Minimizing side reactions in chemoenzymatic dynamic kinetic resolution: organometallic and material strategies

Chemoenzymatic dynamic kinetic resolution (DKR) of rac-1-phenyl ethanol into R-1-phenylethanol acetate was investigated with emphasis on the minimization of side reactions. The organometallic hydrogen transfer (racemization) catalyst was varied, and this was observed to alter the rate and extent of oxidation of the alcohol to form ketone side products. The performance of highly active catalyst [(pentamethylcyclopentadienyl) IrCl2(1-benzyl,3-methyl-imidazol-2-ylidene)] was found to depend on the batch of lipase B used. The interaction between the bio- and chemo-catalysts was reduced by employing physical entrapment of the enzyme in silica using a sol-gel process. The nature of the gelation method was found to be important, with an alkaline method preferred, as an acidic method was found to initiate a further side reaction, the acid catalyzed dehydration of the secondary alcohol. The acidic gel was found to be a heterogeneous solid acid.

Allelic variation at the A218C tryptophan hydroxylase polymorphism influences agitation and aggression in Alzheimer's disease

The behavioural and psychological symptoms of dementia are common, distressing to carers, and directly linked to the requirement for institutional care. Symptoms of aggression and agitation are particularly difficult for carers to tolerate. The origin of these features is unclear although genetic and environmental modification of pre-frontal serotonergic circuitry which regulates the control of negative emotions is proposed. Following the suggestion that the A218C intronic polymorphism of the tryptophan hydroxylase gene influences aggression and anger in non-demented individuals, we tested the influence of A218C on symptoms of agitation/aggression in 396 Alzheimer's disease patients using the Neuropsychiatric Inventory. Overall, 50% of participants experienced agitation/aggression in the month prior to interview. It was observed that male patients with a history of agitation/aggression were more likely to possess C-containing genotypes (P = 0.044, OR = 1.65, CI = 0.98-2.76). We conclude that aggression in male subjects with Alzheimer's disease may be genetically linked to polymorphic variation at the tryptophan hydroxylase gene.

A framework for designing robust food supply chains

After years of emphasis on leanness and responsiveness businesses are now experiencing their vulnerability to supply chain disturbances. Although more literature is appearing on this subject, there is a need for an integrated framework to support the analysis and design of robust food supply chains. In this chapter we present such a framework. We define the concept of robustness and classify supply chain disturbances, sources of food supply chain vulnerability, and adequate redesign principles and strategies to achieve robust supply chain performances. To test and illustrate its applicability, the research framework is applied to a meat supply chain.

The Bright Side of Manufacturing–Remanufacturing Conflict in a Decentralised Closed-Loop Supply Chain

Researchers and managers broadly agree that original equipment manufacturers (OEMs), which have opportunities to produce both new and remanufactured products, are better off by centrally controlling their manufacturing and remanufacturing activities. Thus, OEMs should not remanufacture used products until the remanufacturing cost is sufficiently low to overcome the negative impact of new product cannibalisation. In this paper, we present a contrasting view of the manufacturing–remanufacturing conflict: OEMs sometimes benefit from the decentralised control mode under which they ignore the internal cannibalisation rather than the remanufacturing option. We consider a decentralised closed-loop supply chain in which one OEM can purchase new components from one supplier to produce new products and collect used products from consumers to produce remanufactured products. The key feature of our model is that the OEM can select a centralised or decentralised control mode to manage its manufacturing and remanufacturing activities before the supplier prices the new component. In a steady state period setting, we analyse the players’ optimal decisions and compare the OEM's profits under centralised and decentralised control modes. Our analytic results reveal that the decentralised control within the OEM can outperform the centralised control when the cost structure of producing new and remanufactured products satisfies certain conditions. Finally, the key findings are distilled in a conceptual framework and its managerial implications are discussed.

The Other Side of the Fence:Reconceptualizing the “Camp” and Migration Zones at the Borders of Spain

This article explores the dynamics of the space of exception at the borders of Europe in the Spanish enclave of Melilla, and the neighboring Moroccan city of Oujda. Building upon field research conducted in the spring of 2008, I ask how we can understand the political space of migration not simply as exceptional, but as shaped by the mobility of the irregular migrants moving outside of the frameworks, policies, and practices of the state. By privileging the migrant narrative and making use of Rancière's conception of politics as shaped by the demands of those who “have no part,” I suggest an alternative way of understanding the politics of exception and agency of non-citizens—that is, one of disruption and demands to open up powerful potentials for change in an otherwise rigid regime.

