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Methylation artifacts in the gas chromatography of serum extracts. Competitive suppression with trimethyl-d9 anilinium hydroxide.

In the course of the identification of drugs in body fluids by gas chromatography-mass spectrometry we have observed the appearance of N-methyl derivatives of certain compounds such as phenobarbital and diphenylhydantoin, especially in extracts of serum. With the aid of deuterium labelled phenobarbital it could, however, be shown that the N-methyl derivatives are not endogenous metabolites but artifacts generated upon injection of the serum extract into the gas chromatograph. Conversely, derivatization with trimethyl-d9 anilinium hydroxide (TMAH-d9) demonstrated the absence of any undeuterated methyl derivative and this reagent should be useful for the detection of endogenous N-methyl derivative which would, of course, remain undetected when using unlabelled TMAH in the course of the conventional methylation technique. There are good indications that lecithin is the methylating agent in serum responsible for the formation of these artifacts.

Aniline Compounds↗

Production of mutagenic artifacts by the action of residual chlorine on XAD-4 resin.

XAD resins are commonly used to recover and concentrate organics from chlorinated water. It was found that the action of residual chlorine on XAD-4 resin produced mutagenic artifacts in a dose dependent manner. The production of mutagenic artifacts could be suppressed at least ten-fold by converting free chlorine to monochloramine. Kinetic studies of the reaction between free chlorine and XAD-4 resin showed a reaction rate dependence upon pH and chloride ion concentration that suggests participation of species besides hypochlorous acid.

Chemical Phenomena↗

[Positron-emission tomography/computed tomography: artifacts and pitfalls in cancer patients].

Diagnostic accuracy and correct initial staging (or restaging) are fundamental in the management of oncological patients and can directly influence therapeutic decisions. The combination of positron-emission tomography (PET) and computed tomography (CT) in a single scanner (PET/TC) represents an important achievement in the fields of oncology, nuclear medicine, and radiology. These scanners allow morphologic images (obtained by CT) to be fused and correlated with metabolic images (obtained by PET) to a high degree of accuracy. In addition to an understanding of the physiopathology of cancer and the behavior of the different types of neoplasms, the correct interpretation of PET/CT images requires in-depth knowledge of the physiological distribution of the F-18 fluorodeoxyglucose molecule (FDG, currently the most widely used marker in oncology), of the frequent physiological variations in its distribution, and of the possible causes of non-malignant pathological FDG uptake. Furthermore, the use of CT data to correct attenuation and reconstruct PET images in PET/CT scanners can generate some characteristic artifacts specific to this new diagnostic tool, and these can lead to misinterpretation with potential therapeutic implications. This article reviews and illustrates some of the most common artifacts and pitfalls that can appear in PET/CT studies. The detection and correct interpretation of these findings are essential for the appropriate management of oncologic patients.

Fluorodeoxyglucose F18↗

The overshoot artifact as an aid in differentiating low densities on the computed tomographic scan.

This brief report describes an artifact that is seen as a thin, white rim outlining an air collection on the EMI 80 X 80 and 160 X 160 matrix CT scanners. This artifact is not associated with fat density and, therefore, its recognition allows presumptive differentiation between air and fat densities. The attenuation numbers of the lesion should then be obtained for confirmation.

Adipose Tissue↗

Lange's folds: a meaningful ocular artifact.

Lange's fold is a postmortem artifact seen in enucleated eyes of infants and young humans. We also demonstrate its presence in young monkey eyes obtained at autopsy, but did not find it in the eyes of fetal monkeys removed by cesarean section and immediately preserved by freezing. The artifact is thought to occur in autopsy eyes due to the vitreous base and posterior lens zonules exerting traction upon the periphery of the retina. In the eyes of older humans the peripheral retina is firmly bound down to the subjacent retinal pigment epithelium following the loss of peripheral photoreceptors, and thus, Lange's fold cannot develop. Peripheral cystoid retinal degeneration was also noted in early infancy, became more prevalent with age, and was almost always noted by age 8 years.

