Surprising Reaction Research Articles

Potential Use of Data-Mining Algorithms for the Detection of ???Surprise??? Adverse Drug Reactions

Various data mining algorithms (DMAs) that perform disporportionality analysis on spontaneous reporting system (SRS) data are being heavily promoted to improve drug safety surveillance. The incremental value of DMAs is ultimately related to their ability to detect truly unexpected associations that would have escaped traditional surveillance and/or their ability to identify the same associations as traditional methods but with greater scientific efficiency. As to the former potential benefit, in the course of evaluating DMAs, we have observed what we call 'surprise reactions'. These adverse reactions may be discounted in manual review of adverse drug reaction (ADR) lists because they are less clinically dramatic, less characteristic of drug effects in general, less serious than the classical type B hypersensitivity reactions or may have subtle pharmacological explanations. Thus these reactions may only become recognised when post hoc explanations are sought based on more refined pharmacological knowledge of the formulation. The objective of this study was to explore notions of 'unexpectedness' as relates to signal detection and data mining by introducing the concept of 'surprise reactions' and to determine if the latter associations, often first reported in the literature, represent a type of ADR amenable to detection with the assistance of adjunctive statistical calculations on SRS data. Using commonly cited thresholds, the multi-item gamma Poisson shrinker (MGPS) and proportional reporting ratios (PRRs) were applied to reports in the US FDA Adverse Event Reporting System (AERS) database of well documented 'surprise reactions' compiled by the authors. There were 34 relevant surprise reactions involving 29 separate drugs in 17 different drug classes. Using PRRs (PRR >2, chi(2) >4, N >2), 12 drug-event combinations were signalled before the first ADR citation appeared in MEDLINE, four occurred concurrently and 11 after. With empirical Bayes geometric mean (EBGM) analysis (EBGM >2, N >0), 12 signals occurred before, three concurrently and 11 after publication of the first literature citation. With EB(05) (EB(05)> or =2, N >0), six occurred before, two concurrently and 14 after MEDLINE citation. Pharmacovigilance is rather unique in terms of the number and variety of events under surveillance. Some events may be more appropriate targets for statistical approaches than others. The experience of many organisations is that most statistical disproportionalities represent known associations but our findings suggest there could be events that may be discounted on manual review of adverse event lists, which may be usefully highlighted via DMAs. Identification of surprise reactions may serve as an important niche for DMAs.

Electrochemical Oxidation of CoCp(CO)2: Radical−Substrate Reaction of a 17 e-/18 e- Pair and Production of a Unique Dimer Radical

Anodic oxidation of the important half-sandwich compound CoCp(CO)2, 1, has been studied under gentle electrolyte conditions, e.g., chlorinated hydrocarbons with weakly coordinating anion (WCA) supporting electrolyte anions. The 17-electron cation 1+ produced at E(1/2)(1) = 0.37 V vs FeCp2(0/+) undergoes a surprising reaction with neutral 1 to form the dimer radical cation [Co2Cp2(CO)4] +, 2+, which has a metal-metal bond unsupported by bridging ligands. The dimer radical is oxidized at a slightly more positive potential (E(1/2) = 0.47 V) to the corresponding dication 2(2+). Observation of the oxidation of 2+ is without precedent in confirming a radical-substrate (R-S) dimerization process by direct voltammetric detection of the R-S intermediate, K(eq) = 3 x 10(4) M(-1) for [2+]/[1][1+]. The R-S mechanism and the reaction products have been characterized by voltammetry, electrolysis, fiber-optic IR spectroscopy, and ESR measurements. DFT calculations indicate that removal of an electron from 1 results in rehybridization in 1+, thereby opening the metal center for interaction with the neutral compound 1, which has a relatively basic metal center. The LUMO of the dimer dication 2(2+) is metal-metal antibonding, and its half-occupancy in 2+ results in lengthening of the Co-Co bond from 2.64 A to 3.14 A. Inclusion of solvent in the (COSMO) calculations shows that solvation effects are necessary to account for the fact that E(1/2)(2) > E(1/2)(1). These results show the importance of medium effects in probing the fundamental redox chemistry of half-sandwich metal complexes.

