposition of 2-nitrobenzoyl chloride

The risks associated with batch processing in the manufacture of chemicals and pharmaceuticals via highly exothermic reactions are of special interest due to the possibility of runaway reactions. o-Nitrated benzoyl chlorides are intermediates in the production of agrochemicals and are produced via the reaction of o-nitrated carboxylic acids with thionyl chloride in a solvent mixture. ortho-Nitrated acyl chlorides have exploded violently on attempted distillation on numerous occasions. An inadequate investigation of the process prior to large-scale operation is the most likely cause. Here we present preliminary results of studies on the decomposition of 2-nitrobenzoyl chloride. This study has revealed that the decomposition reaction is strongly condition dependent. The heating rate of the sample plays a preponderant role in the course of the decomposition reaction. That renders the interpretation of differential scanning calorimetry (DSC) or adiabatic calorimetry measurements, which are routinely used to assess the thermochemistry and safety of the large-scale reactions, problematic. Following this on-going study, we report here key features of the system that have been identified.     

Morphological evaluation of bioartificial hydrogels as potential tissue engineering scaffolds

Poly(vinyl alcohol) hydrogels prepared by freeze-thawing procedure represent synthetic systems widely investigated as non-biodegradable scaffolds for tissue regeneration. In order to improve the biocompatibility properties of pure poly(vinyl alcohol) (PVA) hydrogels, blends of PVA with different biological macromolecules, such hyaluronic acid, dextran, and gelatin were prepared and used to produce bioartificial hydrogels. The porosity characteristics of these hydrogels were investigated by scanning electron microscopy and mercury intrusion porosimetry. The morphology of bioartificial hydrogels was evaluated and compared with that of pure PVA hydrogels. In particular the effect exerted by each biological component on pore size and distribution was investigated. The obtained results indicate that when a natural macromolecule is added to PVA the internal structure of the material changes. A small amount of biopolymer induces the structural elements of PVA matrix to take on a well evident lamellar appearance and an apparent preferential orientation. Comparing the results of SEM and mercury intrusion porosimetry it was concluded that hydrogels containing 20% of biological component have the most regular structure and at the same time the lowest total porosity. On the contrary samples with the highest content of natural polymer (40%) show the less regular structure and the highest total porosity.     

Influence of air abrasion preparation on microleakage in glass ionomer cement restorations

The aim of this study was to assess microleakage in class V cavities prepared by air abrasion or high-speed dental bur and restored with different glass ionomer cements. Sixty bovine incisors were equally divided into 6 groups: I, II and III (preparation by high-speed) and IV, V and VI (preparation by air abrasion). Groups I and IV were restored with Fuji IX; groups II and V with Ketac Molar; and groups III and VI with Vitremer. After 24 h (37 °C), specimens were thermocycled, isolated with nail varnish, immersed in a 0.2% Rhodamine B solution for 24 hours, sectioned longitudinally and analyzed for microleakage using an optical microscope connected to a digital camera and a computer. The images were digitized and a software allowed the quantitative evaluation of microleakage in millimeters. Data were analyzed by Wilcoxon and Kruskal-Wallis tests. It was observed that there were significant differences (p ≤ 0.05) between incisal (enamel) and cervical (dentine/cementum) margins, mainly for Ketac Molar; there was no difference (p ≥ 0.05) between preparation methods, except for group II (high-speed/Ketac Molar) that showed higher infiltration; regarding the materials, Ketac Molar demonstrated the highest microleakage values (p ≤ 0.05), and only Vitremer sealed completely both margins of restorations. It was concluded that air abrasion preparation did not influence microleakage in class V restorations with the employed glass ionomer cements.     

