Tryst with a molecular and supramolecular oddity: an anti-Furst-Plattner epoxide opening product as a designer additive for accessing an elusive polymorph

Additive induced polymorphism of a conformationally locked tetraacetate 3 in presence of its diastereomer 4 is described. The ester 3 was specially crafted on a trans-decalin backbone to relegate the O-H center dot center dot center dot O H-bond donors to the molecular interior and have the peripheral H-bond acceptors in 1,3-syndiaxial relationship. The supramolecular assembly of 3 was destined to evolve along two mutually exclusive pathways, namely one, which employs intermolecular O-H center dot center dot center dot O H-bonds (pathway 1) and the other that sacrifices these for intramolecular O-H center dot center dot center dot O H-bonds and settles for a crystal packing dictated by weak intermolecular interactions alone (pathway 2). Exploiting the similarity between the self-assemblies of 4 and the two recently reported dimorphs of 3, the ester 3 has been stimulated to follow the elusive non-hierarchical pathway 2 through preferential inhibition of pathway 1. Interestingly, the inhibitor 4 was obtained serendipitously en route 3 via an apparent breakdown of Furst-Plattner rule.

Reconstructing identity of older people in using day care services in Taiwan: A grounded theory study

Adult day care centers provide a means whereby frail or disabled older people can remain living at home particularly when their family care-givers engage in waged work. In Taiwan, adult day care services appear to meet the cultural needs of both older people and their families for whom filial care is vital. Little research attention has been paid to the use of day care services in Taiwan, the uptake rate of which is low. This grounded theory study explored the ways in which older people and family care-givers construct meanings around the use of day care services in Taiwan. The research methodology drew on the theoretical tenets of symbolic interactionism and methods were informed by the grounded theory. In-depth interviews with 30 participants were undertaken. Reconstructing identity in a shifting world is the core category of the study and reflects a process of reframing whereby older people came to new definitions of social responsibility and independence within the context of the day care center. The implications of the findings is that the older people, rather than seeking to be relieved of social responsibilities, worked very hard to frame and reframe a social role. Rather than letting the institutions undermine or disrupt their identity, the older people worked to actively negotiate and redefine the meaning of self. Thus, although reluctant to come to use the services at the outset, they found a way to manage their lives independently. Social roles and responsibilities as older parents were retained. This study explored the process of meaning construction of day care use and the ways in which this process entailed a reconstruction of the identities of the participants. The evidence from this study underlines the importance of recognizing and acknowledging subjectively conceived identities as work that older people undertake, when in care, to render their lives meaningful.

Day Surgery in Finland : randomized and cross-sectional studies on treatment, quality, and outcome

The aims of this study were to describe Finnish day surgery practice at present and to evaluate quality of care by assessing postdischarge minor morbidity and quality indicators. Potential treatment options were approached by investigating the role of oral dexamethasone as a part of multimodal analgesia and the feasibility of day surgery in patients aged 65 years and older. Over a 2-month period, all patient cases at 14 Finnish day surgery or short-stay units were analyzed (Study I). Quality indicators included rates and reasons for overnight admission, readmission, reoperation, cancellations, and patient satisfaction. Recovery during the first postoperative week was assessed at two units (Study II). Altogether 2732 patients graded daily the intensity of predefined symptoms. To define risk factors of postdischarge symptoms, multinomial regression analysis was used. Sixty patients scheduled to undergo day surgery for hallux valgus were randomized to receive twice perioperatively dexamethasone 9 mg or placebo (Study III). Paracetamol 1 g was administered 3 times daily. Rescue medication (oxycodone) consumption during 0-3 postoperative days (POD), maximal pain scores and adverse effects were documented. Medically stable patients aged 65 years or older, scheduled for open inguinal hernia repair, were randomized to receive treatment either as day cases or inpatients (Study IV). Complications, unplanned admissions, healthcare visits, and patients’ acceptance of the type of care provided were assessed during 2 weeks postoperatively. In Study I, unplanned overnight admissions were reported in 5.9%, return hospital visits during PODs 1-28 in 3.7%, and readmissions in 0.7% of patients. Patient satisfaction was high. In Study II, pain was the most common symptom in adult patients (57%). Postdischarge symptoms were more frequent in adults aged < 40 years, children aged ≥ 7 years, females, and following a longer duration of surgery. In Study III, the total median (range) oxycodone consumption during the study period was 45 (0–165) mg in the dexamethasone group, compared with 78 (15–175) mg in the placebo group (P < 0.049). On PODs 0-1, patients in the dexamethasone group reported significantly lower pain scores. Following inguinal hernia repair, no significant differences in outcome measures were seen between the study groups. Patient satisfaction was equally high in day cases and inpatients (Study IV). Finnish day surgery units provide good-quality services. Minor postdischarge symptoms are common, and they are influenced by several patient-, surgery-, and anesthesia-related factors. Oral dexamethasone combined with paracetamol improves pain relief and reduces the need for oxycodone rescue medication following correction of hallux valgus. Day surgery for open inguinal hernia repair is safe and well accepted by patients aged 65 years or older and can be recommended as the primary choice of care for medically stable patients.

