2,962 research outputs found
Synthetic and Structural Studies on the Novel Formation of Bicyclo[n.2.0]alkan-1-ols
No full textReaction of phenyl vinyl sulfoxide with the lithium enolates of simple ketones of varying ring size (cyclopentanone, cycloheptanone and cyclooctanone) under controlled cyclisation conditions followed by subsequent oxidation resulted in the formation of the bicyclo[n.2.0]alkan-1-ols 253-255, 262, 263, 265, 268 and 269 in conjunction with alkylated species 256, 257, 264, 266 and 267. The ratio of bicyclo[n.2.0]alkan-1-ols to alkylated ketone formation observed was dependent on a number of factors including the variation of enolate reactivity between the different ring sizes, conversion of phenyl vinyl sulfoxide, time, temperature and concentration of reaction and the stability and steric strain observed in the final bicyclo[n.2.0]alkan-1-ol product. X-ray crystal structures of 253, 262 and 265 were obtained and a structural study showed that as the overall steric strain in the bicyclo[n.2.0]alkan-1-ol product is decreased there is a corresponding increase in product distribution in favour of bicyclo[n.2.0]alkan-1-ol formation in conjunction with increased yields. Selected substituted and functionalised ketones (2-methylcyclopentanone, 2,6-dimethylcyclohexanone, 2-methylcyclohexanone and 1,4-cyclohexanedione mono-ethylene ketal) also reacted in the cyclisation reaction to give bicyclo[n.2.0]alkan-1-ols 270, 271, 277, 278, 281, 282, 285 and 286 in conjunction with alkylated products 272, 279, 280, 283, 284 and 287. Incorporation of substitution at the bridgehead and C2 position had a role in the preference of the major stereochemical isomer observed for a bicyclo[n.2.0]alkan-1-ol (n = 3, 4). A structural comparison of the X-ray crystal structures of 278, 281 and 286 indicated that the pseudo chair conformation of the six-membered ring influenced ring torsion and bond angles in the bicyclo[4.2.0]octanol ring system. Two model studies were selected to illustrate the potential application of the cyclisation process as methodology towards natural product synthesis or complex ring systems. No bicyclo[n.2.0]alkan-1-ol formation was evident in an intramolecular example using the starting ketone 291 in which the electrophile is tethered to the ketone. 2,6-Dimethyl-2-cyclohexen-1-one 301 considered as a model study towards the synthesis of the antibiotic mellolide, upon reaction with phenyl vinyl sulfoxide and oxidation displayed poor reactivity. The novel bicyclo[2.2.2]octanones 303, 304 and 305 were formed in very low yields. The lack of reactivity of the ketones 2,6-dimethyl-2-cyclohexen-1-one, 1,2-cyclohexanedione and 1,4-cyclohexanedione towards bicyclo[n.2.0]alkan-1-ol formation suggested that conjugation in the enolate prior to reaction with phenyl vinyl sulfoxide was not favourable. The non-reactivity of these ketones and the hindered ketone camphor indicated the potential limitations to the cyclisation methodology. However, conversion of the ketal functionality of 286 to a ketone resulted in the formation of the functionalised bicyclo[4.2.0]octanol 288 providing positive indications for further synthetic applications.Thesis (PhD Doctorate)Doctor of Philosophy (PhD)School of ScienceFull Tex
Development and validation of a quality of life instrument for patients with oral potentially malignant disorders: studies of impact in a population of Telugu speaking adults
No full textOral Potentially Malignant Disorders (OPMDs) are those oral mucosal conditions that have a predilection for becoming malignant (Warnakulasuriya et al. 2007). Similar to oral cancer itself and other oral conditions, OPMDs can cause significant morbidity that affects physical, social and psychological wellbeing, thus affecting the quality of life (QoL) of those so afflicted. The literature on the assessment of QoL in patients with OPMD is very limited, especially from developing countries, which might be due to the unavailability of a disease-specific QoL instrument (Tadakamadla et al. 2015). This thesis developed and validated a disease-specific self-administered QoL questionnaire for OPMD patients. The study was conducted in two phases in the oral medicine clinics of Panineeya Institute of Dental Sciences and Research Centre, Hyderabad, India. The first phase involved qualitative methodology for developing the OPMDQoL questionnaire. Qualitative data were collected through interviews and focus group discussions with 32 Telugu speaking patients with an OPMD who were undergoing treatment. Patients were those diagnosed with Oral Leukoplakia (OL), Oral Submucous Fibrosis (OSF) and Oral Lichen Planus (OLP) which are the most common OPMDs in the Indian subcontinent. Thematic analysis and coding of the qualitative data were conducted using Nvivo by two individuals independently to generate themes and the items for the questionnaire. Moreover, existing oral health-related QoL questionnaires, including those extant for patients with head and neck cancer, were reviewed to generate the items. A final list of 48 items was prepared, after inputs from oral physicians using a modified Delphi technique, from the 60 items that were generated through qualitative analysis and questionnaires. This was followed by the development of final questionnaire by item reduction using a clinical impact method which involved administration of the list of questions to 15 patients who rated the importance of each item. Based on these importance ratings, the final questionnaire (OPMDQoL) was developed: This consisted of 20 items under four domains: ‘difficulties with diagnosis’, ‘physical impairment and functional limitations’, ‘psychological and social wellbeing’ and the ‘effect of treatment on daily life’. Each item is scored using a five-point Likert scale, and the overall OPMDQoL and domain scores are calculated by summing the scores of each item with a higher score representing poorer QoL.
