Simultaneous quantification of budesonide and its two metabolites, 6beta-hydroxybudesonide and 16alpha-hydroxyprednisolone,in human plasma by liquid chromatography negative electrospray ionization tandem mass spectrometry

A sensitive, rapid and selective liquid chromatography negative electrospray ionization tandem mass spectrometry [LC-(-)ESI-MS-MS] method has been developed and validated for the simultaneous quantification of budesonide (BUD) and its major metabolites, 6beta-hydroxybudesonide (OH-BUD) and 16alpha-hydroxyprednisolone (OH-PRED) in human plasma. The method was validated over a linear range from 0.1 to 10 ng/mL for all three analytes using a solid-phase extraction procedure with 9-fluoro-hydrocortisone as the internal standard. The between-day and within-day coefficients of variation for all compounds were < or =20% at the concentrations of lower limit of quantification and < or =15% at other quality control concentrations. The utility of this assay was demonstrated by monitoring BUD, OH-BUD and OH-PRED plasma concentrations in one healthy subject for 24 h following a 3 mg oral dose of budesonide, administered as a pH modified release capsule (Budenofalk) to healthy volunteers.     

An Unprecedented (1infinity)

A chain of vertex-linked "bare" nido-Ge(9)(2-) clusters (shown in the picture) is featured by the novel polymeric Zintl anion formed from the binary alloy "KGe(4)", ethylenediamine, and [18]crown-6. The polymerization of nido-Ge(9)(4-) clusters is counterintuitive to known two-electron oxidation behavior of nido clusters and the existence of the isolated closo-Ge(9)(2-) ion. The novel semiconducting cluster "wire" establishes direct structural and mechanistic links between molecular Zintl cluster ions with the extended structures of Zintl phases and elemental nanophase materials.     

Asymmetric synthesis of (-)-7-epiaustraline and (+)-1,7-diepiaustraline

A diastereoselective and modular approach to the synthesis of the 3-hydroxymethyl-2,3,5,6,7,7a-hexahydro-1H-pyrrolizine-1,2,7-triol structure, characteristic of several natural pyrrolizidine natural products, has been developed. This approach culminated in the synthesis of (-)-7-epiaustraline and (+)-1,7-diepiaustraline. The oxazolidinone group has been found to be a useful protecting group in the RCM reaction and, as part of a pyrrolo[1,2-c]oxazol-3-one ring system, has functioned as a stereo- and regio-directing group in a key diastereoselective cis-dihydroxylation reaction and a regioselective nucleophilic ring-opening of a S,S-dioxo-dioxathiole.     

An improved synthesis of 3-deazaeytosine, 3-deazauracil, 3-deazacytidine,and 3-deazauridine

3-Dcazacytosine (4-amino-2-pyridone, 3 ), 3-doazauracil (4-hydroxy-2-pyridone, 5 ), 3-deaza-cytidine (4-amino-1-β-D-ribofuranosyl-2-pyridonc, 9 ), and 3-deazauridine (4-hydroxy-1-β-D-ribo-furanosyl-2-pyridone, 11 ) were prepared in high overall yields from 1-methoxy-1-buten-3-yne ( 1 ). Ethyl 3,5,5-triethoxy-3-pentenoate ( 2 ), obtained from acylatioti of 1 with diethyl carbonate and subsequent in situ conjugate addition of ethoxide, was cyelized with ammonia to provide 3 . Diazotization of 3 and subsequent in situ hydroxydediazotization afforded 5 . Nucleoside 9 was obtained from the stannic chloride-catalyzed condensation of bis-trimethylsilylated 3 and 1-O-acetyl-2,3,5-tri-O-benzoyl-β-D-ribofuranose ( 7 ), followed by ammonolysis of the blocking groups. Diazotization of 9 and subsequent in situ hydroxydediazotization afforded nucleosidc 11 .     

Vibrational analyses of silacyclopentanes

The complete infrared and Raman spectra of 1,1-difluoro-1-silacyclopentane and 1,1-dichloro-1-silacyclopentane have been recorded and analyzed. Furthermore, a number of the vibrational frequencies of the silacyclopentane and silacyclopentane-1, 1-d₂ molecules have been reassigned.A normal coordinate calculation for each of these molecules was carried out and this demonstrated the validity of the assignments. Considerable mixing of the modes was found especially where ring vibrations and SiX₂ motions were involved.     

Asymptotic stability of some quasilinear parabolic equations in divergence form. L∞ results

In this paper we study the behavior of solutions of some quasilinear parabolic equations of the form

$\text{(}\text{?u}\text{?t}\text{) ?}\text{∑}\text{i=1}\text{n}\text{(}\text{d}\text{dx}{}_{\mathrm{i}}\text{) a}{}_{\mathrm{i}}\text{(x, t, u, u}{}_{\mathrm{x}}\text{) + a(x, t, u, u}{}_{\mathrm{x}}\text{)u + f(x, t) = O,}$

as t → ∞. In particular, the solutions of these equations will decay to zero as t → ∞ in the L^∞ norm.     

Bond indices and heats of formation of some nitriles

The definition of bond index introduced by Ehrenson, and written in terms of bond order and overlap integrals, has been applied to a series of nitriles. A good correlation between heats of formation and a linear equation in the indices for each bond present is obtained. This was extended to include the results for a set of hydrocarbons.     

LC-ESI-MS Determination of Bilobalide and Ginkgolides in Canine Plasma

A sensitive and selective method using liquid chromatography with electrospray ionization mass spectrometric detection was developed for the quantification of bilobalide and ginkgolides in canine plasma. The analytes were extracted with diethyl ether-dichloromethane-isopropanol (6:3:1, v/v) after spiking the samples with daidzein (internal standard). The lower limit of quantification (LLOQ) of the method was 2.5 μg L⁻¹ for ginkgolide B and 10.0 μg L⁻¹ for bilabolide, ginkgolide A and ginkgolide C. The accuracy of the method was within 15% of the actual values over a wide range of plasma concentrations. The intra-day and inter-day precision was better than 15% (R.S.D.). Finally, the LC-ESI-MS method was successfully applied to study the pharmacokinetics of ginkgolides and bilabolide after administration of Ginkgo biloba extracts to dogs.     

On-line Separation and Detection of Peptides by Capillary Electrophoresis / Electrospray FT-ICR-MS

Recently, capillary electrophoresis/electrospray ionization mass spectrometry (CE/ESI- MS) has been rapidly developed as a powerful analytical tool for charged species ranged from small molecules such as carboxylic acids1, phenolic compounds2, metal species3, tetramines4, herbicides5, drugs and drug metabolites6 to peptides and proteins7, 8. The ESI mode has proven to be sensitive, versatile and relatively easy to use in combination with CE. CE confers rapid analysis and efficient separ…     

Quantum chemistry study on B32 and B32H2–32

The structures of B32 and B₃₂H^2–₃₂ with I_h symmetry have been investigated by means of ab initio calculations at STO-3G level. The relationship between molecular orbitals of them has been analyzed and their bonding properties have been discussed. Then the possibility of their existence, as well as the similarity and difference between B₃₂ (B₃₂H^2–₃₂) and C₆₀ (C₆₀H₆₀) have been inferred.