Theory of asymmetric organocatalysis of Aldol and related reactions: rationalizations and predictions

Computational studies have led to models to understand some classic and contemporary asymmetric reactions involving organocatalysts. The Hajos-Parrish-Eder-Sauer-Wiechert reaction and intermolecular aldol reactions as well as Mannich reactions and oxyaminations catalyzed by proline and other amino acids, and Diels-Alder reactions catalyzed by MacMillan's chiral amine organocatalysts have been studied with density functional theory. Quantitative predictions for several new catalysts and reactions are provided.     

Active Site Crowding of Cytochrome P450 3A4 as a Strategy To Alter Its Selectivity

Substrate‐promiscuous enzymes are a promising starting point for the development of versatile biocatalysts. In this study, human cytochrome P450 3A4, known for its ability to metabolise hundreds of drugs, was engineered to alter its regio‐ and stereoselectivity. Rational mutagenesis was used to introduce steric hindrance in a specific manner in the large active site of P450 3A4 and to favour oxidation at a more sterically accessible position on the substrate. Hydroxylation of a synthetic precursor of (R)‐lisofylline, a compound under investigation for its anti‐inflammatory properties, was chosen as a first proof‐of‐principle application of our protein engineering strategy. In a second example, increasing active site crowding led to an incremental shift in the selectivity of oxidation from an internal double bond to a terminal phenyl group in a derivative of theobromine. The same correlation between crowding and selectivity was found in a final case focused on the hydroxylation of the steroid sex hormone progesterone.     

Relationship Between Physicochemical Properties and Moisture Barrier Property of Confectionery Coating Fats

Moisture migration in food causes deleterious effects on food quality such as loss of crispiness in ice cream cones, drying of chocolate with liquid centers, sugar bloom and cracking of compound/chocolate coating. The present study aimed to investigate the relationship between physicochemical properties of confectionery coating fats such as fatty acids and triacylglycerol (TAG) composition, solid fat contents, rheological and crystalline properties with their moisture barrier property. Coating fats with high content of trisaturated and desaturated TAG; and high SFC at 25 °C were found to have significant (P < 0.05) positive correlation with its moisture barrier property. These fats were able to crystallize into highly crystalline materials (high SFC) with small crystal size and dense networks. Thus, these fats were able to significantly delay moisture migration. Nevertheless, some of the highly crystalline fats also had high G′ value indicating poor mechanical properties and higher tendency of such fats to crack. In order to have good moisture barrier property, coating fats need to have sufficient solids with small crystal size and dense networks; and also low G′ value. Wafer coated with good moisture barrier fat showed less cracking during storage.     

Determination of pressure drop for concentrated suspension in a capillary flow

The rheological behavior of concentrated suspension melts in a capillary die is investigated. Particle migration and wall slip are two major factors affecting the flow behavior. A numerical model is proposed to describe the coupling effect of particle migration and wall slip in a capillary tube flow, incorporating a power‐law model for binder viscosity and a concentrated suspension viscosity model proposed by Krieger. Wall slip of a non‐Newtonian concentrated suspension is characterized by a modified Mooney method for which the conventional Mooney method is not applicable. We characterized the flow behavior of a concentrated suspension of a non‐Newtonian binder, EVA 460 (ethylene vinyl acetate), mixed with spherical glass beads of 40% by volume. Predicted results were compared with experimental observations, with good agreement. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Synthesis and Characterization of Silver Nanoparticles and Silver Inks: Review on the Past and Recent Technology Roadmaps

The synthesis of silver nanoparticles for silver ink formation has attracted broad interest in the electronic part printing and semiconductor chip industry due to the extraordinary electrical and mechanical properties of these materials. The preparation of silver nanoparticles through a physical or chemical reduction process is the most common methodology applied to obtain nanoparticles with the required size, shape and surface morphology. The chemical solution or solvent carrier applied for silver ink formulation must be applied simultaneously with the direct writing technique to produce the desired adherence, viscosity, and reliable performance. This review paper discusses the details concerning the past and recent advancement of the synthesis and characterization of silver nanoparticles and silver ink formation. A review on the advantages of various sintering techniques, which aim to achieve the electrical and mechanical properties of the required printed structure, is also included. A brief summary concerning the recent challenges and improvement approaches is presented at the end of this review.     

Microstructure and mechanical property of irradiated Zr−2.5Nb pressure tube in Wolsong unit-1

With the aim of assessing the degradation of Zr−2.5Nb pressure tubes operating in the Wolsong unit-1 nuclear power plant, characterization tests are being conducted on irradiated Zr−2.5Nb tubes removed after 10-year operation. The examined tube had been exposed to temperatures ranging from 264 to 306°C and a neutron fluence of 8.9×10²¹ n/cm² (E>1 MeV) at the maximum. Tensile tests were carried out at temperatures ranging from RT to 300°C. The density of a-type and c-type dislocations was examined on the irradiated Zr-2.5Nb tube using a transmission electron microscope. Neutron irradiation up to 8.9×10²¹ n/cm² (E>1 MeV) yielded an increase in a-type dislocation density of the Zr−2.5Nb pressure tube to 7.5×10¹⁴ m⁻², which was highest at the inlet of the tube exposed to the low temperature of 275°C. In contranst, the c-component dislocation density did not change with irradiation, keeping an initial dislocation density of 0.8×10¹⁴ m⁻² over the whole length of the tube. As expected, the neutron irradiation increased mechanical strength by about 17–26% in the transverse direction and by 34–39% in the longitudinal direction compared to that of the unirradiated tube at 300°C. The change in the mechanical properties with irradiation is discussed in association with the microstructural change as a function of temperature and neutron fluence.     

