Synthesis and structure of metallated macrocycle-bearing cyclophophazenes. - Part I : The (Li, Mg, Zn)/SPIR0(30203) derivatives

Syntheses and molecular structures of three metallated (Li, Zn, Mg) derivatives of the macrocycle-bearing cyclophosphazene N3P3Cl4 [HN---(CH2)3---O---(CH2)2---O---(CH2)3---NH] (coded as SPIRO 30203, 1) are reported. These three molecular structures reveal three different patterns of metal coordination. In compound 2 one of the two hydrogen atoms in SPIRO 3O2O3 is substituted by lithium generating a dimeric structure with pentacoordinated lithium centers. This structure is further stabilized by N---H hydrogen bonds. In 3 both hydrogen atoms of the macrocyclic loop are replaced by two zinc atoms through a cross-link metallation leading again to a dimeric molecule. In this compound the Zn atom is found to be in a trigonal bipyramidal environment with one very long N---Zn interaction. The origin of the dimerization of the magnesium compound 4 is analogous to 3. Magnesium is in the center of a distorted octahedron, coordinated with the O- and N-donors of the macrocyclic loop and also one nitrogen atom of the N3P3 ring. 4 is the first example of a metallic center coordinated by a neutral phosphazene ligand. Typical metal-N and metal-O distances are (in Å): Li-O, 2.05—2.07; Li-N, 2.07—2.36; Zn-O, 2.08—2.14; Zn---N, 1.94—1.95 (2.49); Mg---O, 2.09—2.14; Mg---N, 2.07—2.31

Synthesis and structure of metallated macrocycle-bearing cyclophophazenes. - Part II : The (Al) /SPIRO (30203) derivatives

Synthesis and molecular structures of two metallated (aluminium) derivatives, [C9H19Cl4AlN5O2P3]· 1.5C7H8 and [C8H16Cl5AiN5O2P3] · 1.5C7H8, of the macrocycle-bearingcyclophosphazene N3P3Cl4 [HN--- (CH2)3---O---(CH2)2---O---(CH2)3-NH] (coded as SPIRO 30203) are reported. These two molecular structures reveal the same pattern of metal coordination where the two hydrogen atoms in SPIRO 30203 are substituted by aluminium generating monomeric structures with pentacoordinated aluminium centres in the inner cavities. In the first compound the exocyclic ligand at aluminium is a methyl group, in the second a chlorine atom. Typical Al---N, Al---O and Al-X distances are (Å):1.84-1.89, 1.97-2.04 and 1.93 in the former, 1.81-1.86, 1.93-2.01 and 2.12 in the latter, respectively

The “Batman Effect”: Improving Perseverance in Young Children

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/138336/1/cdev12695.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/138336/2/cdev12695_am.pd

Where is the Digital Divide? A Survey of Security, Privacy, and Socioeconomics

The behavior of the least-secure user can influence security and privacy outcomes for everyone else. Thus, it is important to understand the factors that influence the security and privacy of a broad variety of people. Prior work has suggested that users with differing socioeconomic status (SES) may behave differently; however, no research has examined how SES, advice sources, and resources relate to the security and privacy incidents users report. To address this question, we analyze a 3,000 respondent, census-representative telephone survey. We find that, contrary to prior assumptions, people with lower educational attainment report equal or fewer incidents as more educated people, and that users’ experiences are significantly correlated with their advice sources, regardless of SES or resources

How Well Do My Results Generalize? Comparing Security and Privacy Survey Results from MTurk and Web Panels to the U.S.

Security and privacy researchers often rely on data collected from Amazon Mechanical Turk (MTurk) to evaluate security tools, to understand users' privacy preferences, to measure online behavior, and for other studies. While the demographics of MTurk are broader than some other options, researchers have also recently begun to use census-representative web-panels to sample respondents with more representative demographics. Yet, we know little about whether security and privacy results from either of these data sources generalize to a broader population. In this paper, we compare the results of a survey about security and privacy knowledge, experiences, advice, and internet behavior distributed using MTurk (n=480), a nearly census-representative web-panel (n=428), and a probabilistic telephone sample (n=3,000) statistically weighted to be accurate within 2.7% of the true prevalence in the U.S. Surprisingly, we find that MTurk responses are slightly more representative of the U.S. population than are responses from the census-representative panel, except for users who hold no more than a high-school diploma or who are 50 years of age or older. Further, we find that statistical weighting of MTurk responses to balance demographics does not significantly improve generalizability. This leads us to hypothesize that differences between MTurkers and the general public are due not to demographics, but to differences in factors such as internet skill. Overall, our findings offer tempered encouragement for researchers using MTurk samples and enhance our ability to appropriately contextualize and interpret the results of crowdsourced security and privacy research

Translocation of Threatened New Zealand Falcons to Vineyards Increases Nest Attendance, Brooding and Feeding Rates

Anthropogenic landscapes can be rich in resources, and may in some cases provide potential habitat for species whose natural habitat has declined. We used remote videography to assess whether reintroducing individuals of the threatened New Zealand falcon Falco novaeseelandiae into a highly modified agricultural habitat affected the feeding rates of breeding falcons or related breeding behavior such as nest attendance and brooding rates. Over 2,800 recording hours of footage were used to compare the behavior of falcons living in six natural nests (in unmanaged, hilly terrain between 4 km and 20 km from the nearest vineyard), with that of four breeding falcon pairs that had been transported into vineyards and nested within 500 m of the nearest vineyard. Falcons in vineyard nests had higher feeding rates, higher nest attendance, and higher brooding rates. As chick age increased, parents in vineyard nests fed chicks a greater amount of total prey and larger prey items on average than did parents in hill nests. Parents with larger broods brought in larger prey items and a greater total sum of prey biomass. Nevertheless, chicks in nests containing siblings received less daily biomass per individual than single chicks. Some of these results can be attributed to the supplementary feeding of falcons in vineyards. However, even after removing supplementary food from our analysis, falcons in vineyards still fed larger prey items to chicks than did parents in hill nests, suggesting that the anthropogenic habitat may be a viable source of quality food. Although agricultural regions globally are rarely associated with raptor conservation, these results suggest that translocating New Zealand falcons into vineyards has potential for the conservation of this species