Fluorogenic reaction between adenine derivatives and chloroacetaldehyde and its application to the determination of 9-(2-chloro-6-fluorobenzyl)adenine in human plasma

A sensitive (1 ng ml^?1) liquid chromatographic method with fluorescence detection is described for the determination of arprinocid and analogous compounds in human plasma. The method is based on chemical derivatization with chloroacetaldehyde to form highly fluorescent derivatives. Extraction of the drug from plasma and separation of the derivative from the reaction mixture are accomplished by solid-phase extraction with two silica cartridges. The effects of pH, solvent, and concentration of the reagents on the efficiency of derivatization were studied. The assay in plasma was validated in the 1–50 ng ml^?1 range. The fluorescent derivatives were synthesized and fully characterized. The derivatives were also found to be efficient as energy acceptors in the oxalate ester/hydrogen peroxide chemiluminescent system.     

Solubility of benzil in binary alkane + dibutyl ether solvent mixtures. Comparison of predictive expressions derived from the nearly ideal binary solvent model

Experimental solubilities are reported for benzil dissolved in six binary mixtures containing dibutyl ether with hexane, heptane, octane, cyclohexane, methylcyclohexane, and 2,2,4-trimethylpentane at 25°C. Results of these measurements are compared to the predictions of equations developed previously for solubility in systems of nonspecific interactions. The most successful equation in terms of goodness of fit involved a volume fraction average of the excess Gibbs energies relative to the Flory-Huggins model, and predicted the experimental solubilities in the six systems studied to within an overall average absolute deviation of 3.4% and with a maximum deviation of 6.0%.     

Rapidly converging lattice sums for nonelectrostatic interactions

The relative energies of one-, two-, and three-dimensional Bravais lattice Lennard-Jones particles can be calculated by lattice sums. The expression of lattice sums over a Lennard-Jones potential can be manipulated into a form that converges rapidly. A formalism capable of calculating the lattice potential at arbitrary points of a completely general lattice has been developed. This method provides an alternative way to calculate the relative energies from the surface and the interior bulk sites of many chemical systems. The method is illustrated with application to hcp and fcc Lennard-Jonesium, both for the relative binding energy and for calculating the potential along the geometric diffusion pathway between tetrahedral and octahedral interstitial sites. Diffusion from the tetrahedral site to the octahedral site experiences a barrier of 752.600 in units of 4 epsilon. The reverse pathway experiences a barrier of 1035.614 in units of 4 epsilon.     

Dinitrogen reduction by TmII,DyII, and NdII with simple amide and aryloxide ligands

Dinitrogen can be reduced to the planar M2(mu-eta2:eta2-N2) structure without employing cyclopentadienyl or complicated polydentate ligands using the recently discovered divalent oxidation states of Tm(II), Dy(II), and Nd(II). Complexes of these ions with common monodentate amide and aryloxide ligands can effect N2 reduction. THF solutions of LnI2 (Ln = Tm, Dy) in the presence of 2 equiv of NaN(SiMe3)2 reduce dinitrogen to form {[(Me3Si)2N]2(THF)Ln}2(mu-eta2:eta2-N2) complexes that have planar Ln2N2 units and 1.264(7) and 1.305(6) A NN bonds consistent with (N2)2- moieties. With the stronger reductant Nd(II), aryloxides are sufficient ancillary ligands: the NdI2/2KOC6H3tBu2-2,6 (KOAr) system forms [(ArO)2(THF)2Nd]2(mu-eta2:eta2-N2), which has a 1.242(7) A NN bond.     

Oxygen adsorption on hydrated gold cluster anions: experiment and theory

The discovery that supported gold clusters act as highly efficient catalysts for low-temperature oxidation reactions has led to a great deal of work aimed at understanding the origins of the catalytic activity. Several studies have shown that the presence of trace moisture is required for the catalysts to function. Using near-atmospheric pressure flow reactor techniques, we have studied humidity and temperature effects on the reactivity of gas-phase gold cluster anions with O2. Near room temperature, the humid source produces abundant gold-hydroxy cluster anions, Au(N)OH(-), and these have a reversed O2 adsorption activity: Nonreactive bare gold clusters become active when in the form Au(N)OH(-), while active bare clusters are inactive when -OH is bound. The binding energies for the stable structures obtained from density functional calculations confirm fully these findings. Moreover, the theory provides evidence that electron-transfer induced by the binding of a OH group enhances the reactivity toward molecular oxygen for odd anionic gold clusters and suppresses the reactivity for the even ones. The temperature dependence of O2 addition to Au(3)OH(-) and Au(4)(-) indicates deviations from equilibrium control at temperatures below room temperature. The effects of humidity on gold cluster adsorption activity support the conclusion drawn for the mechanism of O2 adsorption on "dry" gold cluster anions and provides insight into the possible role of water in the enhanced activity of supported gold cluster catalysts.     

