The Chameleon-Like Nature of Zwitterionic Micelles: Effect of Cation Binding

Addition of salts, especially perchlorates, to zwitterionic micelles of SB3-14, C(14)H(29)NMe(2)(+)(CH(2))(3)SO(3)(-), induces anionic character and uptake of H(3)O(+) by SB3-14 micelles. Thus, the addition of alkali metal perchlorates accelerates the acid hydrolysis of 2-(p-heptoxypheny1)-1,3-dioxolane, HPD, in the presence of SB3-14 micelles, which depends on the local proton concentration at the micelle surface. The addition of metal chlorides to solutions of such perchlorate-modified SB3-14 micelles decreases both the negative zeta potential of the micelles and the observed rate constant for acid hydrolysis of HPD. The effect of the monovalent cations Li(+), Na(+), and K(+) is smaller than that of the divalent cations Be(2+), Mg(2+), and Ca(2+), and much smaller than that of the trivalent cations Al(3+), La(3+), and Er(3+). The major factor responsible for this cation valence dependence of these effects is shown to be electrostatic in nature, reflecting the strong dependence of the micellar surface potential on the cation valence. The fact that the salt effects are not identical after correction for the electrostatic effects indicates that additional secondary nonelectrostatic effects may contribute as well.

Exploring the intrinsic polar [4?+?2+] cycloaddition reactivity of gaseous carbosulfonium and carboxonium ions

Gas-phase reactions of model carbosulfonium ions (CH3-S+?=?CH2; CH3CH2-S+?=?CH2 and Ph-S+?=?CH2) and an O-analogue carboxonium ion (CH3-O+?=?CH2) with acyclic (isoprene, 1,3-butadiene, methyl vinyl ketone) and cyclic (1,3-cyclohexadiene, thiophene, furan) conjugated dienes were systematically investigated by pentaquadrupole mass spectrometry. As corroborated by B3LYP/6-311?G(d,p) calculations, the carbosulfonium ions first react at large extents with the dienes forming adducts via simple addition. The nascent adducts, depending on their stability and internal energy, react further via two competitive channels: (1) in reactions with acyclic dienes via cyclization that yields formally [4?+?2+] cycloadducts, or (2) in reactions with the cyclic dienes via dissociation by HSR loss that yields methylenation (net CH+ transfer) products. In great contrast to its S-analogues, CH3-O+?=?CH2 (as well as C2H5-O+?=?CH2 and Ph-O+?=?CH2 in reactions with isoprene) forms little or no adduct and proton transfer is the dominant reaction channel. Isomerization to more acidic protonated aldehydes in the course of reaction seems to be the most plausible cause of the contrasting reactivity of carboxonium ions. The CH2?=?CH-O+?=?CH2 ion forms an abundant [4?+?2+] cycloadduct with isoprene, but similar to the behavior of such alpha,beta-unsaturated carboxonium ions in solution, seems to occur across the C?=?C bond. Copyright (c) 2012 John Wiley & Sons, Ltd.

Exploring the biofilm of Streptococcus agalactiae to identify virulence factors

Streptococcus agalactiae, also known as Group B Streptococcus (GBS) is the primary colonizer of the anogenital mucosa of up to 40% of healthy women and an important cause of invasive neonatal infections worldwide. Among the 10 known capsular serotypes, GBS type III accounts for 30-76% of the cases of neonatal meningitis. Biofilms are dense aggregates of surface-adherent microorganisms embedded in an exopolysaccharide matrix. Centers for Disease Control and Prevention estimate that 65% of human bacterial infections involve biofilms (Post et al., 2004). In recent years, the ability of GBS to form biofilm attracted attention for its possible role in fitness and/or virulence. Here, a new in vitro biofilm formation protocol was developed to guarantee more stringent conditions, to better discriminate between strong-, low- and non- biofilm forming strains and reduce ambiguous data interpretation. This protocol was applied to screen the in vitro biofilm formation ability of more than 350 GBS clinical isolates from pregnant women and neonatal infections belonging to different serotype, in relation to media composition and pH. The results showed the enhancement of GBS biofilm formation in acidic condition and identified a subset of isolates belonging to serotypes III and V that forms strong biofilms in these conditions. Interestingly, the best biofilm formers belonged to the serotype III hypervirulent clone ST-17.It was also found that pH 5.0 induces down-regulation of the capsule but that this reduction is not enough by itself to ensure biofilm formation. Moreover, the ability of proteinase K to strongly inhibit biofilm formation and to disaggregate mature biofilms suggested that proteins play an essential role in promoting GBS biofilm formation and contribute to the biofilm structural stability. Finally, a set of proteins potentially expressed during the GBS in vitro biofilm formation were identified by mass spectrometry.

