Eyring Activation Energy Analysis of Acetic Anhydride Hydrolysis in Acetonitrile Cosolvent Systems

Acetic anhydride hydrolysis in water is considered a standard reaction for investigating activation energy parameters using cosolvents. Hydrolysis in water/acetonitrile cosolvent is monitored by measuring pH vs. time at temperatures from 15.0 to 40.0 °C and mole fraction of water from 1 to 0.750. This work utilizes a temperature controlled water bath and a Vernier glass-body pH probe with Vernier Logger Pro 3.10.1 software for automated data collection. Data analysis is used to determine observed kinetic rate constants under the assumption that hydrolysis is a pseudo-first-order reaction. Eyring plots were used to compare activation energy parameters under iso-mole fraction conditions. The hydrolysis reaction of acetic anhydride was enthalpically stabilized and entropically destabilized at mole fractions of acetonitrile greater than 0.17 and the reverse occurred at mole fractions less than 0.17. Activation enthalpy and entropy result in the reaction being less favorable to form products as mole fraction of acetonitrile increased

Tribiology of Engineered Surfaces in Aggressive Environments

To improve the performance of sliding systems, surface modifications and coatings are often applied to opposing surfaces. This thesis focuses on characterizing two tribo-systems (DLC-DLC and steel micropatterns-flat) under their predicted application environments. The first section is focused on friction testing of micropatterned surfaces for orthopaedic device design, the second section elucidates how the sliding of diamond-like-carbon (DLC) coatings changes with temperature and humidity. The experimental design and major results of these sections are as follows. (1) The use of micropatterning to create uniform surface morphologies has been cited as yielding improvements in the coefficient of friction during high velocity sliding contact. Studies have not been preformed to determine if these micropatterns could also be useful in biomedical applications, such as total joint replacement surfaces, where the lower sliding velocities are used. In this study, the effect of pattern geometry, feature size and lubricant on contact friction and surface damage was investigated using 316L steel in sliding contact with a stainless steel and polyethylene pins. Using a novel proprietary forming process that creates millions of microstructures in parallel, a variety of micropatterned surfaces were fabricated to study the influence of shape (oval, circular, square), geometry (depressions, pillars) and feature size (10, 50 and 100 mm) on both contact friction and surface damage. The coefficients of friction were measured for each surface/lubricant/pin system using a CETR scratch testing system. Results showed that round depressions with diameters of 10 μm had a significantly lower steady state coefficient of friction than the non-patterned substrates or substrates with greater diameter depression patterns. (2) The use of diamond-like carbon (DLC) has been cited as a friction and wear reducing coating during sliding contact and is widely used in the hard disk drive (HDD) industry. Studies have not shown the simultaneous effects of the temperature and humidity or temperature and load on DLC coatings. This project will show the effects on the friction and wear of non- hydrogenated DLC coatings in high temperature environments (23 to 250 °C), various humid environments (10 – 95 %RH), dependence on load (2.66 to 10 N), and the combined effects each environmental condition. The DLC coatings being used in this study are ta-C (tetrahedral amorphous-carbon) and a-C (amorphous-carbon), which were deposited onto a substrate of Al2O3-TiC (Seagate) and 440C stainless steel counterface pin. The friction for this tribosystem was monitored by a built in-house POD system, which can control the humidity levels and can reach temperatures up to 300°C. It has been shown that the a-C is less sensitive to the humidity levels, but is more sensitive to the surrounding temperature than ta-C DLC coatings

Plain packaging for tobacco: what other countries can learn from the UK's experience

First paragraph: Bans on tobacco advertising, promotion, sponsorship and open display in shops in the UK encouraged tobacco companies to make "the pack the hero". So they opposed plain packaging and claimed there was no evidence it would reduce smoking. They also attempted to thwart the policy through lobbying and third-party interference, and unsubstantiated claims about the effect on price, businesses and illicit trade. Following a review of the potential public health benefits, the government introduced a policy that made plain packaging mandatory for cigarettes and rolling tobacco sold in the UK. The policy was first introduced in May 2016 and, after a transition period, became compulsory in May 2017. But research has shown that tobacco companies appeared to delay introducing plain packs, continued to explore ways to promote products and did not follow through with their predictions that prices would decline.https://theconversation.com/plain-packaging-for-tobacco-what-other-countries-can-learn-from-the-uks-experience-10609

Decision trees in epidemiological research

Background: In many studies, it is of interest to identify population subgroups that are relatively homogeneous with respect to an outcome. The nature of these subgroups can provide insight into effect mechanisms and suggest targets for tailored interventions. However, identifying relevant subgroups can be challenging with standard statistical methods. Main text: We review the literature on decision trees, a family of techniques for partitioning the population, on the basis of covariates, into distinct subgroups who share similar values of an outcome variable. We compare two decision tree methods, the popular Classification and Regression tree (CART) technique and the newer Conditional Inference tree (CTree) technique, assessing their performance in a simulation study and using data from the Box Lunch Study, a randomized controlled trial of a portion size intervention. Both CART and CTree identify homogeneous population subgroups and offer improved prediction accuracy relative to regression-based approaches when subgroups are truly present in the data. An important distinction between CART and CTree is that the latter uses a formal statistical hypothesis testing framework in building decision trees, which simplifies the process of identifying and interpreting the final tree model. We also introduce a novel way to visualize the subgroups defined by decision trees. Our novel graphical visualization provides a more scientifically meaningful characterization of the subgroups identified by decision trees. Conclusions: Decision trees are a useful tool for identifying homogeneous subgroups defined by combinations of individual characteristics. While all decision tree techniques generate subgroups, we advocate the use of the newer CTree technique due to its simplicity and ease of interpretation

