title: Reversible pyranyl complex formation and the mechanism of rearrangement to (η5-6-oxocycloheptadienyl)Mn(CO)3 complexes in the reaction of β-cyclomanganated 1,5-diarylpenta-1,4-dien-3-ones and alkynes; the crystal structure of [2,4-diphenyl-6-(2-phenylethenyl)pyranyl-η5]tricarbonylmanganese

authors: Mace, Wade

subjects: Manganese

abstract: 1-Phenyl-2-[(E)-3-phenylprop-2-en-1-oyl-κO]ethenyl-κC1]tetracarbonylmanganese (1a) reacts with PhCCH in CCl4 at room temperature to form [2,4-diphenyl-6-(2-phenylethenyl)pyranyl-η5]tricarbonylmanganese (2a), whose X-ray crystal structure is reported to complement that of its isomer [6-oxo-2,4,7-triphenylcyclohepta-1,4-dienyl-1,2,3,4,5-η]tricarbonylmanganese (3a), previously obtained from the reaction under reflux; but for 1a and PhCCPh the pyranyl complex cannot be isolated before rearrangement to the 3a analogue occurs. More forcing reaction conditions for 1a with Me3SiCCH and for [1-(2-trifluoromethylphenyl)-2-[(E)-3-(2-trifluoromethylphenyl)prop-2-en-1-oyl-κO]ethenyl-κC1]tetracarbonylmanganese (1b) with Me3SiCCH and PhCCH give new analogues of 3a where previously only 2a analogues had been isolated.
The reaction in CCl4 under reflux of PhCCH and the β-deuterio analogue of 1a, [1-phenyl-2-[(E)-3-phenylprop-2-en-1-oyl-3d-κO]ethenyl-κC1]tetracarbonylmanganese, gave deuteriated 3a with exo-D at the α-carbon, C7. This is inconsistent with the Mn-mediated Ph migration mechanism originally proposed to accommodate the endo position of Ph in 3a, and instead it implicates a cyclopropyl carbonyl-addition intermediate or a cyclopropyl acyl-substitution transition state in the key rearrangement step for 2a → 3a.

text: Reversible pyranyl complex formation and the mechanism of rearrangement to (η5-6-oxocycloheptadienyl)Mn(CO)3 complexes in the reaction of β-cyclomanganated 1,5-diarylpenta-1,4-dien-3-ones and alkynes; the crystal structure of [2,4-diphenyl-6-(2-phenylethenyl)pyranyl-η5]tricarbonylmanganese 1-Phenyl-2-[(E)-3-phenylprop-2-en-1-oyl-κO]ethenyl-κC1]tetracarbonylmanganese (1a) reacts with PhCCH in CCl4 at room temperature to form [2,4-diphenyl-6-(2-phenylethenyl)pyranyl-η5]tricarbonylmanganese (2a), whose X-ray crystal structure is reported to complement that of its isomer [6-oxo-2,4,7-triphenylcyclohepta-1,4-dienyl-1,2,3,4,5-η]tricarbonylmanganese (3a), previously obtained from the reaction under reflux; but for 1a and PhCCPh the pyranyl complex cannot be isolated before rearrangement to the 3a analogue occurs. More forcing reaction conditions for 1a with Me3SiCCH and for [1-(2-trifluoromethylphenyl)-2-[(E)-3-(2-trifluoromethylphenyl)prop-2-en-1-oyl-κO]ethenyl-κC1]tetracarbonylmanganese (1b) with Me3SiCCH and PhCCH give new analogues of 3a where previously only 2a analogues had been isolated.
The reaction in CCl4 under reflux of PhCCH and the β-deuterio analogue of 1a, [1-phenyl-2-[(E)-3-phenylprop-2-en-1-oyl-3d-κO]ethenyl-κC1]tetracarbonylmanganese, gave deuteriated 3a with exo-D at the α-carbon, C7. This is inconsistent with the Mn-mediated Ph migration mechanism originally proposed to accommodate the endo position of Ph in 3a, and instead it implicates a cyclopropyl carbonyl-addition intermediate or a cyclopropyl acyl-substitution transition state in the key rearrangement step for 2a → 3a.

