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PubMed2005

Mass spectrometric studies of the gas phase retro-Michael type fragmentation reactions of 2-hydroxybenzyl-N-pyrimidinylamine derivatives.

The gas-phase fragmentation reactions of 2-hydroxybenzyl-N-pyrimidinylamine derivatives (Compounds 1 to 6), the O-N-type acid-catalyzed Smiles rearrangement products of 2-pyrimidinyloxy-N-arylbenzylamine derivatives, have been examined via positive ion matrix-assisted laser desorption/ionization (MALDI) infrared multiphoton dissociation (IRMPD) mass spectrometry in FT-ICR MS and via negative ion electrospray ionization (ESI) in-source collision-induced dissociation (CID) mass spectrometry, respectively. The major fragmentation pathway of protonated 1 to 6 gives the F ions under IRMPD; theoretical results show that the retro-Michael reaction channel is more favorable in both thermodynamics and kinetics. This explanation is supported by H/D exchange experiments and the MS/MS experiment of acetylated 1. Deprotonated 1 to 6 give rise to the solitary E ions (aromatic nitrogen anions) in the negative ion in-source CID; theoretical calculations show that a retro-Michael mechanism is more reasonable than a gas-phase intramolecular nucleophilic displacement (SN2) mechanism to explain this reaction process.

Amines↗
PubMed2026

Unravelling bioanalytical innovations, degradation processes, and impurity landscapes of VEGFR inhibitors.

From pre-formulation studies to clinical trials, VEGFR-targeted small-molecule tyrosine kinase inhibitors (TKIs) require rigorous analytical standards. Bioanalysis, stability-indicating studies, and impurity profiling are used to examine chromatographic advances for VEGFR-targeted TKIs like sunitinib, pazopanib, axitinib, sorafenib, cabozantinib, vandetanib, apatinib, lenvatinib, nintedanib, and regorafenib. An LC-MS/MS and UPLC-MS/MS routinely show sub ng/mL performance, as shown by LLOQs (0.2 ng/mL) for sunitinib and axitinib, 1 ng/mL for pazopanib, 5-7 ng/mL for sorafenib, 0.5-1.5 ng/mL for regorafenib metabolic products, and 0.1-0.5 ng/mL for lenvatinib. These approaches are used for pharmacokinetics and therapeutic drug monitoring due to their good correlation coefficient of 0.1-10,000 ng/mL, accuracy of 95%-108%, and precision of 15% RSD. UPLC-QTOF-MS/MS distinguishes degradants and metabolites during forced degradation studies, enabling structural elucidation following ICH M7 risk evaluation protocol. HPTLC/MLC offers fast, sensitive screenings, while RP-HPLC/DAD or HPLC-UV offer reliable, cost-effective routine quality-control solutions with LOD/LOQ in the μg/mL range and linearity of 10-240 μg/mL. This review lists the structures and CAS numbers of ten VEGFR-2 TKI degradants and metabolites, as well as pharmacopeial impurities in SMILES forms. It will be useful for future method development and regulatory applications. To ensure VEGFR-targeted TKI quality, safety, and therapeutic efficacy, LC-MS/MS for trace quantification and HRMS for structure elucidation provide a robust, future-oriented framework. To improve VEGFR-targeted TKI quality, safety, and regulatory compliance, analytical development should focus on HRMS-based impurity characterization, AI-assisted degradation prediction, green chromatography, and harmonized bioanalytical validation.

Humans↗
PubMed2004

Analytical solutions for reactive transport under an infiltration-redistribution cycle.