The effects and side-effects of statistics education: Psychology students’ (mis-)conceptions of probability

In three studies we looked at two typical misconceptions of probability: the representativeness heuristic, and the equiprobability bias. The literature on statistics education predicts that some typical errors and biases (e.g., the equiprobability bias) increase with education, whereas others decrease. This is in contrast with reasoning theorists’ prediction who propose that education reduces misconceptions in general. They also predict that students with higher cognitive ability and higher need for cognition are less susceptible to biases. In Experiments 1 and 2 we found that the equiprobability bias increased with statistics education, and it was negatively correlated with students’ cognitive abilities. The representativeness heuristic was mostly unaffected by education, and it was also unrelated to cognitive abilities. In Experiment 3 we demonstrated through an instruction manipulation (by asking participants to think logically vs. rely on their intuitions) that the reason for these differences was that these biases originated in different cognitive processes.

Analysis of Two-Speed Wind Farm Operation From Grid-Side Measurements

This paper analyzes data captured by a phasor measurement unit at a wind farm, employing two-speed induction generators, and investigates aspects of the control system's interaction with the power system. Composite superimposed transient events are proposed as a method to improve the quality of the analysis and reduce errors caused by unknowns, such as wind speed variation. A Mathworks SimPowerSystems model validates the inertia contribution of the wind farm, which is an important parameter in power systems with high wind penetration. Transients caused by turbine speed transitions are identified and explained. The analysis also highlights areas where wind farm control should be improved if useful inertia contribution is to be provided.

Exchange potential from the common energy denominator approximation for the Kohn-Sham Green's function: Application to (hyper)polarizabilities of molecular chains

An approximate Kohn-Sham (KS) exchange potential v(xsigma)(CEDA) is developed, based on the common energy denominator approximation (CEDA) for the static orbital Green's function, which preserves the essential structure of the density response function. v(xsigma)(CEDA) is an explicit functional of the occupied KS orbitals, which has the Slater v(Ssigma) and response v(respsigma)(CEDA) potentials as its components. The latter exhibits the characteristic step structure with "diagonal" contributions from the orbital densities \psi(isigma)\(2), as well as "off-diagonal" ones from the occupied-occupied orbital products psi(isigma)psi(j(not equal1)sigma). Comparison of the results of atomic and molecular ground-state CEDA calculations with those of the Krieger-Li-Iafrate (KLI), exact exchange (EXX), and Hartree-Fock (HF) methods show, that both KLI and CEDA potentials can be considered as very good analytical "closure approximations" to the exact KS exchange potential. The total CEDA and KLI energies nearly coincide with the EXX ones and the corresponding orbital energies epsilon(isigma) are rather close to each other for the light atoms and small molecules considered. The CEDA, KLI, EXX-epsilon(isigma) values provide the qualitatively correct order of ionizations and they give an estimate of VIPs comparable to that of the HF Koopmans' theorem. However, the additional off-diagonal orbital structure of v(xsigma)(CEDA) appears to be essential for the calculated response properties of molecular chains. KLI already considerably improves the calculated (hyper)polarizabilities of the prototype hydrogen chains H-n over local density approximation (LDA) and standard generalized gradient approximations (GGAs), while the CEDA results are definitely an improvement over the KLI ones. The reasons of this success are the specific orbital structures of the CEDA and KLI response potentials, which produce in an external field an ultranonlocal field-counteracting exchange potential. (C) 2002 American Institute of Physics.

Entanglement Spectrum, Critical Exponents and Order Parameters in Quantum Spin Chains

We investigate the entanglement spectrum near criticality in finite quantum spin chains. Using finite size scaling we show that when approaching a quantum phase transition, the Schmidt gap, i.e., the difference between the two largest eigenvalues of the reduced density matrix ?1, ?2, signals the critical point and scales with universal critical exponents related to the relevant operators of the corresponding perturbed conformal field theory describing the critical point. Such scaling behavior allows us to identify explicitly the Schmidt gap as a local order parameter.