year: 2005-07-01

title: A Comparison of Multi-instance Learning Algorithms

authors: Dong, Lin

subjects: machine learning

abstract: Motivated by various challenging real-world applications, such as drug activity prediction and image retrieval, multi-instance (MI) learning has attracted considerable interest in recent years.  Compared with standard supervised learning, the MI learning task is more difficult as the label information of each training example is incomplete. Many MI algorithms have been proposed. Some of them are specifically designed for MI problems whereas others have been upgraded or adapted from standard single-instance learning algorithms.  Most algorithms have been evaluated on only one or two benchmark datasets, and there is a lack of systematic comparisons of MI learning algorithms.

This thesis presents a comprehensive study of MI learning algorithms that aims to compare their performance and find a suitable way to properly address different MI problems. First, it briefly reviews the history of research on MI learning. Then it discusses five general classes of MI approaches that cover a total of 16 MI algorithms. After that, it presents empirical results for these algorithms that were obtained from 15 datasets which involve five different real-world application domains.  Finally, some conclusions are drawn from these results: (1) applying suitable standard single-instance learners to MI problems can often generate the best result on the datasets that were tested, (2) algorithms exploiting the standard asymmetric MI assumption do not show significant advantages over approaches using the so-called collective assumption, and (3) different MI approaches are suitable for different application domains, and no MI algorithm works best on all MI problems.

text: A Comparison of Multi-instance Learning Algorithms Motivated by various challenging real-world applications, such as drug activity prediction and image retrieval, multi-instance (MI) learning has attracted considerable interest in recent years.  Compared with standard supervised learning, the MI learning task is more difficult as the label information of each training example is incomplete. Many MI algorithms have been proposed. Some of them are specifically designed for MI problems whereas others have been upgraded or adapted from standard single-instance learning algorithms.  Most algorithms have been evaluated on only one or two benchmark datasets, and there is a lack of systematic comparisons of MI learning algorithms.

This thesis presents a comprehensive study of MI learning algorithms that aims to compare their performance and find a suitable way to properly address different MI problems. First, it briefly reviews the history of research on MI learning. Then it discusses five general classes of MI approaches that cover a total of 16 MI algorithms. After that, it presents empirical results for these algorithms that were obtained from 15 datasets which involve five different real-world application domains.  Finally, some conclusions are drawn from these results: (1) applying suitable standard single-instance learners to MI problems can often generate the best result on the datasets that were tested, (2) algorithms exploiting the standard asymmetric MI assumption do not show significant advantages over approaches using the so-called collective assumption, and (3) different MI approaches are suitable for different application domains, and no MI algorithm works best on all MI problems.

year: 2006

title: Te manemanerau a te kāwanatanga: A history of the confiscation of Tūhoe lands in the Bay of Plenty

