Treaties as a Tool for Native American Land Reparations

The only compensation for land is land. 1 Hundreds of treaties signed. Hundreds of treaties broken. The juvenile United States grew in size as independent Native nations ceded their territory through treaties. Thirsting for more land, the United States broke its promises and continued its manifest destiny westward. And what of tribes’ treaty rights to land? Some Native nations received financial compensation for treaty violations. But money is crumbs to many whose traditional homelands are still colonized. Tribes are entitled to the land promised to them under treaties—instruments supposedly carrying the force of federal law. Land reparations are a partial resolution to address land theft. It is one apparatus to strengthen tribal sovereignty. This comment provides an inventory of where the federal government may strengthen existing treaty rights to land or increase the acreage of indigenous-held land. Each of the recommendations is a proxy to bolster land reparations for Native Americans. Part I briefly summarizes how the federal government seized land from indigenous tribes and has yet to meaningfully remedy this harm. Part II explores congressional and judicial areas that should be modified to support land reparations. Part III describes treaty rights litigation and explains these cases’ broader impact on land reparations. Part IV explains how treaties can buttress administrative fee-to-trust land acquisitions. Part V discusses examples of how, if adopted into domestic legislation, international legal frameworks provide a structure for land reparations. Northwestern University and Northwestern Pritzker School of Law occupy the traditional land of the Council of the Three Fires: the Ojibwe, Odawa, and Potawatomi tribes. Other tribes impacted by the colonization of Chicago include the Ho’Chunk, Miami, Menominee, Otoe, Missouria, Iowas, Meskwaki, Sauk, Wea, Piankashaw, Kickapoo, and Illini Confederacy. Members of 157 indigenous nations live in Chicago today, which remains the largest population of Native Americans in the Midwest. “The City of Chicago would not exist” if not for the 1795 Treaty of Greenville, 1816 Treaty of St. Louis, 1821 Treaty of Chicago, and the 1833 Treaty of Chicago. encourage every reader: understand the story of the land you occupy. Learn whose traditional homelands you live on. Learn whether an indigenous tribe has treaty rights to, or on, the land you occupy. 1 Sam Levin, ‘This Is All Stolen Land’: Native Americans Want More Than California’s Apology, THE GUARDIAN (Jun. 21, 2019), https://www.theguardian.com/us-news/2019/jun/20/california-native-americans-governor-apology-reparations

How Can Fairness Tools Impact the Understanding of Fairness and the Processes Within a Machine Learning Development Team?

Over the last years, a wide spread of Machine Learning in increasingly more, especially sensitive areas like criminal justice or healthcare has been observed. Popular cases of algorithmic bias illustrate the potential of Machine Learning to reproduce and reinforce biases present in the analogous world and thus lead to discrimination. The realisation of this potential has led to the creation of the research stream on fair, accountable and transparent Machine Learning. One aspect of this research field is the development of fairness tools, algorithmic toolkits that aim to assist developers of Machine Learning in identifying and eliminating bias in their models and thus ensuring fairness. The literature review on fairness tools has revealed a research gap in the impact of these on the understanding of fairness and the processes within a development team. Thus, the aim of this research was to investigate the impact that fairness tools can have on the notion of fairness and the processes in a development team. Therefore, a case study with a development team of a large, globally operating corporation has been conducted. Applying Kallinikos´ theory of technology as a regulative regime and Oudshoorn and Pinch´s idea of the co-construction of users and technologies on the empirical findings revealed two important conclusions. Firstly, it shows that fairness tools act as regulative regimes by shaping the understanding of fairness and the processes within a development team. Secondly, this character of fairness tools as regulative regimes needs to be understood as part of the coconstruction process between the technology and the developer. Keywords: Machine learning; Fairness; Fairness tools; Regulative regime of technology; Co-construction of user and technology.Over the last years, a wide spread of Machine Learning in increasingly more, especially sensitive areas like criminal justice or healthcare has been observed. Popular cases of algorithmic bias illustrate the potential of Machine Learning to reproduce and reinforce biases present in the analogous world and thus lead to discrimination. The realisation of this potential has led to the creation of the research stream on fair, accountable and transparent Machine Learning. One aspect of this research field is the development of fairness tools, algorithmic toolkits that aim to assist developers of Machine Learning in identifying and eliminating bias in their models and thus ensuring fairness. The literature review on fairness tools has revealed a research gap in the impact of these on the understanding of fairness and the processes within a development team. Thus, the aim of this research was to investigate the impact that fairness tools can have on the notion of fairness and the processes in a development team. Therefore, a case study with a development team of a large, globally operating corporation has been conducted. Applying Kallinikos´ theory of technology as a regulative regime and Oudshoorn and Pinch´s idea of the co-construction of users and technologies on the empirical findings revealed two important conclusions. Firstly, it shows that fairness tools act as regulative regimes by shaping the understanding of fairness and the processes within a development team. Secondly, this character of fairness tools as regulative regimes needs to be understood as part of the coconstruction process between the technology and the developer. Keywords: Machine learning; Fairness; Fairness tools; Regulative regime of technology; Co-construction of user and technology

