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Proton as the simplest of all catalysts for [2 + 2] cycloadditions: DFT study of acid-catalyzed imine metathesis.

The mechanism of imine metathesis was studied as a prototype reaction for the impact that heteroatom substitution has on thermally forbidden [2 + 2] addition reactions using high-level density functional theory in combination with a continuum solvation model. The intuitively expected high activation barriers were confirmed for N-alkyl- and N-aryl-substituted imine reactants with transition state free energies of 78.8 and 68.5 kcal/mol, respectively, in benzene. The computed reaction energy profiles were analyzed to discover possible strategies for lowering the transition state energy. Protonation of the imine nitrogen was proposed as a possible catalytic route and was explicitly modeled. The computed reaction energy profile shows that protonation of one of the imine reactants has an enormous effect on the overall rate of metathesis and lowers the activation barrier by as much as 37.3 and 30.6 kcal/mol for the N-alkyl and N-aryl reactants, respectively. These results suggest that acid-catalyzed imine metathesis should be amenable at elevated temperatures. Furthermore, the protonation of both reactants of the metathesis reaction is predicted to be not productive owing to electrostatic repulsion of the reactants, thus suggesting that there should be an optimum pH for the catalytic turnover. A detailed analysis of the catalytic mechanism is presented, and the primary driving force for the catalysis is identified. Upon protonation of the imine nitrogen, the key [2 + 2]-addition step becomes asynchronous and one of the two intermolecular N-C bonds is formed before traversing the transition state, resulting in a substantial net decrease of the overall energy requirement. The general applicability of this intuitively understandable mechanism for designing structural features for lowering the energy of transition state structures is explored.

Journal Article↗

The epistemology of communitarian bioethics: traditions in the public debates.

I consider the problem liberalism poses for bioethics. Liberalism is a view that advocates that the state remain neutral to views of the good life. This view is sometimes supported by a skeptical moral epistemology that tends to propel liberalism toward libertarianism. I argue that the possibilities for shared agreement on moral matters are more promising than is sometimes appreciated by such a view of liberalism. Using two examples of public debates of moral issues, I show that commonly shared intuitions may ground moral principles even if they may be given different weight by persons of different moral and religious traditions. Nevertheless, the fact that the intuition and principle is widely shared may be sufficient to chart some directions for public policy or cooperative action even if they do not lead to complete agreement. As a result, I argue that a liberal communitarianism that presupposes a fairly minimalist epistemology is a legitimate approach to achieving shared agreement in a pluralistic society.

Abortion, Legal↗

Working memory capacity and a notorious brain teaser: the case of the Monty Hall Dilemma.

The Monty Hall Dilemma (MHD) is an intriguing example of the discrepancy between people's intuitions and normative reasoning. This study examines whether the notorious difficulty of the MHD is associated with limitations in working memory resources. Experiment 1 and 2 examined the link between MHD reasoning and working memory capacity. Experiment 3 tested the role of working memory experimentally by burdening the executive resources with a secondary task. Results showed that participants who solved the MHD correctly had a significantly higher working memory capacity than erroneous responders. Correct responding also decreased under secondary task load. Findings indicate that working memory capacity plays a key role in overcoming salient intuitions and selecting the correct switching response during MHD reasoning.

Adolescent↗

Perception of cross-situational consistency.

Eighty-eight undergraduates rated the degree of relation in each of 21 pairs of items that described behavior in the domains of conscientiousness, friendliness, and extraversion. In these three domains, estimates of relations by the average subject correlated, respectively, with actual empirical relations, .63, .58, and .40. Relations corresponding to correlations between .10 to .20 could be significantly distinguished by subjects from relations in the range of .00 to .10 in two of the three domains. The confidence that individuals placed in their perceptions varied directly with the accuracy of their judgments against the empirical criterion. In addition, subjects were more confident of what they perceived to be extreme relations in both directions than of intermediate relations, and they also tended to be more confident of their judgments of strong positive relations than of zero relations. They exhibited an intuitive awareness of the effect of aggregation over occasions and items of behavior on the magnitude of cross-situational relations and the demonstration of traits. They also reported using reasonable strategies in arriving at decisions. Far from being inveterate trait believers, as some have suggested, subjects' intuitions paralleled psychometric principles in several important respects when assessing relations between real-life behaviors.

Adult↗

A framework for the interpretation of first-order interaction in logit modeling.

