Reversible Insertion of Methyl Isothiocyanate into Copper(I)Aryloxides

MeNCS undergoes insertion into the copper(I)-aryloxide bond to form [N-methylimino(aryloxy)methanethiolato]-copper(I) complexes. This insertion occurs in the absence of ancillary ligands unlike the analogous insertion of PhNCS. The reaction with 4-methylphenoxide results in the formation of hexakis[[N-methylimino(4-methylphenoxy) methanethiolato]copper(I)] (1), which has been characterized by X-ray crystallography. Crystal data for 1: hexagonal , a = 12.365(3) Angstrom, c = 36.734(16) Angstrom, gamma = 120 degrees, Z = 3, V = 4863(3) Angstrom(3), R = 0.0306. Reactions of 2,6-dimethyl- and 4-chlorophenoxides also result in analogous copper(I) complexes 2 and 3. Addition of stochiometric amounts of PPh(3) to the oligomeric complexes typically results in the extrusion of MeNCS. The ease of extrusion is dependent on the substituents on the aryloxide, and this deinsertion is accelerated by water. However, the extrusion reaction is slow enough in the case of the N-methylimino(2,6-dimethylphenoxy)-methanethiolate complex and the isolation of an intermediate monomeric product bis(triphenylphosphine)[N-methylimino(2, 6-dimethylphenoxy)methanethiolato] copper(I) (4) is possible. Crystal data for 4: triclinic , a = 10.088(2) Angstrom, b = 11.302(1) Angstrom, c = 17.990(2) Angstrom, alpha = 94.06(1)degrees, beta = 95.22(2)degrees, gamma = 103.94(1)degrees, Z = 2, V = 1974.4(7) Angstrom(3), R = 0.0361. In the presence of of PPh(3), the insertion reaction becomes reversible. This allows the exchange of the heterocumulene MeNCS or the aryloxy group in these molecules with another heterocumulene or a phenol, respectively, when catalytic amounts of PPh(3) are added. Oligomers with exchanged heterocumulmes and phenols could be characterized by independent synthesis.

Flow behavior of LDPE and its blends with LLDPE I and II: A comparative study

Studies on melt rheological properties of blends of low density polyethylene (LDPE) with selected grades of linear low density polyethylene (LLDPE), which differ widely in their melt flow indices, are reported, The data obtained in a capillary rheometer are presented to describe the effects of blend composition and shear rate on flow behavior index, melt viscosity, and melt elasticity. In general, blending of LLDPE I that has a low melt flow index (2 g/10 min) with LDPE results in a decrease of its melt viscosity, processing temperature, and the tendency of extrudate distortion, depending on blending ratio. A blending ratio around 20-30% LLDPE I seems optimum from the point of view of desirable improvement in processability behavior. On the other hand, blending of LLDPE II that has a high melt flow index (10 g/10 min) with LDPE offers a distinct advantage in increasing the pseudoplasticity of LDPE/LLDPE II blends.

“I have to rest all the time because you are not allowed to play”: Exploring children’s perceptions of autonomy during sleep-time in long day care services

Daytime sleep is a significant part of the daily routine for children attending early childhood education and care (ECEC) services in Australia and many other countries. The practice of sleep-time can account for a substantial portion of the day in ECEC and often involves a mandated sleep/rest period for all children, including older preschool-aged children. Yet, there is evidence that children have a reduced need for daytime sleep as they approach school entry age and that continuation of mandated sleep-time in ECEC for preschool-aged children may have a negative impact on their health, development, learning and well-being. Mandated sleep-time practices also go against current quality expectations for services to support children’s agency and autonomy in ECEC. This study documents children’s reports of their experiences of sleep-time in ECEC. Semi-structured interviews were conducted with 54 preschool-aged children (44–63 months) across four long day ECEC services that employed a range of sleep-time practices. Findings provide a snapshot of children’s views and experiences of sleep-time and perceptions of autonomy-supportive practices. These provide a unique platform to support critical reflection on sleep-time policies and practices, with a view to continuous quality improvement in ECEC. This study forms part of a programme of work from the Sleep in Early Childhood research group. Our work examines sleep practices in ECEC, the subsequent staff, parent and child experiences and impacts on family and child learning and development outcomes.