Production and dispersion stability of nanoparticles in nanofluids

This paper presents an experimental study on the homogeneous dispersion of nanoparticles in nanofluids. In this study, various physical treatment techniques based on two-step method, including stirrer, ultrasonic bath, ultrasonic disruptor, and high-pressure homogenizer were systematically tested to verify their versatility for preparing stable nanofluids. Initially carbon black and silver nanoparticles dispersed in base fluids with the presence of surfactant were found to be highly agglomerated with the hydrodynamic diameter of 330 nm to 585 nm, respectively. After both CB and Ag nanofluids were treated by various two-step methods, stirrer, ultrasonic bath, and ultrasonic disrupter was found to do a poor performance in deagglomeration process for the initial particle clusters. However, the high-pressure homogenizer produced the average diameter of the CB and Ag particles of 45 nm and 35 nm, respectively, indicating that among various physical treatment techniques employed in this study, the high-pressure homogenizer was the most effective method to break down the agglomerated nanoparticles suspended in base fluids. In order to prepare another nanofluid with much smaller primary nanoparticles, we also employed a modified magnetron sputtering system, in which the sputtered nanoparticles were designed to directly mix with the running surfactant-added silicon oil thin film formed on a rolling drum (i.e. one-step method). We observed that Ag nanoparticles produced by the modified magnetron sputtering system were homogeneously dispersed and long-term stable in the silicon oil-based fluid, and the average diameter of Ag nanoparticles was found to be ~ 3 nm, indicating that the modified magnetron sputtering system is also an effective one-step method to prepare stable nanofluids.     

Completed double layer boundary element method for periodic fibre suspension in viscoelastic fluid

A numerical method to simulate the periodic fibre suspension in viscoelastic fluid is developed with the completed double layer boundary element method (CDLBEM). The periodic summations that arise in the formulation were well handled by Ewald summation technique to speed up the convergence rate in the computation. The formulation for velocity field in periodic fibre suspension in viscoelastic fluid is derived and is used to simulate multiple fibres suspended in a viscoelastic shear flow. Simulations are carried out for various fibre aspect ratios and volume fractions ranging from dilute to concentrated regimes. Numerical results of macroscopic rheological properties of the system are compared to available experiments on viscoelastic fibre suspensions, and are found to agree reasonably well with the experimental data.     

Measurement and calculation of swelling equilibria for water/poly(acrylamide-sodiumallylsulfonate) systems

Superabsorbent poly(acrylamide-sodiumallylsulfonate) was synthesized from acrylamide (AM) and sodiumallylsulfonate (SAS) by a solution polymerization method. N,N’-methylenebisacrylamide (BIS) was used as the crosslinker; potassium persulfite (PP) and N,N,N’,N’-tetra-methylenediamine (TMEDA) were used as the redox initiator during the synthesis. The absorption capacities of the synthesized superabsorbent poly(AM-SAS) were repeatedly measured to obtain the optimal poly(AM-SAS) according to the variations of monomer concentration at 298.15 K. Its maximal absorption capacity appeared as 811 times at 0.1 mol/L among from 0.01 mol/L to 0.16 mol/L of SAS concentrations. The swelling equilibria at those conditions from 298.15 K to 318.15 K were measured and used to estimate the parameters by correlating with the Flory-Huggins model. The swelling behavior could be described by the parameters and the calculated values agreed satisfactorily with the experimental data.     

Role of Immune Cells in Patients with Hepatitis B Virus-Related Hepatocellular Carcinoma

Hepatocellular carcinoma (HCC) develops almost entirely in the presence of chronic inflammation. Chronic hepatitis B virus (HBV) infection with recurrent immune-mediated liver damage ultimately leads to cirrhosis and HCC. It is widely accepted that HBV infection induces the dysfunction of the innate and adaptive immune responses that engage various immune cells. Natural killer (NK) cells are associated with early antiviral and antitumor properties. On the other hand, inflammatory cells release various cytokines and chemokines that may promote HCC tumorigenesis. Moreover, immunosuppressive cells such as regulatory T cells (Treg) and myeloid-derived suppressive cells play a critical role in hepatocarcinogenesis. HBV-specific CD8+ T cells have been identified as pivotal players in antiviral responses, whilst extremely activated CD8+ T cells induce enormous inflammatory responses, and chronic inflammation can facilitate hepatocarcinogenesis. Controlling and maintaining the balance in the immune system is an important aspect in the management of HBV-related HCC. We conducted a review of the current knowledge on the immunopathogenesis of HBV-induced inflammation and the role of such immune activation in the tumorigenesis of HCC based on the recent studies on innate and adaptive immune cell dysfunction in HBV-related HCC.