Recognition of isozymes via lanthanide ion incorporated polymerized liposomes

We report the selective recognition of carbonic anhydrase isozymes based on the excited-state lifetimes of chelated Eu(3+) ions incorporated in polymerized liposomes.     

Experimental investigation of the response of a harmonically excited hard Duffing oscillator

A single degree-of-freedom torsional vibratory system, which constitutes a third-order dissipative dynamical system, has been fabricated as a mechanical analogue of hard Duffing equation with strong nonlinearity. The forced response of the system reveals complicated and chaotic motion at low frequency regime. Besides usual jump phenomenon, unpredictable jump phenomenon with two and three coexisting periodic attractors is also observed.      

Analysis of drug–protein binding by ultrafast affinity chromatography using immobilized human serum albumin

Human serum albumin (HSA) was explored for use as a stationary phase and ligand in affinity microcolumns for the ultrafast extraction of free drug fractions and the use of this information for the analysis of drug–protein binding. Warfarin, imipramine, and ibuprofen were used as model analytes in this study. It was found that greater than 95% extraction of all these drugs could be achieved in as little as 250 ms on HSA microcolumns. The retained drug fraction was then eluted from the same column under isocratic conditions, giving elution in less than 40 s when working at 4.5 mL/min. The chromatographic behavior of this system gave a good fit with that predicted by computer simulations based on a reversible, saturable model for the binding of an injected drug with immobilized HSA. The free fractions measured by this method were found to be comparable to those determined by ultrafiltration, and equilibrium constants estimated by this approach gave good agreement with literature values. Advantages of this method include its speed and the relatively low cost of microcolumns that contain HSA. The ability of HSA to bind many types of drugs also creates the possibility of using the same affinity microcolumn to study and measure the free fractions for a variety of pharmaceutical agents. These properties make this technique appealing for use in drug-binding studies and in the high-throughput screening of new drug candidates.     

Pyrazolylborates and their importance in tuning single-molecule magnet properties of {Fe(III)2Ni(II)} complexes

A new tricyanoferrate(III) building block and a trinuclear single-molecule magnet derivative are described. The treatment of a 2:1 ratio of [NEt(4)][(Tp*(Bn))Fe(III)(CN)(3)]·H(2)O·MeOH [1; Tp*(Bn) = tris(3,5-dimethyl-4-benzyl)pyrazolylborate] with nickel(II) trifluoromethanesulfonate gives {[(Tp*(Bn))Fe(III)(CN)(3)](2)[Ni(II)(DMF)(4)]}·2DMF (2; DMF = N,N-dimethylformamide). The symmetry-equivalent Fe(III)(LS) ions lead to a favorable alignment of anisotropy tensors (i.e., Fe···B axes) in 2, and an energy barrier of Δ(eff)/k(B) = 16.7 K is found for the S(T) = 2 complex.     

Understanding the solubility of triamino-trinitrobenzene in hydrous tetramethylammonium fluoride: a first principles molecular dynamics simulation study

With the aim to understand the relatively high solubility of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), an important energetic material with a high degree of inter- and intra-molecular hydrogen bonding, in fluoride anion containing ionic liquids (ILs), first principles molecular dynamics simulations in the isobaric-isothermal ensemble were carried out for a system using hydrous tetramethylammonium fluoride as the prototypical solvent. Simulations initiated from both molecular TATB and its Meisenheimer complex (i.e., a σ-complex of the fluoride and the electrophilic ring of TATB) yield a Zundel-type complex where a proton is shared between an amino group and an F(-) ion, whereas the Meisenheimer complex is found to be only transiently stable. An analysis of the electronic structure probing the Wannier function centers supports the finding of a proton-sharing complex with a three-center four-electron like bond. The Zundel-type complex also yields an electronic absorption spectrum consistent with the experimentally observed color change. This study provides evidence that the remarkable solubility of otherwise hard-to-dissolve molecular crystals in ILs can be aided by chemical modification of the solute.     