Dystopian fiction for young people: Instructive tales of resilience

The rise and popularity of dystopian fiction in recent years is quite marked and critics often attribute such high sales of books and box office as being linked to the impact September 11 has had on the world, especially in the United States. While the events of September 11, 2001 saw a heightened anxiety by nations and their citizens about the fear and threat of terrorism – an anxiety which is paradoxically lowered and raised by increased surveillance practices, security checks and warnings – other changes since the last stages of the twentieth century have also raised concerns and anxieties. In this paper I use examples of Young Adult (YA) dystopian fiction to illustrate the potential these texts have for providing their readers with alternative ways of thinking about the challenges that others face and their capacity for resilience.

A thermal molecular migration in the solid-state - structures of isomeric 5-amino-4-(2,6-dichlorophenyl)-1-(2-nitrophenyl)-1h-1,2,3-triazole (yellow form i) and 4-(2,6-dichlorophenyl)-5-(2-nitroanilino)-2h-1,2,3-triazole (red form-ii), c14h9cl2n5o2

Yellow form (I): Mr= 350.09, monoclinic, P2Jn, Z--4, a=9.525(1), b=14.762(1), c= 11.268(1),/t, fl= 107.82 (1) o , V= 1508.3 A 3 , Din(flotation in aqueous KI)= 1.539 (2), D x= 1.541 (2) g cm -3, #(Cu Ka, 2 = 1.5418 A) = 40.58 cm -~, F(000) = 712, T= 293 K, R = 8.8% for 2054 significant refections. Red form (II): Mr= 350.09, triclinic, Pi, Z=2, a=9.796(2), b= 10.750 (2), c= 7.421 (1)A, a= 95.29 (2), fl= 0108-2701/84/111901-05501.50 70.18 (1), y = 92-.76 (2) °, V= 731.9 A 3, Din(flotation in KI) = 1.585 (3), D x = 1.588 (3) g cm -3, ~t(Cu Ka, 2 = 1.5418/~) = 40.58 cm -1, F(000) = 356, T=293 K, R = 5.8% for 1866 significant reflections. There are no unusual bond distances or angles. The triazole and two phenyl rings are planar. On the basis of packing considerations the possibility of intermolecular interactions playing a role in the reactivity of the starting material is ruled out.

Influence of Elastic-Constants on Mode-I Stress-Intensity Factors in 3-Dimensional Crack Problems

Plates with V-through edge notches subjected to pure bending and specimens with rectangular edge-through-notches subjected to combined bending and axial pull were investigated (under live-load and stress-frozen conditions) in a completely nondestructive manner using scattered-light photoelasticity. Stress-intensity factors (SIFs) were evaluated by analysing the singular stress distributions near crack-tips. Improved methods are suggested for the evaluation of SIFs. The thickness-wise variation of SIFs is also obtained in the investigation. The results obtained are compared with the available theoretical solutions.

Scheme of squares: Part I. Systems formalism for potentiostatic studies

The so-called “Scheme of Squares”, displaying an interconnectivity of heterogeneous electron transfer and homogeneous (e.g., proton transfer) reactions, is analysed. Explicit expressions for the various partial currents under potentiostatic conditions are given. The formalism is applicable to several electrode geometries and models (e.g., semi-infinite linear diffusion, rotating disk electrodes, spherical or cylindrical systems) and the analysis is exact. The steady-state (t→∞) expressions for the current are directly given in terms of constant matrices whereas the transients are obtained as Laplace transforms that need to be inverted by approximation of numerical methods. The methodology employs a systems approach which replaces a system of partial differential equations (governing the concentrations of the several electroactive species) by an equivalent set of difference equations obeyed by the various partial currents.

