Chromatographic performance of monolithic and particulate stationary phases. Hydrodynamics and adsorption capacity

Monolithic chromatographic support structures offer, as compared to the conventional particulate materials, a unique combination of high bed permeability, optimized solute transport to and from the active surface sites and a high loading capacity by the introduction of hierarchical order in the interconnected pore network and the possibility to independently manipulate the contributing sets of pores. While basic principles governing flow resistance, axial dispersion and adsorption capacity are remaining identical, and a similarity to particulate systems can be well recognized on that basis, a direct comparison of sphere geometry with monolithic structures is less obvious due, not least, to the complex shape of theskeleton domain. We present here a simple, widely applicable, phenomenological approach for treating single-phase incompressible flow through structures having a continuous, rigid solid phase. It relies on the determination of equivalent particle (sphere) dimensions which characterize the corresponding behaviour in a particulate, i.e. discontinuous bed. Equivalence is then obtained by dimensionless scaling of macroscopic fluid dynamical behaviour, hydraulic permeability and hydrodynamic dispersion in both types of materials, without needing a direct geometrical translation of their constituent units. Differences in adsorption capacity between particulate and monolithic stationary phases show that the silica-based monoliths with a bimodal pore size distribution provide, due to the high total porosity of the material of more than 90%, comparable maximum loading capacities with respect to random-close packings of completely porous spheres.     

Catalytic asymmetric carbohydroxylation of alkenes by a tandem diboration/Suzuki cross-coupling/oxidation reaction

[reaction: see text] Chiral nonsymmetric 1,2-diboron adducts are generated by catalytic enantioselective diboration. Oxidation of these adducts provides 1,2-diols in good yield. Alternatively, 1,2-diboron compounds may be reacted, in situ, with aryl halides wherein the less hindered C-B bond participates in cross-coupling. The remaining C-B bond is then oxidized in the reaction workup thereby allowing for net asymmetric carbohydroxylation of alkenes in a tandem one-pot diboration/Suzuki coupling/oxidation sequence.     

Stereochemical resolution of enantiomeric 2-aryl propionic acid non-steroidal anti-inflammatory drugs on a human serum albumin based high-performance liquid chromatographic chiral stationary phase

Summary The native enantioselectivity in binding of human serum albumin (HSA) towards 2-aryl propionic acid non-steroidal anti-inflammatory drugs (2-APA-NSAIDs, the profens) was found to be preserved when the protein was immobilized within a commercially available diol high-performance liquid chromatographic column. High capacity factors were obtained, reflecting the previously observed extensive binding of the 2-APA-NSAIDs to free HSA. The capacity factors were modified by the addition of octanoic acid to the mobile phase. Chiral resolution of the enantiomers of all nine 2-APA-NSAIDs studied was achieved. Preliminary studies show that in addition to being a useful chiral analytical tool for this therapeutically important series of compounds, the HSA chiral stationary phase may provide useful information on the affinity and binding mechanism of small molecules to HSA.     

Metal-organic approach to binary optical memory

Two new Ru(II) diimine chromophores, each containing a single photochromic dianthryl unit, have been prepared and characterized. The photoluminescence from the Ru(II) complexes is modulated by the photochromic action of the dianthryl species, which serves as a triplet energy transfer quencher in one photochromic state. The coupling of the dianthryl photochromic action to the Ru(II) complex emission permits nondestructive photoluminescence readout of binary information photochemically recorded on the molecular level. Luminescent images stored on polystyrene films that contain these molecules maintained their integrity for periods of months with no apparent degradation or variation in the image resolution, suggesting their durability for long-term storage in read-only memory applications.     

