Sensitivity enhancement and matrix effect evaluation during summation of multiple transition pairs—case studies of clopidogrel and ramiprilat

Sensitivity enhancement via summation of multiple MRM transition pairs is gaining popularity in tandem mass spectrometric assays. Numerous validation experiments describing the assays for two model substrates, clopidogrel and ramiprilat, were performed. The quantitation of clopidogrel was achieved by the summation of transition pairs m/z 322.2 to m/z 212.0 and m/z 322.2 to m/z 184.0, while that of ramiprilat was achieved by the summation of transition pairs m/z 389.2 to m/z 206.1 and m/z 389.2 to m/z156.1. The use of summation approach achieved sensitivities of >2 fold for both compounds as compared with the reported single MRM transition pair assays. The validation experiments addressed some important assay development issues, such as: (a) lack of impact of matrix effect; (b) unequivocal verification of the percentage contribution of each MRM transition pair towards sensitivity; (c) sensitivity enhancement factor achieved by summation approach of MRM transition pairs; and (d) accurate prediction of quality control samples using summation approach vs a single MRM transition pair. In summary, the appropriateness of using two MRM transition pairs for quantitation was demonstrated for both clopidogrel and ramiprilat. Additionally, pharmacokinetic application of the MRM transition pair assays using a summation approach was established for the two compounds. Copyright © 2009 John Wiley & Sons, Ltd.     

Conductimetric immunosensor based on poly(3,4-ethylenedioxythiophene)

A conductimetric reagentless immunosensor using the biospecific binding pair of goat antirabbit IgG and rabbit IgG has been designed and fabricated using poly (3,4-ethylenedioxythiophene) as the immobilization matrix-cumtransducer.     

Relation of coordination number to memory and threshold switching in chalcogenides

The paper reports a structural study of some memory and threshold chalcogenides in terms of coordination numberC, defined byC=8−N, and is the average coordination number for covalently bonded materials. The average number of nearest neighbours surrounding a central atom, obtained for As-Ge-Te (memory) and Se-Ge-Te (threshold) systems have been used to estimate the cohesive energies, assuming simple additivity of bond energies. The bonding pattern so obtained, explains certain properties of these glasses.     

Formation of diaryl(allyl)phosphine in π -allyl palladium(II) induced cleavage of triarylphosphines

A reverse migration of allylic group from palladium to phosphorus and the formation of diaryl(allyl)phosphine in the π -allyl palladium(II) induced cleavage of triarylphosphines has been demonstrated.     

The reaction of PPh3 with Di-μ-chlorobis(arylazooximato)dipalladium(II)

Summary Di--chlorobis(arylazooximato)dipalladiuni(II) compounds react with PPh₃ to give the four-coordinate complexes (5) and (4) in which the azooxime acts as a unidentate and bidentate ligand respectively. Hydrogen bonding in polar solvents such as MeOH or EtOHetc. stabilize (5) whereas, polar solvents such as Me₂CO, py and Et₂O convert (5) into (4). The equilibrium: (4) + PPh₃ (5) exists in PhH solution and equilibrium constants at 30°C have been calculated spectrophotometrically. The variation in equilibrium constants and the stabilities of (5) have been explained on the basis of electron-releasing and electron-withdrawing properties of substituents, R, in the azooxime ligand.     

Mössbauer study of a ferromagnetic metallic glass: Fe74Co10B16

Amorphous Fe₇₄Co₁₀B₁₆ (METGLAS 2605CO) has been studied in the temperature range of 77 K – 700 K by Mössbauer spectroscopy. Its crystallization temperature is found to be 665 ± 5 K and Curie temperature is estimated to be 760±10 K. The observed rapid decrease in reduced hyperfine fields can be explained well by Handrich's model for amorphous ferromagnets if one assumes a temperature dependent δ, a measure of fluctuations in the exchange interactions in such solids.     

Carbon-13 substituent chemical shifts of 4-substituted bicyclo[2.2.2]oct-1-yl cyanides

The carbon-13 substituent chemical shifts of 4-substituted bicyclo[2.2.2]oct-1-yl cyanides are a linear function of the substituent inductive parameters.     

Bismuthiol II as an analytical reagent

Summary Silver can be separated as its Bismuthiol II complex from OsO_{4 4} ^2– , Os⁴⁺, Ir⁴⁺, Ru³⁺, Rh³⁺ with thiosulphate or complexone III as the masking agent at a p_H between 5 and 9. Au³⁺ can be kept in solution only by thiosulphate at a p_H 8–9 and cyanide complexes palladium at a P_H of about 6. Separation from platinum in presence of a mixture of tartaric acid and complexone III is possible only to a limited extent.Part VI see Z. analyt. Chem. 155, 86 (1957)     

Use of non-adiabatic geometric phase for quantum computing by NMR

Geometric phases have stimulated researchers for its potential applications in many areas of science. One of them is fault-tolerant quantum computation. A preliminary requisite of quantum computation is the implementation of controlled dynamics of qubits. In controlled dynamics, one qubit undergoes coherent evolution and acquires appropriate phase, depending on the state of other qubits. If the evolution is geometric, then the phase acquired depend only on the geometry of the path executed, and is robust against certain types of error. This phenomenon leads to an inherently fault-tolerant quantum computation. Here we suggest a technique of using non-adiabatic geometric phase for quantum computation, using selective excitation. In a two-qubit system, we selectively evolve a suitable subsystem where the control qubit is in state |1, through a closed circuit. By this evolution, the target qubit gains a phase controlled by the state of the control qubit. Using the non-adiabatic geometric phase we demonstrate implementation of Deutsch-Jozsa algorithm and Grover's search algorithm in a two-qubit system.