Comparison of UPLC and HPLC for Analysis of Dietary Folates

Ultra performance liquid chromatography (UPLC) using small sub-2 ??m particles and high performance liquid chromatography (HPLC) were compared for separation and determination of the most common dietary folates; 5-methyltetrahydrofolate, tetrahydrofolate, 5-formyltetrahydrofolate, 10-formylfolic acid and folic acid. Two UPLC columns??Acquity BEH C₁₈ and Acquity HSS T3, and two HPLC columns with similar surface chemistry??Xbridge C₁₈ and Atlantis d18 were tested. When using UPLC, the signal-to-noise ratio could be improved by a factor of 2?C50 for different folate derivatives and the run time could be reduced fourfold without sacrificing separation efficiency. The applicability of UPLC to real food samples was demonstrated.     

Unusual multi-step sequential Au(III)/Au(II) processes of gold(III) quinoxalinoporphyrins in acidic non-aqueous media

The electrochemistry of gold(III) mono- and bis-quinoxalinoporphyrins was examined in CH(2)Cl(2) or PhCN containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) before and after the addition of trifluoroacetic acid to solution. The investigated porphyrins are represented as Au(PQ)PF(6) and Au(QPQ)PF(6), where P is the dianion of the 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrin and Q is a quinoxaline group fused to a β,β'-pyrrolic position of the porphyrin macrocycle; in Au(QPQ)PF(6) there is a linear arrangement where the quinoxalines are fused to pyrrolic positions that are opposite each other. The porphyrin without the fused quinoxaline groups, Au(P)PF(6), was also investigated under the same solution conditions. In the absence of acid, all three gold(III) porphyrins undergo a single reversible Au(III)/Au(II) process leading to the formation of a Au(II) porphyrin which can be further reduced at more negative potentials to give stepwise the Au(II) porphyrin π-anion radical and dianion, respectively. However, in the presence of acid, the initial Au(III)/Au(II) processes of Au(PQ)PF(6) and Au(QPQ)PF(6) are followed by an internal electron transfer and protonation to regenerate new Au(III) porphyrins assigned as Au(III)(PQH)(+) and Au(III)(QPQH)(+). Both protonated gold(III) quinoxalinoporphyrins then undergo a second Au(III)/Au(II) process at more negative potentials. The electrogenerated monoprotonated monoquinoxalinoporphyrin, Au(II)(PQH), is then further reduced to its π-anion radical and dianion forms, but this is not the case for the monoprotonated bis-quinoxalinoporphyrin, Au(II)(QPQH), which accepts a second proton and is rapidly converted to Au(III)(HQPQH)(+) before undergoing a third Au(III)/Au(II) process to produce Au(II)(HQPQH) as a final product. Thus, Au(P)PF(6) undergoes one metal-centered reduction while Au(PQ)PF(6) and Au(QPQ)PF(6) exhibit two and three Au(III)/Au(II) processes, respectively. These unusual multistep sequential Au(III)/Au(II) processes were monitored by thin-layer spectroelectrochemistry and a reduction/oxidation mechanism for Au(PQ)PF(6) and Au(QPQ)PF(6) in acidic media is proposed.     

Further studies of intramolecular Michael reactions of nitrosoalkenes for construction of functionalized bridged ring systems

A wide variety of stabilized carbanions have been found to participate as nucleophiles in intramolecular Michael-type conjugate additions to in situ generated nitrosoalkenes to form bridged carbocyclic systems. The vinylnitroso platforms for these cyclizations have been prepared via two key steps involving ring-closing metathesis of vinyl chlorides and regioselective conversion of vinyl chlorides to α-chloroketones with sodium hypochlorite in glacial acetic acid/acetone. An alternative approach to preparation of some cyclization substrates has involved use of more reactive enol ethers as precursors to the requisite α-chloroketones. A sulfonamide anion has also been found to be an effective nucleophile in this type of reaction, leading to formation of a 6-azabicyclo[3.2.1]octane.     

An OFF-ON fluorescent probe for Zn2+ based on a GFP-inspired imidazolone derivative attached to a 1,10-phenanthroline moiety

A green fluorescent protein chromophore inspired chemosenor for Zn(2+) was designed and synthesized. A Zn(2+) specific fluorescence enhancement was observed due to restricted rotation between the 1,10-phenanthroline and imidazolone moieties.     

