Quantification of free mycophenolic acid by high-performance liquid chromatography-atmospheric pressure chemical ionisation tandem mass spectrometry

To facilitate the investigation of free mycophenolic acid concentrations we developed a high-performance liquid chromatography tandem mass spectrometry method using indomethacin as an internal standard. Free drug was isolated from plasma samples (500 mul) using ultrafiltration, The analytes were extracted from the ultrafiltrate (200 mul) using C-18 solid-phase extraction. Detection was by selected reactant monitoring of mycophenolic acid (m/z 318.9-->190.9) and the internal standard (m/z 356.0-->297.1) with an atmospheric pressure chemical ionisation interface. The total chromatographic analysis time was 12 min. The method was found to be linear over the range investigated, 2.5-200 mug/l (r>0.990, n=6). The relative recovery of the method for the control samples studied (7.5, 40.0 and 150 mug/l) ranged from 95 to 104%. The imprecision of the method, expressed in terms of intra- and inter-day coefficients of variation, was

Temperature and atmospheric pressure may be considered as predictors for the occurrence of bacillary dysentery in Guangzhou, Southern China

Introduction The control of bacillary dysentery (BD) remains a big challenge for China. Methods Negative binomial multivariable regression was used to study relationships between meteorological variables and the occurrence of BD during the period of 2006-2012. Results Each 1°C rise of temperature corresponded to an increase of 3.60% (95%CI, 3.03% to 4.18%) in the monthly number of BD cases, whereas a 1 hPa rise in atmospheric pressure corresponded to a decrease in the number of BD cases by 2.85% (95%CI = 3.34% to 2.37% decrease). Conclusions Temperature and atmospheric pressure may be considered as predictors for the occurrence of BD in Guangzhou.

Steam Curing of Portland Cement Concrete at Atmospheric Pressure, HR-40, 1962

The primary reason for using steam in the curing of concrete is to produce a high early strength. This high early strength is very desirable to the manufacturers of precast and prestressed concrete units, which often require expensive forms or stress beds. They want to remove the forms and move the units to storage yards as soon as possible. The minimum time between casting and moving the units is usually governed by the strength of the concrete. Steam curing accelerates the gain in strength at early ages, but the uncontrolled use of steam may seriously affect the growth in strength at later ages. The research described in this report was prompted by the need to establish realistic controls and specifications for the steam curing of pretensioned, prestressed concrete bridge beams and concrete culvert pipe manufactured in central plants. The complete project encompasses a series of laboratory and field investigations conducted over a period of approximately three years.

Radicals from the atmospheric pressure pyrolysis and oxidative pyrolysis of hydroquinone, catechol, and phenol

The burning of tobacco creates various types of free radicals that have been reported to be biologically active. Some radicals are transient but can initiate catalytic cycles that generate other free radicals. Other radicals are environmentally persistent and can exist in total particulate matter (TPM) for extended periods. In spite of their importance, little is known concerning the precursors of these radicals or under what pyrolysis/combustion conditions they are formed. We performed studies of the formation of radicals from the gas-phase pyrolysis and oxidative pyrolysis of hydroquinone (HQ) and catechol (CT) between 750 and 1000 °C and phenol from 500 to 1000 °C. The initial electron paramagnetic resonance (EPR) spectra were complex, indicating the presence of multiple radicals. Using matrix annealing and microwave power saturation techniques, phenoxyl, cyclopentadienyl, and peroxyl radicals were identifiable, but only cyclopentadienyl radicals were stable above 750 °C.

Characterization and antimicrobial efficacy against E. coli of a helium/air plasma at atmospheric pressure created in a plastic package

A plasma source, sustained by the application of a floating high voltage (±15 kV) to parallel-plate electrodes at 50 Hz, has been achieved in a helium/air mixture at atmospheric pressure (P = 105 Pa) contained in a zip-locked plastic package placed in the electrode gap. Some of the physical and antimicrobial properties of this apparatus were established with a view to ascertain its performance as a prototype for the disinfection of fresh produce. The current–voltage (I–V) and charge–voltage (Q–V) characteristics of the system were measured as a function of gap distance d, in the range (3 × 103 ≤ Pd ≤ 1.0 × 104 Pa m). The electrical measurements showed this plasma source to exhibit the characteristic behaviour of a dielectric barrier discharge in the filamentary mode and its properties could be accurately interpreted by the two-capacitance in series model. The power consumed by the discharge and the reduced field strength were found to decrease quadratically from 12.0 W to 4.5 W and linearly from 140 Td to 50 Td, respectively, in the range studied. Emission spectra of the discharge were recorded on a relative intensity scale and the dominant spectral features could be assigned to strong vibrational bands in the 2+ and 1− systems of N2 and ${\rm N}_2^+$ , respectively, with other weak signatures from the NO and OH radicals and the N+, He and O atomic species. Absolute spectral intensities were also recorded and interpreted by comparison with the non-equilibrium synthetic spectra generated by the computer code SPECAIR. At an inter-electrode gap of 0.04 m, this comparison yielded typical values for the electron, vibrational and translational (gas) temperatures of (4980 ± 100) K, (2700 ± 200) K and (300 ± 100) K, respectively and an electron density of 1.0 × 1017 m−3. A Boltzmann plot also provided a value of (3200 ± 200 K) for the vibrational temperature. The antimicrobial efficacy was assessed by studying the resistance of both Escherichia coli K12 its isogenic mutants in soxR, soxS, oxyR, rpoS and dnaK selected to identify possible cellular responses and targets related with 5 min exposure to the active gas in proximity of, but not directly in, the path of the discharge filaments. Both the parent strain and mutants populations were significantly reduced by more than 1.5 log cycles in these conditions, showing the potential of the system. Post-treatment storage studies showed that some transcription regulators and specific genes related to oxidative stress play an important role in the E. coli repair mechanism and that plasma exposure affects specific cell regulator systems.

