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Controlling the Radical 5-exo-trig Cyclization Reaction in the Synthesis of Duocarmycin Analogs
CC-1065 and the duocarmycins are natural products that contain the cyclopyrroloindolone (or CPI) subunit. These compounds and their analogs bind in the minor groove of AT-rich sequences of DNA and they covalent bond with adenine-N3. This leads to potent cytotoxicity against the growth of cancer cells in vitro and in vivo. One efficient approach for synthesizing the CPI moiety is through the 5-exo-trig radical cyclization of a free radical and an adjacent 3-chloro-2-allylic moiety. Recently we reported that the cyclization proceeded via a benzofurano radical. The reaction yielded an unpredictable mixture of 6- benzyloxy-N-t-butoxycarbonyl-3-(chloromethyl)furano[e]indoline and 7-benzyloxy-N-t-butoxycarbonyl-3-chloro-1,2,3,4- tetrahydrofurano[f]quinoline. The purpose of this study is to gain a deeper understanding of the mechanism of the cyclization reaction, therefore allowing researchers to devise a practical way to control the reaction. Also, in this study thiophene and benzo derivatives will be studied to investigate the structure-reactivity relationship of the radical cyclization process. Computational modeling using DFT calculations of the radical reaction will provide further insight into the molecular electrostatic and dipole moment of the intermediates. This will enable us to have a better understanding of how electronic factors can affect reactivity. Results from these studies will be presented
Developing a Time Lapse Camera for Monitoring Sand Dunes
The goal of this project is to develop a time lapse camera system to monitor short-term sand transportation in the sand dunes around Saugatuck, Michigan. A low-cost digital camera captures movement with time lapse still photographs which are then turned into a high speed movie. This lets us observe slow movement and gradual progressions and regressions. The ideal time frame is a single storm or wind event. Some past projects have used expensive equipment and have monitored short term as well as long term movement. Along with minimizing cost, we concentrated on decreasing the chances of theft by making the case as discreet as possible; decreasing site visits by using higher-capacity memory cards, and creating a battery that is compatible with the camera’s voltage yet still has a long lifespan. We use Canon powershot A495 digital cameras, 16GB memory cards, high capacity D-cell batteries, and waterproof camera/battery cases. We control the camera using a Canon Hack Development Kit (CHDK) intervelometer script programmed into the camera. For the video software we use iMovie on Macs and Windows Live Essentials Movie Maker on a PC. In iMovie, we are able to zoom in on detailed portions of the video and in both programs we are able to cut short sections of detailed events out of the videos. The 16GB memory card gives us ample memory space for more than 1,000 pictures. The D-cell batteries we use can last as long as 19 hours when taking a picture every 16 seconds, which is the minimum time interval between images based on the camera’s speed at saving data to the memory card
Validity and Reliability of the Mishel Uncertainty in Illness Scale (MUIS) for Medically Managed Patients with Coronary Artery Disease
Uncertainty is a complex phenomenon that may be detrimental to health and overall quality of life. Although the experience of uncertainty is individualized, nursing interventions to increase patient knowledge and control over disease outcomes have been effective to decrease anxiety and depression. The purpose of this study is to determine the validity and reliability of the Mishel Uncertainty in Illness Scale (MUIS) for use in a larger interventional study on medically managed patients with coronary artery disease. This project is based on Mishel’s Reconceptualized Theory of Uncertainty in Illness, focusing on the experience of uncertainty over time as patients integrate uncertainty into their way of life. A review of the literature was done to determine validity and reliability of the tool, obtaining research articles using the databases CINAHL, Medline, Ovid, PSYCHInfo, and PubMed. Ten articles were chosen for analysis. The inclusion criteria for the articles were limited to primary research studies in English that used the MUIS Adult Form. Studies that did not meet inclusion criteria were those examining children, caregivers, and nonhospitalized adults, and were not included in this review. Therefore, the main limitation of the study is that only the form for one population was examined. Reliability for the total scale ranged a=0.64-0.91, with support for construct and convergent validity. The MUIS Adult Form is a valid and reliable tool. In the future these findings may be used to support the utility of this tool, and subsequently more fully understand the experience of uncertainty
The McDonaldization of Race: Racial Representations in McDonald\u27s Television Advertisements