Transport of reactive solute in unsaturated soils under an infiltration-redistribution cycle is investigated. The study is based on the model of vertical flow and transport in the unsaturated zone proposed by Indelman et al. [J. Contam. Hydrol. 32 (1998) 77], and generalizes it by accounting for linear nonequilibrium kinetics. An exact analytical solution is derived for an irreversible desorption reaction. The transport of solute obeying linear kinetics is modeled by assuming equilibrium during the redistribution stage. The model which accounts for nonequilibrium during the infiltration and assumes equilibrium at the redistribution stage is termed partial equilibrium infiltration-redistribution model (PEIRM). It allows to derive approximate closed form solutions for transport in one-dimensional homogeneous soils. These solutions are further applied to computing the field-scale concentration by adopting the Dagan and Bresler [Soil Sci. Soc. Am. J. 43 (1979) 461] column model. The effect of soil heterogeneity on the solute spread is investigated by modeling the hydraulic saturated conductivity as a random function of horizontal coordinates. The quality of the PEIRM is illustrated by calculating the critical values of the Damköhler number which provide the achievable accuracy in estimating the solute mass in the mobile phase. The distinguishing feature of transport during the infiltration-redistribution cycle as compared to that of infiltration only is the finite depth of solute penetration. For irreversible desorption, the maximum solute penetration W/theta(r) is determined by the amount of applied water W and the residual water content theta(r). For sorption-desorption kinetics, the maximum depth of penetration z(r)(e, infinity ) also depends on the ratio between the rate of application and the column-saturated conductivity. It is shown that z(r)(e, infinity ) is bounded between the depths W/(theta(r)+K(d)) and W/theta(r) corresponding to the maximum solute penetration for equilibrium transport and for irreversible desorption, respectively. This feature of solute penetration explains the unusual phenomena of plume contraction after an initial period of spreading [Lessoff, S.C., Indelman, P., Dagan, G., 2002. Solute transport in infiltration-redistribution cycles in heterogeneous soils. In Raats, P.A.C., Smiles, D.,Warrick, A.W. (Eds), Environmental Mechanics: Water, Mass and Energy Transport in the Biosphere. American Geophysical Union, pp. 133-144]. Unlike transport under equilibrium conditions, when the solute is completely concentrated at the front, the solute under nonequilibrium conditions is spread out behind the front. Heterogeneity leads to additional spreading of the plume.

Adsorption↗
PubMed2004

Categorizing facial identities, emotions, and genders: attention to high- and low-spatial frequencies by children and adults.

Three age groups of participants (5-6 years, 7-8 years, adults) matched faces on the basis of facial identity. The procedure involved either low- or high-pass filtered faces or hybrid faces composed from two faces associated with different spatial bandwidths. The comparison stimuli were unfiltered faces. In the three age groups, the data indicated a significant bias for processing of low-pass information in priority. In a second task, participants were asked to identify the emotion (smiling or grimacing) or gender (male or female) of hybrid high-pass/low-pass faces. Opposite results emerged in the two tasks irrespective of the age group; the gender discrimination task indicated a bias for low-pass information, and the emotion task indicated a bias for high-pass information. These differences suggest independent processing routes for functionally different types of information such as emotion, gender, and identity. These routes are already established by 5 years of age.

Adolescent↗
PubMed2005

Treatment options to optimize display of anterior dental esthetics in the patient with the aged lip.

PURPOSE: With aging a number of predictable changes occur in the upper and lower lips that act to mask otherwise esthetic dental procedures including dental implants, gingival esthetic surgery, and optimal dental restorations. The purpose of this article is to show how lip modification can be used to enhance the esthetic appearance of the patient, with specific attention to esthetic dental smile line characteristics. METHOD: Proper evaluation and diagnosis of senile lip changes, such as lip atrophy, loss of lip architecture, and lip lengthening lead to a reliable treatment plan that provides a more esthetic frame to view the oral aperture. Treatment options will be discussed that act to reverse these problems. Directed lip augmentation procedures are used to correct loss of lip volume and architecture. The subnasal lip lift technique is presented as a method to correct lip lengthening. Risks and limitations of these procedures are addressed. CONCLUSION: Safe and reliable methods are presented that can improve and rejuvenate the lip complex, thus allowing for optimal display of dental esthetics.

Aged↗
PubMed2006

Postural modulation induced by pictures depicting prosocial or dangerous contexts.

