Thermal dehydrochlorination of pure PVC polymer: Part I—thermal degradation kinetics by thermogravimetric analysis

Thermal degradation of PVC occurs in two stages, with each stage subdivided into two substages. The first refers to the dehydrochlorination, where hydrochloric acid is formed, and giving polyene structures. Hitherto, the degradation mechanism and action of hydrochloric acid as a catalyst during the dehydrochlorination stage are poorly known. Recently, the importance of the tacticity has gained attention for its influence on the dehydrochlorination mechanism. The present work focused on the dehydrochlorination stage, studying the molecular structure by FTIR analysis and the kinetic parameters by TGA analysis in Nitrogen atmosphere, based on three mathematical methods: Friedman, Kissinger, and Flynn-Wall-Ozawa. The sample was a pure homopolymer obtained by suspension polymerization. The dehydrochlorination kinetics follows a first order reaction model and occurs by nucleation and growth. The dehydrochlorination begins with the loss of very labile chlorine atoms present in defective and isotactic molecular segments. The formed HCl acts as a catalyst in the degradation. Following 40% conversion, a drop in Ea is observed. After that, chlorine atoms present in syndiotactic and atactic sequences, are released and, added to the large number of polyene chain sequences, and an increase in Ea is observed up to 60% conversion, where the dehydrochlorination stage is concluded.     

Thermal stability of polymers based on acrylamide and 2-acrylamido-2-methylpropane sulfonic acid in different temperature and salinity conditions

Partially hydrolyzed polyacrylamide (PHPA) is the most widely used polymer in enhanced oil recovery (EOR) applications. However, under conditions of high temperature and salinity, the PHPA molecules become hydrolyzed, causing a drastic reduction of the viscosity of the polymer solution due to the presence of negative charges, making the molecules more susceptible to interactions with cations. In this sense, in order to increase the stability of these polymers, an anionic monomer more resistant to cations such as 2-acrylamido-2-methylpropane sulfonic acid (AMPS) has been incorporated into the HPAM molecules. This work evaluated the thermal stability of a copolymer (acrylamide and AMPS - AN125) and a terpolymer (acrylamide, acrylate, and AMPS-FP5115) in the time course of 360 days. The tests were carried out in typical conditions of Brazilian offshore reservoirs, such as absence of oxygen, high temperature, and high salt concentration. The test method involved measurements of intrinsic viscosity in function of time and determination of the hydrolysis degree of the polymers by elemental analysis. The copolymer AN125 was more stable under the test conditions than the terpolymer FP 5115 due to the presence of a higher concentration of AMPS in the copolymer. The AMPS group was hydrolyzed to AA at a temperature of 100 °C, however, the increase in salt concentration delayed the onset of this degradation. The tests indicated that the presence of a higher AMPS content in the copolymer does not prevent the polymer from undergoing hydrolysis, but delays the polymer precipitation step in the solution.     

Early-Life Development of the Bifidobacterial Community in the Infant Gut

The establishment of the gut microbiota poses implications for short and long-term health. Bifidobacterium is an important taxon in early life, being one of the most abundant genera in the infant intestinal microbiota and carrying out key functions for maintaining host-homeostasis. Recent metagenomic studies have shown that different factors, such as gestational age, delivery mode, or feeding habits, affect the gut microbiota establishment at high phylogenetic levels. However, their impact on the specific bifidobacterial populations is not yet well understood. Here we studied the impact of these factors on the different Bifidobacterium species and subspecies at both the quantitative and qualitative levels. Fecal samples were taken from 85 neonates at 2, 10, 30, 90 days of life, and the relative proportions of the different bifidobacterial populations were assessed by 16S rRNA–23S rRNA internal transcribed spacer (ITS) region sequencing. Absolute levels of the main species were determined by q-PCR. Our results showed that the bifidobacterial population establishment is affected by gestational age, delivery mode, and infant feeding, as it is evidenced by qualitative and quantitative changes. These data underline the need for understanding the impact of perinatal factors on the gut microbiota also at low taxonomic levels, especially in the case of relevant microbial populations such as Bifidobacterium. The data obtained provide indications for the selection of the species best suited for the development of bifidobacteria-based products for different groups of neonates and will help to develop rational strategies for favoring a healthy early microbiota development when this process is challenged.     