RILEM recommendation MDT. D.3—Determination “in situ” of the adhesive strength of rendering and plastering mortars to their substrate

RILEM RecommendationsRILEM TC 177-MDT: ‘Masonry Durability and on-site Testing’

RILEM recommendation MDT. D.3—Determination “in situ” of the adhesive strength of rendering and plastering mortars to their substrate     

A graphical tool for parasite genome annotation

A graphical tool to facilitate rapid primary annotation of genomic sequence has been developed. Within a single interface the user can import sequences or database entries, run feature prediction programs and similarity searches, filter results, add additional manually found features and notes, and finally export annotations for database submission. Integrated rule-based feature corroboration and a novel decision support heuristic using ORF orientation, length and base-composition further enhances the efficiency of the annotation process without compromising flexibility. The program has been explicitly tailored to use in protozoan parasite genome projects, but can constitute a useful tool for prokaryote annotation as well. It is successfully being used by our lab in the Trypanosoma cruzi genome project, and can be obtained from the authors upon request.     

Estimating the entropy rate of spike trains via Lempel-Ziv complexity

Normalized Lempel-Ziv complexity, which measures the generation rate of new patterns along a digital sequence, is closely related to such important source properties as entropy and compression ratio, but, in contrast to these, it is a property of individual sequences. In this article, we propose to exploit this concept to estimate (or, at least, to bound from below) the entropy of neural discharges (spike trains). The main advantages of this method include fast convergence of the estimator (as supported by numerical simulation) and the fact that there is no need to know the probability law of the process generating the signal. Furthermore, we present numerical and experimental comparisons of the new method against the standard method based on word frequencies, providing evidence that this new approach is an alternative entropy estimator for binned spike trains.     

Quantifying unfrozen water in frozen soil by high-field 2H NMR

To understand wintertime controls of biogeochemical processes in high latitude soils it is essential to distinguish between direct temperature effects and the effects of changes in water availability mediated by freezing. Efforts to separate these controls are hampered by a lack of adequate methods to determine the proportion of unfrozen water. In this study we present a high-field 2H2O NMR method for quantifying unfrozen water content in frozen soil. The experimental material consisted of the humic layer of a boreal spruce forest soil mixed with varying proportions of quartz sand and humidified with deuterium-enriched water. The relative standard deviation of unfrozen water content (measured as NMR signal integral) was less than 2% for repeated measurements on a given sample and 3.5% among all samples, based on a total of 16 measurements. As compared to 1H NMR, this 2H NMR method was found to be superior for several reasons: it is less sensitive to field inhomogeneity and paramagnetic impurities, it gives a bigger line shape difference between the ice and liquid signal, it shows a sharper response to water fusion, and it excludes the possibility of hydrogen in the organic material interfering with the measurement.     

Assessing blood flow control through a bootstrap method

In order to assess blood flow control, the relationship between blood pressure and blood flow can be modeled by linear filters. We present a bootstrap method, which allows the statistical analysis of an index of blood flow control that is obtained from constrained system identification using an established set of pre-defined filters.     

Automatic classification of heartbeats using ECG morphology and heartbeat interval features

A method for the automatic processing of the electrocardiogram (ECG) for the classification of heartbeats is presented. The method allocates manually detected heartbeats to one of the five beat classes recommended by ANSI/AAMI EC57:1998 standard, i.e., normal beat, ventricular ectopic beat (VEB), supraventricular ectopic beat (SVEB), fusion of a normal and a VEB, or unknown beat type. Data was obtained from the 44 nonpacemaker recordings of the MIT-BIH arrhythmia database. The data was split into two datasets with each dataset containing approximately 50,000 beats from 22 recordings. The first dataset was used to select a classifier configuration from candidate configurations. Twelve configurations processing feature sets derived from two ECG leads were compared. Feature sets were based on ECG morphology, heartbeat intervals, and RR-intervals. All configurations adopted a statistical classifier model utilizing supervised learning. The second dataset was used to provide an independent performance assessment of the selected configuration. This assessment resulted in a sensitivity of 75.9%, a positive predictivity of 38.5%, and a false positive rate of 4.7% for the SVEB class. For the VEB class, the sensitivity was 77.7%, the positive predictivity was 81.9%, and the false positive rate was 1.2%. These results are an improvement on previously reported results for automated heartbeat classification systems.