Since its inception in the early 1960\u27s, McDonald\u27s has served as a cultural juggernaut in the United States, influencing everything from childhood development to food consumption patterns. McDonald\u27s is a pop culture phenomenon that has also played a large role in forming cultural and societal norms in the U.S., including the formation of specific ideologies that dominate both institutions and social consciousness. Given the central role McDonald\u27s plays in the U.S., it is important to discover the messages McDonald\u27s is sending. This study will focus on the messages McDonald\u27s is sending about race and race relations in the United States. This study uses a textual analysis of 10-12 McDonald’s television commercials from the presentday (2010-now) to see if the ideologies of race that are present in the commercials support or negate the dominant white ideology found in the U.S. This white dominant ideology in the U.S. is characterized by white superiority and the inferiority of people of color, as well as certain stereotypes associated with specific racial groups. By noting the frequency, the role, and the depiction of people of color in various McDonald\u27s advertisements, I will be able to determine the media messages McDonald\u27s is sending. I anticipate that, although McDonald\u27s has geared much of its recent advertising towards people of color, it will continue to further dominant ideologies about race, and employ stereotypes and marginalization tactics in the television advertisements to reinforce white superiority and the inferiority of people of color
The Economy’s Effect on College Major Decision
The decision to pick a major has become one of the toughest choices any college student will make during their lifetime. The majority of college freshmen arrive on campus with an idea of their ideal major but throughout the four to six years of college many students will change their major due to a wide variety of factors. This single choice plays a vital role not only during their time at the institution, but also in the years following graduation, and can essentially shape the rest of their lives. There has been an increased focus on the economy across all age groups, since the financial recession of 2008. The slide in the economy made me wonder if it had an impact on the college major decision. This analysis provided a link between the nation’s economy and college major decision. The college major decision is not only affected by fixed factors such as gender and race, but dynamic factors, like the economic climate that wax and wane over time
Public Education Spending and Graduation Rates in Michigan
A belief held throughout much of the industrialized world is that spending on education is an investment in future economic prosperity. Many policy-makers, educators, and citizens unquestioningly assume that higher budgets for education yield better-educated students, who in turn become more productive at their jobs, spurring economic growth. While this appears logical, it is worth investigating these claims to see if increased spending truly is the best way to improve education and to examine the assumption that better education leads to economic growth. This study looks at the first of these two questions by investigating the effects of spending on graduation rates using cross-sectional data on per student spending, allocation of education dollars, graduation rates, and a number of other factors in the state of Michigan’s 301 public school districts with at least 1500 students each. The findings suggest that social factors, especially the racial and economic makeup of the district’s student body, are far more closely related to graduation rates than spending is
“Insanity: The Asylum”: Effects on Agility, Power, Speed, Body Composition and Endurance in Female College Students.
Although the beneficial effects of regular exercise are well known and used to promote exercise videos, the claims made in many advertisements are often not validated. For instance, the creators of “Insanity: The Asylum”, a 30-Day at-home sportbased video, claim their program will facilitate noticeable improvements in fitness, including increased agility, power, speed and endurance, and an overall leaner body composition. The present study was designed to determine whether completion of “Insanity: The Asylum” would result in improved agility, power, speed, endurance and leaner body composition in college age females. Participants were placed in either the control condition (N=9), performing submaximal exercise 4 hours each week, or experimental condition (N=16), participating in the training program 4-5x a wk, 1 disc each day. Before and after the 6-week training program, participants (N=25) were assessed for: 1) peak oxygen consumption (cardiovascular endurance) 2) body fat percentage and body mass, 3) vertical jump height 4) 40m sprint time and 5) agility. Following the 6-week training program, no significant differences were observed between initial and post testing values regarding body mass, body fat percentage, peak oxygen consumption, power or speed (P\u3e.05). Furthermore, no differences were observed between the control and training condition (P\u3e.05). Findings demonstrated significant improvements in agility over time (pre= 5.03±0.11 seconds, post= 4.67±0.08 seconds, P=. 000). Additionally, the training group improved their agility score significantly more than the control group (P= .034) following the training period. The present study has demonstrated that improvements in agility were observed after completion of “Insanity: The Asylum”