In the second phase, the validity and reliability of OPMDQoL was assessed. OPMDQoL, Telugu translations of the Chronic Oral Mucosal Disease Questionnaire (COMDQ) (Ni Riordain et al. 2011b) and Short form 12 item (version 2) of the health survey questionnaire (SF-12v2) (Ware et al. 1996) were administered to 150 OPMD patients (50 each of OL, OSF and OLP) and to controls who were free from any type of OPMD. A thorough clinical examination was conducted and history, including lifestyle habits, was recorded from all patients. OPMDQoL demonstrated good discriminant validity as patients presented poorer scores than the controls. Also, it had good convergent validity evaluated by assessing its correlation with an existing questionnaire (COMDQ) designed for use in patients with any type of oral mucosal disease. An exploratory factor analysis was also conducted, and findings demonstrated a four-factor structure that conforms to the hypothesised four domains.
The impact of the clinical diagnosis (OL, OSF or OLP) and of disease severity on disease-specific and generic QoL was then assessed. Patients with OL reported better OPMDQoL than those with OSF and OLP, while no differences were observed between the three OPMDs for the mental health components of the SF-12v2 questionnaire and for the ‘psychological and functional wellbeing’ domain of the OPMDQoL instrument. When domain scores were compared, OLP patients reported significantly higher scores for the domain ‘difficulties with diagnosis’ while OL patients presented lower scores for the dimension, ‘physical impairment and functional limitations’ than did patients with the other OPMD. Disease severity had a significant association with both OPMDQoL and with the mental health component of SF-12v2, QoL diminishing as disease severity increased.
In conclusion, the newly developed OPMDQoL exhibited good validity and reliability in a sample of Telugu Speaking OPMD patients. Disease severity was found to be associated with poor QoL assessed using OPMDQoL. Taken together, the results of this work indicate that this questionnaire might be used in studies of disease progression and to evaluate response to therapy, in routine clinical practice. OPMDQoL can be used in different cultures and languages following cross-cultural adaptation and can also be used to compare the effectiveness of treatments.Thesis (PhD Doctorate)Doctor of Philosophy (PhD)School of Dentistry&Oral HlthGriffith HealthFull Tex
A New Approach Towards Bicyclo[4.2.0]octan-1-ols: Synthetic and Mechanistic Studies
No full textThe reaction between the lithium enolate of cyclohexanone and phenyl vinyl sulfoxide resulted in the formation of the novel bicyclooctanol sulfoxides 215-217 and the monoalkylated sulfoxide 218. The effects of variation in reaction time, temperature and concentration were studied. Under optimal conditions (10 minutes, -10°C and 0.085 M) the ratio of the bicyclooctanol sulfoxides 215-217 (75% yield) to the monoalkylated sulfoxide 218 was 95:5. The bicyclooctanol sulfoxides 215-217 were characterised as the sulfone derivatives, bicyclooctanol sulfones 219 and 220. X-ray crystal structures were used to determine the relative stereochemistry of the bicyclooctanol sulfoxides 215-217 and the bicyclooctanol sulfones 219 and 220. Bicyclo[4.2.0]octano-1-ol formation was determined to occur via an ionic mechanism. Mechanistic studies were carried out using variations in reaction lighting and reaction solvent, conducting the reaction in the presence of a radical trap and quenching the reaction with a deuterium label. The role of the counterion was determined to be important in the formation of the bicyclooctanol sulfoxides 215-217. Sequestering lithium ions with HMPA and substituting lithium with potassium favoured alkylation. Substituting the lithium enolate of cyclohexanone with the dimethylaluminium enolate of cyclohexanone resulted in a different distribution of the bicyclooctanol sulfoxides 215-217 and the formation of bicyclooctanol sulfoxide 243. Transition states to account for these differences have been proposed. The stability of the bicyclooctanol sulfoxides under conditions of acid, base and heating was studied. Thermal ring opening of the bicyclooctanol sulfoxides 215 and 216 to the monoalkylated sulfoxides 218A and 218B respectively occurred with retention of the configuration at sulfur. The relative stereochemistry of the individual bicyclooctanol sulfoxides 215-217 was considered to account for the observed stability in each case. The reaction between the lithium enolate of cyclohexanone and (R)-(+)-p-tolyl vinyl sulfoxide 193 gave the bicyclooctanol tolyl sulfoxides 246, 251 and 252 and the monoalkylated tolyl sulfoxide 247. This showed that both bond rotation in the side chain of the intermediate and epimerisation at sulfur occurred in the bicyclo[4.2.0]octan-1-ol