Condensed Mode Cooling of Ethylene Polymerization in Fluidized Bed Reactors

This review gives an overview of the evolution of the technology of condensed mode cooling, primarily for the case of ethylene polymerization on supported catalysts in fluidized bed reactors. It is well known that this mode of heat removal is quite effective in allowing polyolefin manufacturers to increase significantly production rates. What is perhaps less well understood are all of the issues that, in addition to the effect of the latent heat of vaporization of injected liquid components, also have an impact on the rate of production and behavior of the reactor. However, the liquid components injected into the reactor can vaporize rapidly under full‐scale conditions, leaving behind several heavy components (with respect to ethylene) that have numerous effects on how the particles behave, on the reaction rate, and on fluidization, fouling, and other parameters related to reactor and process performance.     

Improved Eddy-Viscosity Modelling of Turbulent Flow around Porous–Fluid Interface Regions

Transport in Porous Media - The RANS modelling of turbulence across fluid-porous interface regions within ribbed channels has been investigated by applying double (both volume and Reynolds)...     

No Preferred Reference Frame at the Foundation of Quantum Mechanics

Quantum information theorists have created axiomatic reconstructions of quantum mechanics (QM) that are very successful at identifying precisely what distinguishes quantum probability theory from classical and more general probability theories in terms of information-theoretic principles. Herein, we show how one such principle, Information Invariance and Continuity, at the foundation of those axiomatic reconstructions, maps to “no preferred reference frame” (NPRF, aka “the relativity principle”) as it pertains to the invariant measurement of Planck’s constant h for Stern-Gerlach (SG) spin measurements. This is in exact analogy to the relativity principle as it pertains to the invariant measurement of the speed of light c at the foundation of special relativity (SR). Essentially, quantum information theorists have extended Einstein’s use of NPRF from the boost invariance of measurements of c to include the SO(3) invariance of measurements of h between different reference frames of mutually complementary spin measurements via the principle of Information Invariance and Continuity. Consequently, the “mystery” of the Bell states is understood to result from conservation per Information Invariance and Continuity between different reference frames of mutually complementary qubit measurements, and this maps to conservation per NPRF in spacetime. If one falsely conflates the relativity principle with the classical theory of SR, then it may seem impossible that the relativity principle resides at the foundation of non-relativisitic QM. In fact, there is nothing inherently classical or quantum about NPRF. Thus, the axiomatic reconstructions of QM have succeeded in producing a principle account of QM that reveals as much about Nature as the postulates of SR.     

When light goes astray: Gravitational lensing in astrophysics

Light propagating in an inhomogeneous medium does not travel in straight lines. Light rays wander; they are focused, magnified and dispersed as they travel through an inhomogeneous medium. Such deflections are familiar to physicists. They are the stuff of optics. On cosmic scales light is 'deflected' in a more profound way, tracing inhomogeneities in the underlying space-time. The meandering of light rays as they propagate through the Universe encodes unique information about variations in the space-time metric. General relativity tells us these variations are impressed on the metric by inhomogeneities in the matter distribution. As a result, this 'gravitational lensing' provides information about the distribution of mass in the Universe. In this work we review briefly the main features of gravitational lensing, with an emphasis on observable effects. Remarkable progress has been made in lensing observations since 1990. We discuss some aspects of this rapid development, commenting especially on astrophysical topics where lensing studies have had a major impact. We suggest that gravitational lensing is now a standard part of the astrophysical toolkit, akin in some ways to photometry. We conclude with a discussion of areas in which lensing studies will have a strong impact in years to come, and comment on technical requirements for these future studies.     

Computational and Synthetic Investigation of Cationic Rearrangement in the Putative Biosynthesis of Justicane Triterpenoids

A biomimetic cationic structural rearrangement of the oleanolic acid framework is reported for the gram‐scale synthesis and structural reassignment of justicioside E aglycone. The mechanism of the putative biosynthetic rearrangement is investigated with kinetic, computational, and synthetic approaches. The precursor to rearrangement was accessed through two strategic advancements: (1) synthesis of a 1,3‐diketone via oxidation of a β‐silyl enone, and (2) diastereoselective 1,3‐diketone reduction to form a syn‐1,3‐diol using SmI₂ with PhSH as a key additive.     

Matrix-assisted laser desorption/ionization tandem reflectron time-of-flight mass spectrometry of fullerenes

Atandem reflectron time-of-flight mass spectrometer developed in our laboratory provides a unique opportunity to investigate the collision-induced dissociation of fullerene ions formed by matrix-assisted laser desorption/ionization (MALDI). Specifically, this opportunity arises from the ability to utilize high energy collisional activation (normally available only on tandem sector instruments by using continuous ionization techniques) for ions formed by pulsed laser desorption, whereas most MALDI time-of-flight instruments record product ion mass spectra of ions formed by metastable or postsource decay. In this study we investigate the products of mass-selected and collisionally activated C ₆₀ ⁺ and C ₇₀ ⁺ ions by using different target gases over a range of target gas pressures. In general, heavier target gases produce more extensive fragmentation and improve the mass resolution of lower mass ionic products because a greater portion of these ions are formed by single collisions. Additionally, the tandem time-of-flight instrument utilizes a nonlinear (curved-field) reflectron in the second mass analyzer that enables high energy collision-induced dissociation spectra to be recorded without scanning or stepping the reflectron voltage.     

Constraining Cyclic Peptides To Mimic Protein Structure Motifs

Many proteins exert their biological activities through small exposed surface regions called epitopes that are folded peptides of well‐defined three‐dimensional structures. Short synthetic peptide sequences corresponding to these bioactive protein surfaces do not form thermodynamically stable protein‐like structures in water. However, short peptides can be induced to fold into protein‐like bioactive conformations (strands, helices, turns) by cyclization, in conjunction with the use of other molecular constraints, that helps to fine‐tune three‐dimensional structure. Such constrained cyclic peptides can have protein‐like biological activities and potencies, enabling their uses as biological probes and leads to therapeutics, diagnostics and vaccines. This Review highlights examples of cyclic peptides that mimic three‐dimensional structures of strand, turn or helical segments of peptides and proteins, and identifies some additional restraints incorporated into natural product cyclic peptides and synthetic macrocyclic peptidomimetics that refine peptide structure and confer biological properties.