127 research outputs found

    The genetic and environmental effects of parental age on the expression of psychopathology in adoptees

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    Secondary analysis of 581 adoptees was utilized to determine if parental age is related, either genetically or environmentally, to the development of psychopathology. The significant results showed that proband adoptees (with psychopathology in biologic relatives) with younger birthparents had increased alcohol abuse and those with younger birthfathers had increased antisocial personality while adoptees with older birthparents had increased depression. Analyses on control adoptees (with background free of known genetic disturbances) showed that those with younger adoptive mothers had increased antisocial personality and drug abuse and those with younger adoptive fathers had increased antisocial personality while adoptees with older adoptive fathers had increased depression. Implications of these findings are that adoptees with both younger birth and adoptive parents are more likely to have externalizing symptoms, while adoptees with both older birth and adoptive parents are more like to have internalizing symptoms. This information is beneficial to those involved in adoption placement

    Group 4 metalloporphyrin alkoxido, amido, hydrazido, and imido complexes: synthesis and reactivity

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    Previous examinations of group 4 coordination chemistry have predominately involved cyclopentadienyl, alkoxido, and amido complexes. The systematic exploration of the chemistry of group 4 metalloporphyrin complexes has recently been made possible by facile routes to useful porphyrin starting materials. Of interest are complexes containing hard pi-donor ligands. From these, bonding characteristics and steric constraints of the porphyrin periphery specific to the ligand can be studied;The implementation of the group 4 metal halide complexes, (TTP)MCl 2, in metathesis reactions has provided routes to amido, alkoxido, hydrazido, and imido derivatives. These complexes have subsequently demonstrated unique reactivity properties. It has been found that the formation of zirconium and hafnium imido metalloporphyrin complexes is dependent on the steric bulk of the phenyl substituent of the lithiated amide. Bis(amido) complexes are isolable when the ortho positions of phenyl amide are unsubstituted. The presence of the sterically demanding methyl, tert-butyl, or isopropyl groups at the ortho position of the phenyl amide effects an alpha-elimination of a primary aryl amine from the unstable secondary bis(amido) precursor to produce the imido derivative. These imido compounds were key starting materials for the production and investigation of a number of complexes containing M-O bonds. The zirconium and hafnium imido complexes, (TTP)M= NAriPr , couple two pinacolone molecules with concomitant loss of the amine H2 NAriPr . The hydrazido, (TTP)Ti=NNR2 (R = Me, Ph), and imido, (TTP)Ti=NiPr, derivatives of titanium undergo novel nitrene group metathesis reactions with p-chlorobenzaldehyde and with nitrosobenzene, respectively;Additional examples of atom and group transfer involving titanium(II) metalloporphyrins have been demonstrated. Utilization of a variety of donor molecules has facilitated the estimation of the double bond strength for complexes of the type (TTP)Ti=G (G = O, S, Se, NR). This dissertation focuses on the synthesis and reactivity of group 4 metalloporphyrin complexes containing hard pi-donor ligands and on the properties of titanium(II) metalloporphyrin species

    Synthesis, Structure, and Reactivity of Zirconium and Hafnium Imido Metalloporphyrins