Detection and Characterization of Cholesterol-Oxidized Products Using HPLC Coupled to Dopant Assisted Atmospheric Pressure Photoionization Tandem Mass Spectrometry

Oxidation of cholesterol (Ch) by a variety of reactive oxygen species gives rise mainly to hydroperoxides and aldehydes. Despite the growing interest in Ch-oxidized products, the detection and characterization of these products is still a matter of concern. In this work, the main Ch-oxidized products, namely, 3 beta-hydroxycholest-5-ene-7 alpha-hydroperoxide (7 alpha-OOH), 3 beta-5 alpha-cholest-6-ene-5-hydroperoxide (5 alpha-OOH), 3 beta-hydroxycholest-4-ene-6 alpha-hydroperoxide (6 alpha-OOH), 3 beta-hydroxycholest-4-ene-6 beta-hydroperoxide (6 beta-OOH), and 3 beta-hydroxy-5 beta-hydroxy-B-norcholestane-6 beta-carboxaldehyde (ChAld), were detected in the same analysis using high-performance liquid chromatography (HPLC) coupled to dopant assisted atmospheric pressure photoionization tandem mass spectrometry. The use of selected reaction monitoring mode (SRM) allowed a sensitive detection of each oxidized product, while the enhanced product ion mode (EPI) helped to improve the confidence of the analyses. Isotopic labeling experiments enabled one to elucidate mechanistic features during fragmentation processes. The characteristic fragmentation pattern of Ch-oxidized products is the consecutive loss of 1120 molecules, yielding cationic fragments at m/z 401, 383, and 365. Homolytic scissions of the peroxide bond are also seen. With (18)O-labeling approach, it was possible to establish a fragmentation order for each isomer. The SRM transitions ratio along with EPI and (18)O-labeled experiments give detailed information about differences for water elimination, allowing a proper discrimination between the isomers:Phis is of special interest considering the emerging role of Ch-oxidized products in the development of diseases.

Atmospheric pressure photoionization mass spectrometry as a tool for the investigation of the hydrolysis reaction mechanisms of phosphite antioxidants

The hydrolysis reaction mechanism of phosphite antioxidants is investigated by liquid chromatography-mass spectrometry (LC/MS). The phosphites were chosen because they differed in chemical structure and phosphorus content. Dopant assisted-atmospheric pressure photoionization (DA-APPI) is chosen as the ion source for (lie ionization of the compounds. [it our previous work, DA-APPI was shown to offer an attractive alternative to atmospheric pressure chemical ionization (APCI) since it provided background-ion free mass spectra and higher sensitivity [M. Papanastasiou, et al., Polymer Degradation and Stability 91 (11) (2006) 2675-2682]. In positive ion mode, the molecules are generally detected in their protonated form. In negative ion mode, the phosphites are unstable and only fragment ions are observed: these however, are characteristic of each phosphite and may be used for the identification of the analytes in complex mixtures. The analytes under investigation are exposed to accelerated humid ageing conditions and their hydrolytic pathway and stability is investigated. Different substituents around the phosphorus atom are shown to have a significant effect on the stability of the phosphites, with phenol substituents producing very hydrolytically stable structures. Alkanox P24 and PEP-36 follow a similar hydrolytic pathway via the scission of the first and then the second P-O-phenol bonds, eventually leading to the formation of phenol, Phosphorous acid and pentaerythritol as end products. HP-10 exhibits a rather different Structure and the products detected suggest scission of either the P-O-hydrocarbon or one of the P-O-phenol bonds. A phenomenon similar to that of autocatalysis is observed for all phosphites and is attributed to the formation of dialkyl phosphites as intermediate products. (C) 2008 Elsevier B.V. All rights reserved.

