Crystallographic study of push-pull ethylenes

From structural data of several crystal structure analyses of push-pull ethylenes it is found that C=C bond lengths in this class of molecules are significantly longer than the value for this bond in ethylene. With powerful donors and acceptors such as -NMe2 and -COOMe groups respectively, the C=C bond length is as long as 1.460 å. Correlations are observed between (i) C=C bond lengths and the twist angles about the C=C bond and (ii) C=C bond lengths and the torsional barrier measured by thednmr technique.

Thermal Analysis of Polypropylene Hydroperoxide

Studies on the low temperature oxidation of polyolefins have been the subject matter of several investigations because of interest in understanding the aging and weathering of polymers. One of the key steps in such an oxtdatton is the formation of hydroperoxide. Estimation of the hydroperoxide in oxidized samples, which is conventionally done by iodometric titrations, is quite important to gain knowledge about the kinetics and mechanism of the process. The present investigation is the first report of the thermal analysis of polypropylene hydroperoxide samples from two angles: (1) the thermal behavior of its decomposition and (2) whether such an analysis leads to knowledge of the concentration of hydroperoxide in the sample.

Conformational analysis of hydroxyproline and its protected derivatives by 1H NMR

From a computer simulation of the 270 MHz 1H NMR spectra of hydroxyproline (Hyp) and its protected derivatives, precise values of ring vicinal coupling constants were obtained. These couplings were related to ring torsional angles, using a Karplus type analysis. From the NMR analysis it was observed that the pyrrolidine ring possesses a unique and highly homogeneous conformation (Cγ-exo form). Temperature dependence studies on protected dipeptides suggest that the pyrrolidine ring conformation is independent of backbone conformation. An unusual X-Hyp, β-turn was observed for Boc-Aib-Hyp-NHMe.

Surface waves in the presence of external high frequency fields

The system equations of a collisionless, unmagnetized plasma, contained in a box where a high frequency (HF) electric field is incident, are solved in the electrostatic approximation. The surface modes of the plasma in the semi-infinite and box geometry are investigated. In thi high frequency limit, the mode frequencies are not significantly changed by the HF field but their group velocities can be quite different. Two long wavelength low frequency modes, which are not excited in the absence of HF field, are found. These modes are true surface modes (decaying on one wavelength from the surface) unlike the only low frequency ion acoustic mode in the zero field case. In the short wavelength limit the low frequency mode occurs at omega i/ square root 2, omega i being the ion plasma frequency, as a result similar to the case of no HF field.

Disabled Revolutionary War Veterans and the Construction of Disability in the Early United States, c. 1776-1840

This thesis addresses the following broad research question: what did it mean to be a disabled Revolutionary War veteran in the early United States during the period from 1776 to roughly 1840? The study approaches the question from two angles: a state-centred one and an experiential one. In both cases, the theoretical framework employed comes from disability studies. Consequently, disability is regarded as a sociocultural phenomenon rather than a medical condition. The state-centred dimension of the study explores the meaning of disability and disabled veterans to the early American state through an examination of the major military pension laws of the period. An analysis of this legislation, particularly the invalid pension acts of 1793 and 1806, indicates that the early United States represents a key period in the development of the modern disability category. The experiential approach, in contrast, shifts the focus of attention away from the state towards the lived experiences of disabled veterans. It seeks to address the issue of whether or not the disabilities of disabled veterans had any significant material impact on their everyday lives. It does this through a comparison of the situation of 153 disabled veterans with that of an equivalent number of nondisabled veterans. The former group received invalid pensions while the latter did not. In comparing the material conditions of disabled and nondisabled veterans, a wide range of primary sources from military records to memoirs and letters are used. The most important sources in this regard are the pension application papers submitted by veterans in the early nineteenth century. These provide us with a unique insight into the everyday lives of veterans. Looking at the issue of experience through the window of the pension files reveals that there was not much difference in the broad contours of disabled and nondisabled veteran life. This finding has implications for the theorisation of disability that are highlighted and discussed in the thesis. The main themes covered in this study are: the wartime experiences of injured American soldiers, the military pension establishment of the early United States and the legal construction of disability, and the post-war working and family lives of disabled veterans. Keywords: disability, early America, veterans, military pensions, disabled people, Revolutionary War, United States, disability theory.

African Gamer: Whose Story Is It Anyway?