The ability to identify safety and danger is critical to survival. However, not much is known about human somatic body reactions in these contexts. We performed a posturographic study comparing body reactions to the sight of pictures of smiling babies and families (affiliative) versus matched neutral people, and to pictures depicting body envelope violations (mutilation) versus matched neutral people. The participants stood on a force platform and heart rate and displacement of the center of pressure were recorded while the pictures were presented. Pictures of mutilation induced a freezing-like reaction consisting of a medial-lateral (M-L) decrease in the amplitude of sway (immobility) and increase of the mean power frequency (rigidity), associated with bradycardia. Affiliative stimuli also induced an immobility and rigidity behavior but in the anterior-posterior (A-P) axis. This resembles the "immobility-without-fear reaction" proposed to occur when, upon detection of safety cues, mammals including humans are involved in pro-social activities. We conclude that the sight of visual cues of affiliation and danger produce distinct body somatic reactions.

Adolescent↗
PubMed2004

Functional imaging of face and hand imitation: towards a motor theory of empathy.

Empathy requires the ability to map the feelings of others onto our own nervous system. Until recently, there was no plausible mechanism to explain how such a mapping might occur. The discovery of mirror neurons, however, suggests that the nervous system is capable of mapping the observed actions of others onto the premotor cortex of the self, at least for reaching and grasping movements. Is there a mirroring system for emotive actions, such as facial expression? Subjects (N = 15; all right-handed; eight men, seven women) watched movies of facial expressions (smile or frown) and hand movements (move index or middle finger) while brain activity was imaged using functional magnetic resonance imaging (fMRI). Subjects watched the movies under three different conditions: passive viewing, active imitation, and an active motor control. Subjects also performed a verb generation task to functionally identify language-processing areas. We found evidence for a common cortical imitation circuit for both face and hand imitation, consisting of Broca's area, bilateral dorsal and ventral premotor areas, right superior temporal gyrus (STG), supplementary motor area, posterior temporo-occipital cortex, and cerebellar areas. For faces, passive viewing led to significant activation in the right ventral premotor area, whereas imitation produced bilateral activation. This result is consistent with evidence for right hemisphere (RH) dominance for emotional processing, and suggests that there may be a right hemisphere mirroring system that could provide a neural substrate for empathy.

Adult↗
PubMed2004

Comparison of preschool vision screening tests as administered by licensed eye care professionals in the Vision In Preschoolers Study.

PURPOSE: To compare 11 preschool vision screening tests administered by licensed eye care professionals (LEPs; optometrists and pediatric ophthalmologists). DESIGN: Multicenter, cross-sectional study. PARTICIPANTS: A sample (N = 2588) of 3- to 5-year-old children enrolled in Head Start was selected to over-represent children with vision problems. METHODS: Certified LEPs administered 11 commonly used or commercially available screening tests. Results from a standardized comprehensive eye examination were used to classify children with respect to 4 targeted conditions: amblyopia, strabismus, significant refractive error, and unexplained reduced visual acuity (VA). MAIN OUTCOME MEASURES: Sensitivity for detecting children with > or =1 targeted conditions at selected levels of specificity was the primary outcome measure. Sensitivity also was calculated for detecting conditions grouped into 3 levels of importance. RESULTS: At 90% specificity, sensitivities of noncycloplegic retinoscopy (NCR) (64%), the Retinomax Autorefractor (63%), SureSight Vision Screener (63%), and Lea Symbols test (61%) were similar. Sensitivities of the Power Refractor II (54%) and HOTV VA test (54%) were similar to each other. Sensitivities of the Random Dot E stereoacuity (42%) and Stereo Smile II (44%) tests were similar to each other and lower (P<0.0001) than the sensitivities of NCR, the 2 autorefractors, and the Lea Symbols test. The cover-uncover test had very low sensitivity (16%) but very high specificity (98%). Sensitivity for conditions considered the most important to detect was 80% to 90% for the 2 autorefractors and NCR. Central interpretations for the MTI and iScreen photoscreeners each yielded 94% specificity and 37% sensitivity. At 94% specificity, the sensitivities were significantly better for NCR, the 2 autorefractors, and the Lea Symbols VA test than for the 2 photoscreeners for detecting > or =1 targeted conditions and for detecting the most important conditions. CONCLUSIONS: Screening tests administered by LEPs vary widely in performance. With 90% specificity, the best tests detected only two thirds of children having > or =1 targeted conditions, but nearly 90% of children with the most important conditions. The 2 tests that use static photorefractive technology were less accurate than 3 tests that assess refractive error in other ways. These results have important implications for screening preschool-aged children.