TATTOOING AND PIERCING: INITIATION RITES AND MASCULINE DEVELOPMENT

ABSTRACT Prompted by the surprising reaction of a young man with a borderline personality to an interpretation of castration anxiety, this paper sets out to explore some of the unconscious determinants of tattooing and piercing. Recognizing that such acts can have an initiatory function, sociological, anthropological and psychoanalytic views of initiation and the role of the father in masculine development are examined. In some boys oedipal development is forestalled and castration anxiety is not experienced. A bifocal approach using object relations theories based on regression and Lacanian perspectives that highlight reactions to an oedipal impasse is used to understand these processes. Symbolic body modifications are differentiated from those that are non‐symbolic.

Derrida's Last Conference

Derrida's death caused a surprising reaction in the media, being responsible for a great number of articles, commentaries and announcements. It seems that now, with his death, one of his inventions – the most famous and misinterpreted one which is widely used to define his philosophical style and which is known as “deconstruction” – has finally been understood. Fortunately, in the most respected newspapers in Brasil, articles with a good survey of Derrida's work were published not only by journalists but also by literary critics, economists, lawyers and psychoanalists. But, unfortunately, the philosophers, or the ones that call themselves philosophers, seem to have insisted on ignoring the fertility of his thoughts.

Surprising reactions of a 2H-azaphosphirene complex with a silylene

Reaction of the 2H-azaphosphirene complex with the silylene yielded the bicyclic carbene complex as sole product at ambient temperature; the reaction was less selective at elevated temperatures; additionally, the synthesis and structure of the first 1,2,4,3-azadiphosphasilol-5-ene complex is presented.

Behavioral audiometry: protocols for measuring hearing thresholds in babies aged 4–18 months

This paper provides the first report in English of original behavioral audiometry protocols for measuring hearing thresholds in very young children, including the multiply handicapped. Based on reactions to one or two well-calibrated acoustic stimulations delivered in the sound field, the protocol first involves the use of a vibrator to measure hearing levels by bone conduction. This measurement technique, which is not affected by middle ear infections, is the key diagnostic step. Moreover, in profoundly hearing loss children, it triggers reactions through vibratory stimulation and sets the scene for the conditioning of responses. Next, hearing levels are assessed by air conduction with the aid of headphones, in order to measure hearing levels in each ear as early as possible. A unique set-up is used to facilitate the emergence of reliable "surprise reactions", which may be interpreted by a sole examiner. Classical visual reinforcement is replaced by a highly interactive, dynamic and playful exchange between child and examiner, which gives meaning to the perception of stimuli and heralds the learning of hearing. The results concern 105 babies suffering from bilateral sensorineural hearing loss and aged 4-18 months at the first behavioral test. Group 1 comprised 91 babies with no other handicap, in whom full bilateral air conduction was obtained in 82.4% before 12 months and in 98.9% before 18 months. In this group, air conduction in each ear was obtained in 47.0% before 12 months and in 70.3% before 18 months. In Group 2, which included 14 multiply handicapped babies, full bilateral air conduction was obtained in 37.5% before 12 months and in 78.6% before 18 months. Air conduction in both ears was obtained in 28.6% before 18 months. The protocols described make it possible, in a minimum number of sessions, to measure hearing thresholds early over the whole range of hearing frequencies, even in multiply handicapped babies and those suffering from developmental retardation.

Attention and the processing of emotional words and names: not so special after all.