New Video Gamer: Africa Needs More Technology (CNN 12/12/2011) In December 2011 CNN news service online edition (Sutter, 2011) posted a short item about Cwi Nqane, a Khoisan man who entered Samsung’s Namibian World Cyber Games (WCG) heats held at the 2011 the annual Windhoek Show. Cwi Nqane won a place on the Namibian WCG team playing a smartphone game called Asphalt 6: Adrena-line (Gameloft, 2011). Cwi was presented with a ‘top of the line’ Samsung Galaxy tablet and subsequently sent to compete in Korea. Later, other news and game news websites re-reported the incident, which inspired a variety of enthusiastic comment about tech-nology and ‘new knowledge’. Then Kotaku news service picked up the item (Narcisse, 2011) and took a very different slant. Kotaku proposed that Samsung was exploiting Cwi and had assumed the role of a Techno-Tarzan: “striding into Nqane’s homeland and swinging him off into the wonders of the modern world where they can trot him out as a curiosity”. These two perspectives on the story of Cwi’s WCG entry expose two dominant views on Indigenous knowledges and technologies: ICTs as progress for in-digenous peoples and ICTs as disruptive and exploitative. Neither position, however, allows for the claiming of digital technology by indigenous communities, indeed both views position indigenous cultures as being outsiders.

Geometry Of Proline And Hydroxyproline .1. An Analysis Of X-Ray Crystal-Structure Data

We have carried out an analysis of crystal structure data on prolyl and hydroxyprolyl moieties in small molecules. The flexibility of the pyrrolidine ring due to the pyramidal character of nitrogen has been defined in terms of two projection angles δ1 and δ2. The distribution of these parameters in the crystal structures is found to be consistent with results of the energy calculations carried out on prolyl moieties in our laboratory.

Literaturnaja skazka A.M. Remizova (1900-1920-e gody)

Literary tale of A.M. Remizov (1900’s – 1920’s) The thesis is devoted to a detailed historical-literary description of a tale as a genre tradition in the creative work of Alexei Mikhailovich Remizov (1877-1957), one of the major Russian prose writers of the 20’s century. This very approach allows to specify the place and functional meaning of this genre in literary practice of the writer and to appeal to one of the key problems of the 20-21 century literature history – a specific of modernistic literature composition principle and a role of montage techniques in its formation. Remizov was working on tales during his whole life, though the most productive years of folklore studies fell to 1900’s – 1910’s. During this period he intensively studied folklore materials, narrated several hundreds of folk tales and in 1900’s – 1920’s published eight tale collections which played a significant role in the formation of stylistic and compositional principles of his prose of the 1910’s – 1920’s, especially montage techniques, which in its turn influenced the development of the narrative forms in the Russian post-revolutionary literature. At the same time a tale has specified not only poetics but also problematics of Remizov’s creative work, as when choosing folklore sources the writer always alluded to modern themes and relevant intellectual trends. The current research work, based on various archive materials and a wide spectrum of modern historical-literary data, complies four chapters with a consistent description of creation history, publication and critics’ reviews of Remizov’s tale collections and single tales contributing to his creative evolution characteristic. Furthermore, the work refers to composition and subject of the particular collections. On the whole it enables to follow up genre dynamics. The first chapter of the work is devoted to Posolon’ (Sunwise), the earliest tale collection of Remizov. The main feature of the collection is that its composition is oriented on the agrarian calendar and the subject – on the system of mythological views reflected in the Russian folklore. This very collection to a large extent corresponds to the writer’s views on the myth represented in Pis’mo v redaktsiyu (Letter to the Editor). The history of this manifesto appearing is analyzed in the second chapter. The incident which caused its forthcoming contributed to ‘legitimization’ of Remizov’s narrations as a relevant genre of modern literature and to upgrading the writer in professional hierarchy. The third chapter analyzes Remizov’s collections of 1900’s – early 1920’s, a result of Remizov’s scrupulous work with a specific tale material. He is acting here as a tale repertory researcher and in some cases as a collector as well. The means of such collections’ topical organization is not the myth but the hero of the tale. According to this principle single pieces are grouped into cycles, which then form complicated montage constructs. Texts themselves can be viewed as a sort of hyper-quotations, as they in fact entirely coincide with their original sources. Besides, collections usually have their own ideal patterns. In the fourth chapter a connection of Remizov’s creative work with folk fun culture and a tradition of the folklore noel story is being demonstrated on Zavetnyie skazy (Secret Tales) material. A consistent collections’ history creation analysis convinces us that the tale was a sort of laboratory in which main writer’s prose methods were being worked out.