Designs for phase I clinical trials with multiple courses of subjects at different doses

The goal of this article is to provide a new design framework and its corresponding estimation for phase I trials. Existing phase I designs assign each subject to one dose level based on responses from previous subjects. Yet it is possible that subjects with neither toxicity nor efficacy responses can be treated at higher dose levels, and their subsequent responses to higher doses will provide more information. In addition, for some trials, it might be possible to obtain multiple responses (repeated measures) from a subject at different dose levels. In this article, a nonparametric estimation method is developed for such studies. We also explore how the designs of multiple doses per subject can be implemented to improve design efficiency. The gain of efficiency from "single dose per subject" to "multiple doses per subject" is evaluated for several scenarios. Our numerical study shows that using "multiple doses per subject" and the proposed estimation method together increases the efficiency substantially.

Small-amplitude cyclic voltammetry: Part I. A simple fourier synthesis approach

Current-potential relationships are derived for small-amplitude periodic inputs for linear electrochemical systems using a Fourier synthesis procedure. Specific results have been obtained for a triangular potential waveform for two simple model systems.

Left-handed helices for DNA: studies on poly[d(I-C)]

Earlier, we showed that, for the D form (n = 8 and h = 3.03 A, where n is number of nucleotide units per turn and h is height per nucleotide unit) of poly[d(A-T)], both right- and left-handed double helical models are stereochemically satisfactory and give good agreement with the observed fiber diffraction data. It was also noted that the conformations of the right- and left-handed D-DNA models are very similar to those of the right- and left-handed B-DNA models. This observation was consistent with the D leads to B transition in the solid phase. As a continuation of our earlier studies, we have carried out similar experiments with poly[d(I-C)]. We could obtain a crystalline D-form pattern (n = 8, h = 3.13 A) of the fiber at 75% relative humidity (r.h.); the hydrated (r.h. approximately equal to 95%) form of the same fiber gave the classical B-form pattern (n = 10, h = 3.40 A). In the present report, we show that both right- and left-handed double-helical models are consistent with the fiber diffraction data of poly[d(I-C)] in the D-form. Theoretical energy calculations also suggest that the right- and left-handed B- and D-DNA models are almost equally stable. Hence, we conclude that the right- and left-handed double-helical models of poly[d(I-C)] in a given form (B or D) are equally likely and that the fiber diffraction data do not permit discrimination.

Èto i to v povesti Staruha Daniila Harmsa

This dissertation focuses on the short story Starukha (The Old Woman), one of the last works of the Russian writer Daniil Kharms (1905-1942). The story, written in 1939, is analysed using the Kharmsian concepts èto and to (this and that) as a heuristic interpretative model. The first chapter gives a detailed analysis of this model, as well as a survey of the critical work done to date on Kharms and Starukha. In the second chapter the model is applied to study the different states of consciousness of the male protagonist. This is significant, because he is the "I" of the work, from whose point of view everything is being told. The third chapter takes a closer look at the reality of the world that exists independently of the consciousness of the protagonist. Physical objects can be said to bear - besides their everyday meaning - a hidden symbolic meaning. Similarly, the characters can be considered as representatives of everyday reality and otherworldliness. The fourth chapter deals with the narrative devices of Starukha. The problematics of the relation between fact and fiction plays an essential role in the story. Kharms's use of Ich-Erzählung and different tenses, which contributes to achieving a complicated elaboration of this kind of problematics, is examined in detail. The fifth chapter provides an intertextual reading of Starukha, based on its allusions to the Bible and the Christian tradition. As a result, the whole story can be seen as a kind of meditation on the Passion of Christ. The final chapter examines how the important Kharmsian concepts of the grotesque and the absurd manifest themselves in Starukha. The old woman represents in a grotesque way two opposite systems: the religious and the totalitarian. The absurdity of Starukha can be claimed to be illusory. Therefore, it is better to speak about paradoxicality. Starukha itself is a kind of paradox, in the sense that it tries to say something of the ultimate truth of reality, which inevitably remains ineffable.