forming process. The presence of the sulfoxide functionality in phenyl vinyl sulfoxide was determined to be crucial to the formation of bicyclo[4.2.0]octan-1-ols. In the reaction with the lithium enolate of cyclohexanone, phenyl vinyl sulfide gave no reaction, phenyl vinyl sulfone gave the bicyclic disulfones 260-265, ethyl acrylate gave the diesters 266-268 and diphenylvinylphosphine oxide gave the phosphine oxide 269. The cyclobutanol 270 and the ketone 271 were the products resulting from the reaction between the reaction between the lithium enolate of acetophenone and phenyl vinyl sulfoxide. This demonstrated potential scope for the cyclisation process using both cyclic and acyclic ketones.Thesis (PhD Doctorate)Doctor of Philosophy (PhD)Faculty of ScienceSchool of ScienceFull Tex
Intramolecular allylboration of γ-(ω-formylalkoxy)allylboronates for syntheses of trans- or cis-2-(ethenyl)tetrahydropyran-3-ol and 2-(ethenyl)oxepan-3-ol
No full text3-Alkoxy-1-alkynes 4 were hydroborated with pinacolborane (HBpin) to give 3-alkoxy-1-alkenylboronates 5. The latter gave (E)-3-alkoxyallylboronates (8: (E)-(MeO)2CHCH2(CH2)nCH2OCH=CHCH2Bpin, n=1–3) when they were subjected to iridium-catalyzed isomerization of the double bond. The corresponding (Z)-isomers 10 were synthesized by nickel-catalyzed isomerization of 5. Both allylboronates underwent intramolecular allylboration leading to the formation of trans-2-(ethenyl)tetrahydropyran-3-ol or 2-(ethenyl)oxepan-3-ol from 8 and the corresponding cis-isomers from 10 in the presence of Yb(OTf)3 (20 mol%) in aqueous acetonitrile at 90°C
Thermal and optical characterization of micro-LED probes for in vivo optogenetic neural stimulation
No full textWithin optogenetics there is a need for compact light sources that are capable of delivering light with excellent spatial, temporal, and spectral resolution to deep brain structures. Here, we demonstrate a custom GaN-based LED probe for such applications and the electrical, optical, and thermal properties are analyzed. The output power density and emission spectrum were found to be suitable for stimulating channelrhodopsin-2, one of the most common light-sensitive proteins currently used in optogenetics. The LED device produced high light intensities, far in excess of those required to stimulate the light-sensitive proteins within the neurons. Thermal performance was also investigated, illustrating that a broad range of operating regimes in pulsed mode are accessible while keeping a minimum increase in temperature for the brain (0.5°C). This type of custom device represents a significant step forward for the optogenetics community, allowing multiple bright excitation sites along the length of a minimally invasive neural probe. This paper was published in Optics Letters and is made available as an electronic reprint with the permission of OSA. The paper can be found at the following URL on the OSA website: http://dx.doi.org/10.1364/OL.38.000992. Systematic or multiple reproduction or distribution to multiple locations via electronic or other means is prohibited and is subject to penalties under law
She's Not There: When New Illusions Meet Ol' Time RealTtime; Mo-cap, Virtuality and Live Music Performance
No full textShe’s Not There: new illusions meet ol’ time real time opened the CILECT (Centre International de Liaison des Ecoles de Cinéma et de Télévision) congress, Queensland Conservatorium Theatre, Brisbane, on the morning of November 20, 2016 (see Figure 1). Conceived and directed by the authors, Louise Harvey and Peter Moyes, and produced by Peter, the project used motion capture of a vocal performance by Christine Johnston for the 3D animation of our fictional cabaret singer, “Ms. Burly Chassis.” Louise modelled Burly and was assisted in the animation by Griffith Film School graduate Jessica O’Neill. Retaining the vocal track laid down by Christine, composer Cameron Patrick arranged the music for The Zombie’s 1965 hit She’s Not There with reference to a first pass of animation to assist with synchronisation and the creation of musical highlights. Re-presenting this animation on a screen aloft an empty theatrical stage, a virtual camera operator traverses this space, his movements in replication on the screen above, tracked by the motion capture cameras surrounding ‘the volume’ of the stage. The live orchestra accompaniment further embeds the sense of immediacy created by the virtual camera in its affectation of a ‘live broadcast’. Real confronts virtual towards the end of the song as Christine enters the physical stage to take up the refrain (and the accolades) as Burly’s attempts to hit a high note descend into uncontrollable coughing.Arts, Education & Law Group, Queensland College of ArtFull Tex
Agricultural trade liberalization in the Uruguay Round : one step forward, one step back?
