Determination of olanzapine for therapeutic drug monitoring in schizophrenia patients by LC/MS method

Olanzapine is an atypical antipsychotic drug from the thienobenzodiazepine family which displays efficacy in patients with schizophrenia and related psychoses. A novel LC/MS method was developed and validated for determination of olanzapine in schizophrenia patients' plasma. A liquid–liquid extraction procedure was carried out using 5 mL diethyl ether–diisopropyl ether mixture (1:1, v/v). Average recovery of the extraction procedure was 94.8%. Chromatographic separation was performed on reversed‐phase C₁₈ column (250 × 2.0 mm, 5 μm) using mixture of deionized water (trifluoro acetic acid 0.1%)–acetonitrile (20:80, v/v) as mobile phase at a flow rate of 1 mL/min. Irbesartan was used as internal standart and total run time was 2.5 min. Mass spectrometric analysis were carried out in selective‐ion montoring mode, and detected olanzapine at m/z 313.1 and IS at m/z 429.4 in all forms of the ions. The calibration curve of olanzapine was linear in the range 2–300 ng/mL (r² > 0.9993). The interday and intraday precisions (RSD) were <7.55%, and accuracy was >7.59% (n = 6). The proposed study was successfully validated with respect to the US Food and Drug Administration guidelines.     

The proton transfer process observed in the structure analysis and DFT calculations of (E)-2-ethoxy-6-[(2-methoxyphenylimino)methyl]phenol

The crystal and molecular structures of an o-hydroxy Schiff base derivative, (E)-2-ethoxy-6-[(2-methoxyphenylimino)methyl]phenol, have been determined by single crystal X-ray diffraction analyses at 296 and 100 K. The results from temperature-dependent structural analysis regarding the tautomeric equilibrium of the compound were interpreted with the aid of quantum chemical calculations. To clarify the tautomerization process and its effects on the molecular geometry, the gas-phase geometry optimizations of two possible tautomers of the title molecule, its OH and NH form, were achieved using DFT calculations with B3LYP method by means of 6-31 + G(d,p) basis set. In order to describe the potential barrier belonging to the phenolic proton transfer, nonadiabatic Potential Energy Surface (PES) scan was performed based on the optimized geometry of the OH tautomeric form by varying the redundant internal coordinate, O–H bond distance. The Harmonic Oscillator Model of Aromaticity (HOMA) indices were calculated in every step of the scan process so as to express the deformation in the aromaticities of principal molecular moieties of the compound. The results show that there is a dynamic equilibrium between the aromaticity level of phenol and chelate ring and furthermore π-electron coupling affecting overall molecule of the title compound. Charge transfer from phenol ring to pseudo-aromatic chelate ring increases with increasing temperature, whereas π-electron transfer from chelate ring to anisole ring is decreased as temperature increases. The most strength intramolecular H-bonds are observed for conformers close to transition state.     

Solution processable organic field-effect transistors utilizing an alpha,alpha'-dihexylpentathiophene-based swivel cruciform

A pentathiophene-based swivel cruciform, which allows rotation between the cruciform arms, was synthesized. Homogeneous microcrystalline films were processed from solution, and field-effect transistors utilizing this dimer gave hole mobilities up to 0.012 cm2/V.s.     

Phosphorus-nitrogen compounds. Part 13. Syntheses, crystal structures, spectroscopic, stereogenic, and anisochronic properties of novel spiro-ansa-spiro-, spiro-bino-spiro-, and spiro-crypta phosphazene derivatives

