4,255 research outputs found

    Rhodium Pyrazolate Complexes as Potential CVD Precursors

    Get PDF
    Reaction of 3,5-(CF3)(2)PzLi with [Rh(mu-Cl)(eta(2)-C2H4)(2)](2) or [Rh(mu-Cl)(PMe3)(2)](2) in Et2O gave the dinuclear complexes [Rh(eta(2)-C2H4)(2)(mu-3,5-(CF3)(2)-Pz)](2) (1) and [Rh-2(mu-Cl)(mu-3,5-(CF3)(2)-Pz) (PMe3)(4)] (2) respectively (3,5-(CF3)(2)Pz = bis-trifluoromethyl pyrazolate). Reaction of PMe3 with [Rh(COD)(mu-3,5-(CF3)(2)-Pz)](2) in toluene gave [Rh(3,5-(CF3)(2)-Pz)(PMe3)(3)] (3). Reaction of 1 and 3 in toluene (1 : 4) gave moderate yields of the dinuclear complex [Rh(PMe3)(2)(mu-3,5-(CF3)(2)-Pz)](2) (4). Reaction of 3,5-(CF3)(2)PzLi with [Rh(PMe3)(4)]Cl in Et2O gave the ionic complex [Rh(PMe3)(4)][3,5-(CF3)(2)-Pz] (5). Two of the complexes, 1 and 3, were studied for use as CVD precursors. Polycrystalline thin films of rhodium (fcc-Rh) and metastable-amorphous films of rhodium phosphide (Rh2P) were grown from 1 and 3 respectively at 170 and 130 degrees C, 0.3 mmHg in a hot wall reactor using Ar as the carrier gas (5 cc min(-1)). Thin films of amorphous rhodium and rhodium phosphide (Rh2P) were grown from 1 and 3 at 170 and 130 degrees C respectively at 0.3 mmHg in a hot wall reactor using H-2 as the carrier gas (7 cc min(-1)).Welch Foundation F-816Petroleum Research Fund 47014-ACSNSF 0741973Chemistr

    Why Environmental Laws Fail

    Full text link
    Although governments have deployed an array of environmental protection laws, our planet continues to experience unprecedented environmental “crises,” including climate change, resource depletion, species extinction, ecosystem damage, and toxic air-water-land pollution. Despite universal acknowledgment and recognition of these serious environmental issues, and despite a growing list of laws designed to address these issues, the reality is that these adverse Earth-based environmental changes continue, and may even be worsening. Environmental protection laws have often failed because they usually include certain problematic characteristics: they are anthropocentric, in that their goal is to protect and benefit humans, not the environment in which humans live; they assume human superiority and exceptionalism to nature and natural processes; they are based on the notion that humans are separate from nature; they presume that humans are not ultimately limited by planetary boundaries, because they are superior and somehow insulated from nature. Moreover, these laws use an unrealistic model for humans—where human motivations are consistent with the homo economicus model used by traditional resource economists—the always rational, self-interested economic person motivated by negative laws, which tell humans what not to do. They also rely on an unrealistic model for nature, where nature is perceived too simply, as a closely integrated, self-regulating, complex system that works best when left alone by humans. This view is not consistent with the science of how nature really works, which is as complex adaptive systems. This Article reviews how these assumptions and models have largely influenced legal resources and environmental decision-making over four distinct eras during the past three hundred years—the Use, Conservation, Preservation, and Protection Eras. For environmental laws to work in a new, more Ecocentric Era, laws would be built on three foundations. First, environmental laws would not continue to rely exclusively on the assumptions and models used in previous eras, but instead would reflect the reality of how humans behave and nature works. Second, these laws would impose an affirmative duty on humans to make choices consistent with ecological integrity and planetary boundaries—in other words, rather than telling humans what not to do, laws should tell or encourage humans what to do. And third, rather than rely on rules that seek to prevent humans from creating negative environmental externalities, these new laws would create incentives for humans to create positive ecocentric externalities

    Estrogen and progesterone induce persistent increases in p53-dependent apoptosis and suppress mammary tumors in BALB/c-Trp53+/- mice

