Enantioselective synthesis of (10S)- and (10R)-methyl-anandamides

For the development of novel endocannabinoid templates with potential resistance to hydrolytic and oxidative metabolism, we are targeting the bis-allylic carbons of the arachidonoyl skeleton. Toward this end, we recently disclosed the synthesis and preliminary biological data for the (13S)-methyl-anandamide. We report now the total synthesis of the (10S)- and (10R)-methyl-counterparts. Our synthetic approach is stereospecific, efficient, and provides the analogs without the need for resolution. Peptide coupling, P-2 nickel partial hydrogenation, and cis-selective Wittig olefination are the key steps.     

Numerical Simulation of Turbulent Flow and Heat Transfer in a Three-Dimensional Channel Coupled with Flow Through Porous Structures

This study investigates numerically the turbulent flow and heat transfer characteristics of a T-junction mixing, where a porous media flow is vertically discharged in a 3D fully developed channel flow. The fluid equations for the porous medium are solved in a pore structure level using an Speziale, Sarkar and Gatski turbulence model and validated with open literature data. Overall, two types of porous structures, consisted of square pores, are investigated over a wide range of Reynolds numbers: an in-line and a staggered pore structure arrangement. The flow patterns, including the reattachment length in the channel, the velocity field inside the porous medium as well as the fluctuation velocity at the interface, are found to be strongly affected by the velocity ratio between the transversely interacting flow streams. In addition, the heat transfer examination of the flow domain reveals that the temperature distribution in the porous structure is more uniform for the staggered array. The local heat transfer distributions inside the porous structure are also studied, and the general heat transfer rates are correlated in terms of area-averaged Nusselt number accounting for the effects of Reynolds number, velocity ratio as well as the geometrical arrangement of the porous structures.     

Variational analysis of gradient elastic flexural plates under static loading

Gradient elastic flexural Kirchhoff plates under static loading are considered. Their governing equation of equilibrium in terms of their lateral deflection is a sixth order partial differential equation instead of the fourth order one for the classical case. A variational formulation of the problem is established with the aid of the principle of virtual work and used to determine all possible boundary conditions, classical and non-classical ones. Two circular gradient elastic plates, clamped or simply supported at their boundaries, are analyzed analytically and the gradient effect on their static response is assessed in detail. A rectangular gradient elastic plate, simply supported at its boundaries, is also analyzed analytically and its rationally obtained boundary conditions are compared with the heuristically obtained ones in a previous publication of the authors. Finally, a plate with two opposite sides clamped experiencing cylindrical bending is also analyzed and its response compared against that for the cases of micropolar and couple-stress elasticity theories.     

Statics and dynamics of 2D colloidal crystals in a random pinning potential

We report the first experimental study of a model system of a two-dimensional colloidal crystal in a random pinning potential. The colloidal crystal consists of monodispersed charged polystyrene microspheres suspended in deionized aqueous media and confined near a rough charged surface. It is found that the static orientational correlation function g6(r) decays exponentially for intermediate and strong pinning, in agreement with theories. The driven depinning is dominated by thermally activated creep motion along 1D-like channels between regions with short-range order. A coexistence model is proposed for describing the observations.     

Fast Biosynthesis of GFP Molecules: A Single‐Molecule Fluorescence Study

It's not easy being green : Real‐time visualization of labeled ribosomes and de novo synthesized green fluorescent protein molecules using single‐molecule‐sensitive fluorescence microscopy demonstrates that the mutant GFPem is produced with a characteristic time of five minutes. Fluorescence of the fastest GFP molecules appears within one minute (see picture).

     

Structural,electronic, and magnetoresponsive properties of triangular lanthanide clusters and their free‐standing nitrides

The molecular and electronic structures, stabilities, bonding features, and magnetoresponsive properties of three‐membered [c‐Ln₃]^+/0/? (Ln = La, Ce, Pr, Nd, Gd, Lu) and heterocyclic six‐membered [c‐Ln₃E₃]^q (Ln = La, Ce, Pr, Nd, Gd, Lu; E = C, N; q = 0 or 1) rings have been investigated by means of electronic structure calculation methods at the DFT level. The [c‐Ln₃]^+/0/? clusters are predicted to be bound with respect to dissociation to their constituent atoms, the estimated binding energies ranging from 45.8 to 2056.4 kJ/mol. The [c‐Ln₃] rings capture easily a planar three‐coordinated nitrogen atom at the center or above the center of the ring yielding the lanthanide nitride clusters [c‐Ln₃(μ₃‐N)] adopting a planar geometry, except [c‐La₃(μ₃‐N)] which exhibits pyramidal geometry. The [c‐Ln₃(μ₃‐N)] clusters are predicted to be bound, with respect to dissociation to N (⁴S) atom and [c‐Ln₃] clusters in their ground states, the binding energies ranging from 53.9 to 257.9 kcal/mol. The six‐membered [c‐Ln₃E₃]^q rings are predicted to be bound with respect to dissociation to LnE^q monomers in their ground states with dissociation energies in the range of 173.8 to 318.0 kcal/mol. Calculation of the NICS_zz‐scan curves of the clusters predicted a “hermaphrodic” magnetic response of the [c‐Ln₃]^+/0/? and heterocyclic six‐membered [c‐Ln₃E₃]^q rings, manifested by the coexistence of successive diatropic (aromatic) and paratropic (antiaromatic) zones. The [c‐La₃]^+/0/? and [c‐Lu₃]^? are predicted to be weakly antiaromatic, the [c‐Lu₃]^0/+, [c‐Lu₃C₃]⁺, and [c‐Lu₃N₃] double (σ+π) aromatic, and the [c‐Gd₃C₃] and [c‐Gd₃N₃]⁺ rings (σ+δ)‐aromatic systems. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011     

Synthesis of esters of 4-hydroxy-5-phosphinyl-2-imidazolidinone

The esters of 4-hydroxy-5-phosphinyl-2-imidazolidinone were prepared by reaction of urea with the esters of 2-hydroxy-2-phosphinylethanal in acidic medium. The ir, ¹H nmr and ³¹P nmr spectral data of the products are reported. All the isolated products had cis configuration. The stereochemistry of their formation is discussed.