Several suggestions have been tendered for interpreting first-order interaction in log-linear analysis. Occasionally these methods result either in a loss of information or in results that are difficult to grasp on an intuitive level. It is argued that interpreting effect parameters in terms of odds ratios provides an elegant and intuitively appealing conceptual framework that has great generality across models. The interaction term then resembles a cross-product term in linear regression. In both forms of analysis, the partial effect of a given predictor on the response is composed of a constant and a correction that is a function of the other predictor involved in the interaction. This framework is especially appealing for models in which the logit is based on a bifurcation of the dependent variable. Although odds ratios are still useful for summarizing effects on polytomous dependent variables, greater caution must be exercised to avoid misleading interpretations.

Humans↗

Metrics and mappings: a framework for understanding real-world quantitative estimation.

Estimation is influenced by a variety of processes: application of heuristics, domain-specific reasoning, and intuitive statistical induction, among them. In this article, we propose the metrics and mapping framework to account for how these processes are integrated to generate estimates. This framework identifies 2 types of information as critical: knowledge of distributional properties (metric knowledge) and knowledge of relative status of individual entities within the distribution (mapping knowledge). Heuristics and domain-specific knowledge are both viewed as cues that contribute to mapping knowledge; intuitive statistical induction is viewed as providing cues to metric properties. Results of 4 experiments illustrate the framework's usefulness for integrating these types of information and for predicting when people emphasize heuristics and when they emphasize domain-specific knowledge.

Adolescent↗

DNA overwinds when stretched.

DNA is often modelled as an isotropic rod, but its chiral structure suggests the possible importance of anisotropic mechanical properties, including coupling between twisting and stretching degrees of freedom. Simple physical intuition predicts that DNA should unwind under tension, as it is pulled towards a denatured structure. We used rotor bead tracking to directly measure twist-stretch coupling in single DNA molecules. Here we show that for small distortions, contrary to intuition, DNA overwinds under tension, reaching a maximum twist at a tension of approximately 30 pN. As tension is increased above this critical value, the DNA begins to unwind. The observed twist-stretch coupling predicts that DNA should also lengthen when overwound under constant tension, an effect that we quantitatively confirm. We present a simple model that explains these unusual mechanical properties, and also suggests a possible origin for the anomalously large torsional rigidity of DNA. Our results have implications for the action of DNA-binding proteins that must stretch and twist DNA to compensate for variability in the lengths of their binding sites. The requisite coupled DNA distortions are favoured by the intrinsic mechanical properties of the double helix reported here.

Biomechanical Phenomena↗

Removing chest drains--a critical reflection of a complex clinical decision.

Decision-making is a fundamental element of nursing work (Boblin-Cummings et al, 1999; Berggren and Severinsson, 2000; Bucknall, 2000) which fluctuates according to experience, location and personal boundaries. Nursing judgements are said to portray the nature of nursing knowledge and practice (Thompson, 1999; Buckingham and Adams, 2000a) and can affect others either favourably or adversely (Gordon et al., 1994), with Buckingham and Adams (2000a) emphasizing the benefits to be gained from understanding the process, including improved clinical effectiveness and self-knowledge. It is said that all decisions are made in one of two ways--hypothetico-deductively or intuitively (Dowie and Elstein, 1988; Thompson, 1999; Buckingham and Adams, 2000a)--although different titles are used interchangeably for the same modes. Both of these modalities are examined. Hypothetico-deductive reasoning entails exposure to information before and during the patient encounter. These data are grouped and used to generate a hypothesis or possible diagnosis. The second stance in decision-making is founded upon intuition and closely associated with expertise. The presence of chest drains after cardiothoracic surgery is known to cause severe pain, thereby interfering with respiratory mechanics and the ability to take part in physiotherapy exercises (Owen and Gould, 1997; Fox et al., 1999; Charnock and Evans, 2001; Lazzara, 2002). This work therefore aims to examine the decision-making processes in relation to the prompt removal of chest drains by analysing the options available and the skills required to utilize them effectively.

Aged↗

Persistent crying in early infancy: a non-trivial condition of risk for the developing mother-infant relationship.