Money is not enough: exploring the impact of social and cultural resources on youth health

Findings on socioeconomic health differentials in youth remain fragmented with the role of cumulative and interaction effects of different forms of health resources not well understood.

Climate Change and International Law. Exploring the Linkages Between Human Rights, Environment, Trade and Investment

Mapping the relevant principles and norms of international law, the paper discusses scientific evidence and identifies current legal foundations of climate change mitigation adaptation and communication in international environmental law, human rights protection and international trade regulation in WTO law. It briefly discusses the evolution and architecture of relevant multilateral environmental agreements, in particular the UN Framework Convention on Climate Change. It discusses the potential role of human rights in identifying pertinent goals and values of mitigation and adaptation and eventually turns to principles and rules of international trade regulation and investment protection which are likely to be of crucial importance should the advent of a new multilateral agreement fail to materialize. The economic and legal relevance of rules on tariffs, border tax adjustment and subsidies, services and intellectual property and investment law are discussed in relation to the production, supply and use of energy. Moreover, lessons from trade negotiations may be drawn for negotiations of future environmental instruments. The paper offers a survey of the main interacting areas of public international law and discusses the intricate interaction of all these components informing climate change mitigation, adaptation and communication in international law in light of an emerging doctrine of multilayered governance. It seeks to contribute to greater coherence of what today is highly fragmented and rarely discussed in an overall context. The paper argues that trade regulation will be of critical importance in assessing domestic policies and potential trade remedies offer powerful incentives for all nations alike to participate in a multilateral framework defining appropriate goals and principles.

Must We Forgive?: Exploring the Limits and Possibilities of Forgiveness and Resentment

Conflict has marked civilization from Biblical times to the present day. Each of us, with our different and competing interests, and our desires to pursue those interests, have over time wronged another person. Not surprisingly then, forgiveness is a concern of individuals and groups¿communities, countries, religious groups, races¿yet it is a complex idea that philosophers, theologians, political scientists, and psychologists have grappled with. Some have argued that forgiveness is a therapeutic means for overcoming guilt, pain, and anger. Forgiveness is often portrayed as a coping mechanism¿how often we hear the phrase, ¿forgive and forget,¿ as an arrangement to help two parties surmount the complications of disagreement. But forgiveness is not simply a modus vivendi; the ability to forgive and conversely to ask for forgiveness, is counted as an admirable trait and virtue. This essay will explore the nature of forgiveness, which in Christian dogma is often posited as an unqualified virtue. The secular world has appropriated the Christian notion of forgiveness as such a virtue¿but are there instances wherein offering forgiveness is morally inappropriate or dangerous? I will consider the situations in which forgiveness, understood in this essay as the overcoming of resentment, may not be a virtue¿when perhaps maintaining resentment is as virtuous, if not more virtuous, than forgiving. I will explain the various ethical frameworks involved in understanding forgiveness as a virtue, and the relationship between them. I will argue that within Divine Command Theory forgiveness is a virtue¿and thus morally right¿because God commands it. This ethical system has established forgiveness as unconditional, an idea which has been adopted into popular culture. With virtue ethics in mind, which holds virtues to be those traits which benefit the person who possesses them, contributing to the good life, I will argue unqualified forgiveness is not always a virtue, as it will not always benefit the victim. Because there is no way to avoid wrongdoing, humans are confronted with the question of forgiveness with every indiscretion. Its limits, its possibilities, its relationship to one¿s character¿forgiveness is a concern of all people at some time if for no other reason than the plain fact that the past cannot be undone. I will be evaluating the idea of forgiveness as a virtue, in contrast to its counterpart, resentment. How can forgiveness be a response to evil, a way to renounce resentment, and a means of creating a positive self-narrative? And what happens when a sense of moral responsibility is impossible to reconcile with the Christian (and now, secularized imperative of) forgiveness? Is it ever not virtuous to forgive? In an attempt to answer that question I will argue that there are indeed times when forgiveness is not a virtue, specifically: when forgiveness compromises one¿s own self-respect; when it is not compatible with respect for the moral community; and when the offender is unapologetic. The kind of offense I have in mind is a dehumanizing one, one that intends to diminish another person¿s worth or humanity. These are moral injuries, to which I will argue resentment is a better response than forgiveness when the three qualifications cannot be met.