authors: Melbourne, Sydney

subjects: Ngāi Tūhoe

abstract: This thesis endeavours to show that Tūhoe lands should never have been confiscated and that Tūhoe efforts to gain compensation have been totally unsuccessful to date. When certain lands within the confiscated district of the Bay of Plenty were returned to the tribes there, Tūhoe were not granted any. Furthermore, lands which actually belonged to Tūhoe were granted to other tribes.
Although the major focus is on issues specific to Tūhoe, these are viewed within the wider context of nineteenth century land acquisition in New Zealand. This study looks at Tūhoe historical claims to disputed lands included in the confiscation district of the Bay of Plenty. Chapter One traces the extent of Tūhoe territories within the confiscation district and describes how Tūhoe came to occupy them and the duration of their occupation. Information about these claims came from tribal oral sources and original manuscripts, as well as from more generally accessible sources.
The development of colonial expansion patterns is discussed in Chapter Two. The contention is that they were based on materialistic considerations and legal pretexts to justify the acquisition of Māori lands. Hostilities between Māori and Government in the Bay of Plenty are dealt with in Chapter Three. Particular attention is paid to the causes of the hostilities and the complex racial and political misunderstandings which contributed to the inevitability of war. As a result of these encounters, the New Zealand Settlements Act was imposed.
Chapter Four covers the implementation of its provisions through the Compensation Court. The failings of this Court and its commissioners and field officials are exposed.
Chapter Five examines the settlement of Tūhoe lands in Ōpouriao and Waimana, as well as the changing fortunes of some of the settlers who took advantage of the settlement scheme. After placing the experiences of Tūhoe people within the wider context of what had taken place in New Zealand, Chapter Six focuses on Tūhoe attempts to bring the wrongs they had suffered to the attention of Government. In retrospect these early Tūhoe attempts at redress show that much has to be learnt about presenting substantial submissions. It was obvious that much of what was known by the elders then, though recorded, was never used in evidence to support their petitions. Nonetheless, without the existence of these manuscripts, present attempts would not be possible.
Chapter Seven gives a basis for a proposed just settlement for the confiscation of Tūhoe lands. In order to provide a guide for monetary compensation, details of values of Tūhoe confiscated land have been sought from official records. Compensation for the denial of justice, the loss of human life, land and property, remain open for negotiation.
Finally, while certain conclusions can be and are drawn from these investigations, the end of the story remains unwritten. It will depend on the outcome of new Tūhoe attempts to gain redress from the appropriate statutory body.

text: Te manemanerau a te kāwanatanga: A history of the confiscation of Tūhoe lands in the Bay of Plenty This thesis endeavours to show that Tūhoe lands should never have been confiscated and that Tūhoe efforts to gain compensation have been totally unsuccessful to date. When certain lands within the confiscated district of the Bay of Plenty were returned to the tribes there, Tūhoe were not granted any. Furthermore, lands which actually belonged to Tūhoe were granted to other tribes.
Although the major focus is on issues specific to Tūhoe, these are viewed within the wider context of nineteenth century land acquisition in New Zealand. This study looks at Tūhoe historical claims to disputed lands included in the confiscation district of the Bay of Plenty. Chapter One traces the extent of Tūhoe territories within the confiscation district and describes how Tūhoe came to occupy them and the duration of their occupation. Information about these claims came from tribal oral sources and original manuscripts, as well as from more generally accessible sources.
The development of colonial expansion patterns is discussed in Chapter Two. The contention is that they were based on materialistic considerations and legal pretexts to justify the acquisition of Māori lands. Hostilities between Māori and Government in the Bay of Plenty are dealt with in Chapter Three. Particular attention is paid to the causes of the hostilities and the complex racial and political misunderstandings which contributed to the inevitability of war. As a result of these encounters, the New Zealand Settlements Act was imposed.
Chapter Four covers the implementation of its provisions through the Compensation Court. The failings of this Court and its commissioners and field officials are exposed.
Chapter Five examines the settlement of Tūhoe lands in Ōpouriao and Waimana, as well as the changing fortunes of some of the settlers who took advantage of the settlement scheme. After placing the experiences of Tūhoe people within the wider context of what had taken place in New Zealand, Chapter Six focuses on Tūhoe attempts to bring the wrongs they had suffered to the attention of Government. In retrospect these early Tūhoe attempts at redress show that much has to be learnt about presenting substantial submissions. It was obvious that much of what was known by the elders then, though recorded, was never used in evidence to support their petitions. Nonetheless, without the existence of these manuscripts, present attempts would not be possible.
Chapter Seven gives a basis for a proposed just settlement for the confiscation of Tūhoe lands. In order to provide a guide for monetary compensation, details of values of Tūhoe confiscated land have been sought from official records. Compensation for the denial of justice, the loss of human life, land and property, remain open for negotiation.
Finally, while certain conclusions can be and are drawn from these investigations, the end of the story remains unwritten. It will depend on the outcome of new Tūhoe attempts to gain redress from the appropriate statutory body.

year: 1987