Infants between 1 and 6 months of age (mean age 3.6 months) who were referred to the Munich Interdisciplinary Research and Intervention Programme because of persistent crying and their mothers were examined and compared with an age-matched community-based control sample with no current cry problem. Three groups, referred extreme criers, referred moderate criers, and controls, were compared with regard to measures of psychosocial and organic risks, the mothers' perception of her own psychological state and infant temperament, the quality of mother-infant relationship, and intuitive parenting in mother-infant face-to-face interactions. In comparison with general-community samples of infants with persistent crying, the present clinical sample represents a biased group with particularly high levels of infant distress for long periods of time, with problems of sleep-wake organization, neuromotor immaturity, and difficult temperament. Moreover, extreme crying was associated with a cumulation of organic and psychosocial risks, including high rates of prenatal stress and anxiety, maternal psychopathology and partnership conflicts. Mothers in both referred groups scored similarly low on feelings of self-efficacy, and high on depression, anxiety, exhaustion, anger, adverse childhood memories, and marital distress. Mother-infant relationships were more often distressed or disturbed among referred dyads than among controls, and 40% as compared with 19% showed dysregulatory patterns of interactional failures in face-to-face contexts. The findings suggest that factors related to parental care did not cause persistent crying, but functioned as maintaining or exacerbating factors. Dynamic interactions between persistent crying, difficult temperament, and parenting factors which compromise maternal resources and intuitive parenting may put such families at long-term risk for both relationship and behaviour problems.

Adult↗

Wound care in the community setting: clinical decision making in context.

Sixty-two community nurses in northern England of grades B and D to H were interviewed by a team of four researchers. The interviews were semi-structured, and were tape-recorded, fully transcribed and content analysed. They were conducted as part of a larger study, the aim of which was to examine community nurses' perceptions of quality in nursing care. One of the main themes the work focused on was decision-making as an element of quality. Data relating to wound care were considered from the perspective of the insights they offered into clinical decision-making. Data were interpreted in the light of a literature review in which a distinction had been made between theories which represented clinical decision-making as a linear or staged process and those which represented it as intuitive. Within the former category, three sub-categories were suggested: theorists could be divided into 'pragmatists', 'systematisers' and those who advocated 'diagnostic reasoning'. The interpretation of the data suggested that the clinical decisions made by community nurses in the area of wound care appeared largely intuitive, yet were also closely related to 'diagnostic reasoning'. They were furthermore based on a range of sources of information and justified by a number of different types of rationale.

Community Health Nursing↗

Nursing practice and the definition of human death.

This paper aims to highlight the gap in nursing literature of discussion of the definition of human death--to show that nurses should engage in such discussion. For the nursing role in the care of brain dead patients and their relatives may unwittingly promote and foster a definition of human death which is fundamentally flawed. A person can be warm, pink, have an independently beating heart and be breathing, yet still be diagnosed as brainstem dead. Nursing literature which discusses issues surrounding brain death (as opposed to brain death itself), proposes that nurses should suppress any reservations which they may have in accepting that a patient with the characteristics described is dead; and that they should try to allay any reservations which relatives of such dead patients might have. But what if the concept of brainstem death is flawed? Surely, as accountable professionals, nurses should not accept the role just referred to without satisfying themselves that the concept of brainstem death is coherent and robust. This paper tries to show that, on examination, this is not the case. The definition of human death which guides practice in the UK and elsewhere is fundamentally flawed. Instead of suppressing their own intuitions, and the intuitions of patients' relatives in the management of patients diagnosed as brainstem dead, nurses should critically examine the definition of death which currently informs clinical practice. Our conclusion is that this definition is false.

Adaptation, Psychological↗

Subjectivity and vulnerability: reflections on the foundation of ethical sensibility.

This paper investigates the possibility of understanding the rudimentary elements of clinical sensitivity by investigating the works of Edmund Husserl and Emmanuel Levinas on sensibility. Husserl's theory of intentionality offers significant reflections on the role of pre-reflective and affective intuition as a condition for intentionality and reflective consciousness. These early works of Husserl, in particular his works on the constitution of phenomenological time and subjective time-consciousness, prove to be an important basis for Levinas' works on an ethics of alterity and infinite responsibility for the other person. In fact, it is difficult to understand the core of Levinasian ethics, of vulnerability as proximity, of ethical sensitivity as passivity and a suffering for the suffering of another, without understanding the influence from Husserl's work. Crucially, the paper will, on the basis of Levinasian ethics, establish an understanding of sensibility as vulnerability and receptivity that is fundamental also for understanding significant intuitions in clinical nursing. Clinical sensitivity and carefulness in nursing are shaped by the concrete and also bodily expressions of vulnerabilities in a receptivity that is pre-reflective and pre-ontological.