The Monumental Barrows of the Period 700-1100 AD at the Russian North-West

Nicholas Petrov. The Monumental Barrows of the Period 700-11 AD in the Russian North-West The research deals with the monumental barrows erected in the Russian north-west in the period of 700-1100 AD, which Russian archaeological literature has traditionally named sopka-barrows. These sopka-barrows were analysed as original sacral and funeral structures and considered in the context of cultural processes under way in that region at the time. The position occupied by the sopka-barrows in the culture of the people who erected them was reconstructed on the basis of a synthesis of various kinds of sources - archaeological, written, folklore. The high barrows are not in fact a determining type of the sites of the so-called "culture of the sopka-barrows" in modern literature, which focuses rather on settlements near to which sopka-barrows are absent. Recent excavations have revealed the presence of "surface" burial places (cremation located on the top of the barrow repeatedly rather than only once) in the majority of the sopka-barrows. The materials only provide evidence about the sacrificial nature of the graves in the "body" of the sopka-barrows. They thus offer an embodiment of one element of the widespread views about the dead man's path to the world of the dead (mountain) which is traced in folklore texts. Special attention was paid to the question of the disappearance of the tradition of erecting sopka-barrows and to the nature of their role in the culture of the region during the period 1000-1200 AD. The functioning of the sopka-barrows as funeral monuments in the second millennium AD is also traced on the inlet inhumatios found in them.

Russian Writers and the Third Section

The Third Section was an instrument not so much of oppression as of information, propaganda and education. Under Nicholas I, the press did not represent public opinion, but rather the official point of view. It was intended to shape public opinion rather than to express it and much of the Third Section's activity focused on creating the best possible contacts with journalists and men of letters. The Third Section supervised literary activities by examining works in print and collecting information through its agents. It rewarded those authors whose work was approved by the emperor, it used writers to pursue its goals, especially in order to "direct minds", but acted as a mediator between the tsar, censors and writers, or sometimes as arbiter in conflicts between writers themselves, and it also acted as a censor. Writers, for their part, served in the Third Section, becoming its agents or consultants, delivering reports to it and writing texts commissioned by the Section. The majority of writers did not see any problems with serving or assisting the Third Section. Ideologies offering an alternative to state monarchism /in professional literature or individual liberalism/ were very weak. The only exception was a small group, mostly composed of eminent and highly educated aristocrats who possessed alternative moral and financial resources. Reitblat showed that the strong ties maintained by some journalists and writers with the Third Section were not unfortunate exceptions due to the low moral qualities of those individuals, but rather a natural phenomenon which reflected the specific nature of the Russian literary system and, more generally, of Russian society as a whole.

THE POTENTIAL OF INDUSTRIAL WASTE AND AGRICULTURAL FEEDSTOCK TOWARDS SUSTAINABLE BIOFUELS PRODUCTION: TECHNO-ECONOMIC AND ENVIRONMENTAL IMPACT PERSPECTIVES