Quantification of impact of a cricket ball

The cricket is one of most popular games in the Asian subcontinent and its popularity is increasing every day. The issue of replacement of the cricket ball amidst the matches is always an uncomfortable situation for teams, umpires and even supporters. At present the basis of the replacement is solely on the judgement, experience and expertise of the umpires, which is subjective, controversial and debatable. In this paper, we have attempted a new approach to quantify the number of impacts or impact factor of a 4-piece leather ball used in the Intemational one-day and test cricket matches. This gives a more objective and scientific basis/ criteria for the replacement of the ball. Here, we have used a well known and widely used Thermal Infra-Red (TIR) imaging to capture the dynamics of the thermal profice of the cricket ball, which has been heated for about 15 seconds. The idea behind this approach is the simple observation that an old ball (ball with a few impacts) has different thermal signature/profice compared to the that of a new ball. This could be due to the change in the surface profice and internal structure, minor de-shaping, opening of seam etc. The TIR video and its frames, which is inherently noisy, are restored using Hebbian learning based FIR (sic), which performs optimal smoothing in relatively less number of iteration. We have focussed on the hottest region of the ball i.e., the inner core and tracked its thermal profice dynamics. Finally we have used multi layer perceptron model (MLP) to quantify the impact factor with fairly good accuracy.

Forecasting day-ahead electricity load using a multiple equation time series approach

The quality of short-term electricity load forecasting is crucial to the operation and trading activities of market participants in an electricity market. In this paper, it is shown that a multiple equation time-series model, which is estimated by repeated application of ordinary least squares, has the potential to match or even outperform more complex nonlinear and nonparametric forecasting models. The key ingredient of the success of this simple model is the effective use of lagged information by allowing for interaction between seasonal patterns and intra-day dependencies. Although the model is built using data for the Queensland region of Australia, the method is completely generic and applicable to any load forecasting problem. The model’s forecasting ability is assessed by means of the mean absolute percentage error (MAPE). For day-ahead forecast, the MAPE returned by the model over a period of 11 years is an impressive 1.36%. The forecast accuracy of the model is compared with a number of benchmarks including three popular alternatives and one industrial standard reported by the Australia Energy Market Operator (AEMO). The performance of the model developed in this paper is superior to all benchmarks and outperforms the AEMO forecasts by about a third in terms of the MAPE criterion.

Water in Action : Encounters among 2- to 3-Year-Old Children, Adults, and Water in Day Care

In line with cultural psychology and developmental theory, a single case approach is applied to construct knowledge on how children s interaction emerge interlinked to historical, social, cultural, and material context. The study focuses on the negotiation of constraints and meaning construction among 2-to 3-year-old children, a preschool teacher, and the researcher in settings with water. Water as an element offers a special case of cultural canalization: adults selectively monitor and guide children s access to it. The work follows the socio-cultural tradition in psychology, particularly the co-constructivist theory of human development and the Network of Meanings perspective developed at the University of São Paulo. Valsiner s concepts of Zone of Free Movement and Zone of Promoted Action are applied together with studies where interactions are seen as spaces of construction where negotiation of constraints for actions, emotions, and conceptions occur. The corpus was derived at a Finnish municipal day care centre. During a seven months period, children s actions were video recorded in small groups twice a month. The teacher and the researcher were present. Four sessions with two children were chosen for qualitative microanalysis; the analysis also addressed the transformations during the months covered by the study. Moreover, the data derivation was analyzed reflectively. The narrowed down arenas for actions were continuously negotiated among the participants both nonverbally and verbally. The adults expectations and intentions were materialized in the arrangements of the setting canalizing the possibilities for actions. Children s co-regulated actions emerged in relation to the adults presence, re-structuring attempts, and the constraints of the setting. Children co-constructed novel movements and meanings in relation to the initiatives and objects offered. Gestures, postures, and verbalizations emerged from the initially random movements and became constructed to have specific meanings and functions; meaning construction became abbreviated. The participants attempted to make sense of the ambiguous (explicit and implicit) intentions and fuzzy boundaries of promoted and possible actions: individualized yet overlapping features were continuously negotiated by all the participants. Throughout the months, children s actions increasingly corresponded adults (re-defined) conceptions of water researchers as an emerging group culture. Water became an instrument and a context for co-regulations. The study contributes to discussions on children as participants in cultural canalization and emphasizes the need for analysis in early childhood education practices on the implicit and explicit constraint structures for actions.

