Electron impact and chemical ionization mass spectral analyses of methyl esters species of free mycolic acid fraction from Rhodococcus lentifragmentus

The free mycolic acid fraction from Rhodococcus lentifragmentus was derivatized to methyl esters and further fractionated into saturated (F-0), monounsaturated (F-1) and diunsaturated (F-2) species using argentation-TLC. Methyl esters fractions F-0, F-1 and F-2, accounting for approximately 7.4%, 53.1% and 39.5%, respectively, were analyzed by electron impact (EI) and chemical ionization (CI) mass spectrometries. According to EI-MS, peaks observed for M(+)-18, that were prominent compared to those representing M(+)-32 and M(+)-(18 + 32), indicated that the carbon chain size ranged from C-36 to C-48. The pyrolytic cleavage of methyl mycolates (R(2)-CHOH-CH(R(1))-COOCH3), following the McLafferty rearrangement released fragment ions corresponding to, (a) the alpha-subunit, representing the fatty acid methyl ester (R(1)-CH2-COOCH3), methyl hexadecanoate, methyl tetradecanoate and methyl dodecanoate in decreasing order of relative intensity of peaks, and (b) the beta-subunit, representing the meroaldehyde moiety (R(2)-CHO). The saturated meroaldehyde species exhibited peaks representing meroaldehyde minus 18 mass units in which R(2) ranged from C19H39 to C31H63. The monunsaturated species exhibited peaks representing the meroaldehyde in which R(2) ranged from C19H37 to C31H61; peaks corresponding to meroaldehyde minus 18 mass units appeared only in the most abundant components, C29H57CHO, C27H53CHO, C25H49CHO and C31H61CHO, in a decreasing order of relative abundance. The diunsaturated species exhibited peaks essentially corresponding to meroaldehyde in which R(2) corresponded to C31H59 and C29H55; the latter displayed a relative intensity that was about one-half compared to that of the former. Fractions F-0, F-1 and F-2 showed a more intense pyrolytic fragmentation under CI-MS in contrast to results found under EI-MS. Therefore, peaks representing the alpha-subunit and the beta-subunit were more prominent than the ones representing the fragmentation of the hydrocarbon chain. Moreover, the beta-subunit of saturated species exhibited peaks corresponding to meroaldehyde plus hydrogen, and no dehydration of the beta-subunit occurred in this case. In turn, the beta-subunit of monounsaturated and diunsaturated species showed peaks representing both the meroaldehyde plus hydrogen and its dehydration product plus hydrogen. Thus, the presence of unsaturation in the meroaldehyde subunit of methyl mycolate facilitates appearance of dehydration fragment ions under chemical ionization procedure.

Residues of organochlorine pesticides and PCBs in some Brazilian municipal solid waste compost

Persistent organic pollutants (POPs), organochlorine pesticides and polychlorinated biphenyls (PCBs), listed as per the Stockholm Convention (α -HCH, β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, p,p′-DDE, aldrin, endrin, dieldrin, PCBs 28, 52, 118, 138, 153, and 180), were analyzed in municipal solid waste (MSW) compost samples from three different Brazilian composting plants located in three São Paulo State cities: Araras, Araraquara and São Paulo (Vila Leopoldinha). Quantitative and qualitative analyses were carried out using gas chromatography electron capture detection (GC-ECD) and gas chromatography mass spectrometry (GC-MS) (Ion Trap, electron impact ionization), respectively. The samples were analyzed in triplicate and the target POPs were not detected by GC-ECD. Twelve pollutants were identified in two samples when qualitative analysis (GC-MS) was used (β -HCH, γ -HCH, p,p′-DDT, o,p′-DDT, p,p′-DDD, and p,p′-DDE, PCBs 28, 118, 138, 153 and 180). The composting process has advantages such as urban solid waste reduction and landfill life-span increase, however the MSW compost quality, which can be utilized for agricultural purposes, should be evaluated and be controlled. This kind of study is the first step in making available information to answer questions regarding MSW compost for sustainable agricultural use, such as the pollutants accumulation in soil and in groundwater, and plants uptake. Copyright © Taylor & Francis Group, LLC.

