Quantitative 13C NMR analysis of sequence distributions in poly(ethylene-co-1-hexene)

Different 13C NMR methods of determining triad distributions in two poly(ethylene-co-1-hexene) copolymers are examined using high signal-to-noise ratio 13C NMR spectra of the copolymers dissolved in deuterated 1,2,4-trichlorobenzene at 398 K. This examination includes a comparison of three integration techniques. The experimental impact of decoupler sidebands and significantly nonequal 13C NOE values are examined. A least-squares regression analysis technique for solving for triad mole fractions is tested and appears to be more reliable than two published algebraic expressions (and other expressions examined in the work reported here). The resultant triad mole fractions are compared to sequence distribution parameters expected by Bernoullian and first-order Markovian statistical models. On the basis of 13C NMR-determined average reactivity ratios, the copolymer designated sample B (5.3 mol % 1-hexene) appears to be a Bernoullian copolymer resulting from a single-site catalytic system. The copolymer designated sample S (3.6 mol % 1-hexene overall) is better described as a mixture of polyethylene and a Bernoullian copolymer with 6.4 mol % 1-hexene content, and thus appears to result from a multisite catalytic system.     

Evaluation of Atmospheric and Vacuum Residues Using Molecular Distillation and Optimization

The term atmospheric residue describes the material at the bottom of the atmospheric distillation tower having a lower boiling point limit of about 340°C; the term vacuum residue (heavy petroleum fractions) refers to the bottom of the vacuum distillation, which has an atmospheric equivalent boiling point (AEBP) above 540°C. In this work, the objective is to evaluate the behavior of different kinds of Brazilian atmospheric and vacuum residues using molecular distillation. The Falling Film Molecular Distillator was used. For the results obtained through this process, a significant range of temperature can be explored avoiding the thermal decomposition of the material. So these results are very important to the refinery decisions and improvements. The Experimental Factorial Design results showed that the temperature has more influence on the process than the feed flow rate, when a higher percentage of distillate is required.     

The Adaptive Immune Landscape of the Colorectal Adenoma–Carcinoma Sequence

Background. The tumor immune microenvironment exerts a pivotal influence in tumor initiation and progression. The aim of this study was to analyze the immune context of sporadic and familial adenomatous polyposis (FAP) lesions along the colorectal adenoma–carcinoma sequence (ACS). Methods. We analyzed immune cell counts (CD3+, CD4+, CD8+, Foxp3+, and CD57+), tumor mutation burden (TMB), MHC-I expression and PD-L1 expression of 59 FAP and 74 sporadic colorectal lesions, encompassing adenomas with low-grade dysplasia (LGD) (30 FAP; 30 sporadic), adenomas with high-grade dysplasia (22 FAP; 30 sporadic), and invasive adenocarcinomas (7 FAP; 14 sporadic). Results. The sporadic colorectal ACS was characterized by (1) a stepwise decrease in immune cell counts, (2) an increase in TMB and MHC-I expression, and (3) a lower PD-L1 expression. In FAP lesions, we observed the same patterns, except for an increase in TMB along the ACS. FAP LGD lesions harbored lower Foxp3+ T cell counts than sporadic LGD lesions. A decrease in PD-L1 expression occurred earlier in FAP lesions compared to sporadic ones. Conclusions. The colorectal ACS is characterized by a progressive loss of adaptive immune infiltrate and by the establishment of a progressively immune cold microenvironment. These changes do not appear to be related with the loss of immunogenicity of tumor cells, or to the onset of an immunosuppressive tumor microenvironment.     

Experimental campaign,modeling, and sensitivity analysis for the molecular distillation of petroleum residues 673.15 K+

This research activity proposes a sensitivity analysis of the molecular distillation process by focusing the attention on the response of the overall distillate flow rate under several conditions of distillation temperature and feed flow rate. Specific equations to characterize physicochemical properties of petroleum residues have been formulated by means of ASTM-based experimental campaigns combined with specific optimization techniques.     

