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.

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.

Observational study on efficacy of negative expiratory pressure test proposed as screening for obstructive sleep apnea syndrome among commercial interstate bus drivers - protocol study

Background: Obstructive sleep apnea (OSA) is a respiratory disease characterized by the collapse of the extrathoracic airway and has important social implications related to accidents and cardiovascular risk. The main objective of the present study was to investigate whether the drop in expiratory flow and the volume expired in 0.2 s during the application of negative expiratory pressure (NEP) are associated with the presence and severity of OSA in a population of professional interstate bus drivers who travel medium and long distances.Methods/Design: An observational, analytic study will be carried out involving adult male subjects of an interstate bus company. Those who agree to participate will undergo a detailed patient history, physical examination involving determination of blood pressure, anthropometric data, circumference measurements (hips, waist and neck), tonsils and Mallampati index. Moreover, specific questionnaires addressing sleep apnea and excessive daytime sleepiness will be administered. Data acquisition will be completely anonymous. Following the medical examination, the participants will perform a spirometry, NEP test and standard overnight polysomnography. The NEP test is performed through the administration of negative pressure at the mouth during expiration. This is a practical test performed while awake and requires little cooperation from the subject. In the absence of expiratory flow limitation, the increase in the pressure gradient between the alveoli and open upper airway caused by NEP results in an increase in expiratory flow.Discussion: Despite the abundance of scientific evidence, OSA is still underdiagnosed in the general population. In addition, diagnostic procedures are expensive, and predictive criteria are still unsatisfactory. Because increased upper airway collapsibility is one of the main determinants of OSA, the response to the application of NEP could be a predictor of this disorder. With the enrollment of this study protocol, the expectation is to encounter predictive NEP values for different degrees of OSA in order to contribute toward an early diagnosis of this condition and reduce its impact and complications among commercial interstate bus drivers.

The correlation between subordinate fish eye colour and received attacks: a negative social feedback mechanism for the reduction of aggression during the formation of dominance hierarchies

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Field-theory Two-point Functions via Negative Dimension Integration

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Negative dimensional integration: Lab testing at two loops

Negative dimensional integration method (NDIM) is a technique to deal with D-dimensional Feynman loop integrals. Since most of the physical quantities in perturbative Quantum Field Theory (pQFT) require the ability of solving them, the quicker and easier the method to evaluate them the better. The NDIM is a novel and promising technique, ipso facto requiring that we put it to test in different contexts and situations and compare the results it yields with those that we already know by other well-established methods. It is in this perspective that we consider here the calculation of an on-shell two-loop three point function in a massless theory. Surprisingly this approach provides twelve non-trivial results in terms of double power series. More astonishing than this is the fact that we can show these twelve solutions to be different representations for the same well-known single result obtained via other methods. It really comes to us as a surprise that the solution for the particular integral we are dealing with is twelvefold degenerate.

Probing negative-dimensional integration: Two-loop covariant vertex and one-loop light-cone integrals

The negative-dimensional integration method (NDIM) seems to be a very promising technique for evaluating massless and/or massive Feynman diagrams. It is unique in the sense that the method gives solutions in different regions of external momenta simultaneously. Moreover, it is a technique whereby the difficulties associated with performing parametric integrals in the standard approach are transferred to a simpler solving of a system of linear algebraic equations, thanks to the polynomial character of the relevant integrands. We employ this method to evaluate a scalar integral for a massless two-loop three-point vertex with all the external legs off-shell, and consider several special cases for it, yielding results, even for distinct simpler diagrams. We also consider the possibility of NDIM in non-covariant gauges such as the light-cone gauge and do some illustrative calculations, showing that for one-degree violation of covariance (i.e. one external, gauge-breaking, light-like vector n μ) the ensuing results are concordant with the ones obtained via either the usual dimensional regularization technique, or the use of the principal value prescription for the gauge-dependent pole, while for two-degree violation of covariance - i.e. two external, light-like vectors n μ, the gauge-breaking one, and (its dual) n * μ - the ensuing results are concordant with the ones obtained via causal constraints or the use of the so-called generalized Mandelstam-Leibbrandt prescription. © 1999 Elsevier Science B.V.

Birth of a closed universe of negative spatial curvature

We propose a modified form of the spontaneous birth of the universe by quantum tunneling. It proceeds through topology change and inflation, to eventually become a universe with closed spatial sections of negative spatial curvature and nontrivial global topology.

