Measurement of Total and Unbound Mycophenolic Acid and Its Glucuronide by LC Coupled with MS. Application to a Pharmacokinetic Study of Mycophenolate Mofetil in Patients with Autoimmune Diseases

Liquid chromatography coupled with mass spectrometry for the determination of total and unbound mycophenolic acid and its major metabolite in human plasma has been developed. Sample preparations were based on a fully automated solid-phase extraction process and ultrafiltration. Mass spectrometric data were acquired in a single-ion monitoring method. The analytes and nevirapine (internal standard) were well separated in an isocratic mode over 8 min. Validation study exhibited excellent linearity, with intra- and inter-day precision and accuracy of less than 12%. The assay was successfully applied to the pharmacokinetic study of mycophenolic acid in patients with autoimmune diseases.     

Surface free energy of films of alkali-treated cellulose microfibrils from banana rachis

Cellulose microfibrils extracted by various alkaline treatments of vascular bundles from banana rachis were used to elaborate films. The films were comparatively studied to determine changes in polarity induced by various treatments. Atomic force microscopy was used to characterize the surface morphology of the films and transmission electron microscopy was employed to characterize the microfibrils used to elaborate the films. Contact angles were measured to determine surface free energy (SFE) and thermogravimetric analyses were carried out to determine changes in composition of the films. The results showed that the films of cellulose microfibrils prepared by the peroxide alkaline (PA) and peroxide alkaline-hydrochloric acid (PA-HCl) treatments had lower content of non-cellulosic constituents like xylose and had lower SFE than films of microfibrils treated with KOH-5. Furthermore, specimens treated with the most concentrated KOH solution (18 wt%) and sodium chloride presented the highest SFE and polar component.     

Optimizing the source distribution in fluid mixing

A passive scalar is advected by a velocity field, with a nonuniform spatial source that maintains concentration inhomogeneities. For example, the scalar could be temperature with a source consisting of hot and cold spots, such that the mean temperature is constant. Which source distributions are best mixed by this velocity field? This question has a straightforward yet rich answer that is relevant to real mixing problems. We use a multiscale measure of steady-state enhancement to mixing and optimize it by a variational approach. We then solve the resulting Euler-Lagrange equation for a perturbed uniform flow and for simple cellular flows. The optimal source distributions have many broad features that are as expected: they avoid stagnation points, favour regions of fast flow, and their contours are aligned such that the flow blows hot spots onto cold and vice versa. However, the detailed structure varies widely with diffusivity and other problem parameters. Though these are model problems, the optimization procedure is simple enough to be adapted to more complex situations.     

Synthesis of rel-(3RS,3aSR,7aSR)-3-(4-Chlorophenyl)-3a,4,5,6,7,7a-hexahydro-1-methylindolin-6-one,the Main Metabolite of the Analgesic Ro 15-8081: A Potent Amine-Uptake Inhibitor

The synthesis of the title compound 2 and its diastereoisomer 3 was accomplished using tricarbonyl[1-5-n-(4-methoxycyclohexa-2,4-dien-1-yl)]iron tetrafluoroborate ( 4 ) as a precursor to the cyclohexanone ring. The assignments of the relative configurations of 2 and 3 are based on the X-ray analysis of compound 3 . Both compounds 2 and 3 are potent inhibitors of neuronal noradrenaline uptake in rats with similar potencies in vitro as compared to amitriptyline and desipramine. Compounds 2 and 3 are less potent as serotonin-uptake inhibitors, very weak inhibitors of dopamine uptake, and virtually devoid of antinociceptive activity.     

Fullerodendrimers with peripheral triethyleneglycol chains

Triethylene glycol terminated poly(aryl ether) dendritic branches with an aldehyde function at the focal point have been prepared and attached to C₆₀ by a 1,3-dipolar cycloaddition.     

Light-induced degradation of the active layer of polymer-based solar cells

Polymer-based organic solar cells are known to offer a poor stability in real use conditions, and the photodegradation of the active organic layer plays an important role in the reduced lifetime of the devices. This paper focuses on the photodegradation of two conjugated polymers used in organic solar cells, namely poly(2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene (MDMO-PPV) and poly(3-hexyylthiophene) (P3HT), and their blends with [60]PCBM (methano-fullerene[6,6]-phenyl C61-butyric acid methyl ester), a fullerene derivative. MDMO-PPV and P3HT thin films were submitted to photoageing (λ > 300 nm) in the presence and in the absence of oxygen. The mechanisms by which these polymers degrade were elucidated. P3HT, pristine and blended with PCBM, was shown to be much more stable under illumination than MDMO-PPV. The results showed that, if deposited on an inert substrate and well protected from oxygen with a convenient encapsulation, P3HT:PCBM based active layer should be intrinsically stable for several years in use conditions.     

Selection of suitable operating conditions to minimize the gradient equilibration time in the separation of drugs by Ultra-High-Pressure Liquid Chromatography with volatile (mass spectrometry-compatible) buffers

Reversed phase gradient elution is the method of choice for pharmaceuticals analysis since it allows reducing the analysis time while improving both the quality of the separation and the detection limits. The current trends are towards faster separations which can be achieved thanks to equipments withstanding ultra-high pressures and/or high temperatures. Under such conditions, gradient separations can be carried out within a few minutes or even a few tens of seconds. A long equilibration time in addition to the gradient time can be therefore very detrimental. In this work, we investigated the extent to which the gradient equilibration time can be reduced and which parameters mainly affect the retention variability of ionizable compounds when using volatile buffers. We first found out an excellent repeatability between run-to-run experiments whatever the equilibration time and the operating conditions. We then pointed out the key operating parameters which allow achieving reproducible runs when varying the equilibration time between runs. With a view of reducing the equilibration time, the effects of various conditions were examined. The latter include the type of additive for mobile phase pH adjustment, the initial eluent composition, the type of stationary phase, the temperature and the flow-rate. Although much remains to be understood about the equilibration process, our study allows making progress in the knowledge of this phenomenon. Based on the present results, a beneficial effect of both temperature and flow-rate was highlighted and operating conditions leading to faster column equilibration are suggested.     

Influence of deposition conditions on the optical properties of erbium-doped yttrium oxide films grown by aerosol-UV assisted MOCVD

Erbium-doped Y₂O₃ films were prepared by aerosol-UV assisted metal-organic chemical vapour deposition (MOCVD) at 410 °C. The effects of humidity of carrier gas and UV-assistance on their structure and optical properties were investigated on the as-deposited and thermal annealed films using infrared spectroscopy, X-ray diffraction and transmission electron microscopy. It was found that the as-deposited Er:Y₂O₃ films crystallise in the Y₂O₃ cubic structure and present a very low organic contamination when the deposition takes place under high air humidity and, even better, with UV-assistance. After annealing, two different structural phases are observed corresponding to the cubic and the monoclinic structures of Y₂O₃. The Er³⁺ luminescence analysed in the visible and IR regions, shows the classical green transitions. The best optical properties were obtained with as-deposited and annealed Er:Y₂O₃ films grown under high air humidity with UV-assistance. Under such deposition conditions, ⁴I_13/2 lifetimes was found to be 3.07 and 6.1 ms for films annealed at 800 and 1000 °C, respectively, and up-conversion phenomena were underlined. This indicates that the deposition conditions, in particular air humidity, play an important role in the luminescent properties even after annealing.