Polymer solutions as a pseudostationary phase for capillary electrochromatographic separation of DNA diastereomers

The solutions of linear polymers traditionally used for DNA separation have been employed for the capillary electrophoresis (CE) of diastereomers of chemically modified DNA. The selectivity of diastereomeric separation of the phosphorothioate (PS) and 2'-O-methylated (2-OMe) PS oligonucleotides depends on the nature of the polymer additive in the CE background electrolyte. The selectivity of separation for different polymers increases in the line: linear polyacrylamide < polyethylene glycol < polyvinyl pyrrolidone. The separation of oligomer diastereomers was shown to be primarily based on the hydrophobic interaction with the polymer network that acts as a pseudostationary phase. While lowering the temperature resulted in improved separation, the addition of organic modifiers such as formamide, methanol or acetonitrile counteracts the solute adsorption on the polymer network, and decreases the selectivity of DNA diastereoseparation. The effect of molecular mass and concentration of the polymer on the separation selectivity was investigated.     

The free loop space and the algebraic k-theory of spaces

Let A(X) be the space defined by Waldhausen whose homotopy groups define the algebraic K-groups of the space X and let . Here (X) denotes the free loop space of X and Q denotes the functor . For X = Y, the suspension of a connected space Y, we shall prove that the homotopy fibers Ã(X), B(X) of the maps A(X) A (point), B(X) B (point) are equivalent as infinite loop spaces.     

Note on the fractal dimension of hard sphere trajectories

Using Monte Carlo molecular dynamics, a new, careful study is made of the approach of the trajectory of a typical particle in a hard sphere fluid to that of a Brownian particle, discussed before by Powles and Quirke and Rapaport. The apparent fractal dimension of the trajectory, as a function of reduced length scale,(), characterizes the transition from mechanical to Brownian motion and differs markedly from 2 in all present computer simulations.     

Free-standing metal–organic framework (MOF) monolayers by self-assembly of polymer-grafted nanoparticles

We report a general method for the synthesis of free-standing, self-assembled MOF monolayers (SAMMs) at an air–water interface using polymer-brush coated MOF nanoparticles. UiO-66, UiO-66-NH₂, and MIL-88B-NH₂ were functionalized with a catechol-bound chain-transfer agent (CTA) to graft poly(methyl methacrylate) (PMMA) from the surface of the MOF using reversible addition-fragmentation chain transfer polymerization (RAFT). The polymer-coated MOFs were self-assembled at the air–water interface into monolayer films ∼250 nm thick and capable of self-supporting at a total area of 40 mm². Mixed-particle films were prepared through the assembly of MOF mixtures, while multilayer films were achieved through sequential transfer of the monolayers to a glass slide substrate. This method offers a modular and generalizable route to fabricate thin-films with inherent porosity and sub-micron thickness composed of a variety of MOF particles and functionalities.

We report a general method for the synthesis of free-standing, self-assembled MOF monolayers (SAMMs) at an air–water interface using polymer-brush coated MOF nanoparticles.     

Synthesis and characterization of an anomeric sulfur analogue of CMP-sialic acid

alpha-2,3-Sialyltransferase catalyzes the transfer of sialic acid from CMP-sialic acid (1) to a lactose acceptor. An analogue of 1 was synthesized in which the anomeric oxygen atom was replaced with a sulfur atom (1S). The key step in the synthesis of 1S was a tetrazole-promoted coupling of a cytidine-5'-phosphoramidite with a glycosyl thiol of a protected sialic acid. Compounds 1 and 1S were characterized for their activity in a sialyl transfer assay. The rate of solvolysis in aqueous buffer of analogue 1S was 50-fold slower than that of 1. Analogue 1S was found to be substrate for alpha-2,3-sialyltransferase. The K(m) of 1S was just 3-fold higher than that of 1, while the k(cat) of 1S was 2 orders of magnitude lower compared to 1.     

Where is the sodium in self-assembled monolayers of single-stranded DNA?

Monolayers of single-stranded DNA (ssDNA) immobilized on surfaces form the basis of a number of important biotechnology applications, including DNA microarrays and biosensors. The organization of ssDNA as layer on a solid substrate allows one to investigate various properties of the DNA in a controlled manner and to use DNA for analytical applications as well as for exploring futuristic schemes for molecular electronics. It is commonly assumed that the adsorbed DNA layer contains some structural water and the cations. Here we show, based on XPS studies, that when monolayers of ssDNA are formed from sodium phosphate buffer and washed thoroughly, no Na+ signal is detected. A finite concentration of ions is observed when the DNA is made from a solution of Mg2+ ions, but it is still only a fifth of what it would be if all the phosphate ions were fully neutralized by the metal cations.