The condensation reactions of N2Ox (x = 2, 3) donor-type aminopodand (4) and dibenzo-diaza-crown ethers (5, 6, and 9) with hexachlorocyclotriphosphazatriene, N3P3Cl6, produce two kinds of partially substituted novel phosphazene derivatives, namely, spiro-bino-spiro- (19) and spiro-crypta (21, 22, and 25) phosphazenes. The partially substituted spiro-ansa-spiro-phosphazene (11) reacted with pyrrolidine and 1,4-dioxa-8-azaspiro[4,5]decane (DASD) give the corresponding new fully substituted phosphazenes (14 and 16). Unexpectedly, the reactions of 23 and 24 with pyrrolidine result in only geminal crypta phosphazenes (26 and 27). The solid-state structures of 16 and 22 have been determined by X-ray diffraction techniques. The relative inner hole-size of the macrocycle in the radii of 22 is 1.27 A. The relationship between the exocyclic NPN (alpha') and endocyclic (alpha) bond angles for spiro-crypta phosphazenes and exocyclic OPN (alpha') bond angles for spiro-ansa-spiro- and spiro-bino-spiro-phosphazenes with 31P NMR chemical shifts of NPN and OPN phosphorus atoms, respectively, have been investigated. The structures of 10, 14, 16, 19, 21, 22, and 25-27 have also been examined by FTIR, 1H, 13C, and 31P NMR, HETCOR, MS, and elemental analyses. The 31P NMR spectra of 10, 21, 22, and 25 indicate that the compounds have anisochrony. In compounds 16 and 22, the spirocyclic nitrogen atoms have pyramidal geometries resulting in stereogenic properties.     

Trilayer Bethe lattices in the form of spin-(1/2,3/2,1/2)

The critical behaviors of the trilayer Bethe lattice in the form of spin-(1/2,3/2,1/2) with the exterior two layers consisting of spin-1/2 and the interior one having only spin-3/2 Ising spins are studied in terms of the recursion relations with either ferromagnetic or antiferromagnetic bilinear exchange interactions between the nearest-neighbor spins. The ground-state phase diagrams are calculated and it is found that the model presents six different ground state phase configurations. The thermal variations of the order-parameter and free energy are investigated, therefore, topologically different phase diagrams of the model are obtained. It is found that the model exhibits second- and first-order phase transitions, tricritical and bicritical points for the values of the coordination numbers q=3, 4 and 6 and, the reentrant behavior for q=4 and 6, respectively.     

The mixed-spins 1/2 and 3/2 Blume—Capel model with a random crystal field

The random crystal field(RCF) effects are investigated on the phase diagrams of the mixed-spins 1/2 and 3/2 Blume-Capel(BC) model on the Bethe lattice.The bimodal random crystal field is assumed and the recursion relations are employed for the solution of the model.The system gives only the second-order phase transitions for all values of the crystal fields in the non-random bimodal distribution for given probability.The randomness does not change the order of the phase transitions for higher crystal field values,i.e.,it is always second-order,but it may introduce first-order phase transitions at lower negative crystal field values for the probability in the range about 0.20 and 0.45,which is only the second-order for the non-random case in this range.Thus our work claims that randomness may be used to induce first-order phase transitions at lower negative crystal field values at lower probabilities.     

Spectral and photophysical studies on cruciform oligothiophenes in solution and the solid state

The photophysical and spectroscopic properties of a new class of oligothiophene derivatives, designated as cruciform oligomers, have been investigated in solution (room and low temperature) and in the solid state (as thin films in Zeonex matrixes). The study comprises absorption, emission, and triplet-triplet absorption spectra, together with quantitative measurements of quantum yields (fluorescence, intersystem crossing, internal conversion, and singlet oxygen formation) and lifetimes. The overall data allow the determination of the rate constants for all decay processes. From these, several conclusions are drawn. First, in solution, the main deactivation channels for the compounds are the radiationless processes: S(1) --> S(0) internal conversion and S(1) --> T(1) intersystem crossing. Second, in general, in the solid state, the fluorescence quantum yields decrease relative to solution. A comparison is made with the analogous linear alpha-oligothiophenes, revealing a lower fluorescence quantum efficiency and, in contrast to the normal oligothiophenes, that internal conversion is an important channel for the deactivation of the singlet excited state. Replacement of thiophene by 1,4-phenylene units in the longer-sized cruciform oligomer increases the fluorescence efficiency. The highly efficient generation of singlet oxygen through energy transfer from the triplet state (S(Delta) approximately 1) provides support for the measured intersystem crossing quantum yields and suggests that reaction with this may be an important pathway to consider for degradation of devices produced with these compounds.     

Investigation of the Molecular Structure of (E)-2-Bromo-6-[(4-bromo-2-methylphenylimino)methyl]-4-chlorophenol

Crystallography Reports - In this study, the molecular structure of (E)-2-bromo-6-[(4-bromo-2-methylphenylimino)methyl]-4-chlorophenol has been investigated using crystallographic (XRD),...