Adolescent↗

Different neural systems for recognizing plants, animals, and artifacts.

The purpose of this study was to investigate functional organization in the human brain involved in the representation of knowledge regarding plants. We measured the brain activity of eight male volunteers during the recognition of visual stimuli representing plants, animals and artifacts, using positron emission tomography. The participants were presented with and were required to name silently two different images each of 15 entities belonging to three ontological categories, and 30 series of four to six digits. Marked increases in regional cerebral blood flow were found in the hippocampus and the parahippocampal areas bilaterally and the right lateral occipital cortex during the silent naming of all three categories, compared with that during the silent reading of digits. The right lateral occipital cortex was specifically activated in association with the naming of plants, and the right fusiform cortex was specifically activated in association with the naming of animals. In addition, the right temporo-occipital cortex was activated only during animals and plants, not artifacts. Our results indicate that there were a few characteristic activations for the different categories, and that entities belonging to the different categories are not necessarily represented in different locations of the brain.

Cerebral Cortex↗

Overview of testing methods used in inhalation toxicity: from facts to artifacts.

For smaller rodent species, homogenous in size and growth, small head or nose-only chambers are commonly used up to subchronic exposure durations, whereas larger whole-body exposure chambers are used for long-term exposures or exposure paradigms exceeding the normal working day. The advantages and disadvantages of each different technique have already been identified and published in detail. It is often believed best that whole-body inhalation chambers simulate potential human exposure to environmental chemicals or pesticides and this serves as a justification for preferring this mode of exposure. However, real-life exposure conditions of humans cannot be readily duplicated. A comparable mode of exposure may be employed rather than duplicating both the exposure regimens and atmospheres similar to those present in real-world settings. Especially in inhalation studies with complex mixtures, in which atmosphere generation is difficult to control, non-homogenous exposure atmospheres and artifacts are more likely to occur in larger whole-body chambers than in the smaller nose-only inhalation chambers. Inhalation studies with complex mixtures not only face all the challenges of traditional inhalation toxicity testing, but also they are frequently subject to artifacts not readily detected. Thus, a disproportionation of volatile and particulate constituents might occur in inhalation chambers depend on selected technical features, i.e., whether a dynamic or (quasi)static mode of exposure is chosen. Inappropriate timing of the sampling of biological specimens may lead to the underestimation of effects, especially in whole-body exposed animals.

Administration, Inhalation↗

Formation of cyclic enol ethers from a labile biological precursor: an example of analytical artifacts.

Three isomeric enol ethers are among those constituents apparently unique to mouse urine as identified by gas chromatographic analysis. These compounds appear to be artifacts arising from the cyclization and dehydration of 6-hydroxy-6-methyl-3-heptanone. Identification of the trimethylsilyl ether of 6-hydroxy-6-methyl-3-heptanone in the silylated ether extract of mouse urine indicates that the precursor keto alcohol is indeed present in the urine. Since similar heterocyclic compounds are often identified in urine samples analyzed by gas chromatography, formation of various analysis artifacts arising from analogous cyclization and dehydration reactions is likely.

Animals↗

Bias and artifacts in multitemplate polymerase chain reactions (PCR).

Polymerase chain reaction (PCR) is often used for the amplification of a mixture of homologous genes. PCR bias and artifact formation can occur in multitemplate PCR, and provide incorrect information on the abundance and diversity of genes. PCR bias and artifact formation occur at a higher rate during the last few cycles of the reaction, and therefore can be avoided by stopping the PCR earlier.

Journal Article↗

Structure elucidation of an artifact discharging from rubber-based vial closures by means of gas chromatography/tandem mass spectrometry.