Ethics, Nursing↗

Effect of light filters on reading speed in normal and low vision due to age-related macular degeneration.

PURPOSE: To investigate the effects of light filters on reading speed in normal and low vision due to age-related macular degeneration (AMD). METHODS: Reading speed was determined for 12 subjects with normal vision and 12 subjects with non-exudative AMD using stationary lowercase nonsensical print in Times Roman font and four light filters; a yellow Corning Photochromic Filter (CPF) 450, a grey neural density (ND) filter, an individual filter obtained using the Intuitive Colorimeter and a clear filter. RESULTS: There was no statistically significant light filter effect on reading speed for the normal subjects. The AMD group demonstrated a statistically significant 5% average improvement in reading speed with the CPF450 compared with the other filters although some AMD subjects had improvements of 10-15%. CONCLUSIONS: Light filters obtained using the Intuitive Colorimeter(R) performed poorly when compared with the CPF450, ND and clear filters for both the study groups. For the AMD group, average reading speed was statistically greater with the CPF450 than the other filters, however it is questionable whether the improvement (5%) would be clinically significant. As some of the subjects with AMD had greater improvements with the CPF450 we advocate clinical assessment of light filters using existing protocols on an individual basis.

Aged↗

Body size, dialysis dose and death risk relationships among hemodialysis patients.

BACKGROUND: The normalized treatment ratio, Kt/V derived from urea kinetic models (UKM), is a commonly used measure of dialysis dose. This measure assumes that smaller patients with low volume of urea distribution (V) require proportionately less total treatment (Kt) than larger patients. The conclusion has been questioned because the UKM use assumptions that could make them invalid for accurately predicting a clinical outcome like survival. It is possible that a relationship exists between Kt and body size whereby a different Kt is required for different sizes. This study therefore explored the relationships among body size, Kt, and death risk focusing on possible interactions between Kt and size. METHODS: The sample included 43,334 patients treated on January 1, 1999. Survival time was modeled using Kt or body size groups to evaluate the shape of the risk profiles. Kt and the size measures were then evaluated together as continuous functions both in main effects (that is, Kt and size) and interaction models to see if the association of Kt with risk might be different for different sizes. The size measures were body weight, weight adjusted statistically for height, body surface area (BSA), weight divided by height (wt/ht) and the body mass index (BMI). RESULTS: The log of risk decreased in rough linear fashion for Kt, weight, weight for height, and BSA. The log-risk relationships were "reverse J-shaped" for wt/ht and BMI. The main effects models suggested improved survival with increasing Kt and all of the size measures. Adding an interaction term increased the benefit associated with increasing Kt and for weight, weight for height and BSA at low values of Kt and size. A significant, positive interaction term mitigated those effects at higher values. Thus, the death risk penalties associated with reducing Kt among small patients were as great as or greater than they were among large patients. A similar pattern was observed for V. Adding the interaction to the BMI model destroyed the main effects, so that there was no significant association between risk and either Kt or BMI. A cross-categorical model of BMI and Kt, however, revealed improving survival with increasing Kt among both low and high BMI patients throughout the range of Kt. CONCLUSIONS: Evidence supporting the intuition that smaller patients require proportionately lower dialysis dose than larger patients was not found. To the contrary, smaller patients suffer as much risk as or more risk than larger patients from reducing Kt. Deciding dialysis treatment using a Kt/V based intuition may lead to avoidable under-dialysis particularly among small patients.

Adult↗

A study of decision making among U.S. psychiatric nurses.

The purpose of this study was to describe psychiatric nurses' decision making and to test a Finnish instrument. A 56-item survey was mailed to 351 psychiatric nurses with a return rate of 48%. A varimax factor analysis showed 5 factors (intuitive, self-confidence, interpretive, collected information, and analytic processing) with alphas ranging from .71 to .85. Results indicate U.S. psychiatric nurses extensively use intuitive interpretive decision making and cultural bias needs to be considered when using a foreign instrument. Further research is needed to refine this instrument and describe psychiatric nurses' decision making.

Culture↗

Robotic-assisted cardiac surgery: anesthetic and postoperative considerations.