Amblyopia↗
PubMed2005

An analysis of maxillary anterior teeth: facial and dental proportions.

STATEMENT OF PROBLEM: The size and form of the maxillary anterior teeth are important in achieving pleasing dental and facial esthetics. However, little scientific data have been defined as criteria for evaluating these morphological features. PURPOSE: This study analyzed the clinical crown dimensions of maxillary anterior teeth to determine whether consistent relationships exist between tooth width and several facial measurements in a subset of the Turkish population. MATERIAL AND METHODS: Full-face and anterior tooth images of 100 Turkish dental students viewed from the front and engaged in maximum smiling were recorded with digital photography under standardized conditions. Gypsum casts of the maxillary arches of the subjects were also made. The dimensions of the anterior teeth, the occurrence of the golden ratio, the difference between the actual and perceived sizes, and the relationship between the anterior teeth and several facial measurements by gender were analyzed using the information obtained from both the computer images and the casts. One-sample, 2-sample, and paired t tests, and repeated-measures analysis of variance and Duncan multiple-range tests were performed to analyze the data (alpha=.05). RESULTS: The dimensions of the central incisors (P<.05) and canines (P<.01) varied by gender. The existence of the so-called "golden proportion" for the maxillary anterior teeth as a whole was not found. Significant differences emerged when the mean ratios between various perceived widths were compared with their ideal golden ratios (P<.01). Proportional relationships between the bizygomatic width and the width of the central incisor, and the intercanine distance and the interalar width in women were observed. CONCLUSION: The maxillary central incisor and canine dimensions of men were greater than those of women in the Turkish population studied, with the canines showing the greatest gender variation. Neither a golden proportion nor any other recurrent proportion for all anterior teeth was determined. Bizygomatic width and interalar width may serve as references for establishing the ideal width of the maxillary anterior teeth, particularly in women.

Adult↗
PubMed2006

Laughter and the mesial and lateral premotor cortex.

We report the induction of laughter and smiling by cortical electrical stimulation of the frontal lobe of two patients: an 18-month-old boy with a left frontal cortical lesion extending to the vertex and the central gyrus, and a 35-year-old woman with a lesion in the right supplementary sensorimotor area (SSMA). The subjects underwent presurgical epilepsy evaluation with subdural grid electrodes to determine surgical candidacy. Stimulation of the prefrontal area reproducibly induced laughter. The adult patient reported absence of emotional content. Slowing of speech occurred under stimulation of electrodes in the upper and posterior vicinity. In this patient laughter was elicited in the anterior part of the SSMA. In the child, this response was induced by stimulation of the lateral prefrontal cortex near the midline. We conclude that the anterior portion of the SSMA/lateral premotor cortex is involved in generating the motor pattern of laughter.

Adult↗
PubMed1998

Variables affecting high school students' perceptions of school foodservice.

OBJECTIVE: To determine if student satisfaction with high school foodservice is directly related to participation in the foodservice. DESIGN: A valid and reliable survey was conducted in a variety of classes such as English, history, and health science in grades 9 through 12, representing students aged 13 through 19 years. Students were asked 38 questions concerning variety of food, food quality, foodservice staff, aesthetics of the serving and dining area, and demographics. SUBJECTS/SETTING: The study was conducted with 1,823 students from 9 schools representing 4 geographic regions. STATISTICAL ANALYSIS: Stepwise multiple regression was used to determine the independent variables (attributes desired by the students) that most highly correlated with the dependent variable (satisfaction with the school foodservice overall). RESULTS: Variables most highly correlated with overall satisfaction were variety of food offered, flavor of food, attractiveness of food on the serving line, staff smiling and greeting students, quality of food choices, choices that allow students to meet cultural and ethnic preferences, courteousness of the staff, and quality of ingredients. Variety of food offered was the best predictor of satisfaction. A statistically significant difference was found (P<.01) between groups that never ate school lunch and those that ate school lunch 3 to 5 times per week on dining ambiance, food quality, and staff. The results indicate that satisfaction with foodservice is associated with purchase behavior in school foodservice programs. APPLICATIONS: School foodservice and nutrition programs are critically important for providing nutrition to millions of our future leaders. Today it is not enough to prepare healthful, good-tasting food. High school students are sophisticated and are exposed at an early age to a variety of dining experiences including fast foods, ethnic cuisine, and fine dining. These factors have influenced the attributes students use to evaluate school foodservice. To maintain participation levels and financial stability, school foodservice professionals should evaluate student satisfaction with food quality, variety, and other variables that affect overall satisfaction and participation. These data may then be incorporated into continuous quality improvement and strategic planning. Marketing must be incorporated into the strategic plan to influence student participation.