Influence of environmental and instrumental variables on the non-invasive prediction of Brix in pineapple using near infrared spectroscopy

The Brix content of pineapple fruit can be non-invasively predicted from the second derivative of near infrared reflectance spectra. Correlations obtained using a NIRSystems 6500 spectrophotometer through multiple linear regression and modified partial least squares analyses using a post-dispersive configuration were comparable with that from a pre-dispersive configuration in terms of accuracy (e.g. coefficient of determination, R2, 0.73; standard error of cross validation, SECV, 1.01°Brix). The effective depth of sample assessed was slightly greater using the post-dispersive technique (about 20 mm for pineapple fruit), as expected in relation to the higher incident light intensity, relative to the pre-dispersive configuration. The effect of such environmental variables as temperature, humidity and external light, and instrumental variables such as the number of scans averaged to form a spectrum, were considered with respect to the accuracy and precision of the measurement of absorbance at 876 nm, as a key term in the calibration for Brix, and predicted Brix. The application of post-dispersive near infrared technology to in-line assessment of intact fruit in a packing shed environment is discussed.

Laboratory investigation on the effects of overburden pressure, water, and time on slaking induced material property degradation of coal mine spoil

In open-cut strip mining, waste material is placed in-pit to minimise operational mine costs. Slope failures in these spoil piles pose a significant safety risk to personnel, along with a financial risk from loss of equipment and scheduling delays. It has been observed that most spoil pile failures occur when the pit has been previously filled with water and then subsequently dewatered. The failures are often initiated at the base of spoil piles where the material can undergo significant slaking (disintegration) over time due to overburden pressure and water saturation. It is important to understand how the mechanical properties of base spoil material are affected by slaking when designing safe spoil pile slope angles, heights, and dewatering rates. In this study, fresh spoil material collected from a coal mine in Brown Basin Coalfield of Queensland, Australia was subjected to high overburden pressure (0 – 900 kPa) under saturated condition and maintained over a period of time (0 – 6 months) allowing the material to slake. To create the above conditions, laboratory designed pressure chambers were used. Once a spoil sample was slaked under certain overburden pressure over a period of time, it was tested for classification, permeability, and strength properties. Results of this testing program suggested that the slaking of saturated coal mine spoil increase with overburden pressure and the time duration over which the overburden pressure was maintained. Further, it was observed that shear strength and permeability of spoil decreased with increase in spoil slaking.

Elastic analysis of pin joints in plates under some combined pin and plate loads

Joints are primary sources of weakness in structures. Pin joints are very common and are used where periodic disassembly of components is needed. A circular pin in a circular hole in an infinitely large plate is an abstraction of such a pin joint. A two-dimensional plane-stress analysis of such a configuration is carried out, here, subjected to pin-bearing and/or biaxial-plate loading. The pin is assumed to be rigid compared to the plate material. For pin load the reactive stresses at the edges of the infinite plate tend to zero though their integral over the external boundary equals to the pin load. The pin-hole interface is unbonded and so beyond some load levels the plate separates from the pin and the extent of separation is a non-linear function of load level. The problem is solved by inverse technique where the extent of contact is specified and the causative loads are evaluated directly. In the situations where combined load is acting the separation-contact zone specification generally needs two parameters (angles) to be specified. The present report deals with analysing such a situation in metallic (or isotropic) plates. Numerical results are provided for parametric representation and the methodology is demonstrated.

Catalytic transformation of aliphatic alcohols to corresponding esters in O2 under neutral conditions using visible-light irradiation

Selective oxidation of aliphatic alcohols under mild and base-free conditions is a challenging process for organic synthesis. Herein, we report a one-pot process for the direct oxidative esterification of aliphatic alcohols that is significantly enhanced by visible-light irradiation at ambient temperatures. The new methodology uses heterogenerous photocatalysts of gold–palladium alloy nanoparticles on a phosphate-modified hydrotalcite support and molecular oxygen as a benign oxidant. The alloy photocatalysts can absorb incident light, and the light-excited metal electrons on the surface of metal nanoparticles can activate the adsorbed reactant molecules. Tuning the light intensity and wavelength of the irradiation can remarkably change the reaction activity. Shorter wavelength light (<550 nm) drives the reaction more efficiently than light of longer wavelength (e.g., 620 nm), especially at low temperatures. The phosphate-exchanged hydrotalcite support provides sufficient basicity (and buffer) for the catalytic reactions; thus, the addition of base is not required. The photocatalysts are efficient and readily recyclable. The findings reveal the first example of using “green” oxidants and light energy to drive direct oxidative esterification of aliphatic alcohols under base-free, mild conditions.

