An experimental study on the early stages of gas‐phase olefin polymerizations using supported Ziegler–Natta and metallocene catalysts

The initial stages of gas‐phase polymerizations of propylene and ethylene are analyzed using a fixed bed stopped flow reactor. The very early development of particle morphology and polymer properties is analyzed for three different commercial catalyst systems: MgCl₂‐ and SiO₂‐supported Ziegler–Natta and SiO₂‐supported metallocene. It is shown that, depending on the operating conditions, distinct nonuniform catalyst fragmentation patterns can develop, confirming different scenarios described by published fragmentation models. In addition, it is shown that the molecular weight distributions and polymer yields obtained during the very early stages of the polymerization suggest the existence of significant temperature gradients inside the growing polymer particles. Finally, it is shown that the ratio of catalyst to glass beads in the bed can have a pronounced effect on the evolution of the polymerization reaction. This can be interpreted in terms of the significant temperature difference between the polymer particles and the gaseous monomer stream. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Global optimization of mass and property integration networks with in-plant property interceptors

This paper presents a mathematical programming model for the optimal design of mass and property integration networks that include property interceptors within the structure of the network, as opposed to the end-of-pipe use of such interceptors. The model is based on a recycle and reuse scheme that simultaneously satisfies process and environmental constraints. The properties considered in this work are composition, toxicity, theoretical oxygen demand, pH, density and viscosity. The property mixing rules included in the model give rise to bilinear terms for the property operators, and a global optimization algorithm is used for the solution of the model. The model minimizes the total annual cost of the network, which includes the fresh sources cost and the annualized property treatment system and the piping costs. Three examples are included to show the applicability and advantages of the proposed model.     

Fluid-structure interaction study of the start-up of a rocket engine nozzle

The aim of this paper is to analyze the aeroelastic processes developed during the starting phase of a rocket engine via a coupling fluid/structure code. This analysis gives a better understanding of the behavior of the structure as the shock waves propagate inside the engine nozzle. The gasdynamics Euler equations are solved for the fluid and constitutive linear elastic solid assuming large displacements and rotations with no material damping is adopted for the structure. The coupling of each subproblem is carried out with a Gauß-Seidel algorithm over the fluid and structure states. For the fluid problem an ALE (Arbitrary Lagrangian-Eulerian) formulation is used. It allows us to define a reference system following the moving boundaries while the structure is deformed. The code is validated with a study of the flutter phenomena that may occur when a supersonic compressible fluid flows over a flat solid plate. Regarding the rocket engine ignition problem, a modal analysis of the structure is performed in order to analyze the eigenfrequency shifts when considering the coupling with the fluid flow.     

Synthesis of optimal thermal membrane distillation networks

Thermal membrane distillation (TMD) is an emerging separation method which involves simultaneous heat and mass transfer through a hydrophobic semipermeable membrane. Traditionally, studies of this technology have focused on the performance of individual modules. Because of purity and recovery requirements, multiple TMD modules may be used in various configurations including series, parallel, and combinations. Furthermore, there may be a need to reroute streams from one module to another or to recycle a stream to the same unit. The objective is to develop a systematic approach to synthesize an optimal TMD network. A structural representation is developed to embed potential configurations of interest. A mathematical formulation is developed to transform the design problem into an optimization task that seeks to minimize the cost of the system. Two case studies are presented to illustrate the applicability of the developed approach and its merit over conventional design scenarios. © 2014 American Institute of Chemical Engineers AIChE J, 61: 448–463, 2015     

Kinetic Modeling of Inhibition of Ammonia Oxidation by Nitrite under Low Dissolved Oxygen Conditions

In recent years the application of partial nitrification techniques has been denoted as very promising. These methods are based on the oxidation of ammonia to nitrite and the inhibition of the nitratation using different strategies. In most cases, this inhibition causes an increase in the concentration of nitrite. However, the effect of high nitrite concentrations under low dissolved oxygen (DO) conditions on the nitrification process is not well understood. In this paper, the effect of ammonia, nitrite, and nitrate concentrations on the nitrification process under low dissolved oxygen concentrations were studied using respirometric techniques. Results showed that the specific oxygen uptake rate (SOUR) followed a Monod-type equation with respect to the DO concentration. The coefficient SOURm was constant with respect to the ammonia, nitrite, and nitrate within the tested concentrations; in addition, KO was constant with respect to ammonia and nitrate but it increased linearly with the nitrite concentration, suggesting that nitrite was a competitive inhibitor of the SOUR. The inhibitory effect of nitrite was reverted by washing, in accordance with a competition model. From the data obtained using the open respirometer, the ratio between the oxygen consumption (OC) corresponding to each pulse of ammonia at different nitrite concentrations and the OC in the absence of nitrite (OCO) was calculated. The experimental ratio OC/OCO was almost constant with respect to the nitrite concentration and it was close to the literature value. Finally, simulation results agree with the experimental data confirming that the proposed competition model represented adequately the inhibitory effect of nitrite on the respiration rate of ammonia-oxidizing bacteria.     