No full textAfter evaluating the Uruguay Round's impact on agriculture and border protection in the next decade, the author concludes that while there was significant reform of the rules - particularly the conversion of nontariff barriers into tariffs and the reduction and binding of all tariffs - in practice, trade will probably be liberalized less than expected. The objective of the Round was to reverse protectionism and remove trade distortions. This may not be achieved in practice, at least not until further reductions are carried out in future rounds of negotiations. The major exception to this conclusion is in high-income Asian countries, where protection for major commodities will be significantly reduced. The tariffication and binding of all tariffs on agricultural products represents a significant step forward. Liberalization is implicit because countries are prohhibited from arbitrarily raising tariffs to new higher levels. But many of the newly established tariffs are so high in many countries as to effectively prohibit trade. Patterns of liberalization vary considerably by commodity and by country. Generally, the extent of liberalization was diminished by binding tariffs to the base period of 1986-88, when border protection was at a high point. In most OECD countries, this was worsened by"dirty tariffication:"the new base tariffs offered even greater protection than the nontariff barriers they replaced. Even after the commitments to tariff reductions in the Round, the ad valorem measure of the final binding tariffs will remain higher than the average rate of protection in 1982-93. A number of developing countries in East Asia, Latin America, and the Middle East chose to lock in prior liberalization efforts on some products. But for most commodities, there will be little actual liberalization, since most developing countries chose to bind their tariffs at a maximum level. Even when countries reduced already-bound rates, bound tariffs remained significantly higher than current applied rates, giving countries the flexibility to raise tariffs later. The high level of bound tariffs may allow countries to apply variable tariffs below the bound level, thus failing to stabilize tariffs and improve market access. Moreover, the Round did not touch many of the worst distortions in developing countries, such as import subsidies, export taxes, state-trading monopolies, and domestic policies that implicitly tax agriculture.Trade Policy,Environmental Economics&Policies,Economic Theory&Research,Export Competitiveness,Rules of Origin,Trade Policy,Rules of Origin,TF054105-DONOR FUNDED OPERATION ADMINISTRATION FEE INCOME AND EXPENSE ACCOUNT,Environmental Economics&Policies,Economic Theory&Research
MICROWAVE SPECTROSCOPY OF BUTAN-2-OL - CONFORMATIONS, COMPLEXES AND CLUSTERS
No full textA. K. King and B. J. Howard Chem. Phys. Lett. 348(343), 2001. A. K. King and B. J. Howard J. Mol. Spectrosc., Submitted for publication. A. K. King and B. J. Howard J. Mol. Spectrosc. 201/1(38), 2001.Author Institution: Physical and Theoretical Chemistry Department, University of OxfordThe first rotationally-resolved spectrum of a van der Waals complex formed between two chiral molecules will be presented. The complex is a hetero-chiral dimer of butan-2-ol and the spectrum was observed by Fourier Transform Microwave Spectroscopy in a supersonic . The results of the ab initio calculations used to identify the dimer will also be presented. The microwave spectrum of a complex formed between a butan-2-ol molecule and an argon atom will also be discussed, including a limited amount of structural . This too will be accompanied by an ab initio study. Finally, mention will be made of the detection of six of the nine possible conformational isomers of the butan-2-ol molecule in expansions of argon and . There are still a large number of unassigned lines in the spectrum of butan-2-ol, some of which must be due to the homo-chiral dimer. Work to assign them is ongoing, any new results will be presented
A Critique on the Book Haqiqat-ol Hadiqat: Selections & Selections & Excerpts of All Chapters of Sanai Ghaznavis Hadiqat-ol Haqiqat