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    The zirconium and hafnium porphyrin imido complexes (TTP)MNAriPr [TTP = meso-tetra-p-tolylporphyrinato dianion, M = Zr (1), Hf (2), AriPr = 2,6-diisopropylphenyl] were synthesized from (TTP)MCl2 and 2 equiv of LiNHAriPr. The zirconium imido complex, (TTP)ZrNAriPr, was also obtained from the preformed imido complex Zr(NAriPr)Cl2(THF)2 and (TTP)Li2(THF)2. Treatment of (TTP)HfCl2 with excess LiNH(p-MeC6H4) resulted in the formation of a bis(amido) complex, (TTP)Hf(NH-p-MeC6H4)2 (3), instead of an imido complex. In the presence of excess aniline, 2 formed an equilibrium mixture of bis(amido) compounds, (TTP)Hf(NHPh)(NHAriPr) and (TTP)Hf(NHPh)2. The nucleophilic character of the imido moiety is exhibited by its reaction with tBuNCO, producing isolable N,O-bound ureato metallacycles. The kinetic product obtained with zirconium, (TTP)Zr(η2-NAriPrC(NtBu)O) (4a), isomerized to (TTP)Zr(η2-NtBuC(NAriPr)O) (4b) in solution. Upon being heated to 80 °C, 4a produced the carbodiimide AriPrNCNtBu and a transient Zr(IV) oxo complex. The analogous hafnium complex (TTP)Hf(η2-NAriPrC(NtBu)O) (5a) did not eject the carbodiimide upon heating to 110 °C but isomerized to (TTP)Hf(η2-NtBuC(NAriPr)O) (5b). To support the formulation of 4a and 5a as N,O bound, the complex (TTP)Hf(η2-NAriPrC(NAriPr)O) (6) was studied by variable-temperature NMR spectroscopy. The corresponding thio- and selenoureato metallacycles were not isolable in the reaction between 1 and 2 with tBuNCS and tBuNCSe. Concomitant formation of the metallacycle with decomposition to the carbodiimide, AriPrNCNtBu, reflects the lower C−Ch bond strength in the proposed N,Ch-bound metallacycles. Treatment of 2 with 1,3-diisopropylcarbodiimide resulted in the η2-guanidino complex (TTP)Hf(η2-NAriPrC(NiPr)NiPr) (7a), which isomerized to the less sterically crowded isomer (TTP)Hf(η2-NiPrC(NAriPr)NiPr) (7b). Complexes 1, 2, 4a, 4b, and7a were characterized by X-ray crystallography. The monomeric terminal imido compounds, 1and 2, are isomorphous:  M−Nimido distances of 1.863(2) Å (Zr) and 1.859(2) Å (Hf); M−Nimido−C angles of 172.5(2)° (Zr) and 173.4(2)° (Hf). The structures of the ureato complexes 4aand 4b and the guanidino complex 7a exhibit typical alkoxido and amido bond distances (Zr−N = 2.1096(13) Å (4a), 2.137(3) Å (4b); Zr−O = 2.0677(12) Å (4a), 2.066(3) Å (4b); Hf−N = 2.087(2) Å, 2.151(2) Å (7a))

    Addition and Metathesis Reactions of Zirconium and Hafnium Imido Complexes

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    The zirconium and hafnium imido metalloporphyrin complexes (TTP)MNAriPr (TTP = meso-5,10,15,20-tetra-p-tolylporphyrinato dianion; M = Zr (1), Hf; AriPr = 2,6-diisopropylphenyl) were used to mediate addition reactions of carbonyl species and metathesis of nitroso compounds. The imido complexes react in a stepwise manner in the presence of 2 equiv of pinacolone to form the enediolate products (TTP)M[OC(tBu)CHC(tBu)(Me)O] (M = Zr (2), Hf (3)), with elimination of H2NAriPr. The bis(μ-oxo) complex [(TTP)ZrO]2 (4) is formed upon reaction of (TTP)ZrNAriPr with PhNO. Treatment of compound 4 with water or treatment of compound 2 with acetone produced the (μ-oxo)bis(μ-hydroxo)-bridged dimer [(TTP)Zr]2(μ-O)(μ-OH)2 (5). Compounds 2, 4, and 5 were structurally characterized by single-crystal X-ray diffraction

    Synoptic Conditions and Potential Causes of the Extreme Heavy Rainfall Event of January 2009 Over Mindanao Island, Philippines