OBJECTIVE: To assess the feasibility of endoscopic telemanipulated cardiac surgery and describe the anesthetic, postoperative, and surgical implications of minimally invasive robotic-assisted cardiac surgery. DESIGN: Prospective study. SETTING: Cardiovascular and transplant center, university hospital. PARTICIPANTS: Twenty patients (13 men, 7 women) scheduled for either coronary artery bypass graft surgery or valve surgery. Mean age was 53 +/- 5 years (range, 31 to 75 years) and mean New York Heart Association class was 2.4. Three patients (6 %) were having redo procedures, and 1 patient had bacterial endocarditis. INTERVENTIONS: Surgery was done with the aid of the daVinci surgical robot (Intuitive Surgical, Mountain View, CA). Induction and maintenance of anesthesia consisted of a target-controlled infusion of remifentanil and propofol. In 11 cases (55%), cardiopulmonary bypass was performed with Port-Access technology (Heartport, Redwood City, CA), and in the remaining 9 cases (45%), conventional femorofemoral bypass was used. MEASUREMENTS AND MAIN RESULTS: Fifteen patients (75 %) were extubated within 6 hours and discharged from the cardiac surgery intensive care unit on postoperative day 1. Two patients (10%) were reexplored in the immediate postoperative period. Two conversions to thoracotomy were reported. One reoperation at 6 months and 1 late death occurred. At 1-year follow-up, excellent functional results were observed in 18 cases. CONCLUSION: Caution should be used when assessing innovative medical-surgical techniques. Despite technical difficulties and lengthy procedures, results were satisfactory. The feasibility of robotic-assisted surgery for coronary artery bypass graft and valve procedures is intuitively appealing.

Adult↗

Modifications in vertical scar breast reduction.

The use of vertical-scar breast reduction techniques is only slowly increasing, even though they have been advocated by Lassus and Lejour and are requested by patients. Possible reasons why surgeons are reluctant to use these techniques are that they are said to be more difficult to learn, they require considerable experience and intuition, and their applicability is confined to small breasts. Several surgeons have developed modifications, combining vertical-scar breast reduction techniques with details of the familiar inverted-T-scar technique. We present a procedure involving two further modifications of the vertical-scar breast reduction technique: first, a standardised, geometrical preoperative drawing from our superior-pedicle T technique, with the aim of establishing a reproducible method of reduction requiring no particular intuitive touch, and, second, the addition of a periareolar skin resection, to give the breast the desired round shape. Between September 1998 and December 1999 we used this technique in a prospective series of 52 patients. The median resection weight was 450 g. The maximal postoperative follow-up was 15 months. There were no acute postoperative complications necessitating reoperation. The late complication rate was within the expected range for such procedures (seven patients, 13.5%) and included vertical-scar widening, areolar distortion, residual wrinkles due to incomplete shrinkage of the undermined skin in the inferior pole and asymmetry of the breast. This procedure enables us to offer patients with moderate to marked hypertrophy a reproducible versatile vertical breast reduction technique. The technique is easy to teach and easy to learn, especially for those who are familiar with the superior pedicle inverted-T-scar technique.

Adolescent↗

[CompuRecord--A perioperative information management-system for anesthesia].

Since 1977 procedures for automatic documentation of anesthesias have repeatedly been described. Because of a limited arrangement of the desk top and because of its focussing on intraoperative documentation only a widespread introduction could not be established so far. Todays systems are offered with graphically orientated desktops which can be operated by intuition. The CompuRecord(R)-System (Philips Healthcare) is a perioperative management system for anaesthesia. It is constructed with modular components, recording the complete anaesthesiological care of a patient from preanaesthesiological assessment to the recovery room. Additional modules allow an economical check, provide for quality management and exportation of a core data base. Except for the original software all other components of the system including the net work components are IT standard products allowing reduced costs for supplementation, expansion and support. The advantage of an automatical documentation system of anaesthesia is frequent and detailed recording of anaesthesiological data as well as the possibility of a meticulous calculation of cost for each patient. The anaesthesiologist's time used for documentation is reduced remarkably with a limited and reasonable amount of data to be recorded. This leaves more time of attention for the patient himself. Time necessary for training is kept low with the touch screens of the CompuRecord(R) - System, which can be operated intuitively. Primary to purchase an exact analysis of process and of subsequent costs should be done. Standardized documentation allows to establish Standard Operating Procedures in a department of Anaesthesia. Using the given systems an implementation is possible already today despite restricted resources of man power.

Anesthesia↗