No full text“Haqiqat-ol Hadiqat: Selections & Excerpts of All Chapters of Sanai Ghaznavis Hadiqat-ol Haqiqat” is a book compiled by Homeira Zomorodi, with the aim of providing a selection from “Sanai Ghaznavis Hadiqat-ol Haqiqat” book and related commentary. Was the book successful in achieving its purpose of familiarizing Persian literature readers and students with this significant Persian literary work? In order to evaluate the text accuracy, the author refers to valid sources such as Persian dictionaries, the original text of Sana’i Ghaznavi’s book, old Persian texts sharing common anecdotes with the original text, and commentaries and explications. As a result of such evaluation, few shortcomings have been found, some of which can be cited as various writing, editing, and printing-related flaws in the text, and the citations of verses in many cases are incorrect. In several instances, there are also inaccurate interpretations of verses, incorrect presentation of anecdotes and allusions origins, and flawed translation of cited Arabic phrases. Also, many verses are left unexplained
Introducing Kholasat ol-Maqamat and its stylistic and lingual characteristics
No full textAbstract
Kholasat ol-Maqamat is a manuscript on spiritual stations of famous mystic and Sofi, Sheikh Ahmad Jam. This manuscript has been written by Ab ol-Makarem Ibn Alaâ ol-Molk Jami, one of Sheikh Ahmad's descendants, in the time of Shahrokh Mirzaâs reign (840) to whom that manuscript was presented.
The style of this book is similar to that of Asrar ot-Towhid and as it appears from its name, it is a concise of some books on maqamat written in Sheikh Jam's time. Therefore, maqamt is a name applied generally to papers written about spiritual stations of special characters. Historically, it so happened that this work probably belongs to Sheikh Ahmad's time, because at that time or afterwards some books have been written on his spiritual stations which we will point out. We believe works of this kind which has been written afterwards, such as Asrar ot-Towhid on Abu Saeed's spiritual stations are affected by the method of maqamat-writing in the time of Ahmad Jam, and Kholasat ol-Maqamat is an anthology of early works on this subject.
To write this book, Alaâ ol-Molk, in addition to Mohammad Ghaznavi's Maqamat which is a description of the Ahmad Jam's Maqamat, has used four Maqamats: Imam razi od-Din Ilias Taybadi's Maqamat, Sheikh Ahmad Tarkhestani's Maqamat, Taj ed-Din Mahmoud buzjani's Maqamat and Darwish Ali Buzjani's Maqamat.
Moreover, he has benefited from Khaje Mohammad Heisamâs History, Jameâ ol-Osul, Some of Sihahe Sitte and Masanid Arbaâe, apparently complete works of Several poets including Sheikh Attar Neishaburi and also some works of Sheikh Jam (Ons ot-Taebin, Seraj os-Saâerin, Rawzat ol-Moznebin, Konuz ol-Hekme, Miftah on-Nijat, Bihar ol-Haqiqe and a collection of Sheikh Jamâs poems). Additionally, this book contains mystical, geographical, historical benefits and stylistic and lingual characteristics.
This manuscript is distinguishable for some reasons such as availability of some other manuscripts titled maqamat of which the author made used, all have been written in jam's time by his cohorts. Each of them has a great value, since that time is probably the beginning of writing maqamat. Because on the basis of notes remained, Alaâol-Molk has used four maqamats named Imam Razi od-Din Ilias Taibadi, Sheikh Ahmad Tarkhestani, Darvish Ali Buzjani that now there is no information about. This point increases the value of Kholasat ol-Maqamat.
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He had also some of his ancestor's works that contain more accurate and detailed subjects as well as more complete information about family and descendents of Sheikh than Mohammad Ghaznavi's Maqamat.
Three manuscripts of Kholasat ol-Maqamat are available with different mode of hand writing: Manuscript in Ganj Bakhsh library of Lahur, manuscript in theology faculty of University of Mashhad and digital library of parliament.
Finally, necessary to say, this manuscript indicates Sheikh's spiritual stations happened to and written by his cohorts at that time. Since that papers except Mohammad Ghaznavi's Maqamat have been disappeared, Kholasat ol-Maqamat which is the extract of those maqamats could be known as the most important and exquisite manuscript about Sheikh's spiritual stations and Keramat.
Actually, recognition, introduction and emendation of this manuscript will be an effective and fruitful step to know more about Sheikh Ahmad Jam and his spiritual stations and tunes and the style of writing maqamat which is of high importance for researchers in getting information about Sheikh's dignity and styles of writing maqamat. There is a hope that this book has the success of unveilin
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