Green photoluminescence from platinum(II) complexes bearing silylacetylide ligands

The synthesis, structural characterization, photoluminescence properties, and density functional theory analysis of three Pt(II) diimine complexes, Pt(dbbpy)(C triple bond CR)2 [dbbpy = 4,4'-di(tert-butyl-2,2'-bipyridine; R = -SiMe3, -CC-SiMe3, or -t-Bu], are presented. The Pt(dbbpy)(C triple bond C-tBu)2 complex serves as a carbon-based ligand structure for which the photophysical properties of the two silicon-bearing complexes are compared in dichloromethane. Pt(dbbpy)(C triple bond C-SiMe3)2 and Pt(dbbpy)(C triple bond C-C triple bond C-SiMe3)2 display visible absorptions with strong green emission (lambda(emmax) = 526 and 524 nm, respectively) while Pt(dbbpy)(C triple bond C-t-Bu)2 displays efficient, long-lived yellow emission (lambda(emmax) = 557 nm). Direct side by side comparisons of Pt(dbbpy)(C triple bond C-SiMe3)2 and Pt(dbbpy)(C triple bond C-t-Bu)2 suggest that the difference in excited state energy results from the relative sigma-donor strength of the acetylide ligands.     

Evaluation of MNDO calculated proton affinities

A large set of charged species arising mainly from protonation or deprotonation of hydrocarbons, alcohols, ethers, carboxylic acids, amines, imines, and nitriles has been studied by means of the semiempirical self-consistent-field (SCF ) molecular orbital (MO ) MNDO method. From the calculated heats of formation of such charged species and those of neutral molecules, MNDO -estimated proton affinities have been obtained and the results compared with experimental gas-phase proton affinities. If the small size anions and acetylides, for which the method predicts heats of formation too large, are ruled out, the mean absolute error in calculated proton affinities is ca. 7 kcal/mol for hydrocarbons (22 acid-base pairs) and ca. 8 kcal/mol for oxygen-containing compounds (25 acid-base pairs). For nitrogen-containing molecules it is necessary to discard, in addition, the values corresponding to the protonation of alkylamines and imines in order to achieve a reasonable mean absolute error of 7–8 kcal/mol.     

Manganese(I)-Catalyzed Regioselective C−H Allenylation: Direct Access to 2-Allenylindoles

A Mn^I-catalyzed regioselective C−H allenylation is reported that allows a broad range of 2-allenylindoles to be synthesized regioselectively on a gram scale under simple conditions. Notably, a highly efficient chirality transfer was observed (up to 93 % ee) in this transformation. This procedure was further found to allow, for the first time, the direct preparation of ketones by Mn^I-catalyzed C−H activation. Mechanistic investigations revealed that the precoordination of the oxygen atom to the manganese center as well as the congested tertiary carbon atom in the propargylic carbonates play a crucial role.     

An amphibious vibration-driven microrobot with a piezoelectric actuator

This article concerns microrobots for solid and liquid environments. A short overview of microrobotics, suitable actuators and energy systems is given. The principles of terrestrial and aquatic locomotion are discussed and illustrated with examples from the literature on robotics. The state of the art with a focus on piezo microrobots for solid and liquid environments is presented. Furthermore, we report an amphibious prototype, which can move on flat solid ground and on the free surface of water. The design, characteristic parameters and experiments on locomotion are described. The robot is characterized by a light and simple design and can perform twodimensional locomotion in different environments with a speed up to 30 mm/s. An analytical model to predict the maximum carrying capacity of the robot on water is solved numerically.     

Facile synthesis of potassium tetrathiooxalate – The “true” monomer for the preparation of electron-conductive poly(nickel-ethylenetetrathiolate)

Herein, aiming at optimization of the polymerization process leading to a family of hole- and electron-conducting 1,1,2,2-ethenetetrathiolate-based polymers, such as poly(nickel-1,1,2,2-ethenetetrathiolate), poly[K_x(Ni-ett)], we investigated transformations of the monomer precursor 1,3,4,6-tetrathiapentalene-2,5-dione (TPD) occurring under polymerization conditions. We found that only one ring of TPD opens upon its reaction with potassium methoxide under inert conditions at room temperature which leads to the formation of potassium 2-oxo-1,3-dithiol-4,5-dithiolate (K₂[3]). Heating of K₂[3] under reflux in methanol solution under inert conditions opens the second ring, however the resulting product is not potassium ethenetetrathiolate (K₄[2]), the product of an exhaustive methanolysis of TPD, but potassium tetrathiooxalate (K₂[4]), the product of the decarbonylation of K₂[3]. Preliminary experiments reveal that the involvement of K₂[4] in the polymerization process is beneficial for reproducible formation of high quality 1,1,2,2-ethenetetrathiolate-based polymers suitable for thermoelectric applications.