Synthesis and structural investigation of N,N',N' '-trialkylguanidinato-supported zirconium(IV) complexes

The addition of 2 equiv of N,N',N' '-triisopropylguanidine (guanH(2)) to Zr(CH(2)Ph)(4) produced the bis(guanidinato)bis(benzyl)zirconium complex [((i)PrNH)C(N(i)Pr)(2)](2)Zr(CH(2)Ph)(2) (1). The mono(guanidinato) complex [((i)PrN)(2)C(NH(i)Pr)]ZrCl(3) (2) was accessible by the reaction of 2 equiv of guanH(2) with ZrCl(4). Guanidinium hydrochloride, [C(NH(i)Pr)(3)]Cl, is a byproduct of this reaction. When crystallized from THF, complex 2 was isolated as the THF adduct [((i)PrNH)C(N(i)Pr)(2)]ZrCl(3)(THF) (2-THF). The mixed cyclopentadienyl guanidinato complex [eta(5)-1,3-(Me(3)Si)(2)C(5)H(3)][((i)PrNH)C(N(i)Pr)(2)]ZrCl(2) (3) was prepared by treatment of [1,3-(Me(3)Si)(2)C(5)H(3)]ZrCl(3) with the in situ generated lithium triisopropylguanidinate salt. The reaction of guanH(2) with [1,3-(Me(3)Si)(2)C(5)H(3)]ZrMe(3) affords the dimethyl derivative [eta(5)-1,3-(Me(3)Si)(2)C(5)H(3)][((i)PrNH)C(N(i)Pr)(2)]ZrMe(2) (4). Definitive evidence for the molecular structures of these products is provided through single-crystal X-ray characterization of 1, 2-THF, and 3, which are presented. The extent of pi delocalization within the guanidinato ligand is discussed in the context of the metrical parameters obtained from these structural studies.     

Modeling and simulation of mixed-culture interactions in anaerobiosis of inhibitory substrate

Applied Biochemistry and Biotechnology - The model describes the anaerobiosis of 2-ethylhexanoic acid (2-EHA), which is a persistent and inhibitory organic waste. Model development was based on a...     

Routine screening and quantitation of urinary corticosteroids using bench-top gas chromatography-mass-selective detection.

A method was developed for the routine screening, confirmation and quantitation of corticosteroids in human urine using bench top capillary gas chromatography (GC)-mass-selective detection. The free and conjugated corticosteroid fractions were isolated by liquid-liquid partition. After evaporation to dryness under vacuum the corticosteroid residues were derivatized to form the methyloxime trimethylsilyl ether derivatives. Both GC retention data and characteristic spectral data based on authentic reference standards were used for the identification and quantitation of cortisol, cortisone, tetrahydrocortisol and tetrahydrocortisone in the ppb (ng/ml) concentration range. The method is simpler and more efficient than the other GC-mass spectrometric (MS) techniques. It is also more sensitive than the liquid chromatographic-MS method.     

51V magic angle spinning NMR spectroscopy of Keggin anions [PVnW12-nO40](3+n)-: effect of countercation and vanadium substitution on fine structure constants

Vanadium environments in Keggin oxopolytungstates were characterized by (51)V solid-state MAS NMR spectroscopy. (C(4)H(9))(4)N(+)-, K(+)-, Cs(+)-, as well as mixed Na(+)/Cs(+)- salts of the mono-, di-, and trivanadium substituted oxotungstates, [VW(11)O(40)](4-), [V(2)W(10)O(40)](5-), and [V(3)W(9)O(40)](6-), have been prepared as microcrystalline and crystalline solids. Solid-state NMR spectra report on the local environment of the vanadium site in these Keggin ions via their anisotropic quadrupolar and chemical-shielding interactions. These (51)V fine structure constants in the solid state are determined by the number of vanadium atoms present in the oxoanion core. Surprisingly, the quadrupolar anisotropy tensors do not depend to any significant extent on the nature of the countercations. On the other hand, the chemical-shielding anisotropy tensors, as well as the isotropic chemical shifts, display large variations as a function of the cationic environment. This information can be used as a probe of the local cationic environment in the vanadium-substituted Keggin solids.     

Comparative evaluation of software for retention time alignment of gas chromatography/time-of-flight mass spectrometry-based metabonomic data

In chromatography-based metabonomic research, retention time (RT) alignment of chromatographic peaks poses a challenge for the accurate profiling of biomarkers. Although a number of RT alignment software has been reported, the performance of these software packages have not been comprehensively evaluated. This study aimed to evaluate the RT alignment accuracy of publicly available and commercial RT alignment software. Two gas chromatography/mass spectrometry (GC/MS) datasets acquired from a mixture of standard metabolites and human bladder cancer urine samples, were used to assess three publicly available software packages, MetAlign, MZmine and TagFinder, and two commercial applications comprising the Calibration feature and Statistical Compare of ChromaTOF software. The overall RT alignment accuracies in aligning standard compounds mixture were 93, 92, 74, 73 and 42% for Calibration feature, MZmine, MetAlign, Statistical Compare and TagFinder, respectively. Additionally, unique trends were observed for the individual software with regards to the different experimental conditions related to extent and direction of RT shifts. Conflicting performance was observed for human urine samples suggesting that RT misalignments still occurred despite the use of RT alignment software. While RT alignment remains an inevitable step in data preprocessing, metabonomic researchers are recommended to perform manual check on the RT alignment of important biomarkers as part of their validation process.     

Establishing a quality assurance plan for nucleic acid-based diagnostic laboratories: from planning to implementation

Nucleic acid-based technologies have opened new perspectives in diagnosis, prognosis, and treatment in clinical medicine. To maintain patient confidence in this rapidly expanding field and to provide the highest standard of analysis, strict laboratory quality assurance procedures must be followed. While impressive break-through are taking place in this field, the need for an appropriate and suitable quality assurance (QA) plan for nucleic acid-based diagnostic laboratories must be a top priority. In this study, we developed a systematic QA plan for this kind of diagnostic laboratories that would enable us to assure the highest quality standards of their services. We focus on those labs that would like to start introducing a quality system for the first time and discuss the most appropriate ways to pave the way to implement a QA plan from the beginning. This QA plan is suitable for any nucleic acid-based techniques laboratory regardless of the field or services provided.