Long-Time Convergence of an Adaptive Biasing Force Method: The Bi-Channel Case

We present convergence results for an adaptive algorithm to compute free energies, namely the adaptive biasing force (ABF) method (Darve and Pohorille in J Chem Phys 115(20):9169–9183, 2001; Hénin and Chipot in J Chem Phys 121:2904, 2004). The free energy is the effective potential associated to a so-called reaction coordinate ξ(q), where q = (q ₁, … , q _3N ) is the position vector of an N-particle system. Computing free energy differences remains an important challenge in molecular dynamics due to the presence of metastable regions in the potential energy surface. The ABF method uses an on-the-fly estimate of the free energy to bias dynamics and overcome metastability. Using entropy arguments and logarithmic Sobolev inequalities, previous results have shown that the rate of convergence of the ABF method is limited by the metastable features of the canonical measures conditioned to being at fixed values of ξ (Lelièvre et al. in Nonlinearity 21(6):1155–1181, 2008). In this paper, we present an improvement on the existing results in the presence of such metastabilities, which is a generic case encountered in practice. More precisely, we study the so-called bi-channel case, where two channels along the reaction coordinate direction exist between an initial and final state, the channels being separated from each other by a region of very low probability. With hypotheses made on ‘channel-dependent’ conditional measures, we show on a bi-channel model, which we introduce, that the convergence of the ABF method is, in fact, not limited by metastabilities in directions orthogonal to ξ under two crucial assumptions: (i) exchange between the two channels is possible for some values of ξ and (ii) the free energy is a good bias in each channel. This theoretical result supports recent numerical experiments (Minoukadeh et al. in J Chem Theory Comput 6:1008–1017, 2010), where the efficiency of the ABF approach is demonstrated for such a multiple-channel situation.     

Application of reversible amide-bond protection to suppress peptide segment epimerisation

Reversible alkylation of the C-terminal amide-bond of a protected peptide segment with 2-hydroxy-4-methoxybenzyl dramatically suppresses epimerisation during activation and coupling. However, due to the formation of a 4,5-dihydro-8-methoxy-1,4-benzoxazepin-2(3H)-one species upon activation the rate of coupling is low. A safety-catch amide-bond protecting group, 6-hydroxy-5-methyl-1,3-benzoxathiolyl, has been designed to suppress epimerisation and couple with excellent yield.     

Aromatization of cyclohexadienes by TEMPO electro-mediated oxidation: Kinetic and structural aspects

Cyclohexadienes are easily converted into the corresponding aromatics in excellent yield (>90%) in the presence of 2,2,6,6-tetramethyl-1-oxopiperidinium ion (TEMPO⁺). The TEMPO radical was used in catalytic amount and was electrochemically regenerated in the presence of 2,6-lutidine as a base in hydro-organic medium (AcCN/H₂O 95/5). This work has been focused on the kinetic aspects. We have demonstrated that the reactivity of different cyclohexadienes is strongly dependent on the configuration of the double bonds and on the nature of the substituents. Competition between allylic functionalization and aromatization has been observed during the oxidation of 1,2-dihydro-4-phenylnaphthalene.     

Children’s use of realistic considerations in problem solving: some English evidence

This is the second of two papers exploring children’s responses to an extended version of a division-with-remainder problem intended to elicit general rather than particular realistic considerations during mathematical problem solving. Responses to two problems are analyzed. The first is a ‘realistically’ contextualised item drawn from national tests in England whose ambiguities have been previously discussed (Cooper, 1992); the second is a version of this problem revised to encourage a wider range of realistic responses. In Cooper and Harries (2002), the responses of children at the end of their first year of secondary schooling were analyzed. Here the responses of children at the end of their primary schooling are analyzed and compared with the previous results. It is shown that many children, given suitable encouragement, are willing and able to enter into an extended form of realistic thinking during problem solving, although the original test item renders this invisible.     

Catalytic enantioselective epoxidation with arabinose-derived uloses containing tunable steric sensors

Readily available arabinose-derived 4-uloses, containing a tunable butane-2,3-diacetal as the steric sensor, displayed increasing enantioselectivity (up to 93% ee) with the size of the acetal alkyl group in catalytic asymmetric epoxidation of trans-disubstituted and trisubstituted alkenes.     

A choice probability characterization of generalized extreme value models

A set of necessary and sufficient conditions is established for the representability of choice probabilities by additive random utility models with generalized extreme value (GEV) distributions of utilities. These conditions yield an operational testing procedure for GEV-representability which does not require explicit construction of the underlying distribution of utilities. In addition, this characterization of GEV models reveals a number of their underlying behavioral features.