Arachidin-1, a Prenylated Stilbenoid from Peanut,Induces Apoptosis in Triple-Negative Breast Cancer Cells

Triple-negative breast cancer (TNBC) is unresponsive to typical hormonal treatments, causing it to be one of the deadliest forms of breast cancer. Investigating alternative therapies to increase survival rates for this disease is essential. The goal of this study was to assess cytotoxicity and apoptosis mechanisms of prenylated stilbenoids in TNBC cells. The prenylated stilbenoids arachidin-1 (A-1) and arachidin-3 (A-3) are analogs of resveratrol (RES) produced in peanut upon biotic stress. The anticancer activity of A-1 and A-3 isolated from peanut hairy root cultures was determined in TNBC cell lines MDA-MB-231 and MDA-MB-436. After 24 h of treatment, A-1 exhibited higher cytotoxicity than A-3 and RES with approximately 11-fold and six-fold lower IC₅₀, respectively, in MDA-MB-231 cells, and nine-fold and eight-fold lower IC₅₀, respectively, in MDA-MB-436 cells. A-1 did not show significant cytotoxicity in the non-cancerous cell line MCF-10A. While A-1 blocked cell division in G2-M phases in the TNBC cells, it did not affect cell division in MCF-10A cells. Furthermore, A-1 induced caspase-dependent apoptosis through the intrinsic pathway by activating caspase-9 and PARP cleavage, and inhibiting survivin. In conclusion, A-1 merits further research as a potential lead molecule for the treatment of TNBC.     

Geometric invariance and reference conditioning ideas for control of overflow metabolism

In many biotechnological processes, the optimal productivity corresponds to operating at critical substrate concentration. The problem, then, consists in finding the feeding rate compatible with the critical constraint which gives a specific growth rate as close as possible to the desired one, so as to avoid overflow metabolism. This value may be unknown and may change from experiment to experiment and from strain to strain, and even in the same experiment due to changing environmental and/or process conditions. Particularly, in the fed-batch fermentation of the industrial strain Saccharomyces cerevisiae a small amount of ethanol is allowed to be present in the culture, and the control problem is one of regulating the ethanol concentration at a given low reference value. In this paper, an approach based on geometric invariance via sliding mode reference conditioning is proposed to achieve the closest specific growth rate to the desired reference which is compatible with system constraints (e.g. ethanol concentration lower than a given threshold). It is shown how this approach is robust with respect to uncertainties in the process dynamics and with respect to unknown perturbations affecting the critical point.     

New fir laser lines and frequency measurements from optically pumped13CD3OH3

We report the discovery of 57 new fir laser lines from¹³CD₃OH molecule optically pumped by a waveguide CO₂ laser of 300 MHz tunability. For all lines, precise frequency offset measurements between the CO₂ line center and the center of the absorbing¹³CD₃OH line were performed using the transferred Lamb-Dip technique. We have also measured directly the frequency of seven FIR laser lines by heterodyning with already known laser lines. We present a complete list of all known laser lines (134) and frequency measurements (24) for this molecule.     

Caries removal with Er:YAG laser followed by dentin biomodification with carbodiimide and chitosan: Wettability and surface morphology analysis

This study aimed to investigate dentin wettability and surface morphology after selective removal of carious lesion by erbium‐doped yttrium aluminum garnet (Er:YAG) laser, followed by dentin biomodification with carbodiimide (EDC) and chitosan (CHI). Seventy‐eight bovine dentin specimens were submitted to caries induction. Specimens were distributed according to methods of carious removal (n = 39): bur at low‐speed (40,000 rpm) or Er:YAG laser (noncontact mode, 250 mJ/pulse and 4Hz). All specimens were etched with 35% phosphoric acid, and subdivided according to dentin biomodification (n = 13): Control (no biomodification), EDC or CHI. The contact angle (n = 10) between adhesive system (3M ESPE) and dentin surface was measured by a goniometer. Eighteen specimens (n = 3) were analyzed by scanning electron microscopy. Data were analyzed by two‐way ANOVA and Tukey's test (α = .05). The method used to remove carious lesion did not influence the wettability of dentinal surface (p = .748). The angles produced on the remaining dentin after biomodification were influenced (p = .007). CHI promoted higher contact angles (p = .007) and EDC did not differ from the control group (p = .586). In the bur‐treated group, most tubules were open, regardless of which biomodifier was used. Laser modified the organic matrix layer. CHI promoted partially closed tubules in some areas while EDC exposed dentinal tubules. Regardless of which method was used for selective removal of carious lesion, biomodification with EDC did not affect the dentin wettability, whereas CHI changed the wettability of remaining dentin. Both biomodifiers promoted a slight change on dentin morphology.