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The controlled isomerization and functionalization of alkenes is a cornerstone achievement in organometallic catalysis that is now widely used throughout industry. In particular, the addition of CO and H2 to an alkene, also known as the oxo-process, is used in the production of linear aldehydes from crude alkene feedstocks. In these catalytic reactions, isomerization is governed by thermodynamics, giving rise to functionalization at the most stable alkylmetal species. Despite the ubiquitous industrial applications of tandem alkene isomerization/functionalization reactions, selective functionalization at internal positions has remained largely unexplored. Here we report that the simple W(0) precatalyst W(CO)6 catalyses the isomerization of alkenes to unactivated internal positions and subsequent hydrocarbonylation with CO. The six- to seven-coordinate geometry changes that are characteristic of the W(0)/W(II) redox cycle and the conformationally flexible directing group are key factors in allowing isomerization to take place over multiple positions and stop at a defined unactivated internal site that is primed for in situ functionalization.

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Developing strategies to study reactivity and selectivity in flexible catalyst systems has become an important topic of research. Herein, we report a combined experimental and computational study aimed at understanding the mechanistic role of an achiral DABCOnium cofactor in a regio- and enantiodivergent bromocyclization reaction. It was found that electron-deficient aryl substituents enable rigidified transition states via an anion-π interaction with the catalyst, which drives the selectivity of the reaction. In contrast, electron-rich aryl groups on the DABCOnium result in significantly more flexible transition states, where interactions between the catalyst and substrate are more important. An analysis of not only the lowest-energy transition state structures but also an ensemble of low-energy transition state conformers via energy decomposition analysis and machine learning was crucial to revealing the dominant noncovalent interactions responsible for observed changes in selectivity in this flexible system.

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The human casualties from simulated nuclear detonation scenarios in New Delhi, India are analyzed, with a focus on the distribution of casualties in urban environments and the theoretical application of a nuclear-specific triage system with significant innovation in interdisciplinary disaster management applicable generally to urban nuclear detonation medical response. Model estimates of nuclear war casualties employed ESRI's ArcGIS 9.3, blast and prompt radiation were calculated using the Defense Nuclear Agency's WE program, and fallout radiation was calculated using the Defense Threat Reduction Agency's (DTRA's) Hazard Prediction and Assessment Capability (HPAC) V404SP4, as well as custom GIS and database software applications. ESRI ArcGISTM programs were used to calculate affected populations from the Oak Ridge National Laboratory's LandScanTM 2007 Global Population Dataset for areas affected by thermal, blast and radiation data. Trauma, thermal burn, and radiation casualties were thus estimated on a geographic basis for New Delhi, India for single and multiple (six) 25 kt detonations and a single 1 mt (1000 kt) detonation. Major issues related to the emergency management of a nuclear incident are discussed with specific recommendations for improvement. The consequences for health management of thermal burn and radiation patients is the worst, as burn patients require enormous resources to treat, and there will be little to no familiarity with the treatment of radiation victims. Of particular importance is the interdisciplinary cooperation necessary for such a large-scale emergency response event, which would be exemplified by efforts such as the application of a Nuclear Global Health Workforce.

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BACKGROUND: The proliferation of nuclear technology in the politically volatile Middle East greatly increases the likelihood of a catastrophic nuclear war. It is widely accepted, while not openly declared, that Israel has nuclear weapons, and that Iran has enriched enough nuclear material to build them. The medical consequences of a nuclear exchange between Iran and Israel in the near future are envisioned, with a focus on the distribution of casualties in urban environments. METHODS: Model estimates of nuclear war casualties employed ESRI's ArcGIS 9.3, blast and prompt radiation were calculated using the Defense Nuclear Agency's WE program, and fallout radiation was calculated using the Defense Threat Reduction Agency's (DTRA's) Hazard Prediction and Assessment Capability (HPAC) V404SP4, as well as custom GIS and database software applications. Further development for thermal burn casualties was based on Brode, as modified by Binninger, to calculate thermal fluence. ESRI ArcGISTM programs were used to calculate affected populations from the Oak Ridge National Laboratory's LandScanTM 2007 Global Population Dataset for areas affected by thermal, blast and radiation data. RESULTS: Trauma, thermal burn, and radiation casualties were thus estimated on a geographic basis for three Israeli and eighteen Iranian cities. Nuclear weapon detonations in the densely populated cities of Iran and Israel will result in an unprecedented millions of numbers of dead, with millions of injured suffering without adequate medical care, a broad base of lingering mental health issues, a devastating loss of municipal infrastructure, long-term disruption of economic, educational, and other essential social activity, and a breakdown in law and order. CONCLUSIONS: This will cause a very limited medical response initially for survivors in Iran and Israel. Strategic use of surviving medical response and collaboration with international relief could be expedited by the predicted casualty distributions and locations. The consequences for health management of thermal burn and radiation patients is the worst, as burn patients require enormous resources to treat, and there will be little to no familiarity with the treatment of radiation victims. Any rational analysis of a nuclear war between Iran and Israel reveals the utterly unacceptable outcomes for either nation.