Base-base interactions in nucleic acids containing A-T base pairs: Structure of poly[d(A-T)]

The Watson-Crick type of base pairing is considered to be mandatory for the formation of duplex DNA. However, conformational calculations carried out in our laboratory, have shown that some combinations of backbone torsion angles and sugar pucker lead to duplexes with Hoogsteen type of base pairing also. Here we present the results of energy calculations performed on A-T containing doublet sequences in the D-form with both Hoogsteen and Watson-Crick type of base pairing and the 3 viable models for the A-T containing polynucleotide duplex poly[d(A-T)].

Drink and drug driving in Australian young adult users and non-users of illicit stimulants

- Introduction There is limited understanding of how young adults’ driving behaviour varies according to long-term substance involvement. It is possible that regular users of amphetamine-type stimulants (i.e. ecstasy (MDMA) and methamphetamine) may have a greater predisposition to engage in drink/drug driving compared to non-users. We compare offence rates, and self-reported drink/drug driving rates, for stimulant users and non-users in Queensland, and examine contributing factors. - Methods The Natural History Study of Drug Use is a prospective longitudinal study using population screening to recruit a probabilistic sample of amphetamine-type stimulant users and non-users aged 19-23 years. At the 4 ½ year follow-up, consent was obtained to extract data from participants’ Queensland driver records (ATS users: n=217, non-users: n=135). Prediction models were developed of offence rates in stimulant users controlling for factors such as aggression and delinquency. - Results Stimulant users were more likely than non-users to have had a drink-driving offence (8.7% vs. 0.8%, p < 0.001). Further, about 26% of ATS users and 14% of non-users self-reported driving under the influence of alcohol during the last 12 months. Among stimulant users, drink-driving was independently associated with last month high-volume alcohol consumption (Incident Rate Ratio (IRR): 5.70, 95% CI: 2.24-14.52), depression (IRR: 1.28, 95% CI: 1.07-1.52), low income (IRR: 3.57, 95% CI: 1.12-11.38), and male gender (IRR: 5.40, 95% CI: 2.05-14.21). - Conclusions Amphetamine-type stimulant use is associated with increased long-term risk of drink-driving, due to a number of behavioural and social factors. Inter-sectoral approaches which target long-term behaviours may reduce offending rates.

Ruumiillinen esine, materiaalinen suku : Tutkimus Pyhä Anna itse kolmantena -aiheisista keskiajan puuveistoksista Suomessa

Embobied Object, Material Family. Late-Medieval Wood Sculptures Depicting Saint Anne with the Virgin and Child in Finland Saint Anne, the mother of the Virgin Mary, was one of the most popular saints in Western Europe in the late Middle Ages. She was often depicted with two other figures, the Virgin and the Christ Child (Anna Selbdritt). The dissertation examines the polychrome wood sculptures showing this motif, with a special focus on those remaining in Finland. It investigates the meanings these sculptures had to their observers in the fifteenth-century Finland. The study sheds light to important material heritage which is little known and offers new insights into the cult and imagery of the holy grandmother. Methodologically the study is based on iconology and post-formalist art history, and it appropriates concepts such as spatiality, sanctity, corporeality, and gender. Taking a comparative approach it knits together larger tendencies and local people and incidents. By conflating methodological domains it renews the ways how fragmentary wood sculptures, lacking documentary written sources, can be contextually interpreted and comprehended. The sculptures are analyzed from three angles. Firstly, the study explores the sculptures by focusing on their materiality and facture, which is to consider them as records of their own making. The analysis provides new information concerning the quantity, location, and current condition of the sculptures and it also elucidates problems regarding attribution, dating, display, and craftsmanship. The book presents the results of the empirical study of 45 Saint Anne groups; these works are individually described in the large Appendix. Secondly, the works are contextualized to the specific historical conditions in which they were observed. The study discusses closely the circumstances in the Turku Cathedral around the shrine of Saint Anne, the popular belief, and the piety of individual persons. The sculptures, deemed as the embodiments of the holy characters, interacted with the devotees. Thirdly, the works are examined within the wider theological and ideological currents of the era centered on the body and Incarnation. Saint Anne with the Virgin and Child motif demonstrated the Carnal Trinity, the motherly side of the Holy Trinity. The dissertation argues that Saint Anne was interpreted as the female counterpart or, in a mythical sense, wife of God. Furthermore, the Child s implicit, simultaneous presence as a suffering or dead man imbues the sculptures with a sense of the Passion, thus associating them with the pietà and the Mater dolorosa motifs. The naked Christ Child underlines him as the offering and, eventually, the Eucharistic wafer. The study suggests that the sculptures mediate continuity and the bloodline between the generations by the intertwined and repeated gestures, clothing and positions of the portrayed figures. Regardless of the ostensible homeliness of the sculptures, so readily reiterated by earlier scholars, these sculptures represented creation and birth through the carnal yet holy mothers.