Characterization of Si : O : C : H films fabricated using electron emission enhanced chemical vapour deposition

Silicon-based polymers and oxides may be formed when vapours of oxygen-containing organosilicone compounds are exposed to energetic electrons drawn from a hot filament by a bias potential applied to a second electrode in a controlled atmosphere in a vacuum chamber. As little deposition occurs in the absence of the bias potential, electron impact fragmentation is the key mechanism in film fabrication using electron-emission enhanced chemical vapour deposition (EEECVD). The feasibility of depositing amorphous hydrogenated carbon films also containing silicon from plasmas of tetramethylsilane or hexamethyldisiloxane has already been shown. In this work, we report the deposition of diverse films from plasmas of tetraethoxysilane (TEOS)-argon mixtures and the characterization of the materials obtained. The effects of changes in the substrate holder bias (Vs) and of the proportion of TEOS in the mixture (XT) on the chemical structure of the films are examined by infrared-reflection absorption spectroscopy (IRRAS) at near-normal and oblique incidence using unpolarised and p-polarised, light, respectively. The latter is particularly useful in detecting vibrational modes not observed when using conventional near-normal incidence. Elemental analyses of the film were carried out by X-ray photoelectron spectroscopy (XPS), which was also useful in complementary structural investigations. In addition, the dependencies of the deposition rate on Vs and XT are presented. (c) 2007 Elsevier B.V. All rights reserved.

Multiresidue determination of pesticides in honey samples by gas chromatography-mass spectrometry and application in environmental contamination

A simple and fast multiresidue method has been developed to determine 48 pesticides within the major groups of pesticides (organohalogen, organophosphorous, pyrethroids and organonitrogen) in representative samples of locally produced honey, in Bauru (State of São Paulo, Brazil) during 2003-2004. The recovery results found ranged from 76% to 95% and the limits of detection were lower than 0.01 mg/kg for gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode (GC-MS-SIM). The results indicated that most pesticides found in the samples belonged to the organohalogen and organophosphorous groups and lower levels of residues of some organonitrogen and pyretroids were also detected. Malathion residues were detected in all the samples, in a high concentration, owing to its applications to control dengue mosquitoes in the area studied. (c) 2005 Elsevier Ltd. All rights reserved.

Light and thermal excitation of depolarization current in indirect bandgap Alx Ga1-xAs

Monochromatic light excitation in conjunction with thermally stimulated depolarization current measurements are applied to indirect bandgap AlxGa1-xAs. The obtained average activation energy for dipole relaxation is in very close agreement with the DX center binding energy. Monochromatic light induces state transition in the defect and makes possible the identification of dipoles observed in the dark. Charge relaxation currents are destroyed by photoionization of Al0.5Ga0.5As using either 647 nm Kr+ or 488 nm Ar+ laser lines, which are above the DX center threshold photoionization energy. It suggests that correlation may exist among charged donor states DX--d+. Sample resistance as a function of temperature is also measured in the dark and under illumination and shows the probable X valley effective mass state participation in the electron trapping. Ionization with energies of 0.8 eV and 1.24 eV leads to striking current peak shifts in the thermally stimulated depolarization bands. Since vacancies are present in this material, they may be responsible for the secondary band observed in the dark as well as participation in the light induced recombination process.

Positronium impact excitation of hydrogen molecule to B-1 Sigma(+)(u) and b(3)Sigma(+)(u) states

Calculation for the electronic excitation of the ground state of H-2 to B (1) Sigma(u)(+) and b(3) Sigma(u)(+) states by positronium- (Ps) atom impact has been carried out using the first Born approximation considering discrete Ps excitations up to n = 6 and Ps ionization in the final state. To include the effect of electron exchange, we propose an alternative approximation scheme in the light of the Rudge approach, which takes into account the composite nature of the Ps-atom projectile.

Effect of electron exchange in positronium-hydrogen scattering

The elastic and inelastic scattering of ortho-positronium (Ps) by the hydrogen atom have been investigated using a three-Ps-state close-coupling approximation. The higher (n greater than or equal to 3) excitations and ionization of the Ps atom are treated within the framework of the Born approximation. In both cases the effect of electron exchange has been included by a parameter-free nonlocal model potential derived from an antisymmetrization of the wavefunction followed by the removal of nonorthogonality. Calculations are reported of scattering lengths,phase shifts, and of elastic, Ps excitation, and total cross sections. The trend of present target elastic total cross section agrees qualitatively with available experimental results on Ps-impact scattering.

