A Detailed Model for the Sintering of Polydispersed Nanoparticle Agglomerates

In this study the coagulation, condensation, and sintering of nanoparticles is investigated using a stochastic particle model. Each stochastic particle consists of interacting polydisperse primary particles that are connected to each other. In the model sintering occurs between each individual pair of neighboring primary particles. This is important for particles in which the range of the size of the primary particles varies significantly. The sintering time is obtained from the viscous flow model. The model is solved using a stochastic particle algorithm. The particles are represented in a binary tree that contains the connectivity as well as the degree of sintering information. Particles are forme, coagulate, sinter, and experience condensation according to known rate laws. The particle binary tree, along with it the degree of sintering, is updated after each time step according to the rates of the different processes. The stochastic particle method uses the technique of fictitious jumps and linear process deferment. The theoretical results are fitted against experimental values for the formation of SiO ₂ nanoparticles and computer generated TEM pictures are presented and compared to experiments.     

Impact of Particle Generation Method on the Apparent Hygroscopicity of Insoluble Mineral Particles

Calcite (CaCO ₃ ) mineral particles are commonly generated by atomization techniques to study their heterogeneous chemistry, hygroscopicity, and cloud nucleation properties. Here we investigate the significant artifact introduced in generating calcium mineral particles through the atomization of a saturated suspension of the powder in water, by measuring particle hygroscopicity via CCN activation curves. Particles produced from atomization displayed hygroscopicities as large as κ_app > 0.1, 100 times more hygroscopic than that obtained for dry-generated calcite, κ_app = 0.0011. The hygroscopicity of the wet-generated particles increased as a function of time the calcite powder spent in water, and with decreasing particle size. Wet-generated calcium oxalate was more hygroscopic through wet- (κ_app = 0.34) versus dry-generation (κ_app = 0.048). Atomized calcium sulfate particles, however, were only slightly more hygroscopic (κ_app = 0.0045) than those generated dry (κ_app = 0.0016). Single-particle analysis by ATOFMS and SEM/EDX, and bulk analysis of the calcite powders by ICP-MS and IC revealed no significant soluble contaminants. The atomized particles were likely composed of components that dissolved from the powder and then re-precipitated, and appeared to contain little of the original mineral powder. The increased hygroscopicity of atomized calcite may have been caused by aqueous carbonate chemistry producing Ca(OH) ₂ , Ca(HCO ₃ ) ₂ , and metastable hydrates with increased solubility. Surface water adsorption may have also played a role, in addition to uncharacterized soluble components produced by wet-generation, and the precipitation of amorphous phases including glassy states. This study suggests that using wet-generation methods to suspend mineral dust samples will not produce particles with the correct physicochemical properties in laboratory studies, a finding which has important implications for past and future laboratory studies focusing on understanding relationships between the hygroscopicity and chemistry of mineral dust particles.     

Modeling Solar Drying Rate of Wastewater Sludge

Efficient solar drying requires that the drying rate is quantitatively known as a function of the environment and the control. To develop a drying-rate model for wastewater sludge, data were collected at a solar drying installation in Füssen, Germany. In this solar dryer, wet sludge is uniformly spread over a concrete floor under a greenhouse-like transparent cover. The sludge is mixed mechanically several times a day by an autonomous robot (electric mole®), the structure is fan-ventilated horizontally, and the indoor air is mixed by electric fans. Data of evaporation rate, environmental conditions, and control operations were collected over three drying cycles. Evaporation rate via sludge sampling and via vapor balance across the structure compared favorably, justifying the use of hourly vapor-balance data. Four types of prediction models were considered: physical, additive, multiplicative, and neural network. The multiplicative model has been selected for potential implementation. The most important predictors of evaporation rate, for the conditions under consideration, were (1) solar radiation, (2) outdoor temperature, (3) ventilation rate, and (4) dry solids content of the sludge. Air mixing is an order of magnitude less effective (per unit of air discharge) than ventilation.     

Effect of fluoride varnish with added casein phosphopeptide-amorphous calcium phosphate on bond strength to enamel

To investigate the effect of fluoride varnish with added casein phosphopeptide-amorphous calcium phosphate on the shear bond strength (SBS) of two adhesive systems to enamel. Specimens obtained from permanent teeth were randomly distributed among four groups for enamel pretreatment [Control (no treatment, CNT), Duraphat varnish (DV), Clinpro White varnish (CWV), MI Varnish (MIV)], and each group was further divided into two subgroups according to adhesive [Etch&rinse (Adper Single Bond, ASB), self-etch (Clearfil SE Bond, CSE)]. Specimens were stored in distilled water at 37 °C for 24 h. Cylindrical composite specimens (2.3 mm in diameter, 3.0 mm in height) were then bonded to the enamel surfaces. SBS tests were performed and data were analyzed with two-way ANOVA and Tukey’s tests. For both CSE and ASB, SBS values of the CNT groups were significantly higher than those of all the enamel pretreatment groups (p < 0.05). Among the enamel pretreatment groups, SBS values with both adhesive systems were lowest in the MIV groups, followed by CWV and DV groups. In conclusion, pretreatment of enamel surfaces with fluoride-containing varnishes reduced bonding performance of adhesive systems to enamel. MIV appeared to cause greater enamel surface alterations and precipitation, which interfered with adhesive bonding mechanisms.     