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This special issue moves us forward in the discussion on disproportionality and disparate outcomes and in the identification and implementation of strategies and solutions. What is clear from this journal's articles is that addressing the disparities of children of color in foster care will require that we take an approach that is comprehensive and inclusive to allow us get to the root causes and create real sustainable change. This means we have to address the issue not only inside child welfare but across all systems and institutions that touch the lives of children and families; not only from the perspective of the child's well being but also from the perspective of the family's well being; and not only on the local level but also on the state and federal levels through policy change that aligns with our goals to keep all children safe by strengthening families. As the articles indicate, if we are to achieve any measure of success, we must build our efforts and strategies on a foundation that embraces and encourages an integrated response. Too often child welfare and other child-serving agencies address the needs of children on a very individual basis, outside the context of their families. That is the way the system is set up. However, to improve outcomes for all children, including children of color, we have to change our paradigm from that of child welfare to that of family well being, always seeing children in the context of their families; families in the context of their communities; and any intervention in the context of an integrated family and community support network. For example, addressing child neglect associated with poverty issues requires that we not only address the needs of that child or poor families, but we must also ultimately take actions to address the needs of the poor communities in which those children and families are trying to exist. Such an integrated response leads us to acknowledge the interconnectedness of children, families and their communities and to design strategies of intervention with an understanding that only when we address causative factors across each of these three spectrums (child, family, community) can we truly create the change we seek--improved outcomes for children of color--for all children--in or at risk of entering foster care.

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BACKGROUND: The threat posed by the use of weapons of mass destruction (WMD) within the United States has grown significantly in recent years, focusing attention on the medical and public health disaster capabilities of the nation in a large scale crisis. While the hundreds of thousands or millions of casualties resulting from a nuclear weapon would, in and of itself, overwhelm our current medical response capabilities, the response dilemma is further exacerbated in that these resources themselves would be significantly at risk. There are many limitations on the resources needed for mass casualty management, such as access to sufficient hospital beds including specialized beds for burn victims, respiration and supportive therapy, pharmaceutical intervention, and mass decontamination. RESULTS: The effects of 20 kiloton and 550 kiloton nuclear detonations on high priority target cities are presented for New York City, Chicago, Washington D.C. and Atlanta. Thermal, blast and radiation effects are described, and affected populations are calculated using 2000 block level census data. Weapons of 100 Kts and up are primarily incendiary or radiation weapons, able to cause burns and start fires at distances greater than they can significantly damage buildings, and to poison populations through radiation injuries well downwind in the case of surface detonations. With weapons below 100 Kts, blast effects tend to be stronger than primary thermal effects from surface bursts. From the point of view of medical casualty treatment and administrative response, there is an ominous pattern where these fatalities and casualties geographically fall in relation to the location of hospital and administrative facilities. It is demonstrated that a staggering number of the main hospitals, trauma centers, and other medical assets are likely to be in the fatality plume, rendering them essentially inoperable in a crisis. CONCLUSION: Among the consequences of this outcome would be the probable loss of command-and-control, mass casualties that will have to be treated in an unorganized response by hospitals on the periphery, as well as other expected chaotic outcomes from inadequate administration in a crisis. Vigorous, creative, and accelerated training and coordination among the federal agencies tasked for WMD response, military resources, academic institutions, and local responders will be critical for large-scale WMD events involving mass casualties.

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BACKGROUND: Government reports have persistently indicated the intent of terrorists and hostile nations to acquire and "weaponize" nuclear materials for deliberate attack on a major US metropolitan city. METHODS: A modeling analysis of the effects of 20- and 550-kiloton nuclear detonations on the 2 major metropolitan centers of Los Angeles and Houston is presented with a focus on thermal casualties. Brode's work as modified by Binninger was used to calculate thermal fluence, using thermal fractions. The EM-1 and WE programs were used to calculate blast effects. Fallout radiation was calculated using the Defense Threat Reduction Agency's Hazard Prediction and Assessment Capability V404SP4 with "urban effects" turned on. The ESRI ArcView program calculated affected populations from 2000 US Census block-level data for areas affected by thermal effects. RESULTS: The population affected by a 550-kiloton nuclear weapon detonated in Los Angeles and Houston is staggering: surviving thermal casualties are estimated at 185,000 and 59,000, respectively. Even the 20-kiloton detonations in Los Angeles and Houston are significant: the numbers of surviving thermal casualties requiring care exceed 28,000 and 10,000, respectively. CONCLUSIONS: The surviving health care community postdetonation would be faced with an unprecedented burden of care for thermal casualties. A great expansion of personnel involved in emergency burn care response is critical. Bold, new approaches such as regionalization and predetermined medical air transport need to be considered.

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