Search for displaced supersymmetry in events with an electron and a muon with large impact parameters

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of electron magnetic trapping in a plasma immersion ion implantation system

In this work we describe a two-dimensional computer simulation of magnetic field enhanced plasma immersion implantation system. Negative bias voltage of 10.0 kV is applied to a cylindrical target located on the axis of a grounded vacuum chamber filled with uniform nitrogen plasma. A pair of external coils creates a static magnetic field with main vector component along the axial direction. Thus, a system of crossed ExB field is generated inside the vessel forcing plasma electrons to rotate in azimuthal direction. In addition, the axial variation of the magnetic field intensity produces magnetic mirror effect that enables axial particle confinement. It is found that high-density plasma regions are formed around the target due to intense background gas ionization by the trapped electrons. Effect of the magnetic field on the sheath dynamics and the implantation current density of the PIII system is investigated. By changing the magnetic field axial profile (varying coils separation) an enhancement of about 30% of the retained dose can be achieved. The results of the simulation show that the magnetic mirror configuration brings additional benefits to the PIII process, permitting more precise control of the implanted dose.

Electron exchange model potential: Application to positronium helium scattering

The formulation of a suitable nonlocal model potential for electron exchange is presented, checked with electron-hydrogen and electron-helium scattering, and applied to the study of elastic and inelastic scattering and ionization of orthopositronium (Ps) by helium. The elastic scattering and the n=2 excitations of Ps are investigated using a three-Ps-state close-coupling approximation. The higher (n greater than or equal to 3) excitations and ionization of Ps atoms are treated in the framework of the Born approximation with present exchange. Calculations are reported of phase shifts and elastic, Ps excitation, and total cross sections. The present target elastic total cross section agrees well with experimental results at thermal to medium energies. [S1050-2947(99)04201-8].

Conformational basis for the biological activity of TOAC-labeled angiotensin II and bradykinin: Electron paramagnetic resonance, circular dichroism, and fluorescence studies

N-Terminally and internally labeled analogues of the hormones angiotensin (AII, DRVYIHPF) and bradykinin (BK, RPPGFSPFR) were synthesized containing the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amino-4- carboxylic acid (TOAC). TOAC replaced Asp 1 (TOAC 1-AII) and Val 3 (TOAC 3-AII) in AII and was inserted prior to Arg 1 (TOAC 0-BK) and replacing Pro 3 (TOAC 3-BK) in BK. The peptide conformational properties were examined as a function of trifluoroethanol (TFE) content and pH. Electron paramagnetic resonance spectra were sensitive to both variables and showed that internally labeled analogues yielded rotational correlation times (TC) considerably larger than N-terminally labeled ones, evincing the greater freedom of motion of the N-terminus. In TFE, τ C increased due to viscosity effects. Calculation of τ Cpeptide/τ CTOAC ratios indicated that the peptides acquired more folded conformations. Circular dichroism spectra showed that, except for TOAC 1-AII in TFE, the N-terminally labeled analogues displayed a conformational behavior similar to that of the parent peptides. In contrast, under all conditions, the TOAC 3 derivatives acquired more restricted conformations. Fluorescence spectra of All and its derivatives were especially sensitive to the ionization of Tyr 4. Fluorescence quenching by the nitroxide moiety was much more pronounced for TOAC 3-AII The conformational behavior of the TOAC derivatives bears excellent correlation with their biological activity, since, while the N-terminally labeled peptides were partially active, their internally labeled counterparts were inactive [Nakaie, C. R., et al., Peptides 2002, 23, 65-70]. The data demonstrate that insertion of TOAC in the middle of the peptide chain induces conformational restrictions that lead to loss of backbone flexibility, not allowing the peptides to acquire their receptor-bound conformation. © 2004 Wiley Periodicals, Inc.