Previous research has suggested that a person's own name or emotionally charged stimuli automatically "grab" attention, potentially challenging limited-capacity theories of perceptual processing. In this study, subjects were shown two digits surrounding a word and asked to make a speeded judgment about whether the parity of the two digits matched. When the subject's own name was presented on a few scattered trials, responses were markedly slowed (replicating a previous study). However, in a subsequent block of trials in which half the words were the subject's name, the slowing did not occur. The same slowing occurred (but even more fleetingly) when an emotionally charged word was presented between the digits. When the name was embedded among multiple distractor words, it ceased to slow reaction times. The results suggest that perceptual analysis of high-priority stimuli is subject to the usual capacity limitations of other stimuli, but when enough capacity is available for a high-priority stimulus to be perceived, a transient surprise reaction may interrupt ongoing processing.

Beyond Surprise: The Puzzle of Infants' Expressive Reactions to Expectancy Violation.

The reactions of 58 infants to expectancy violation by digitally filtering the experimenter's voice were studied in a cross-sectional design for ages 5, 7, 9, 11-12, and 14 months. The results show that behavioral freezing and changes in gaze direction, but not facial or vocal expression, are reliable responses to expectancy violation. The pattern suggests that a transition in the infant's capacity for cognitive evaluation of novel and discrepant events may occur around age 9 months. These findings confirm the consistent failure to find prototypical facial surprise reactions in research on novel or impossible situations. Componential theories of emotion, which predict adaptive behavior patterns from appraisal processes, may provide clues for underlying mechanisms and generate hypotheses on age-related changes in emotional expression.

Personal relationships with an intelligent interactive telephone health behavior advisor system: a multimethod study using surveys and ethnographic interviews

The burgeoning of consumer health informatics and virtual health care can help people improve their health. However, little is known about individuals' reactions to such systems. We conducted an evaluation of the telephone-linked care (TLC) system, a computer-based telecommunications system, that functions as an at home monitor, educator, and counselor for patients with chronic health conditions. Our multimethod assessment of individuals' reactions to using TLC included both quantitative and qualitative methods. Ethnographic in-depth open-ended interviews indicated more subtle and surprising reactions to TLC than the overall positive responses from surveys: individuals formed personal relationships with this technology. This relationship formation suggests that TLC designers may have been successful in their attempts to emulate a conversation with a human being. Our study adds to evidence that technology can serve as a projective device for peoples' values and psychological issues. Both designers and users project values and goals onto computer-based technologies and take on different identities through it. Different groups of users, therefore, may see the same technology differently. People also form relationships with technologies, as they did with TLC. These findings, as well as implications for system design and health outcomes, need to be explored in additional studies.

An unprecedented mode of ligation for a bridged amido-cyclopentadienide (constrained geometry) ligand; pi-olefinic interactions with gallium and indium.

The surprising reaction of GaCl3 or InBr3 with the di-Grignard reagent [Me2Si(C5Me4)(N-t-Bu)](MgCl)2 x THF results in salts of the bimetallic anions of composition [X3M[C5Me4(N-t-Bu)]MX2]- (M = Ga, X = Cl; M = In; X = Br) in which the MX2 moiety undergoes an eta2-interaction with one of the double bonds of the localized cyclopentadienide ring.

Research Watch: Surprise reactions yield atmospheric aerosols

ADVERTISEMENT RETURN TO ISSUEPREVDepartmentsNEXTResearch Watch: Surprise reactions yield atmospheric aerosolsCite this: Environ. Sci. Technol. 2003, 37, 1, 15APublication Date (Web):January 1, 2003Publication History Published online1 January 2003Published inissue 1 January 2003https://doi.org/10.1021/es032345yRIGHTS & PERMISSIONSArticle Views107Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (50 KB) Get e-AlertsSUBJECTS:Aerosols,Atmospheric chemistry Get e-Alerts

Uberraschende Reaktion von 5-(Phenylthio)- und 5-(Methylthio)pent-2-en-4-inal mit HCl

Surprising Reaction of 5-(Phenylthio)- and 5-(Methylthio)pent-2-en-4-inal with HCl Contrary to expectations (Scheme 1), 5-(phenylthio)-(1a) as well as 5-(methylthio)pent-2-en-4-inal (1b) react with a slight excess of HCl to give 2-[bis(phenylthio)methyl]furan (17a, 77% yield) and 2-[bis(methylthio)methyl]furan (17b, 61% yield), respectively. Structures 17a and 17b are supported by the results of an X-ray crystal-structure analysis, by spectroscopic data in comparison to those of model compounds, and by synthesis of 17a. This surprising reaction is tentatively explained by a mechanism (Scheme 4), including a special pyranfuran ring-contraction sequence, which is in agreement with a labelling experiment.