Treatment of PET and PU polymers by atmospheric pressure plasma generated in dielectric barrier discharge in air

Plasma treatments are frequently employed to modify surface properties of materials such as adhesivity, hydrophobicity, oleophobicity etc. Present work deals with surface modification of common commercial polymers such as polyethylene terephthalate (PET) and polyurethane (PU) by an air dielectric barrier discharge (DBD) at atmospheric pressure. The DBD treatment was performed in a plain reactor in wire-duct geometry (non-uniform field reactor), which was driven by a 60 Hz power supply. Material characterization was carried out by water contact angle measurements, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The plasma-induced modifications are associated with incorporation of polar oxygen and nitrogen containing groups on the polymer surface. The AFM analysis reveals that the plasma treatment roughens the material surface. Due to these structural and morphological changes the surface of DBD-treated polymers becomes more hydrophilic resulting in enhanced adhesion properties. (C) 2010 Elsevier B.V. All rights reserved.

Surface modification of siloxane containing polyurethane polymer by dielectric barrier discharge at atmospheric pressure

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Modification of polyethylene terephthalate by atmospheric pressure dielectric barrier discharge (DBD) in view of improving the polymer wetting properties

Surface treatment of polymers by discharge plasmas has increasingly found industrial applications due to its capability of modifying uniformly the surface without changing the material bulk properties. This work deals with surface modification of polyethylene terephthalate (PET) by a dielectric barrier discharge (DBD) at atmospheric pressure. The treatments were conducted in air, nitrogen or argon plasma. The polymer surface was characterized by contact angle measurement, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The results show that the plasma treatment introduces oxygen-and nitrogen-related polar groups on the polymer surface and promotes the surface roughening. Both plasma-induced surface modifications contribute to the enhancement of the polymer wettability.

Surface Modification of Polycarbonate by Atmospheric-Pressure Plasma Jets

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Surface characteristics analysis of polypropylene treated by dielectric barrier discharge at atmospheric pressure

Polypropylene (PP) samples were treated by Dielectric Barrier Discharge (DBD) in order to modify their surface characteristics. The XPS analysis reveals that the DBD treatment added oxygen atoms to the PP surface. These polar groups cause increase in the wettability as shown by water contact angle measurements. The formation of low-molecular-weight oxidized materials (LMWOMs) in the form of small nodules on the PP surface was observed by atomic force microscopy (AFM). The presence of oxygen polar groups on the PP surface was also confirmed by infrared spectroscopy (FTIR). All analysis were performed before and after rinsing the treated samples in water and showed that the LMWOM can be removed from the surface by polar solvents.

Argon-based atmospheric pressure plasma enhances early bone response to rough titanium surfaces

This study investigated the effect of an Argon-based atmospheric pressure plasma (APP) surface treatment operated chairside at atmospheric pressure conditions applied immediately prior to dental implant placement in a canine model. Surfaces investigated comprised: rough titanium surface (Ti) and rough titanium surface + Argon-based APP (Ti-Plasma). Surface energy was characterized by the Owens-Wendt-Rabel-Kaelble method and chemistry by X-ray photoelectron spectroscopy (XPS). Six adult beagles dogs received two plateau-root form implants (n = 1 each surface) in each radii, providing implants that remained 1 and 3 weeks in vivo. Histometric parameters assessed were bone-to-implant contact (BIC) and bone area fraction occupancy (BAFO). Statistical analysis was performed by Kruskall-Wallis (95% level of significance) and Dunn's post-hoc test. The XPS analysis showed peaks of Ti, C, and O for the Ti and Ti- Plasma surfaces. Both surfaces presented carbon primarily as hydrocarbon (C?C, C?H) with lower levels of oxidized carbon forms. The Ti-Plasma presented large increase in the Ti (+11%) and O (+16%) elements for the Ti- Plasma group along with a decrease of 23% in surface-adsorbed C content. At 1 week no difference was found in histometric parameters between groups. At 3 weeks significantly higher BIC (>300%) and mean BAFO (>30%) were observed for Ti-Plasma treated surfaces. From a morphologic standpoint, improved interaction between connective tissue was observed at 1 week, likely leading to more uniform and higher bone formation at 3 weeks for the Ti-Plasma treated implants was observed. (C) 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part A 2012.

Determination of aldicarb, aldicarb sulfoxide and aldicarb sulfone in some fruits and vegetables using high-performance liquid chromatography-atmospheric pressure chemical ionization mass spectrometry

An analytical method for the determination of aldicarb, and its two major metabolites, aldicarb sulfoxide and aldicarb sulfone in fruits and vegetables is described. Briefly the method consisted of the use of a methanolic extraction, liquid-liquid extraction followed by solid-phase extraction clean-up. Afterwards, the final extract is analyzed by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS). The specific fragment ion corresponding to [M-74](+) and the protonated molecular [M+K](+) ion were used for the unequivocal determination of aldicarb and its two major metabolites. The analytical performance of the proposed method and the results achieved were compared with those obtained using the common analytical method involving LC with post-column fluorescence detection (FL). The limits of detection varied between 0.2 and 1.3 ng but under LC-FL were slightly lower than when using LC-APCI-MS. However both methods permitted one to achieve the desired sensitivity for analyzing aldicarb and its metabolites in vegetables. The method developed in this work was applied to the trace determination of aldicarb and its metabolites in crop and orange extracts. (C) 2000 Elsevier B.V. B.V. All rights reserved.