Synthesis of Unnatural Selenocystines and beta-Aminodiselenides via Regioselective Ring-Opening of Sulfamidates Using a Sequential, One-Pot, Multistep Strategy

A variety of N-alkyl-beta-aminodiselenides have been synthesized in high yield from sulfamidates under mild reaction conditions using potassium selenocyanate and benzyltriethylammonium tetrathiomolybdate ([BnNEt3](2)MoS4) in a sequential, one-pot, multistep reaction. The tolerance of multifarious protecting groups under the reaction conditions is discussed. The methodology was successfully extended to the synthesis of selenocystine,3,3'-dialkylselenocystine, and 3,3'-diphenylisoselenocystine and their direct incorporation into peptides.

Ring-Opening-Induced Toughening of a Low-Permittivity Polymer-Metal Interface

Integrating low dielectric permittivity (low-k) polymers to metals is an exacting fundamental challenge because poor bonding between low-polarizability moieties and metals precludes good interfacial adhesion. Conventional adhesion-enhancing methods such as using intermediary layers are unsuitable for engineering polymer/metal interfaces for many applications because of the collateral increase in dielectric permittivity. Here, we demonstrate a completely new approach without surface treatments or intermediary layers to obtain an excellent interfacial fracture toughness of > 13 J/m(2) in a model system comprising copper. and a cross-linked polycarbosilane with k similar to 2.7 obtained by curing a cyclolinear polycarbosilane in air.Our results suggest that interfacial oxygen catalyzed molecularring-opening and anchoring of the opened ring moieties of the polymer to copper is the main toughening mechanism. This novel approach of realizing adherent low-k polymer/metal structures without intermediary layers by activating metal-anchoring polymer moieties at the interface could be adapted for applications such as device wiring and packaging, and laminates and composites.

Growing up in Affiliation with a Religious Community : A Case Study of Seventh-day Adventist Youth in Finland

This study investigates how the religious community as a socialization context affects the development of young people's religious identity and values, using Finnish Seventh-day Adventism as a context for the case study. The research problem is investigated through the following questions: (1) What aspects support the intergenerational transmission of values and tradition in religious home education? (2) What is the role of social capital and the social networks of the religious community in the religious socialization process? (3) How does the religious composition of the peer group at school (e.g., a denominational school in comparison to a mainstream school) affect these young people s social relations and choices and their religious identity (as challenged versus as reinforced by values at school)? And (4) How do the young people studied negotiate their religious values and religious membership in the diverse social contexts of the society at large? The mixed method study includes both quantitative and qualitative data sets (3 surveys: n=106 young adults, n=100 teenagers, n=55 parents; 2 sets of interviews: n=10 young adults and n=10 teenagers; and fieldwork data from youth summer camps). The results indicate that, in religious home education, the relationship between parents and children, the parental example of a personally meaningful way of life, and encouraging critical thinking in order for young people to make personalized value choices were important factors in socialization. Overall, positive experiences of the religion and the religious community were crucial in providing direction for later choices of values and affiliations. Education that was experienced as either too severe or too permissive was not regarded as a positive influence for accepting similar values and lifestyle choices to those of the parents. Furthermore, the religious community had an important influence on these young people s religious socialization in terms of the commitment to denominational values and lifestyle and in providing them with religious identity and rooting them in the social network of the denomination. The network of the religious community generated important social resources, or social capital, for both the youth and their families, involving both tangible and intangible benefits, and bridging and bonding effects. However, the study also illustrates the sometimes difficult negotiations the youth face in navigating between differentiation and belonging when there is a tension between the values of a minority group and the larger society, and one wants to and does belong to both. It also demonstrates the variety within both the majority and the minority communities in society, as well as the many different ways one can find a personally meaningful way of being an Adventist. In the light of the previous literature about socialization-in-context in an increasingly pluralistic society, the findings were examined at four levels: individual, family, community and societal. These were seen as both a nested structure and as constructing a funnel in which each broader level directs the influences that reach the narrower ones. The societal setting directs the position and operation of religious communities, families and individuals, and the influences that reach the developing children and young people are in many ways directed by societal, communal and family characteristics. These levels are by nature constantly changing, as well as being constructed of different parts, like the pieces of a jigsaw puzzle, each of which alters in significance: for some negotiations on values and memberships the parental influence may be greater, whereas for others the peer group influences are. Although agency does remain somewhat connected to others, the growing youth are gradually able to take more responsibility for their own choices and their agency plays a crucial role in the process of choosing values and group memberships. Keywords: youth, community, Adventism, socialization, values, identity negotiations

