Stereoselective Synthesis of α-Methylene-β-Hydroxy-γ-Alkoxy Esters and Ketones

The amine catalysed aldol-type addition of vinylcarbonyl units to α-alkoxy aldehydes proceeds with reasonable diastereoface selectivity to afford the title compounds in good yield.     

Effects of membrane degradation on the removal of pharmaceutically active compounds (PhACs) by NF/RO filtration processes

The impacts of membrane degradation due to chlorine attack on the rejection of pharmaceutically active compounds (PhACs) by nanofiltration and reverse osmosis membranes were investigated in this study. Membrane degradation was simulated by soaking the membranes in a sodium hypochlorite solution of various concentrations over 18 h. Changes in membrane surface properties were characterised by contact angle measurement, atomic force microscopy analysis, and streaming potential measurement. The impacts of hypochlorite exposure to the membrane separation processes were ascertained by comparing the rejection of PhACs by virgin and chlorine-exposed membranes. Overall, the reverse osmosis BW30 membrane and the tight nanofiltration NF90 membrane were much more resilient to chlorine exposure than the larger pore size TFC-SR2 and NF270 nanofiltration membranes. In fact, rejection of all three PhACs selected in this study by the BW30 remained largely unchanged after hypochlorite exposure and further characterisation did not reveal any evidence of compromised separation capability. In contrast, the effects of chlorine exposure to the two loose nanofiltration membranes were quite profound. While chlorine exposure generally resulted in reduced rejection of PhACs, a small increase in rejection was observed when a more dilute hypochlorite solution was used. Changes in the membrane surface morphology as well as observed rejection of inorganic salts and PhACs were found to be consistent with mechanisms of chlorine oxidation of polyamide membranes reported in the literature. Chlorine oxidation consistently resulted in a more negative zeta potential of all four membranes investigated in this study. Conformational alterations of the membrane polyamide active skin layer were also evident as reflected by changes in surface roughness before and after chlorine exposure. Such alterations can either loosen or tighten the effective membrane pore size, leading to either a decrease or an increase in rejection. Both of these phenomena were observed in this study, although the decrease in the rejection of PhACs was overwhelming from exposure to highly concentrated hypochlorite solution.     

(-)-8-Phenylmenthyl Acrylate as Chiral Inducer in the Baylis-Hillman Reaction

8-Phenylmenthol 1 is used as a chiral auxiliary in the Baylis-Hillman reaction using a range of aldehydes as substrate. Best results (70% d. e.) are obtained when the reaction is rapid, as is the case with trichloroacetaldehyde.     

Nanostructured block-random copolymers with tunable magnetic properties

It was recently shown that block copolymers (BCPs) produced room-temperature ferromagnetic materials (RTFMs) due to their nanoscopic ordering and the cylindrical phase yielded the highest coercivity. Here, a series of metal-containing block-random copolymers composed of an alkyl-functionalized homo block (C(16)) and a random block of cobalt complex- (Co) and ferrocene-functionalized (Fe) units was synthesized via ring-opening metathesis polymerization. Taking advantage of the block-random architecture, the influence of dipolar interactions on the magnetic properties of these nanostructured BCP materials was studied by varying the molar ratio of the Co units to the Fe units, while maintaining the cylindrical phase-separated morphology. DC magnetic measurements, including magnetization versus field, zero-field-cooled, and field-cooled, as well as AC susceptibility measurements showed that the magnetic properties of the nanostructured BCP materials could be easily tuned by diluting the cobalt density with Fe units in the cylindrical domains. Decreasing the cobalt density weakened the dipolar interactions of the cobalt nanoparticles, leading to the transition from a room temperature ferromagnetic (RTF) to a superparamagnetic material. These results confirmed that dipolar interactions of the cobalt nanoparticles within the phase-separated domains were responsible for the RTF properties of the nanostructured BCP materials.     

Nanoparticle-driven assembly of block copolymers: a simple route to ordered hybrid materials

The addition of nanoparticles that selectively hydrogen bond with one of the segments of a block copolymer is shown to induce order in otherwise disordered systems. This enables the fabrication of well-ordered hybrid materials with spherical, cylindrical, or lamellar domains at particle loadings of more than 40%, as evidenced by TEM and SAXS. The approach described is simple and applicable to a wide range of nanoparticles and block copolymers, and it lays the groundwork for the design of cooperatively assembled functional devices.     

The kinematics of cosmic reheating

We calculate the relaxation rate of a scalar field in a plasma of other scalars and fermions with gauge interactions using thermal quantum field theory. It yields the rate of cosmic reheating and thereby determines the temperature of the “hot big bang” in inflationary cosmology. The total rate originates from various processes, including decays and inverse decays as well as Landau damping by scatterings. It involves quantum statistical effects and off-shell transport. Its temperature dependence can be highly non-trivial, making it impossible to express the reheating temperature in terms of the model parameters in a simple way. We pay special attention to the temperature dependence of the phase space due to the modified dispersion relations in the plasma. We find that it can have a drastic effect on the efficiency of perturbative reheating, which depends on the way particles in the primordial plasma interact. For some interactions thermal masses can effectively close the phase space for the dominant dissipative processes and thereby impose an upper bound on the reheating temperature. In other cases they open up new channels of dissipation, hence increase the reheating temperature. At high temperatures we find that the universe can even be heated through couplings to fermions, which are often assumed to be negligible due to Pauli-blocking. These effects may also be relevant for baryogenesis, dark matter production, the fate of moduli and in scenarios of warm inflation.     

Formation of Silver and Gold Dendrimer Nanocomposites

Structural types of dendrimer nanocomposites have been studied and the respective formation mechanisms have been described, with illustration of nanocomposites formed from poly(amidoamine) PAMAM dendrimers and zerovalent metals, such as gold and silver. Structure of {(Au(0))_n–PAMAM} and {(Ag(0))_n–PAMAM} gold and silver dendrimer nanocomposites was found to be the function of the dendrimer structure and surface groups as well as the formation mechanism and the chemistry involved. Three different types of single nanocomposite architectures have been identified, such as internal (I), external (E) and mixed (M) type nanocomposites. Both the organic and inorganic phase could form nanosized pseudo-continuous phases while the other components are dispersed at the molecular or atomic level either in the interior or on the surface of the template/container. Single units of these nanocomposites may be used as building blocks in the synthesis of nanostructured materials.     

Optimal threshold policies in a workload model with a variable number of service phases per job

We consider an M|E _N |1 queue in which there are two essential on-line decisions that have to be taken. The first one is the decision to either accept or reject new jobs. The second one is the decision to either continue or abort the service of a job. We show that under certain regularity conditions, there exist optimal threshold policies for these two types of decisions.