Measurements of normal boiling points of fatty acid ethyl esters and triacylglycerols by thermogravimetric analysis

At present, a large number of studies of biodiesel production process using simulation packages are being developed. In these studies, vegetable oils and biodiesels are characterized in the software through representative compounds because of they are not in the compounds database of commercial simulators. With the aim to achieve a successfully characterization in these kinds of software, some properties of the substances must be available. The normal boiling point (NBP) is the most important property due to the fact that this property along with group contribution methods allows other properties calculation such as, e.g., critical properties and temperature dependency properties. In this work, a thermogravimetric analysis (TGA) method for rapid measurement of normal boiling points of two triacylglycerols and four ethyl esters, i.e., triolein, tripalmitin, ethyl oleate, ethyl palmitate, ethyl linoleate and ethyl ricinoleate, was used. Nowadays, in the open literature exists few data available about ethyl esters properties; hence, the results obtained here will contribute in the proposal, analysis, and evaluation of ethyl esters (biodiesel) virtual plants using reliable simulation packages. In addition, a more accurate characterization of compounds and therefore more accurate simulation results can be obtained when they are used.     

Influence of anthocyanins and derivative pigments from blueberry (Vaccinium myrtillus) extracts on MPP intestinal uptake: A structure–activity approach

The aim of the present study was to investigate the influence of an anthocyanin extract (extract I), and two other derivative extracts (extracts II and III), which are being developed aiming to be further applied in the food industry, on intestinal uptake of organic cations. For this purpose, the effect of these compounds on ³H-MPP⁺ uptake was evaluated in Caco-2 cells (an enterocyte-like cell line derived from a human colonic adenocarcinoma).     

Correlated color temperature preferred by observers for illumination of artistic paintings

The visual effects of lighting on art paintings is an important aspect that should be considered by museum curators. The aim of this work was to determine the correlated color temperature (CCT) of daylight illumination preferred by observers when appreciating art paintings. Hyperspectral images of 11 oil paintings were collected at the museum, and the appearance of the paintings under daylight illuminants with CCT from 25,000 K to 3600 K was computed. In a psychophysical experiment using precise CRT reproductions of the paintings, observers had to adjust the CCT of the illuminant such that it produced the best visual impression. It was found that the distribution of observers' preferences had a maximum at a CCT of about 5100 K and that this value did not depend on whether the observers were undergraduate students or museum visitors or on the degree of adaptation to the color of the illumination. These results suggest that observers prefer a more bluish-white light than that normally used in museums.     

Approximation of ill-posed boussinesq equations

In this paper we compare the dynamics on the centre manifold of the solutions of an ill-posed Boussinesq equation with a well-posed version. We show that the dynamics in the centre manifold of the ill-posed equation tracks the dynamics of the well-posed equation. Our results give partial justification to the long-wave perturbation theory.     

Bulk mass flow in a vibratory finisher: mechanisms and effect of process parameters

Vibratory finishing is a widely-used manufacturing process in which a vibrating container filled with granular media becomes fluidized. The resulting bulk flow entrains workpieces and exposes their surfaces to the impacts resulting from the small-scale media vibrations. The bulk flow is responsible for entrainment and mixing, while the media vibration does work on the surfaces. The selection of machine vibration parameters is commonly based on experience due to the difficulty in predicting the fluidized bed behavior. In this work, a discrete element method was used to investigate how the bulk flow in an actual tub finisher filled with steel balls depends on the tub motion parameters through a parametric study. The underlying mechanisms that create and drive the bulk flow were identified by examining the relationships between the bulk flow rates and the wall forces. Finally, the connection between the wall motion and the wall forces was investigated. The tub frequency was the most effective control parameter and there was an optimal phase difference between the horizontal and vertical vibrations to maximize bulk flow. The relationship between the media packing at the walls and the tangential forces between the walls and the media explained the formation and speed of the bulk flow. Lastly, it was shown that the tangential wall forces, unlike the normal forces, cannot be obtained from the known wall motion alone since they also depend on the media velocities relative to the walls.