Finnish Short-Term Stock Returns

Functioning capital markets are a crucial part of a competitive economy since they provide the mechanisms to allocate resources. In order to be well functioning a capital market has to be efficient. Market efficiency is defined as a market where prices at any time fully reflect all available information. Basically, this means that abnormal returns cannot be predicted since they are dependent on future, presently unknown, information. The debate of market efficiency has been going on for several decades. Most academics today would probably agree that financial markets are reasonably efficient since virtually nobody has been able to achieve continuous abnormal positive returns. However, it is clear that a set of return anomalies exists, although they are apparently to small to enable substantial economic profit. Moreover, these anomalies can often be attributed to market design. The motivation for this work is to expand the knowledge of short-term trading patterns and to offer some explanations for these patterns. In the first essay the return pattern during the day is examined. On average stock prices move during two time periods of the day, namely, immediately after the opening and around the formal close of the market. Since stock prices, on average, move upwards these abnormal returns are generally positive and cause the distinct U-shape of intraday returns. In the second essay the results in the first essay are examined further. The return pattern around the former close is shown to partly be the result of manipulative action by market participants. In the third essay the focus is shifted towards trading patterns of the underlying stocks on days when index options and index futures on the stocks expire. Generally no expiration day effect was found. However, some indication of an expiration day effect was found when a large amount of open in- or at-the-money contracts existed. Also, the effects were likelier to be found for shares with high index-weight but fairly low trading volume. Last, in the forth essay the attention is turned to the behaviour of different tax clienteles around the dividend ex-day. Two groups of investors showed abnormal trading behaviour. Domestic non-financial investors, especially domestic companies, showed a dividend capturing behaviour, i.e. buying cum-dividend and selling ex-dividend shares. The opposite behaviour was found for foreign investors and domestic financial institutions. The effect was more notable for high yield, high volume stocks.

The expiration day effect of indexoptions and index futures on the underlying shares

This paper studies the effect of the expiration day of index options and futures on the trading volume, variance and price of the underlying shares. The data consists of all trades for the underlying shares in the FOX-index for expiration days during the period October 1995 to the mid of yer 1999. The main results seem to support the findings of Kan 2001, i.e. no manipulation on a larger scale. However, some indication of manipulation could be found if certain characteristics are favorable. These characteristics include: a) a large quantity of outstanding futures or at/in the money options contracts, b) there exists shares with high index weight but fairly low trading volume. Lastly, there is some indication that manipulation might be more popular towards the end of the examined time period.

The Day of the Week Effect and Option Pricing - A Study of the German Option Market

The use of different time units in option pricing may lead to inconsistent estimates of time decay and spurious jumps in implied volatilities. Different time units in the pricing model leads to different implied volatilities although the option price itself is the same.The chosen time unit should make it necessary to adjust the volatility parameter only when there are some fundamental reasons for it and not due to wrong specifications of the model. This paper examined the effects of option pricing using different time hypotheses and empirically investigated which time frame the option markets in Germany employ over weekdays. The paper specifically tries to get a picture of how the market prices options. The results seem to verify that the German market behaves in a fashion that deviates from the most traditional time units in option pricing, calendar and trading days. The study also showed that the implied volatility of Thursdays was somewhat higher and thus differed from the pattern of other days of the week. Using a GARCH model to further investigate the effect showed that although a traditional tests, like the analysis of variance, indicated a negative return for Thursday during the same period as the implied volatilities used, this was not supported using a GARCH model.

Observation of crack closure using a crack mouth opening displacement gauge

A crack mouth opening displacement (CMOD) gauge has been designed to estimate the crack length as well as the crack opening stress level in an automated fatigue crack propagation test programme. The CMOD gauge accurately predicts crack tip opening levels in K-controlled tests with constant K, K increasing or K decreasing. In all three K-controlled tests with a single 100% overload cycle, the CMOD gauge does not measure the crack tip opening stress level over a large range of crack lengths after the application of the overload. The CMOD gauge measures the stress level at which the overload plastic zone site opens. Caution should thus be exercised in using the crack opening stress level, estimated by the CMOD gauge, to explain fatigue crack propagation under arbitrary load sequences from the viewpoint of crack closure phenomena.