Raman Structural Study of Copolymers of Propylene with Ethylene and High Olefins

Nascent form of random copolymers of propylene with ethylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene was studied by Raman spectroscopy. The most significant spectral alterations with a change in propylene content were observed in two lines at 809 and 841 cm⁻¹. The first line corresponds to vibrations of polypropylene helical chains in the crystalline phase, while the second one is associated with vibrations of polypropylene helical chains having isomeric defects. Raman data confirm that conformational composition and phase state of copolymer macromolecules strongly depend on the comonomer content as well as on the size of the comonomer units.     

W Boson production cross section at the Large Hadron cCllider with Omicron(alpha(2)(s)) corrections

We compute the Omicron(alpha(2)(s)) QCD corrections to the fully differential cross section pp --> WX --> lnuX, retaining all effects from spin correlations. The knowledge of these corrections makes it possible to calculate with high precision the boson production rate and acceptance at the CERN Large Hadron Collider (LHC), subject to realistic cuts on the lepton and missing energy distributions. For certain choices of cuts we find large corrections when going from next-to-leading order (NLO) to next-to-next-to-leading order in perturbation theory. These corrections are significantly larger than those obtained by parton-shower event generators merged with NLO calculations. Our result may be used to assess and significantly reduce the QCD uncertainties in the many studies of boson production planned at the LHC.     

Effect of Inertial Terms on Fluid–Porous Medium Flow Coupling

The study considers an effect of the nonlinear inertial terms in the Brinkman filtration equation on the characteristics of coupled flows in a pure fluid and porous medium in the frameworks of two independent problems. The first problem is the forced boundary-layer flow overlying the Darcy–Brinkman porous medium. The Prandtl theory is used, and the self-similar equations are built to describe it. It is shown that the inertial terms have a valuable effect on the boundary-layer structure because of the large velocity gradient in the transition zone. The boundary-layer thickness in a porous medium rapidly grows at large Reynolds numbers. The velocity magnitude and gradient at the interface also change. The second independent problem is an analysis of the inertial terms effect on the flow stability. The neutral curves of the full and linearized flow models are built using the shooting method. They have different short-wave asymptotic, but there are no significant changes in the critical Reynolds numbers and corresponding wave numbers.     

Inertial and Darcy’s Terms Ratio in Boundary Layer at Fluid–Porous Medium Interface

The study considers the forced boundary-layer flow overlying the Darcy–Brinkman porous medium and gives a quantitative analysis of the nonlinear inertial terms in the Brinkman filtration equation. The inertial terms are shown to be larger than the Darcy’s drag near the porous medium interface. The applicability range of boundary-layer approach is determined. It is suitable in high-permeable media with moderate velocities of an external flow. If it is slow enough, the inertial terms can be omitted in spite of interface effect. On the other hand, fast external flow produces the filtration with large pore-scale Reynolds number; therefore, the Forchheimer’s drag should be taken into account. It is shown the Brinkman term as well as inertial terms have a significant role in boundary-layer formation within the porous medium.     

A Ferrocenyl Kaleidoscope: Slow Interconversion of Six Diastereo‐atropisomers of 2,6‐Di‐tert‐butyl‐9,10‐diferrocenyltriptycene

The title triptycene, 6 , has been isolated as the product of 9,10‐cycloaddition of benzyne to 9,10‐diferrocenyl‐2,6‐di‐tert‐butylanthracene, 5 , whose X‐ray crystal structure is reported. Each ferrocenyl unit in 6 has access to the same three non‐equivalent molecular environments, and their rotations relative to the molecular paddlewheel give rise to six slowly interconverting atropisomers. Their dynamic behaviour in solution is a challenging NMR puzzle that can be successfully solved by taking advantage of the recently described very large diamagnetic anisotropy of the ferrocenyl moiety, together with the C₂ symmetry of particular atropisomers. Application of one‐ and two‐dimensional NMR techniques over a range of temperatures together, with a detailed analysis of the homo‐ and heteronuclear correlations in 6 , resulted in unequivocal mapping of the 99 ¹H and 162 ¹³C positions in the six interconverting systems. Variable‐temperature 2D‐EXSY measurements revealed that, while the stability of the atropisomers is almost identical, they are separated by energy barriers which the ferrocenyls must overcome in the course of their interconversions. The heights of two different rotational barriers have been identified and these experimental findings are in good agreement with DFT calculations.     

Isotopic separation of lithium ions by capillary zone electrophoresis

Separation of ⁶Li and ⁷Li isotopes by CZE was demonstrated. The BGE contained 5 mM 4‐aminopyridine, 0.9 mM oxalic acid, 0.25 mM CTAB, and 0.25% w/v Tween 20 (рН = 9.2). The running conditions were +25 kV at 30°C with indirect photometric detection at 261 nm. Under optimal experimental conditions, the analysis time was less than 21 min. Separation of Li preparations with mole fraction of ⁶Li ranging from 3.44 up to 90.38% was demonstrated.