Adolescent↗
PubMed1998

Detection of negative and positive audience behaviours by socially anxious subjects.

Nineteen subjects high in social anxiety and 20 subjects low in social anxiety were asked to give a 5-min speech in front of three audience members. Audience members were trained to provide indicators of positive evaluation (e.g., smiles) and negative evaluation (e.g. frowns) at irregular intervals during the speech. Subjects were instructed to indicate, by depressing one of two buttons, when they detected either positive or negative behaviours. Results indicated that subjects high in social anxiety were both more accurate at, and had a more liberal criterion for, detecting negative audience behaviours while subjects low in social anxiety were more accurate at detecting positive audience behaviours.

Adolescent↗
PubMed2001

Error monitoring in the hemispheres: the effect of lateralized feedback on lexical decision.

Does each hemisphere have its own system for monitoring and responding to errors? Three experiments investigate the effect of presenting lateralized accuracy feedback in a bilateral lexical decision task. We presented feedback after each trial in either the left visual field (LVF) or right visual field (RVF). In Experiment 1 the feedback stimuli were faces smiling or frowning, in Experiment 2 we used colored squares, and Experiment 3 tested the effect of verbal feedback. Negative feedback presented in the LVF tended to improve performance on the following trial, while the same negative feedback in the RVF tended to disrupt performance on the following trial. This result was strongest with the faces as feedback, was less pronounced with colored squares, and disappeared with verbal feedback. The results are interpreted as suggesting a right hemisphere superiority for error monitoring that depends on the mode of feedback.

Analysis of Variance↗
PubMed1992

Subjective mood state and perception of emotion in chimeric faces.

Levy, Heller, Banich, and Burton (1983) have shown that hemispheric activational, or arousal, style, as measured by direction and consistency of choice of the "happer face" on a free-viewing Chimeric Faces Test, is highly reliable and varies across individuals who otherwise presumably have similar cortical organization (e.g., right-handed college students). The current experiment asks whether such individual differences in hemispheric arousal style are moderated by long-term, in the sense of enduring, individual differences in mood, as measured by the Profile of Mood States (POMS) questionnaire. Like Levy et al.'s subjects, most of our subjects (126 right-handed college students) made most of their choices on the Chimeric Faces Test based on the emotional cue (the smile) positioned in the half of the face to the viewer's left, or left visual hemifield (LVH), whereas a small minority were equally consistent in making their choice based on the emotional cue positioned in the half of the face to the viewer's right, or right visual hemifield (RVH). Performance on the Chimeric Faces Test, however, proved to be unrelated to scores on the POMS questionnaire. This suggests that hemispheric arousal style, as indexed by the Chimeric Faces Test, is robust enough, for a population of normal right-handers, to transcend any differences in mood as measured by the POMS questionnaire.

Adolescent↗
PubMed1988

Impact of delayed development in premature infants on mother-infant interaction: a prospective investigation.