    Get PDF
    INTRODUCTION Treatment with estrogen and progesterone (E+P) mimics the protective effect of parity on mammary tumors in rodents and depends upon the activity of p53. The following experiments tested whether exogenous E+P primes p53 to be more responsive to DNA damage and whether these pathways confer resistance to mammary tumors in a mouse model of Li-Fraumeni syndrome. METHODS Mice that differ in p53 status (Trp53+/+, Trp53+/-, Trp53-/-) were treated with E+P for 14 days and then were tested for p53-dependent responses to ionizing radiation. Responses were also examined in parous and age-matched virgins. The effects of hormonal exposures on tumor incidence were examined in BALB/c-Trp53+/- mammary tissues. RESULTS Nuclear accumulation of p53 and apoptotic responses were increased similarly in the mammary epithelium from E+P-treated and parous mice compared with placebo and age-matched virgins. This effect was sustained for at least 7 weeks after E+P treatment and did not depend on the continued presence of ovarian hormones. Hormone stimulation also enhanced apoptotic responses to ionizing radiation in BALB/c-Trp53+/- mice but these responses were intermediate compared with Trp53+/+ and Trp-/- tissues, indicating haploinsufficiency. The appearance of spontaneous mammary tumors was delayed by parity in BALB/c-Trp53+/- mice. The majority of tumors lacked estrogen receptor (ER), but ER+ tumors were observed in both nulliparous and parous mice. However, apoptotic responses to ionizing radiation and tumor incidence did not differ among outgrowths of epithelial transplants from E+P-treated donors and nulliparous donors. CONCLUSION Therefore, E+P and parity confer a sustained increase in p53-mediated apoptosis within the mammary epithelium and suppress mammary tumorigenesis, but this effect was not retained in epithelial outgrowths.This work was supported by grants from the US Army Medical Research and Materiel Command (W81XWH0410385 to KAD and DAMD17-01-1-0315 to ACB) and the National Institutes of Health (RO1-CA095164 to DJJ)

    Theoretical open-loop model of respiratory mechanics in the extremely preterm infant

    Get PDF
    Non-invasive ventilation is increasingly used for respiratory support in preterm infants, and is associated with a lower risk of chronic lung disease. However, this mode is often not successful in the extremely preterm infant in part due to their markedly increased chest wall compliance that does not provide enough structure against which the forces of inhalation can generate sufficient pressure. To address the continued challenge of studying treatments in this fragile population, we developed a nonlinear lumped-parameter model of respiratory system mechanics of the extremely preterm infant that incorporates nonlinear lung and chest wall compliances and lung volume parameters tuned to this population. In particular we developed a novel empirical representation of progressive volume loss based on compensatory alveolar pressure increase resulting from collapsed alveoli. The model demonstrates increased rate of volume loss related to high chest wall compliance, and simulates laryngeal braking for elevation of end-expiratory lung volume and constant positive airway pressure (CPAP). The model predicts that low chest wall compliance (chest stiffening) in addition to laryngeal braking and CPAP enhance breathing and delay lung volume loss. These results motivate future data collection strategies and investigation into treatments for chest wall stiffening.Comment: 22 pages, 5 figure

    The Parentless Child\u27s Right to a Permanent Family

    Get PDF
    More than 420,000 children in the United States are in foster care, and more than 110,000 of them are waiting to be adopted. State adoption statutes typically seek to achieve adoption for these children as promptly as possible, but some limit the pool of potential adoptive parents in one way or another. In this Article, we argue that such restrictions violate the State’s constitutional duties to parentless children in its care. Specifically, we contend that children in State custody have a substantive liberty interest in a secure and stable family relationship, because such a relationship is essential in order for these children to attain the capacities needed to function as autonomous adults. Developmental science demonstrates that children need an enduring attachment relationship with a primary caregiver in order to achieve the self-regulation and social competence necessary to function in society, and to receive the essential feedback they need to develop a sense of who they are – that is, to acquire “the ability independently to define one’s identity that is central to any concept of liberty.” A secure and stable family relationship is therefore a component of the minimally adequate nurturing that the State is constitutionally obligated to provide to parentless children in its custody, and this constitutional obligation constrains the State’s choices in establishing its foster care and adoption policies. In particular, given the unstable placements that typify foster care in the United States, laws and regulations categorically disqualifying a class of people from adopting work a direct and substantial interference with the child’s right to a secure and stable family relationship, and therefore must survive strict scrutiny in order to pass muster. However, we suggest that careful thought is needed before the child’s right to a secure and stable family relationship is extended to contexts in which it conflicts with the right of a parent

    Open to Exploitation: American Shoppers Online and Offline

    Get PDF
    Most Americans who use the Internet have little idea how vulnerable they are to abuse by online and offline marketers and how the information they provide can be used to exploit them. That is one conclusion from this unprecedented national phone survey conducted by the Annenberg Public Policy Center. The study indicates that many adults who use the internet believe incorrectly that laws prevent online and offline stores from selling their personal information. They also incorrectly believe that stores cannot charge them different prices based on what they know about them. Most other internet-using adults admit that they simply don’t know whether or not laws protect them. The survey further reveals that the majority of adults who use the internet do not know where to turn for help if their personal information is used illegally online or offline. The study\u27s findings suggest a complex mix of ignorance and knowledge, fear and bravado, realism and idealism that leaves most internet-using adult American shoppers open to financial exploitation by retailers
    • …
    corecore