Two dimensional computer simulation of plasma immersion ion implantation

The biggest advantage of plasma immersion ion implantation (PIII) is the capability of treating objects with irregular geometry without complex manipulation of the target holder. The effectiveness of this approach relies on the uniformity of the incident ion dose. Unfortunately, perfect dose uniformity is usually difficult to achieve when treating samples of complex shape. The problems arise from the non-uniform plasma density and expansion of plasma sheath. A particle-in-cell computer simulation is used to study the time-dependent evolution of the plasma sheath surrounding two-dimensional objects during process of plasma immersion ion implantation. Before starting the implantation phase, steady-state nitrogen plasma is established inside the simulation volume by using ionization of gas precursor with primary electrons. The plasma self-consistently evolves to a non-uniform density distribution, which is used as initial density distribution for the implantation phase. As a result, we can obtain a more realistic description of the plasma sheath expansion and dynamics. Ion current density on the target, average impact energy, and trajectories of the implanted ions were calculated for three geometrical shapes. Large deviations from the uniform dose distribution have been observed for targets with irregular shapes. In addition, effect of secondary electron emission has been included in our simulation and no qualitative modifications to the sheath dynamics have been noticed. However, the energetic secondary electrons change drastically the plasma net balance and also pose significant X-ray hazard. Finally, an axial magnetic field has been added to the calculations and the possibility for magnetic insulation of secondary electrons has been proven.

Effects of copper vapor laser radiation on the root canal wall of human teeth: A scanning electron microscope study

Objective: The aim of this study is to analyze the effects of copper vapor laser radiation on the radicular wall of human teeth. Materials and Methods: Immediately after the crowns of 10 human uniradicular teeth were cut along the cement-enamel junction, a chemical-surgical preparation of the radicular canals was completed. Then the roots were longitudinally sectioned to allow for irradiation of the surfaces of the dentin walls of the root canals. The hemi-roots were separated into two groups: one (control) with five hemi-roots that were not irradiated, and another (experimental) with 15 hemi-roots divided into three subgroups that were submitted to the following exposure times: 0.02,0.05, and 0.1 s. A copper vapor laser (510.6 nm) with a total average power of 6.5 W in green emission, frequency of 16.000 Hz, and pulse duration of 30 ns was used. Results: The results obtained by scanning electron microscope analysis showed the appearance of a cavity in the region of laser beam impact, with melting, recrystallization, and cracking on the edges of the dentin of the cavity due to heat diffusion. Conclusions: We determined that the copper vapor laser produces significant morphologic changes in the radicular wall of human teeth when using the parameters in this study. However, further research should be done to establish parameters that are compatible with dental structure in order to eliminate thermal damages. © Mary Ann Liebert, Inc.

The impact of hydrofluoric acid etching followed by unfilled resin on the biaxial strength of a glass-ceramic

Objectives: To evaluate the null hypotheses that hydrofluoric (HF) acid etching time would neither decrease the biaxial flexural strength of a glass-based veneering ceramic nor enhance it after silane and unfilled resin (UR) applications. Methods: Disc-shaped IPS e.max ZirPress specimens were allocated into 12 groups: G1-control (no-etching), G2-30 s, G3-60 s, G4-90 s, G5-120 s, G6-60 s + 60 s. Groups (G7-G12) were treated in the same fashion as G1-G6, but followed by silane and UR applications. Surface morphology and roughness (Ra and Rq) of the ceramics were assessed by means of scanning electron microscopy (SEM) and profilometry, respectively. Flexural strength was determined by biaxial testing. Data were analyzed by two-way ANOVA and the Sidak test (α = 0.05). Weibull statistics were estimated and finite element analysis (FEA) was carried out to verify the stress concentration end areas of fracture. Results: The interaction (etching time vs. surface treatment) was significant for Ra (p = 0.008) and Rq (0.0075). Resin-treated groups presented significantly lower Ra and Rq than non-treated groups, except for the 60 s group (p < 0.005). SEM revealed that etching affected the ceramic microstructure and that the UR was able to penetrate into the irregularities. A significant effect of etching time (p = 0.029) on flexural strength was seen. G7-G12 presented higher strength than G1-G6 (p < 0.0001). None of experimental groups failed to show 95% confidence intervals of σ 0 and m overlapped. FEA showed lower stress concentration after resin treatment. Significance: HF acid etching time did not show a damaging effect on the ceramic flexural strength. Moreover, the flexural strength could be enhanced after UR treatment. © 2013 Academy of Dental Materials.

Impact of fipronil on the mushroom bodies of the stingless bee Scaptotrigona postica

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