Feynman integrals with tensorial structure in the negative dimensional integration scheme

The negative-dimensional integration method (NDIM) is revealing itself as a very useful technique for computing massless and/or massive Feynman integrals, covariant and noncovanant alike. Up until now however, the illustrative calculations done using such method have been mostly covariant scalar integrals/without numerator factors. We show here how those integrals with tensorial structures also can be handled straightforwardly and easily. However, contrary to the absence of significant features in the usual approach, here the NDIM also allows us to come across surprising unsuspected bonuses. Toward this end, we present two alternative ways of working out the integrals and illustrate them by taking the easiest Feynman integrals in this category that emerge in the computation of a standard one-loop self-energy diagram. One of the novel and heretofore unsuspected bonuses is that there are degeneracies in the way one can express the final result for the referred Feynman integral.

Esthetic influence of negative space in the buccal corridor during smiling

The purpose of this study was to measure and verify the esthetic influence of the bilateral spaces between maxillary teeth and lip corners, called negative space (NS), during smile. The sample was comprised of 60 smile photographs obtained from 60 individuals (30 men and 30 women) aged 18 to 25 years old. Two orthodontists and two lay people evaluated these pictures regarding esthetics by a visual analogue scale. In each picture, the right and left NS were measured in millimeters and in proportion to the smile width (SW). Data were analyzed for statistical significance (P = .05). The mean NS of the sample was 6.68 ± 1.99 mm, and the NS proportion in relation to the SW was 9.6 ± 2.56%, for both sides of the arch. No significant asymmetries were observed between the right and left sides. The NS was significantly larger in men than in women when measured in millimeters (P = .028) (7.08 ± 2.24 mm in men vs 6.28 ± 1.62 mm in women), but the NS proportion to the SW was similar (9.94 ± 2.24% in men vs 9.26 ± 1.61% in women). When the 12 individuals with the smallest NS in proportion to SW were compared with the 12 individuals with the largest NS in proportion to SW, there was no statistical difference regarding the esthetic evaluation (P = .11). It was concluded that the NS did not influence the esthetic evaluation of smile photographs in the sample in this study, for both orthodontists and lay people. © 2006 by The EH Angle Education and Research Foundation, Inc.

Evaluating residues and integrals through negative dimensional integration method (NDIM)

The standard way of evaluating residues and some real integrals through the residue theorem (Cauchy's theorem) is well-known and widely applied in many branches of Physics. Herein we present an alternative technique based on the negative dimensional integration method (NDIM) originally developed to handle Feynman integrals. The advantage of this new technique is that we need only to apply Gaussian integration and solve systems of linear algebraic equations, with no need to determine the poles themselves or their residues, as well as obtaining a whole class of results for differing orders of poles simultaneously.

Risk of peritonitis during peritoneal dialysis in carriers of Staphylococcus aureus and coagulase-negative staphylococci

The presence of Staphylococcus aureus in the nasal cavities and pericatheter skin of peritoneal dialysis patients put them at high risk of developing peritonitis. However, it is not clear whether the presence of coagulase-negative staphylococci (CNS) in the nasal passages and skin of patients is related to subsequent occurrence of peritoneal infection. The aim of the present study was to verify the relationship between endogenous sources of S. aureus and CNS and occurrence of peritonitis in patients undergoing peritoneal dialysis. Thirty-two patients on peritoneal hemodialysis were observed for 18 months. Staphylococcus species present in their nasal passage, pericatheter skin and peritoneal effluent were identified and compared based on drug susceptibility tests and dendrograms, which were drawn to better visualize the similarity among strains from extraperitoneal sites as well as their involvement in the causes of infection. Out of 288 Staphylococcus strains isolated, 155 (53.8%) were detected in the nasal cavity, 122 (42.4%) on the skin, and 11 (3.8%) in the peritoneal effluent of patients who developed peritonitis during the study. The most frequent Staphylococcus species were CNS (78.1%), compared with S. aureus (21.9%). Among CNS, S. epidermidis was predominant (64.4%), followed by S. warneri (15.1%), S. haemolyticus (10.7%), and other species (9.8%). Seven (64%) out of 11 cases of peritonitis analyzed presented similar strains. The same strain was isolated from different sites in two (66%) out of three S. aureus infection cases. In the six cases of S. epidermidis peritonitis, the species that caused infection was also found in the normal flora. From these, two cases (33%) presented highly similar strains and in three cases (50%), it was difficult to group strains as to similarity. Patients colonized with multidrug-resistant S. epidermidis strains were more predisposed to infection. Results demonstrated that an endogenous source of S. epidermidis could cause peritonitis in peritoneal dialysis patients, similarly to what has been observed with S. aureus.