This Ph.D. research is comprised of three major components; (i) Characterization study to analyze the composition of defatted corn syrup (DCS) from a dry corn mill facility (ii) Hydrolysis experiments to optimize the production of fermentable sugars and amino acid platform using DCS and (iii) Sustainability analyses. Analyses of DCS included total solids, ash content, total protein, amino acids, inorganic elements, starch, total carbohydrates, lignin, organic acids, glycerol, and presence of functional groups. Total solids content was 37.4% (± 0.4%) by weight, and the mass balance closure was 101%. Total carbohydrates [27% (± 5%) wt.] comprised of starch (5.6%), soluble monomer carbohydrates (12%) and non-starch carbohydrates (10%). Hemicellulose components (structural and non-structural) were; xylan (6%), xylose (1%), mannan (1%), mannose (0.4%), arabinan (1%), arabinose (0.4%), galatactan (3%) and galactose (0.4%). Based on the measured physical and chemical components, bio-chemical conversion route and subsequent fermentation to value added products was identified as promising. DCS has potential to serve as an important fermentation feedstock for bio-based chemicals production. In the sugar hydrolysis experiments, reaction parameters such as acid concentration and retention time were analyzed to determine the optimal conditions to maximize monomer sugar yields while keeping the inhibitors at minimum. Total fermentable sugars produced can reach approximately 86% of theoretical yield when subjected to dilute acid pretreatment (DAP). DAP followed by subsequent enzymatic hydrolysis was most effective for 0 wt% acid hydrolysate samples and least efficient towards 1 and 2 wt% acid hydrolysate samples. The best hydrolysis scheme DCS from an industry's point of view is standalone 60 minutes dilute acid hydrolysis at 2 wt% acid concentration. The combined effect of hydrolysis reaction time, temperature and ratio of enzyme to substrate ratio to develop hydrolysis process that optimizes the production of amino acids in DCS were studied. Four key hydrolysis pathways were investigated for the production of amino acids using DCS. The first hydrolysis pathway is the amino acid analysis using DAP. The second pathway is DAP of DCS followed by protein hydrolysis using proteases [Trypsin, Pronase E (Streptomyces griseus) and Protex 6L]. The third hydrolysis pathway investigated a standalone experiment using proteases (Trypsin, Pronase E, Protex 6L, and Alcalase) on the DCS without any pretreatment. The final pathway investigated the use of Accellerase 1500® and Protex 6L to simultaneously produce fermentable sugars and amino acids over a 24 hour hydrolysis reaction time. The 3 key objectives of the techno-economic analysis component of this PhD research included; (i) Development of a process design for the production of both the sugar and amino acid platforms with DAP using DCS (ii) A preliminary cost analysis to estimate the initial capital cost and operating cost of this facility (iii) A greenhouse gas analysis to understand the environmental impact of this facility. Using Aspen Plus®, a conceptual process design has been constructed. Finally, both Aspen Plus Economic Analyzer® and Simapro® sofware were employed to conduct the cost analysis as well as the carbon footprint emissions of this process facility respectively. Another section of my PhD research work focused on the life cycle assessment (LCA) of commonly used dairy feeds in the U.S. Greenhouse gas (GHG) emissions analysis was conducted for cultivation, harvesting, and production of common dairy feeds used for the production of dairy milk in the U.S. The goal was to determine the carbon footprint [grams CO2 equivalents (gCO2e)/kg of dry feed] in the U.S. on a regional basis, identify key inputs, and make recommendations for emissions reduction. The final section of my Ph.D. research work was an LCA of a single dairy feed mill located in Michigan, USA. The primary goal was to conduct a preliminary assessment of dairy feed mill operations and ultimately determine the GHG emissions for 1 kilogram of milled dairy feed.

Exploring the World's Largest ERP Implementation: the Role of ERP in Strategic Alignment

As one of the largest and most complex organizations in the world, the Department of Defense (DoD) faces many challenges in solving its well-documented financial and related business operations and system problems. The DoD is in the process of implementing modern multifunction enterprise resource planning (ERP) systems to replace many of its outdated legacy systems. This paper explores the ERP implementations of the DoD and seeks to determine the impact of the ERP implementations on the alignment of the DoD’s business and IT strategy. A brief overview of the alignment literature and background on ERP are followed by case study analysis of the DoD ERP development and current implementation status. Lastly, the paper explores the current successes and failures of the ERP implementation and the impact on the DoD’s goal of strategic alignment.

Path Dependence in Decision-Making Processes: Exploring the Impact of Complexity under Increasing Returns

The development of path-dependent processes basically refers to positive feedback in terms of increasing returns as the main driving forces of such processes. Furthermore, path dependence can be affected by context factors, such as different degrees of complexity. Up to now, it has been unclear whether and how different settings of complexity impact path-dependent processes and the probability of lock-in. In this paper we investigate the relationship between environmental complexity and path dependence by means of an experimental study. By focusing on the mode of information load and decision quality in chronological sequences, the study explores the impact of complexity on decision-making processes. The results contribute to both the development of path-dependence theory and a better understanding of decision-making behavior under conditions of positive feedback. Since previous path research has mostly applied qualitative case-study research and (to a minor part) simulations, this paper makes a further contribution by establishing an experimental approach for research on path dependence.