A Tandem Hexaannulation Reaction of Benzyllithium Involving Base-Induced Cyclodehydrogenation

The reaction of the tribenzo[3.3.3]propellane ketone 1 (triptindan-9-one) with benzyllithium/TMEDA affords an efficient one-pot peri annulation of a dihydronaphthalene across two wings of the propellane framework. The key step of this surprising tandem reaction was determined to be a nucleophilic cyclization of (Z)-9-benzylidenetriptindane (4) with concomitant hydride elimination. The formation of the novel centrotetracyclo[5.5.5.6] framework bearing a distorted (E)-stilbene unit was confirmed by single-crystal X-ray structure analysis.

Children’s and Adults’ Reactions to a Schema-discrepant Event: A Developmental Analysis of Surprise

Three studies investigated age-related differences in the surprise reaction. Study 1 revealed that children and seniors showed a more pronounced action delay in response to a simple, hedonically neutral surprising event than young adults that could not be attributed to a general slowing of information processing. Studies 2 and 3 provided evidence that these age-related differences in action delay between children and young adults were due to children’s greater difficulties to ”nd an explanation for the occurrence of the surprising event and to decide on its relevance for action. These results support the idea that the core mechanism of surprise is evolutionary-based and age-invariant, but its eliciting conditions and consequences depend on developmental changes of knowledge structures.

Photochemistry ofortho-Phenoxymethyl-Substituted Aryl Azides: A Novel Nitrene Rearrangement En Route to Isolable Iminoquinone Methides?

The answer to the question in the title is: probably yes. A surprising reaction is observed upon photolysis of aryl azide 1 in the presence of diethylamine. The iminoquinone methide 2 is isolable and is probably formed by a shift of the phenoxy group to the nitrene center followed by nucleophilic attack of diethylamine and elimination of phenol.

The Thermally and Photochemically Induced Ring Opening ofcis-3,4-Dichlorocyclobutene andtrans-3,4-Dichlorocyclobutene: New Insights from a Matrix-Spectroscopic Study

The thermally induced ring opening of 1 and 5 proceeds with high stereospecifity in a conrotatory fashion in agreement with the Woodward-Hoffmann rules. Upon flash pyrolysis of 1 the matrix-isolated (Xe, 12 K) products 2a and 2b were found, whereas the corresponding reaction of 5 yielded 3a and 3b. The s-cis conformers 2b and 3b were identified for the first time by comparison of the experimental and calculated (BLYP-6-311G*) IR absorptions. A non-stereospecific photochemical reaction could be observed if matrix-isolated (Ar or Xe, 12 K) 1 was excited directly with λ = 193 nm. Products of the allowed disrotatory pathway as well as those of the forbidden conrotatory reaction were found, a behaviour that corresponds with the known photochemistry of cyclobutenes. A surprising reaction was found if 1 and 5 were irradiated in a xenon matrix with λ > 270 nm. The precursors, which were photostable in an argon matrix, opened the ring in a conrotatory fashion, the expected pathway for a thermal reaction. In this case the light is absorbed by the solid xenon in a cooperative process with the precursor molecules. A detailed discussion of the possible energy transfer mechanisms is given. Most probably, a hot ground-state reaction of vibrationally excited 1 and 5 occurs, although the reaction of the radical cations cannot be excluded.