The use of vial closures equipped with butyl rubber septa may lead to sample contamination by rubber additives discharging from the septum material. In this study, the structure elucidation of an artifact causing intense signals in gas chromatography/electron capture negative ion mass spectrometry (GC/ECNI-MS) and gas chromatographic analyses with electron capture detection is described. Tentative identification of the leached compound was achieved by employing tandem mass spectrometric techniques both in electron capture negative ion and in electron ionization modes. The artifact could thus be characterized as 2-benzothiazolyl-N,N-dimethyl dithiocarbamate, which is a known vulcanization accelerator for rubber. It is conceivable that the identified compound or related substances are also used in other applications. Therefore, two food-related matrixes were investigated for a possible migration of this compound into foods. During these analyses, the tentatively identified rubber additive was detected in an aqueous extract of a rubber seal ring for canning jars. GC/ECNI-MS provided better sensitivity and selectivity than GC/EI-MS for the determination of the rubber additive and other mercaptobenzothiazole-derived substances.

Chromatography, Gas↗

Resonance Raman and Fourier transform infrared spectroscopic studies of the acyl carbonyl group in [3-(5-methyl-2-thienyl)acryloyl]chymotrypsin: evidence for artifacts in the spectra obtained by both techniques.

The acyl carbonyl group of [3-(5-methyl-2-thienyl)acryloyl]chymotrypsin (5MeTA-chymotrypsin) has been investigated by using both resonance Raman (RR) and Fourier transform infrared (FTIR) spectroscopies. The spectrum of the acyl-enzyme carbonyl group has been obtained as a function of pH over the range 3.0-10.0 in the RR experiments and over the range 3.4-7.6 (p2H) in the FTIR experiments. The carbonyl spectral profiles obtained by using FTIR spectroscopy are substantially different from the carbonyl profiles obtained by using RR spectroscopy. The FTIR spectra were obtained by subtracting the spectrum of the free enzyme from that of the acyl-enzyme. Use of the active-site inhibitor phenylmethanesulfonyl fluoride demonstrates that part of the intensity observed in the FTIR spectra of 5MeTA-chymotrypsin is due to a subtraction artifact giving rise to enzyme-associated bands, probably from peptide groups perturbed by substrate binding. The enzyme bands can be removed by subtracting the FTIR spectrum of 13C=O acyl-enzyme from that of 12C=O acyl-enzyme. Additionally, this procedure reveals that one of the acyl-enzyme carbonyl bands observed at 1727 cm-1 using RR spectroscopy is absent in the FTIR acyl-enzyme spectrum. However, a feature near 1720 cm-1 can be induced in the FTIR spectrum by actinic light in the near-UV region. Thus, it is proposed that the 1727 cm-1 RR carbonyl band results from a population of acyl-enzymes which is generated by exposure to the laser beam during RR data collection. When both the RR and FTIR data are adjusted to remove artifacts, they provide essentially identical carbonyl stretching profiles.

Binding Sites↗

Atmospheric size distribution of PAHs: evidence of a high-volume sampling artifact.

The purpose of this study was to characterize atmospheric levels of four- to six-ring polycyclic aromatic hydrocarbons (PAHs) in the vicinity of a horizontal stud Söderberg aluminum smelter in terms of the size distribution of particulate matter (September to December 2002). It was found that the vast majority of the PAHs was associated with particle diameters less than 1 and 3 microm. A profile comparison of the PAH mixture--using benzo[a]pyrene (B[a]P) relative abundance ratios (PAH/B[a]P)--for the cascade impactor filters indicated the formation of a sampling artifact. Overall, the PAH stability scale generated in this study agrees with those produced experimentally for ozone and nitrogen dioxides or developed using other in situ measurement techniques. Correlations of the four- to six-ring PAHs with other atmospheric variables suggested that smelter plume conditions and particle characteristics may play a potentially important role in the overall PAH reactivity. To our knowledge, this is the first study to report a sampling artifact for the four- to six-ring PAHs during in situ high volume sampling under real world conditions.