Formulation of photocleavable liposomes and the mechanism of their content release

In pursuit of designing photocleavable liposomes as drug delivery vehicles, we synthesized several amphiphilic lipids by connecting stearyl amine (as the non-polar tail) and charged amino acids (as polar heads) via the o-nitrobenzyl derivatives. The lipids containing Glu, Asp, and Lys amino acids were subjected to photocleavage reaction by UV light, and the overall spectral changes of the chromophoric o-nitrobenzyl conjugates were determined as a function of time. The experimental data revealed that the feasibility of the cleavage reaction, nature and magnitude of the spectral changes during the course of the cleavage reaction, and their overall kinetic profiles were dictated by the type of amino acid constituting the polar head groups. The cleavage reactions of the Asp and Glu containing lipids were found to be more facile than that of the lysine-containing lipid. Using these lipids, we formulated photocleavable liposomes, and investigated the photo-triggered release of an encapsulated (within the liposomal lumen) dye as a function of time. The kinetic data revealed that the release of the liposomal content conformed to a two-step mechanism, of which the first (fast) step involved the photocleavage of lipids followed by the slow release of the liposomal content during the second step. The overall mechanistic features intrinsic to the photocleavage of Asp, Glu and Lys containing o-nitrobenzyl conjugated lipids, and their potential applications in formulating liposomes (whose contents can be "unloaded" by the UV light) as drug delivery vehicles are discussed.     

Studies on manganese nodule leached residue 4. Physicochemical characterization and catalytic activity of acetic acid treated manganese nodule leached residue

The catalytic activity of water-washed manganese nodule leached residue (WMNLR) samples improved by treating with acetic acid. The effects of acetic acid treatment on the physicochemical properties and catalytic activity of manganese nodule leached residue have been studied. The surface area, surface oxygen, surface hydroxyl groups, surface acidity, electron donating properties, etc., increase gradually with acid treatment up to 0.5 M and thereafter show a decreasing trend. The rate constant of H2O2 decomposition, catalytic activity of CO oxidation, and esterification of acetic acid also show a similar trend to that of surface properties.     

Hydrogen bond and residence dynamics of ion-water and water-water pairs in supercritical aqueous ionic solutions: dependence on ion size and density

We have carried out a series of molecular dynamics simulations to investigate the hydrogen bond and residence dynamics of X(-)-water (X=F, Cl, and I) and pairs in aqueous solutions at a temperature of 673 K. The calculations are done at six different water densities ranging from 1.0 to 0.15 g cm(-3). The hydrogen bonds are defined by using a set of configurational criteria with respect to the anion(oxygen)-oxygen and anion(oxygen)-hydrogen distances and the anion(oxygen)-oxygen-hydrogen angle for an anion(water)-water pair. The F(-)-water hydrogen bonds are found to have a longer lifetime than all other hydrogen bonds considered in the present study. The lifetime of Cl(-)-water hydrogen bonds is shorter than that of F(-)-water hydrogen bonds but longer than the lifetime of water-water hydrogen bonds. The lifetimes of I(-)-water and water-water hydrogen bonds are found to be very similar. Generally, the lifetimes of both anion-water and water-water hydrogen bonds are found to be significantly shorter than those found under ambient conditions. In addition to hydrogen bond lifetimes, we have also calculated the residence times and the orientational relaxation times of water molecules in ion(water) hydration shells and have discussed the correlations of these dynamical quantities with the observed dynamics of anion(water)-water hydrogen bonds as functions of the ion size and density of the supercritical solutions.     

Affinity monolith chromatography

The combined use of monolithic supports with selective affinity ligands as stationary phases has recently given rise to a new method known as affinity monolith chromatography (AMC). This review will discuss the basic principles behind AMC and examine the types of supports and ligands that have been employed in this method. Approaches for placing affinity ligands in monoliths will be considered, including methods based on covalent immobilization, biospecific adsorption, entrapment, and the formation of coordination complexes. Several reported applications will then be presented, such as the use of AMC for bioaffinity chromatography, immunoaffinity chromatography, immobilized metal-ion affinity chromatography, dye-ligand affinity chromatography, and biomimetic chromatography. Other applications that will be discussed are chiral separations and studies of biological interactions based on AMC.