Carbenes: Clean new make-to-order method and a surprising reaction

Carbenes: Clean new make-to-order method and a surprising reaction

Analytical Evaluation of Warning Onset Rules for Lane Change Crash Avoidance Systems

This study assessed the potential effectiveness of two warning onset rules for lane change Crash Avoidance Systems (CAS). A minimum-separation rule triggers a driver warning whenever the Subject Vehicle (SV) and Principal Other Vehicle (POV) are within some minimum lateral separation distance. A turn-signal onset rule triggers a driver warning when the driver activates the turn signal indicator and there is a vehicle in the blind spot. A software program to simulate lane change crashes determined the maximum time available for driver surprise reaction time to the warning and estimated the proportion of crashes avoided with each warning rule. Results indicate that the minimum separation rule is unlikely to be effective for lane change crash avoidance but may help prevent lane-drift-related crashes. The turn-signal onset rule will likely be effective for drivers who use their turn signals but is not free of nuisance alarm problems. Recommendations for lane change CAS research and development are provided.

Development of Blue-Yellow and Red-Green Discriminations in Infants during the First Year of Life

Colour discrimination was investigated in infants aged 4 – 14 months. 250 healthy subjects and 80 subjects with slight defects in basic visual functions (the risk group) participated. A coloured toy was moved in front of the subject and disappeared behind a screen, reappearing after 2 – 3 s at the other side. Sometimes when the toy was hidden, the experimenter replaced it with another one that differed only in colour: yellow was replaced by blue or vice versa (Y/B switch), or red by green or vice versa (R/G switch). The form and size of the toy remained constant. The emotional reaction of surprise showed whether the infant discriminated these colour pairs. The brightness of the stimuli was slightly varied make sure that the infant reacted to the change in colour rather than brightness. About 75% of healthy 4 – 5-month-olds showed good expressive reactions to the Y/B switch, and practically all children did so at 7 – 8 months. The discrimination of red and green develops more slowly: only at 12 months did practically all children show good reactions to the R/G switch. In all children, Y/B discrimination preceded R/G discrimination. The mean difference between the numbers of children discriminating these two pairs was 7.6%. The infants of the risk group were as good as their healthy age-mates in Y/B discrimination, but performed significantly less well on R/G: the mean difference between the numbers discriminating the former but not the latter was 17.0%. Possible reasons for the retardation of chromatic discrimination in the risk group are discussed.

Decamethylsilicocene Chemistry: Unprecedented Multistep Reactions of a Silicon(II) Compound with the Heterocumulenes CO2, COS, CS2, and RNCS (R = Methyl, Phenyl)

In the reaction of the nucleophilic decamethylsilicocene, ((Me5C5)2Si (1), with the electrophilic heterocumulenes CO2, COS, CS2, and RNCS, multistep processes are observed, which in most cases proceed via several highly reactive intermediates. In all reactions, the formal oxidation state of the silicon atom changes from +2 in 1 to +4, and the hapticity of the pentamethylcyclopentadienyl ligands changes from η5 to η1. In the reaction of 1 with CO2, COS, or RNCS, double-bond species of the type (Me5C5)2SiX (X = O, S) are formed, which are stabilized via different routes. Thus, reaction of 1 with CO2 in toluene as solvent finally leads to the spiro compound [(Me5C5)2SiO2]2C (4), whereas in pyridine as solvent, the eight-membered heterocycle [(Me5C5)2SiO2CO]2 (5) is formed. The dithiadisiletane [(Me5C5)2SiS]2 (9) results from the reaction of 1 with COS. Dithiasiletane derivates of the type (Me5C5)2SiS2CNR (10, 11) are the final products from the reaction of 1 with RNCS (R = CH3, C6H5). Multistep rearrangement processes have to be postulated to explain the formation of the dithiadisiletane derivate 15 in the surprising reaction of 1 with CS2; ligands that initially are bonded to the silicon (Me5C5) and to the carbon atom (S) have to be completely exchanged to build up the final product. The silaheterocycles 4, 5, 10, and 15 and also some of the basic molecular framework have been unknown in the literature. The crystal strucutres of 4, 5, 10, and 15 were determined by X-ray crystallography and are presented.