Immune-Pineal Axis: Nuclear Factor κB (NF-κB) Mediates the Shift in the Melatonin Source from Pinealocytes to Immune Competent Cells

Pineal gland melatonin is the darkness hormone, while extra-pineal melatonin produced by the gonads, gut, retina, and immune competent cells acts as a paracrine or autocrine mediator. The well-known immunomodulatory effect of melatonin is observed either as an endocrine, a paracrine or an autocrine response. In mammals, nuclear translocation of nuclear factor κ-light-chain-enhancer of activated B cells (NF-κB) blocks noradrenaline-induced melatonin synthesis in pinealocytes, which induces melatonin synthesis in macrophages. In addition, melatonin reduces NF-κB activation in pinealocytes and immune competent cells. Therefore, pathogen- or danger-associated molecular patterns transiently switch the synthesis of melatonin from pinealocytes to immune competent cells, and as the response progresses melatonin inhibition of NF-κB activity leads these cells to a more quiescent state. The opposite effect of NF-κB in pinealocytes and immune competent cells is due to different NF-κB dimers recruited in each phase of the defense response. This coordinated shift of the source of melatonin driven by NF-κB is called the immune-pineal axis. Finally, we discuss how this concept might be relevant to a better understanding of pathological conditions with impaired melatonin rhythms and hope it opens new horizons for the research of side effects of melatonin-based therapies.     

A novel type of equipment for reactive distillation: Model development,simulation, sensitivity and error analysis

A simulation study of heterogeneously catalyzed reactive distillation experiments carried out with the D + R tray, a novel type of laboratory equipment, is presented. One advantage of the D + R tray is that reaction and distillation are alternating stage‐wise, in a well‐defined way that can be modeled straightforwardly. An equilibrium stage model is used to describe the distillation and a plug flow reactor model to describe the catalyst bed reactors. The model parameters are derived from a systematic experimental characterization of the D + R tray both as a reactor and as a distillation unit. A validated physicochemical fluid property model is used. The primary experimental data are reconciled. Results from the predictive simulations are in good agreement with the experimental results. The influence of errors in the input parameters on the simulation results is investigated by means of a sensitivity and error analysis. © 2012 American Institute of Chemical Engineers AIChE J, 59: 1533–1543, 2013     

Hydrogenolysis of Hydroxymatairesinol Over Carbon-Supported Palladium Catalysts

The natural lignan hydroxymatairesinol was hydrogenolysed to a potential anticarcinogenic substance matairesinol over different carbon-supported palladium catalysts. The reaction was conducted in 2-propanol at 70 °C under hydrogen flow in a stirred glass reactor. The catalysts were characterised by N₂-physisorption, CO pulse chemisorption and pH measurement of aqueous catalyst slurries. The most active catalyst (Degussa-Hüls) gave yields of matairesinol over 90% in 4 h. It was concluded that the acidity of the catalyst had a profound influence on the reaction rate.     

Detailed Molecular Structure Modeling – A Path Forward to Designing Application Properties of ldPE

Summary: This paper describes a step on the ambitious aim to “design” application properties of ldPE by first simulating the detailed molecular structure of a high‐pressure tubular reactor product. The reactor of a certain configuration produces under well‐defined operating conditions. The next step is to correlate the structure with the application properties. Finally, the sequence will be reversed in order to deduce the operating conditions, which lead to the desired product quality. Two‐dimensional distributions, in molecular weight and branching frequency, as well a two compartment models with a core and a shell stream were simulated and compared with experimental results. Therefore, CFD simulations were carried out to discretize the reaction medium. Samples were taken from both pilot and commercial plants. The TREF‐SEC analytical method was successfully applied in order to measure the microscopic structure of the material. The tremendous numerical problems were solved with the help of the software PREDICI .

Detailed MWD for a pilot scale reactor product.     

A Novel Route to Multiphase Polymer Systems Containing Nano‐Droplets: Radical Polymerization of Vinylic Monomers in Gelled Water‐in‐Oil Miniemulsions

Summary: A new strategy for the synthesis of composite polymers with larger volume fraction of aqueous inclusions less than 1 µm in diameter is presented. A water‐in‐oil miniemulsion of aqueous droplets in a continuous, cross‐linkable monomer phase is prepared. The addition of an organo‐gelator allows the immobilization of the droplets in a solid gel, thus avoiding the usual demixing upon polymerization of the continuous phase. This pregelled system is then converted into a composite polymer by photoinitiated free radical polymerization. Such coatings may be used for an improved climate control of buildings or as a deposit for the controlled release of actives from polar nano‐droplets.

SEM image of a cross‐linked composite polymer showing controlled droplet inclusions with a maximal diameter of 500 nm.     

Gut Microbiota and Short Chain Fatty Acids: Implications in Glucose Homeostasis

Gut microbiota encompasses a wide variety of commensal microorganisms consisting of trillions of bacteria, fungi, and viruses. This microbial population coexists in symbiosis with the host, and related metabolites have profound effects on human health. In this respect, gut microbiota plays a pivotal role in the regulation of metabolic, endocrine, and immune functions. Bacterial metabolites include the short chain fatty acids (SCFAs) acetate (C2), propionate (C3), and butyrate (C4), which are the most abundant SCFAs in the human body and the most abundant anions in the colon. SCFAs are made from fermentation of dietary fiber and resistant starch in the gut. They modulate several metabolic pathways and are involved in obesity, insulin resistance, and type 2 diabetes. Thus, diet might influence gut microbiota composition and activity, SCFAs production, and metabolic effects. In this narrative review, we discuss the relevant research focusing on the relationship between gut microbiota, SCFAs, and glucose metabolism.