Rotation of Coulomb crystals in a magnetized inductively coupled complex plasma

Under suitable conditions, micron-sized dust particles introduced into inductively coupled argon plasma form a stable microscopic crystal lattice, known as a Coulomb (or plasma) crystal. In the experiment described, an external axial magnetic field was applied to various configurations of Coulomb crystal, including small crystal lattices consisting of one to several particles, and large crystal lattices with many hundreds of particles. The crystals were observed to rotate collectively under the influence of the magnetic field. This paper describes the experimental procedures and the preliminary results of this investigation

Tuning transcriptional regulation through signaling: A predictive theory of allosteric induction

Allosteric regulation is found across all domains of life, yet we still lack simple, predictive theories that directly link the experimentally tunable parameters of a system to its input-output response. To that end, we present a general theory of allosteric transcriptional regulation using the Monod-Wyman-Changeux model. We rigorously test this model using the ubiquitous simple repression motif in bacteria by first predicting the behavior of strains that span a large range of repressor copy numbers and DNA binding strengths and then constructing and measuring their response. Our model not only accurately captures the induction profiles of these strains but also enables us to derive analytic expressions for key properties such as the dynamic range and $[EC_{50}]$. Finally, we derive an expression for the free energy of allosteric repressors which enables us to collapse our experimental data onto a single master curve that captures the diverse phenomenology of the induction profiles.Comment: Substantial revisions for resubmission (3 new figures, significantly elaborated discussion); added Professor Mitchell Lewis as another author for his continuing contributions to the projec

Does Function Follow Organizational Form? Evidence From the Lending Practices of Large and Small Banks

Theories based on incomplete contracting suggest that small organizations may do better than large organizations in activities that require the processing of soft information. We explore this idea in the context of bank lending to small firms, an activity that is typically thought of as relying heavily on soft information. We find that large banks are less willing than small banks to lend to informationally 'difficult' credits, such as firms that do not keep formal financial records. Moreover, controlling for the endogeneity of bank-firm matching, large banks lend at a greater distance, interact more impersonally with their borrowers, have shorter and less exclusive relationships, and do not alleviate credit constraints as effectively. All of this is consistent with small banks being better able to collect and act on soft information than large banks.

Does Function Follow Organzizational Form? Evidence From the Lending Practices of Large and Small Banks

Theories based on incomplete contracting suggest that small organizations may do better than large organizations in activities that require the processing of soft information. We explore this idea in the context of bank lending to small firms, an activity that is typically thought of as relying heavily on soft information. We find that large banks are less willing than small banks to lend to informationally “difficult†credits, such as firms that do not keep formal financial records. Moreover, controlling for the endogeneity of bank-firm matching, large banks lend at a greater distance, interact more impersonally with their borrowers, have shorter and less exclusive relationships, and do not alleviate credit constraints as effectively. All of this is consistent with small banks being better able to collect and act on soft information than large banks. The opinions in this paper do not necessarily reflect those of the Federal Reserve Board or its staff. This work has been supported by the National Science Foundation (Rajan, Stein), and the George J. Stigler Center for Study of the State and Economy (Rajan). Thanks also to seminar participants at Yale, the Federal Reserve Bank of New York, Tulane, Babson, the University of Illinois, the Federal Reserve Bank of Chicago Bank Structure Conference, the NBER and the Western Finance Association meetings, as well as to Abhijit Banerjee, Michael Kremer, David Scharfstein, Andrei Shleifer, Greg Udell, Christopher Udry and James Weston for helpful comments and suggestions.

Household income differences in food sources and food items purchased

<p>Abstract</p> <p>Background</p> <p>The present study examined income-related household food purchases among a sample of 90 households from the community.</p> <p>Methods</p> <p>Annotated food purchase receipts were collected for a four-week period by the primary household shopper. Receipt food source and foods items were classified into specific categories, and food quantities in ounces were recorded by research staff. For home sources, a limited number of food/beverage categories were recorded. For eating out sources, all food/beverage items were recorded. Median monthly per person dollars spent and per person ounces purchased were computed. Food sources and food categories were examined by household income tertile.</p> <p>Subjects and Setting</p> <p>A community-based sample of 90 households.</p> <p>Results</p> <p>Higher income households spent significantly more dollars per person per month from both home and eating out sources compared with lower income households ($163 versus$100, p < .001). Compared with lower income households, higher income households spent significantly more home source dollars on both fruits/vegetables (21.5 versus 10.2, p < .001) and sweets/snacks (17.3 versus 8.3, p < .001), but did not differ on home dollars spent on sugar sweetened beverages (2.0 versus 1.7, p < .46). The proportion of home beverages that were sugar sweetened beverages was significantly higher among lower income households (45% versus 26%, p < .01). Within eating out sources, lower income households spent a significantly greater percent of dollars per person at carry out places (54% versus 37%, p < .01). No income differences were observed for dollars spent at discount grocery stores, small grocery stores or convenience stores.</p> <p>Conclusions</p> <p>Higher income households spent more money on both healthy and less healthy foods from a wide range of sources. Lower income households spent a larger proportion of their eating out dollars at carry out places, and a larger proportion of their home beverage purchases were sugar sweetened beverages.</p