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    This study investigates the synoptic conditions that led to the heavy rainfall/flood (HRF) event in Mindanao Island, Philippines (122 −127°E; 5 −10°N), on January 2009 (JAN2009 HRF) that are less emphasized in previous works. Extensive flooding was reported over Cagayan de Oro City in the northern part of Mindanao, where the rainfall on January 10, 11, and 13, 2009, exceeded the 99th percentile of daily rainfall records of all January of the city from 1979 to 2017 by almost two times. A similar exceedance was also felt in Hinatuan station over the eastern coast of Mindanao Island on January 15, 2009. The interaction of a cold surge shearline over the northern Mindanao Island and the warm tropical easterlies led to enhanced moisture convergence. The warmer air mass is forced to ascend by the advancing colder air mass because it has lower density than the colder air mass. The enhanced moisture convergence and buoyancy difference by the air masses led to enhanced ascent and consequently rainfall along the cold surge shearline. Further analysis shows that enhanced anomalous easterly and northerly winds at 925 hPa are apparent over the Philippines. The anomalous easterly winds sustained the supply of warmer easterlies and collaboratively interacted with the northerly winds that supplied colder temperature air mass. The climatology of this HRF event was examined for all January from 1979 to 2017. The authors identified 15 other cases that are similar to the JAN2009 HRF event and performed lag composite analyses. The results show that the occurrence of these HRF events is facilitated by the southward expansion of the high-pressure system to the north of the Philippines, enhanced cold and warm temperature advections, and enhanced moisture convergence along the cold surge shearline. The results of this study have important implications for disaster mitigation during the northeast monsoon season when rainfall activities are, in general, less intensive over this region

    Fitness Portal Needs and Feasibility Assessment for M-NCPPC Prince George’s County Department of Parks and Recreation

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    Final project for INST490: Integrated Capstone for Information Science (Fall 2019). University of Maryland, College Park.The Prince George’s County Parks and Recreation Department is seeking to develop an online portal to deliver fitness content. This report presents an initial needs and feasibility assessment of the opportunities and challenges that setting up a portal would involve. The report also includes information on how a portal could be implemented.Prince George's Count

    Forensic Investigation of Cyberstalking Cases using Behavioural Evidence Analysis

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    Behavioural Evidence Analysis (BEA) is, in theory, useful in developing an understanding of the offender, the victim, the crime scene, and the dynamics of the crime. It can add meaning to the evidence obtained through digital forensic techniques and assist investigators with reconstruction of a crime. There is, however, little empirical research examining the application of BEA to actual criminal cases, particularly cyberstalking cases. This study addresses this gap by examining the utility of BEA for such cases in terms of understanding the behavioural and motivational dimensions of offending, and the way in which digital evidence can be interpreted. It reports on the forensic analysis of 20 cyberstalking cases investigated by Dubai Police in the last five years. Results showed that BEA helps to focus an investigation, enables better understanding and interpretation of victim and offender behaviour, and assists in inferring traits of the offender from available digital evidence. These benefits can help investigators to build a stronger case, reduce time wasted to mistakes, and to exclude suspects wrongly accused in cyberstalking cases

    Tinkering with the Unbearable Lightness of Being: Meditation, Mind-Body Medicine and Placebo in the Quantum Biology Age

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    There are empirical indications that mind-body therapies have a nonlocal quantum component, in addition to the psychoneuroimmunological pathways that have been the focus of the predominant experimental paradigm.  The discussion below addresses the evidence and proposed theoretical mechanisms supporting this conclusion, and makes the case that there should be a convergence of research agendas between mind-body interventions (including placebo),  photomedicine and quantum biology.  Specifically, the role of endogenously generated biophotons in the regulation of genetic expression and the apparent ability of mental intent to direct biophoton emissions to specifically targeted tissues needs to be further evaluated from the perspective of photobiomodulation mechanisms, with a special focus on the spectroscopy and dosimetry of these emissions. Finally, the possible role of long-term meditation in enhancing quantum biological effects has to be further investigated at the level of cellular and macromolecular remodeling, both in the brain and the body

    Deploying the NASA Valkyrie Humanoid for IED Response: An Initial Approach and Evaluation Summary

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    As part of a feasibility study, this paper shows the NASA Valkyrie humanoid robot performing an end-to-end improvised explosive device (IED) response task. To demonstrate and evaluate robot capabilities, sub-tasks highlight different locomotion, manipulation, and perception requirements: traversing uneven terrain, passing through a narrow passageway, opening a car door, retrieving a suspected IED, and securing the IED in a total containment vessel (TCV). For each sub-task, a description of the technical approach and the hidden challenges that were overcome during development are presented. The discussion of results, which explicitly includes existing limitations, is aimed at motivating continued research and development to enable practical deployment of humanoid robots for IED response. For instance, the data shows that operator pauses contribute to 50\% of the total completion time, which implies that further work is needed on user interfaces for increasing task completion efficiency.Comment: 2019 IEEE-RAS International Conference on Humanoid Robot
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