Air Pollutants↗

Isolation and unambiguous synthesis of cryptolepinone: An oxidation artifact of cryptolepine

Cryptolepinone (3) was isolated as an artifact of extraction from Cryptolepis sanguinolenta. Previously, this compound had been identified as the natural products hydroxycryptolepine (2) and 3. Synthesis via an unambiguous pathway has confirmed the structure of cryptolepinone. Spectroscopic studies in various solvents have shown that the natural product artifact or its synthetic equivalent can exist in the keto (cryptolepinone) or enol (hydroxycryptolepine) form.

Journal Article↗

Fluorescence correlation spectroscopy for flow rate imaging and monitoring--optimization, limitations and artifacts.

We recently demonstrated a new method for mapping fluid velocities in 3 dimensions and with exceptionally high spatial resolution for the characterization of flow in microfluidic devices. In the method, a colloidal suspension containing fluorescent tracer particles, dye doped polymer spheres, is pumped through a microchannel and confocal microscopy combined with fluorescence correlation spectroscopy is used to measure fluid velocities. In this report, we further characterize the technique and report on optimizations that allow a 5-fold increase in speed of single point velocity measurements. This increase in measurement speed will yield a 25 fold reduction in the time needed to collect a complete velocity image. The precision of measured velocities was characterized as a function of tracer particle concentration, measurement time, and fluid velocity. In addition, we confirm the linearity of the measurement method (velocity vs. applied pressure) over a range of velocities spanning four orders of magnitude. Furthermore, we demonstrate that an artifact in velocity measurements using fluorescence correlation spectroscopy (FCS) that was interpreted by others as being caused by optical trapping forces is actually an artifact caused by detector saturation and can be avoided by careful choice of experimental conditions.

Journal Article↗

[Sonographic artifacts of round reflectors].

The appearance of the proximal curved edge artifact using linear-array systems is demonstrated in five cases. Furthermore simulation of this artifact was achieved in a waterbath. A physical explanation of this phenomenon is discussed.

Cholelithiasis↗

[Risks and artifacts in MRT (1.5 tesla) caused by metallic foreign bodies. Studies on phantoms and 60 patients].

Our experience of the effects of metallic foreign bodies on MRT high field examinations is described. In vitro measurements showed moderate magnetic torsion or displacement in a few cases. The findings in 60 patients with various metal foreign bodies and the resulting artifacts are discussed. Despite local loss of information, in the majority of cases there is additional evidence provided by MRT, which suffers less from foreign body artifacts than does CT. Stainless steel implants result in some signal loss and geometric distortion, but do not usually constitute a danger to the patient and do not affect the diagnostic information from surrounding structures.

Foreign Bodies↗

Sources of artifacts in rotational scanography.

The images produced in rotational scanography, currently under investigation at several institutions, may contain several kinds of artifacts. The sources of such artifacts are: 1. vertical and horizontal misalignment of the focal spot with the axis of rotation; 2 misalignment of the primary and secondary slits; 3 a density gradient due to slit cut-off; 4 vibration of the x-ray tube during rotation; 5. A density gradient due to variation in motor speed; 6. radiographic striations due to ripple of the tube output. Striations are present even if a 12-pulse generator is used, but they disappear if a constant potential generator is employed.

Humans↗

Dual-task results and the lateralization of spatial orientation: artifact of test selection?

An investigation was conducted to identify the degree to which results regarding the lateralization of spatial orientation among men and women are artifacts of test selection. A dual-task design was used to study possible lateralization differences, providing baseline and dual-task measures of spatial-orientation performance, right- and left-hand tapping, and vocalization of "cat, dog, horse." The Guilford-Zimmerman Test (Guilford & Zimmerman, 1953), the Eliot-Price Test (Eliot & Price, 1976), and the Stumpf-Fay Cube Perspectives Test (Stumpf & Fay, 1983) were the three spatial-orientation tests used to investigate possible artifacts of test selection. Twenty-eight right-handed male and 39 right-handed female undergraduates completed random baseline and dual-task sessions. Analyses indicated no significant sex-related differences in spatial-orientation ability for all three tests. Furthermore, there was no evidence of differential lateralization of spatial orientation between the sexes.

Adult↗