Precision Oncology via NMR-Based Metabolomics: A Review on Breast Cancer

Precision oncology is an emerging approach in cancer care. It aims at selecting the optimal therapy for the right patient by considering each patient’s unique disease and individual health status. In the last years, it has become evident that breast cancer is an extremely heterogeneous disease, and therefore, patients need to be appropriately stratified to maximize survival and quality of life. Gene-expression tools have already positively assisted clinical decision making by estimating the risk of recurrence and the potential benefit from adjuvant chemotherapy. However, these approaches need refinement to further reduce the proportion of patients potentially exposed to unnecessary chemotherapy. Nuclear magnetic resonance (NMR) metabolomics has demonstrated to be an optimal approach for cancer research and has provided significant results in BC, in particular for prognostic and stratification purposes. In this review, we give an update on the status of NMR-based metabolomic studies for the biochemical characterization and stratification of breast cancer patients using different biospecimens (breast tissue, blood serum/plasma, and urine).     

Near‐infrared spectroscopy for analysis of oil content and fatty acid profile in almond flour

Almond kernels show large variability for oil content and fatty acid profile. The objective of this research was to evaluate the potential of near infrared (NIR) reflectance spectroscopy (NIRS) for the analysis of these traits in almond flour. Ground kernels of 181 accessions collected in 2009 were used for developing calibration equations for oil content and concentrations of individual fatty acids. Calibration equations were developed using second derivative transformation and modified partial least squares regression. They were validated with samples from 179 accessions collected in 2010. The accuracy of calibration equations was measured through the coefficient of determination (r²) in external validation and the ratio of the SD in the validation set to the standard error of prediction (RPD). Both r² and RPD were high for oil content (r² = 0.99; RPD = 9.24) and concentrations of oleic (r² = 0.97; RPD = 5.37) and linoleic acids (r² = 0.98; RPD = 7.35), revealing that calibration equations for these traits are highly accurate. Conversely, the accuracy of the calibration equations for palmitic (r² = 0.54; RPD = 1.41) and stearic acids (r² = 0.52; RPD = 1.44) was too low for allowing their application in practice. NIRS discrimination of oil content and concentrations of oleic and linoleic acids was mainly based on the spectral region from 2240 to 2380 nm. Practical applications : NIRS is a high‐throughput analytical technique that allows fast measurement of several traits in a single analysis without using chemical reagents. We evaluated the feasibility of analyzing oil content and concentrations of palmitic, stearic, oleic, and linoleic acids in almond flour using fruits collected during 2 years from a world germplasm collection. The fruits collected in 2009 were used for NIRS calibration, whereas the fruits collected in 2010 were used for validation. NIRS equations were highly accurate for measuring oil content and concentrations of oleic and linoleic acids, which are important traits defining the quality of almond flour for specific uses in the food industry. These results have applications both in the research laboratory and the food industry, where NIRS is becoming a widely used technique for quality control.     

Influence of pH cycling and mechanical loading on the resin-dentin microtensile bond strength

The durability of adhesive interfaces is still a problem in adhesive restorations in dentistry. Laboratorial ageing methods have been proposed to predict the performance of materials, but they still require standardization. The objective of this study was to evaluate the resin-dentin microtensile bond strength of composite restorations subjected to pH cycling and different levels of mechanical loading. Resin blocks were built over a flat superficial dentin of bovine incisors (n = 40), using a three-step adhesive system. Half of the specimens were submitted to 10 cycles of pH cycling, followed by mechanical loading (0, 500,000; 1,000,000; 2,000,000 cycles – 98 N, 4 Hz). The other half was directly subjected to mechanical loading. After ageing, all groups were subjected to a microtensile bond test. Data were analyzed using two-way ANOVA and Tukey’s test (α = 0.05). The frequency of the early de-bonding was compared using the Chi-square test (α = 0.05). The statistical analysis revealed that the cross-product interaction ‘pH cycling’ vs. ‘number of mechanical loading cycles’ (p = 0.72) as well as the main factor ‘pH cycling’ (p = 0.49) was not statistically significant, and they were not able to reduce the resin–dentin bond strength values. Regarding the number of mechanical loading cycles, the groups subjected to 2,000,000 cycles showed lower bond strength values than the others (p = 0.003). The frequency of debonded specimens increased with mechanical loading. Therefore, it can be concluded that in this restorative model, at least 2,000,000 mechanical cycles are need to decrease the microtensile strength and simulate the ageing of the interface.     