Synthesis, Characterization, and Oxygenation Studies of Carboxylate-Bridged Diiron(II) Complexes with Aromatic Substrates Tethered to Pyridine Ligands and the Formation of a Unique Trinuclear Complex

In this study, diiron(II) complexes were synthesized as small molecule mimics of the reduced active sites in the hydroxylase components of bacterial multicomponent monooxygenases (BMMs). Tethered aromatic substrates were introduced in the form of 2-phenoxypyridines, incorporating hydroxy and methoxy functionalities into windmill-type diiron(II) compounds [Fe[subscript 2](μ-O[subscript 2]CAr[superscript R])[subscript 2](O[subscript 2]CAr[superscript R])[subscript 2](L)[subscript 2]] (1–4), where[superscript –]O[subscript 2]CAr[superscript R] is a sterically encumbering carboxylate, 2,6-bis(4-fluorophenyl)-, or 2,6-bis(p-tolyl)benzoate (R = 4-FPh or Tol, respectively). The inability of 1–4 to hydroxylate the aromatic substrates was ascertained. Upon reaction with dioxygen, compounds 2 and 3 (L = 2-(m-MeOPhO)Py, 2-(p-MeOPhO)Py, respectively) decompose by a known bimolecular pathway to form mixed-valent diiron(II,III) species at low temperature. Use of 2-(pyridin-2-yloxy)phenol as the ligand L resulted in a doubly bridged diiron complex 4 and an unprecedented phenoxide-bridged triiron(II) complex 5 under slightly modified reaction conditions.National Institute of General Medical Sciences (U.S.) (Grant GM032134

Modeling the active sites of non-heme diiron metalloproteins with sterically hindered carboxylates and syn N-Donor ligands