We examined events that precede a diagnosis of developmental delay by comparing 16 very low birth weight premature infants whose condition was diagnosed as developmental delay at 18 months corrected age with 16 matched developmentally normal infants. All infants were observed with their mothers during maternal visits to the nursery and during home visits 1, 3, 6, and 9 months after discharge. The mothers' reactions to their infants were rated at these times. All the children were followed up at a neonatal clinic, and detailed clinic records were used to document the time when a physician first suspected a delay and when this delay was first mentioned to the mother. The results indicate that parents had usually been told of their child's handicap by the time the child was 6 to 9 months old; yet mothers of the delayed children changed the interaction with their children as early as 1 month after discharge from hospital. These mothers initially touched, smiled at, and talked to their developmentally delayed infants significantly more often, but by 9 months they did so much less often than mothers of nondelayed children. The degree of change in mothers' behavior was related to their psychosocial background, with better-adjusted mothers showing the most change. We conclude that mothers' statements about their infants are usually valid and that physicians may share their potential concerns about infants more freely.

Adult↗
PubMed1999

The emotional lability questionnaire: a new measure of emotional lability in amyotrophic lateral sclerosis.

In an ALS Clinic, use of the Pathological Laughter and Crying Scale of Robinson et al. [Robinson RG, Parikh RM, Lipsey JR, Starkstein SE, Price TR. Pathological laughter and crying following stroke: validation of a measurement scale and double-blind treatment study. American Journal of Psychiatry 1993;150(2):286-293] revealed several problems: reliance on self-rating, insufficient period of assessment, inadequate exploration of 'appropriateness of emotion', lack of an item for abnormal smiling, amusement rather than happiness being the cause of laughter in ALS, and a frequency-based rating system. The necessary modifications produced a new Emotional Lability Questionnaire (ELQ) that was tested in 43 ALS patients and 43 healthy controls. The self-rated version of the ELQ was administered as a structured interview to each participant, and the independent-relationship between subscales of the ELQ for both versions, thus confirming its internal validity. Greater emotional lability appeared associated with pseudobulbar symptoms. The question why 14 patients rated themselves as severely labile in the crying domain alone and four in the laughter domain alone, required further study.

Adult↗
PubMed2003

Amygdala damage impairs emotion recognition from scenes only when they contain facial expressions.

Bilateral damage to the human amygdala impairs recognition of negatively valenced emotions from facial expressions, but it is unclear if this finding generalizes to richer visual stimuli that contain cues in addition to faces. We investigated this issue in 4 subjects with bilateral amygdala damage, 23 with unilateral amygdala damage, 22 brain-damaged controls and 16 normal individuals. Subjects were shown two blocks of complex social scenes; all stimuli in the two blocks were identical, except that the first block had all facial expressions in the image erased. While control subjects were more accurate in recognizing emotions when facial expressions were present, subjects with bilateral amygdala damage did not show the same benefit for negative emotions, often performing equivalently across the two conditions. Most striking, subjects with bilateral amygdala damage were more accurate in recognizing scenes showing anger with faces erased than with faces present, an effect resulting in part from highly abnormal recognition of certain angry facial expressions. All four subjects with bilateral amygdala damage were impaired in recognizing angry faces shown in isolation, and frequently mistook expressions of anger for smiles, a mistake never made by any control subject. Bilateral amygdala damage thus disproportionately impairs recognition of certain emotions from complex visual stimuli when subjects utilize information from facial expressions.

Adult↗
PubMed1997

Perceptual asymmetries in judgements of facial attractiveness, age, gender, speech and expression.

Lateralization of perception of various facial attributes (age, attractiveness, gender, lip-reading and expression) was studied using chimaeric faces in which the sides of the face differed along one dimension (e.g. the left side was male and the right side female). Computer graphics were used to eliminate naturally occurring physical asymmetries (e.g. those present in the mouth during speech and spontaneous smiles) and obvious vertical mid-line joins in the photo-realistic chimaeric stimuli. Following previous studies, we found that subjects' judgements of gender and expression were influenced more by the left than the right side of the face (viewer's perspective). This left of face stimulus bias extended to judgements about facial attractiveness and facial age. This was not true of lip-reading stimuli; for these stimuli subjects were influenced more by the right than the left side of the face. Thus using free fixation, it appears possible to demonstrate in normal subjects that brain processes underlying judgements of facial speech display different lateralization from the judgements of other facial dimensions.

Adult↗