A Sequential and Iterative Testing Procedure to Identify the Nature of a Time Series Generating Process

Abstract

An inferential approach is proposed to identify the nature of the generating process corresponding to a real time series. This new sequential and iterative testing procedure goes beyond the Box and Jenkins methodology for the identification, estimation, and validation of linear data generating processes by investigating the probabilistic structure of non-Gaussian estimated residuals {? _t } for the possible presence of nonlinear serial dependence. The testing procedure aims at indicating the right type of dependence present in a series by means of specific inferential tests on the moments of the generating structure probability distribution. The test statistics adopted are very popular and powerful and encompass a wide range of stochastic nonlinearity alternatives. The U.S. Industrial Production Index series is used to illustrate the iterative testing procedure proposed.     

Fungal fucoidanase production by solid-state fermentation in a rotating drum bioreactor using algal biomass as substrate

Fucoidanase enzymes able to degrade fucoidan were produced by solid-state fermentation (SSF). The fermentation assays were initially carried out in a laboratory-scale rotating drum bioreactor, and two fungal strains (Aspergillus niger PSH and Mucor sp. 3P) and three algal substrates (untreated, autohydrolyzed, and microwave processed seaweed Fucus vesiculosus) were evaluated. Additionally, fermentations were carried out under rotational (10 rpm) and static conditions in order to determine the effect of the agitation on the enzyme production. Agitated experiments showed advantages in the induction of the enzyme when compared to the static ones. The conditions that promoted the maximum fucoidanase activity (3.82 U L^?1) consisted in using Mucor sp. 3P as fungal strain, autohydrolyzed alga as substrate, and the rotational system. Such conditions were subsequently used in a 10 times larger scale rotating drum bioreactor. In this step, the effect of controlling the substrate moisture during the enzyme production by SSF was investigated. Moreover, assays combining the algal substrate with an inert support (synthetic fiber) were also carried out. Fermentation of the autohydrolyzed alga with the moisture content maintained at 80% during the fermentation with Mucor sp. 3P gave the highest enzyme activity (9.62 U L^?1).     

The Efficacy of the Quorum Sensing Inhibitor FS8 and Tigecycline in Preventing Prosthesis Biofilm in an Animal Model of Staphylococcal Infection

We investigated the efficacy of tigecycline and FS8, alone or combined, in preventing prosthesis biofilm in a rat model of staphylococcal vascular graft infection. Graft infections were established in the back subcutaneous tissue of adult male Wistar rats by implantation of Dacron prostheses followed by topical inoculation with 2 × 10⁷ colony-forming units of Staphylococcus aureus, strain Smith diffuse. The study included a control group, a contaminated group that did not receive any antibiotic prophylaxis, and three contaminated groups that received: (i) intraperitoneal tigecycline, (ii) FS8-soaked graft, and (iii) tigecycline plus FS8-soaked graft, respectively. Each group included 15 animals. The infection burden was evaluated by using sonication and quantitative agar culture. Moreover, an in vitro binding-study was performed to quantify the how much FS8 was coated to the surface of the prosthesis. Tigecycline, combined with FS8, against the adherent bacteria showed MICs (2.00 mg/L) and MBCs (4.00 mg/L) four-fold lower with respect to tigecycline alone in in vitro studies. The rat groups treated with tigecycline showed the lowest bacterial numbers (4.4 × 10⁴ ± 1.2 × 10⁴ CFU/mL). The FS8-treated group showed a good activity and significant differences compared to control group with bacterial numbers of 6.8 × 10⁴ ± 2.0 × 10⁴ CFU/mL. A stronger inhibition of bacterial growth was observed in rats treated with a combined FS8 and tigecycline therapy than in those that were singly treated with bacterial numbers of 10¹ CFU/mL graft. In conclusion, the ability to affect biofilm formation as well, its property to be an antibiotic enhancer suggests FS8 as alternative or additional agent to use in conjunction with conventional antimicrobial for prevention of staphylococcal biofilm related infection.     

Validation of a UV Spectrophotometric Method for Determination of Proteolytic Activity of Enzymatic Detergents

Enzymatic detergents are widely used in health services. These products should be controlled to ensure their activity. In this paper, a UV spectrophotometric method for the determination of proteolytic activity in enzymatic detergents was validated. An artificial substrate (azocasein) was used to quantify the enzyme activity at 340 nm. The results showed that the method was satisfactory in respect to its specificity, linearity, precision, accuracy and robustness. This method fulfills both ICH’s and Brazilian criteria, demonstrating its suitability for routine analysis as well as its potential application for regulatory purposes.