Self-Enhancement and Ratings of Mate Desirability
Past research has shown that people often view themselves more positively than is warranted in order to protect their feelings of self-worth. Past work also has shown that individuals are particularly likely to self-enhance on traits that are personally important and traits that are global, rather than specific, in nature. The goal of our research is to extend previous research by examining correlates and potential consequences of people’s tendency to self-enhance their own desirability as a spouse. 502 unmarried adults were recruited from college night courses, community organizations, and social media sites. Participants completed an online questionnaire assessing their personal qualities, general desirability as a partner, psychological and behavioral investment in marrying, and dating and relationship success. Each participant also nominated 2-3 peers to provide “outside” ratings of their mate value. Self-enhancement was calculated by comparing people’s self-ratings of attribute-specific and global mate value to the average of their peers’ ratings. As predicted, the tendency to self-enhance on global mate value was significantly higher for romantically involved individuals (t(499)=-2.468, p\u3c.05) and those who definitively wanted to marry someday (t(484)= 3.15, p\u3c.01). Greater self-enhancement on global mate value was also associated with greater psychological investment in marrying (β=.12, p\u3c.01), greater behavioral investment in marrying (β=.25, p\u3c.001), and higher expectations to marry (β=.29, p\u3c.001). For attribute-specific mate value, self-enhancement was only associated with behavioral investment in marrying (β=.20, p\u3c.01) and expectations to marry (β=.19, p\u3c.01). Although discrepancies between self-reported and peer-reported mate value were not associated with participants’ success establishing relationships, people with less accurate global self-perceptions reported lower relationship satisfaction (β=-.17, p\u3c.05) and a lower likelihood of marrying their current partner (β=-.16, p\u3c.05). Taken together, we found that placing greater value on getting married is associated with greater selfenhancement on mate value and inaccurate self-perceptions are associated with poorer relationship quality
The Relationship between Activity Preference in Children and Parents
Today, children seem to be considerably less physically active than previous generations and rising childhood obesity is presenting itself as a major problem (CDC, 2006). Leary et al. (2008) investigated the self-reported activity preferences of parents and the preferences reported by their preschool children and found a significant positive correlation between the two. The present study strives to establish a relationship between the activity preference in children and their parents for young elementary students. Two questionnaires were developed, one for parents’ self-evaluation and one for each parent’s evaluation of their children. The self-evaluation for parents included various sociodemographic items and 15 activity preference items, each presenting one sedentary and one physically active option. Sedentary activities included watching TV, reading, crafts/projects, and art. Active options included walking/jogging, riding bike, playing sports, and park/playground. The parents were asked to identify their most preferred activity in each pair. Child participants completed their activity preference measures during class time. The sedentary and active activities were nearly identical to those offered to parents but were presented using child-friendly options. Physically active choices were given a “1” and sedentary activities given a “0”. The scores of all preferred activities were totaled to establish a summed score, which was categorized based on an adaptation of Leary’s (2008) scale. A summed score of 0-5 was classified as Sedentary, a score of 6-9 was Neutral, and a score of 10-15 was Active. We expected that self-reported Active parents would have children who reported active preferences. Likewise, self-reported Sedentary parents would have children who reported sedentary preferences. Support of our hypothesis would suggest that parents could be targeted to influence healthy lifestyles for future generations
Controlling The Radical 5-exo-trig Cyclization, And Selective Synthesis Of Seco-iso-cyclopropylfurano[e]indoline (seco-iso-cfi) And Seco-cyclopropylthiophene[e]indoline (seco-cti) Dna Alkylating Subunit Of The Duocarmycins
The free radical cyclization of benzofuran bromo-allylic chloride 6 in toluene produced an unpredicted mixture of 6-benzyloxy-N-t-Boc-3-(chloromethyl)furano[e]indoline (1) and 7-benzyloxy-N-Boc-3-(chloromethyl)furano[f]quinoline (2). DFT calculations indicated that the indoline radical (6B), formed from 5-exo-trig closure of intermediate 6A, was less polar than the corresponding quinoline radical (6C). Based on this result, we report herein that cyclization of chlorides 6-8 in a polar aromatic solvent consistently and exclusively produced the indoline product in good yield (74-83%). (C) 2013 Elsevier Ltd. All rights reserved