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2009.Cataloged from PDF version of thesis. Vita.Includes bibliographical references.Chapter 1. Different Synthetic Approaches to Modeling the Active Sites of Carboxylate-Bridged Non-Heme Diiron Enzymes Carboxylate-bridged non-heme diiron enzymes activate dioxygen to perform a variety of biological functions. Synthetic model compounds have been prepared to gain insight into the intricacies of dioxygen activation in these enzymes. In this introductory chapter, the challenges and advances of different diiron systems with terphenyl and dendrimer-appended carboxylates, nitrogen-rich, and syn Ndonor ligands are highlighted. Chapter 2. 9-Triptycenecarboxylate-Bridged Diiron(ll) Complexes: Capture of the Paddlewheel Geometric Isomer The synthesis and characterization of diiron(ll) complexes supported by 9- triptycenecarboxylate ligands (-O2CTrp) is described. The interlocking nature of the triptycenecarboxylates facilitates formation of quadruply bridged diiron(ll) complexes of the type [Fe 2(-O 2CTrp) 4(L) 2] (L = THF, pyridine or imidazole derivative) with a paddlewheel geometry. A systematic lengthening of the Fe-Fe distance occurs with the increase in steric bulk of the neutral donor L, resulting in values of up to 3 A without disassembly of the paddlewheel structure. Reactions with an excess of water do not lead to decomposition of the diiron(ll) core, indicating that these quadruply bridged complexes are exceptionally stable. The red-colored complexes [Fe2(f-O2CTrp) 4(4-AcPy) 2] (10) and [Fe2(M-O2CTrp)4(4- CNPy)2] (11) exhibit solvent-dependent thermochromism in coordinating solvents that was studied by variable temperature UV-vis spectroscopy.(cont.) Reaction of [Fe 2(1-O2CTrp)4(THF)2] with N,N,N',N'-tetramethylethylenediamine (TM EDA), tetra-n-butyl ammonium thiocyanate, or excess 2-methylimidazole resulted in the formation of mononuclear complexes [Fe(O 2CTrp) 2(TMEDA)] (13), (nBu 4N)2[Fe(O2CTrp) 2(SCN)2] (14), and [Fe(O 2CTrp)2(2-Melm) 2] (15) having an 04/N2 coordination sphere composition. Chapter 3. Synthesis, Characterization, and Oxygenation Studies of Carboxylate-Bridged Diiron(ll) Complexes with Aromatic Substrates Tethered to Pyridine Ligands and the Formation of a Unique Trinuclear Complex In this study, diiron(ll) complexes were synthesized as small molecule mimics of the reduced active sites in the hydroxylase components of bacterial multicomponent monooxygenases (BMMs). Tethered aromatic substrates were introduced in the form of 2-phenoxypyridines, incorporating hydroxy and methoxy functionalities into windmill-type diiron(llII) compounds [Fe 2(M-0 2CArR)2 - (O2CArR) 2(L) 2] (1-4), where -O2CArR is a sterically encumbering carboxylate, 2,6- di(4-fluorophenyl)- or 2,6-di(p-tolyl)benzoate (R = 4-FPh or Tol, respectively). The inability of 1-4 to hydroxylate the aromatic substrates was ascertained. Upon reaction with dioxygen, compounds 2 and 3 (L = 2-(m-MeOPhO)Py, 2-(p- MeOPhO)Py, respectively) decompose by a known bimolecular pathway to form mixed-valent diiron(ll,lll) species at low temperature. Use of 2-(pyridin-2- yloxy)phenol as the ligand L resulted in a doubly bridged diiron complex (4) and 5 an unprecedented phenoxide-bridged triiron(ll) complex (5) under slightly modified reaction conditions. Chapter 4.(cont.) Modeling the Syn-Disposition of Nitrogen Donors in Non-Heme Diiron Enzymes. Synthesis, Characterization and Hydrogen Peroxide Reactivity of Diiron(lll) Complexes with the Syn N-Donor Ligand H2BPG2DEV In order to model the syn disposition of histidine residues in carboxylate-bridged non-heme diiron enzymes, we prepared a new dinucleating ligand, H2BPG 2DEV, that provides this geometric feature. The ligand incorporates biologically relevant carboxylate functionalities, which have not been explored as extensively as nitrogen-only analogs. Three novel oxo-bridged diiron(lll) complexes [Fe 2( - O)(H20) 2(BPG2DEV)](CI0 4)2 (6), [Fe 2(p-O)(-O02CAriPro)(BPG 2DEV)](CIO 4) (7), and [Fe 2(,1-O)(-CO 3)(BPG 2DEV)] (8) were prepared. Single crystal X-ray structural characterization confirms that two pyridines are bound syn with respect to the Fe-Fe vector in these compounds. The carbonato-bridged complex 8 forms quantitatively from 6 in a rapid reaction with gaseous CO02 in organic solvents. A common maroon-colored intermediate (max = 490 nm; e= 1500 M- 1 cm - 1) forms in reactions of 6, 7, or 8 with H20 2 and NEt 3 in CH 3CN/H 20 solutions. Mass spectrometric analyses of this species, formed using 180-labeled H20 2, indicate the presence of a peroxide ligand bound to the oxo-bridged diiron(lll) center. The Mossbauer spectrum at 90 K of the EPR-silent intermediate exhibits a quadrupole doublet with 6 = 0.58 mm/s and AEQ = 0.58 mm/s. The isomer shift is typical for a peroxodiiron(lll) species, but the quadrupole splitting parameter is unusually small compared to related complexes.(cont.) These Mossbauer parameters are comparable to those observed for a peroxo intermediate formed in the reaction of reduced toluene/o-xylene monooxygenase hydroxylase (ToMOH) with dioxygen. Resonance Raman studies reveal an unusually low-energy 0-0 stretching mode in the peroxo intermediate that is consistent with a short diiron distance. Although peroxodiiron(lll) intermediates generated from 6, 7, and 8 are poor O-atom transfer catalysts, they display highly efficient catalase activity, with turnover numbers up to 10,000. In contrast to hydrogen peroxide reactions of diiron(Ill) complexes that lack a dinucleating ligand, the intermediates generated here could be reformed in significant quantities after a second addition of H20 2, as observed spectroscopically and by mass spectrometry. Appendix 1. Supporting Tables and Figures for Chapter 2 Appendix 2. Supporting Information for Chapter 4 Appendix 3. Synthesis of Triptycene Carboxylate-Bridged Dimetallic Complexes with First Row Transition Metals The synthesis and structural characterization of dimetallic complexes of the type [M2(1t-02CTrp) 4(THF)2] (M = Mn, Co, Ni, Cu, Zn) supported by triptycenecarboxylate ligands (-O2CTrp) is described. Appendix 4. Synthesis and Structure of a Molecular Ferrous Wheel, [Fe(0 2CH)(O 2CArPro)(1,4-dioxane)]6 The structural characterization of a novel, hexanuclear iron(ll) compound with the carboxylate ArPrOCO2- is described.by Simone Friedle.Ph.D