Organogold(III) metallacyclic chemistry. Part 4. Synthesis, characterisation, and biological activity of gold(III)-thiosalicylate and -salicylate complexes

The silver(I) oxide mediated reactions of the gold(III) dichloride complex [{C₆H₃(CH₂

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uCl₂] 2a with thiosalicylic or salicylic acid gives the respective complexes [{C₆H₃(CH₂

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)-2}] 3a (X=S) or 6b (X=O), containing chelating thiosalicylate or salicylate dianion ligands. X-ray studies show that for the thiosalicylate system, the thiosalicylate sulfur atom is trans to the N,N-dimethylamino group, whereas in the structure of the salicylate complex, it is the carboxylate group that is trans to NMe₂. Both complexes show puckered metallacycles in the solid state. Electrospray mass spectrometry (ESMS) shows strong [M+H]⁺ and [2M+H]⁺ ions for both the gold-thiosalicylate and -salicylate complexes, and these ions possess a high stability towards cone voltage-induced fragmentation. ESMS was also used to identify a minor impurity, the bis(cyclo-aurated) cationic complex [A

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Me₂)-2-(OMe)-5}2]⁺ in the starting dihalide complex 2a and in the product 3a. This complex can be formed by reaction of Me₄N[AuCl₄] with 2 equivalents of the organomercury precursor [Hg{C₆H₃(CH₂NMe₂)-2-(OMe)-5}Cl]. The biological (antitumour, antimicrobial and antiviral) activities are also reported, and these reveal the complexes have moderate to high anti-tumour, antibacterial and antifungal activity.     

Separation of biomolecules by μ-high-performance anion-exchange chromatography using a tentacle-like stationary phase

A variety of biomolecules and their variants, which have previously been problematic to separate, have been analysed using a novel anion-exchange resin based on a non-porous polystyrene polymeric support with a hydrophilic coating and grafted tentacular quaternary ammonium functional groups. The hydrophilic coating results in minimal interaction between the support and the biomolecule, while the highly flexible tentacular-like anion-exchange groups increase the ionic interaction potential and act as an umbrella to hold the proteins away from the surface. Because of the removal of silanophilic interactions, minimisation of hydrophobic interactions, and the highly flexible nature of the tentacle-like ion exchangers, ionic interactions can therefore dominate the separation. As such this phase is highly suited to the separation of highly charged biomolecules and their variants. This polymeric strong anion-exchange (SAX) support was packed into a fused-silica capillary column and, using a salt concentration gradient, various recombinant proteins were analysed by -HPLC resulting in baseline resolution.Awarded a poster prize on the occasion of the Euranalysis XIII conference, Salamanca, Spain, 5–10 September 2004     

Distant-dipole field in liquids and diffusion: a perturbative approach

A perturbative approach is employed to solve the Bloch-Torrey equations in the presence of distant-dipole fields in nuclear magnetic resonance. The procedure, although only carried out to first order in the perturbation parameter a=1/k2Dtaud, could, in principle, be generalized to higher orders. Here D is the diffusivity, taud the dipolar demagnetization time, and k is the wave vector of the spatial modulation of magnetization produced by the magnetic field gradient. The results are especially interesting for dilute binary mixtures consisting of molecular species with different diffusivities. In this case the calculated two-dimensional correlation spectroscopy revamped by asymmetric Z-gradient echo detection spectra are shown to be free from some inadequacies resulting from a simplistic application of standard approximations.     

Very long-lived doubly vibrationally excited states above dissociation threshold: non-RRKM behavior in model triatomic systems

For couplings and mass ratios appropriate to molecules such as H₂O, D₂O, and CH₂ large volumes of the classical vibrational phase space are found to be non-dissociating even well above threshold. Fully quantum calculations yield families of exceptionally long-lived quantum states corresponding to these trapped volumes.     

Facile homogeneous hydrogenations of hindered olefins with [Ir(cod)py(PCy3)]PF6

The title complex readily hydrogenates a number of hindered steroidal olefin groups from the α face, without reducing ketone carbonyl groups, carbon—halogen bonds or cyclopropane rings.