Forest Resource Use, Land-Use, and Ecotourism in the Río Plátano Biosphere Reserve, Honduras

The Río Pláttano Biosphere Reserve, a tropical rainforest reserve in the northeastern corner of Honduras, is home to several subsistence-based indigenous groups, including the Miskito, Pech and Garifuna, as well as the non-indigenous Ladinos. Communities within the reserve depend on forest resources, swidden agriculture, marine resources and/or small-scale ranching as the foundations for local economies. Regulations placed on these subsistence practices, after establishment of the biosphere reserve in 1980, have created unique and new pressures and resulted in a blend of traditional and innovative resource use. A notable result is the promotion of ecotourism as a solution for meeting the economic needs of local populations while conserving local resources. This thesis documents current resource use in the Miskito and Ladino communities of Banaka, Brans, and Fuente de Jacob, in the Río Pláttano Biosphere Reserve and the potential of ecotourism to maintain both local economies and consumption of tropical rainforest resources in these communities. Analysis suggests that a community-based approach to ecotourism can result in economic benefits and maintain local culture. This thesis documents current resource use (agricultural crops and trees, gathered and cultivated plants, tree-use, and hunting), resident perspectives on ecotourism development and industry, and provides the foundation for long-term monitoring and analysis on the effects of ecotomism on forest resource and land-use in the greater Banaka region

Heat exchanger/reactors (HEX reactors): Concepts, technologies: State-of-the-art

Process intensification is a chemical engineering field which has truly emerged in the past few years and is currently rapidly growing. It consists in looking for safer operating conditions, lower waste in terms of costs and energy and higher productivity; and away to reach such objectives is to develop multifunctional devices such as heat exchanger/reactors for instance. This review is focused on the latter and makes a point on heat exchanger/reactors. After a brief presentation of requirements due to transposition from batch to continuous apparatuses, heat exchangers/reactors at industrial or pilot scales and their applications are described

Technical guidelines on testing the migration of primary aromatic amines from polyamide kitchenware and of formaldehyde from melamine kitchenware - 1st edition 2011

Comparability of results is an important feature of the measurements carried out for official controls purposes. In the area of food contact materials and articles comparability of results is dependent on the availability of samples representative of the consignment, the type of exposure and the test conditions used as well as on the performance of the method of analysis. These guidelines contain practical information on sampling, migration testing and methodologies for the analytical determination of primary aromatic amines and of formaldehyde. These guidelines were developed specifically in the context of the Regulation 284/2011 laying down specific conditions and detailed procedures for the import of polyamide and melamine plastic kitchenware originating in or consigned from [the] People's Republic of China and Hong Kong Special Administrative Region, China. These guidelines have been prepared by the European Union Reference Laboratory in collaboration with its EU official Network of National Reference Laboratories and have been endorsed by the European Commission competent service DG Health and Consumers (DG SANCO) and its network of Member State Competent Authorities. They are primarily addressed to official control laboratories, national reference laboratories and third party laboratories for providing certificates of compliance. The sampling strategy is addressed to the points of first introduction of import goods in the EU.JRC.I.1-Chemical Assessment and Testin