Robust food supply supply chains:An integrated framework for vulnerability assessment and disturbance management

The operation of supply chains (SCs) has for many years been focused on efficiency, leanness and responsiveness. This has resulted in reduced slack in operations, compressed cycle times, increased productivity and minimised inventory levels along the SC. Combined with tight tolerance settings for the realisation of logistics and production processes, this has led to SC performances that are frequently not robust. SCs are becoming increasingly vulnerable to disturbances, which can decrease the competitive power of the entire chain in the market. Moreover, in the case of food SCs non-robust performances may ultimately result in empty shelves in grocery stores and supermarkets.
The overall objective of this research is to contribute to Supply Chain Management (SCM) theory by developing a structured approach to assess SC vulnerability, so that robust performances of food SCs can be assured. We also aim to help companies in the food industry to evaluate their current state of vulnerability, and to improve their performance robustness through a better understanding of vulnerability issues. The following research questions (RQs) stem from these objectives:
RQ1: What are the main research challenges related to (food) SC robustness?
RQ2: What are the main elements that have to be considered in the design of robust SCs and what are the relationships between these elements?
RQ3: What is the relationship between the contextual factors of food SCs and the use of disturbance management principles?
RQ4: How to systematically assess the impact of disturbances in (food) SC processes on the robustness of (food) SC performances?
To answer these RQs we used different methodologies, both qualitative and quantitative. For each question, we conducted a literature survey to identify gaps in existing research and define the state of the art of knowledge on the related topics. For the second and third RQ, we conducted both exploration and testing on selected case studies. Finally, to obtain more detailed answers to the fourth question, we used simulation modelling and scenario analysis for vulnerability assessment.
Main findings are summarised as follows.
Based on an extensive literature review, we answered RQ1. The main research challenges were related to the need to define SC robustness more precisely, to identify and classify disturbances and their causes in the context of the specific characteristics of SCs and to make a systematic overview of (re)design strategies that may improve SC robustness. Also, we found that it is useful to be able to discriminate between varying degrees of SC vulnerability and to find a measure that quantifies the extent to which a company or SC shows robust performances when exposed to disturbances.
To address RQ2, we define SC robustness as the degree to which a SC shows an acceptable performance in (each of) its Key Performance Indicators (KPIs) during and after an unexpected event that caused a disturbance in one or more logistics processes. Based on the SCM literature we identified the main elements needed to achieve robust performances and structured them together to form a conceptual framework for the design of robust SCs. We then explained the logic of the framework and elaborate on each of its main elements: the SC scenario, SC disturbances, SC performance, sources of food SC vulnerability, and redesign principles and strategies.
Based on three case studies, we answered RQ3. Our major findings show that the contextual factors have a consistent relationship to Disturbance Management Principles (DMPs). The product and SC environment characteristics are contextual factors that are hard to change and these characteristics initiate the use of specific DMPs as well as constrain the use of potential response actions. The process and the SC network characteristics are contextual factors that are easier to change, and they are affected by the use of the DMPs. We also found a notable relationship between the type of DMP likely to be used and the particular combination of contextual factors present in the observed SC.
To address RQ4, we presented a new method for vulnerability assessments, the VULA method. The VULA method helps to identify how much a company is underperforming on a specific Key Performance Indicator (KPI) in the case of a disturbance, how often this would happen and how long it would last. It ultimately informs the decision maker about whether process redesign is needed and what kind of redesign strategies should be used in order to increase the SC’s robustness. The VULA method is demonstrated in the context of a meat SC using discrete-event simulation. The case findings show that performance robustness can be assessed for any KPI using the VULA method.
To sum-up the project, all findings were incorporated within an integrated framework for designing robust SCs. The integrated framework consists of the following steps: 1) Description of the SC scenario and identification of its specific contextual factors; 2) Identification of disturbances that may affect KPIs; 3) Definition of the relevant KPIs and identification of the main disturbances through assessment of the SC performance robustness (i.e. application of the VULA method); 4) Identification of the sources of vulnerability that may (strongly) affect the robustness of performances and eventually increase the vulnerability of the SC; 5) Identification of appropriate preventive or disturbance impact reductive redesign strategies; 6) Alteration of SC scenario elements as required by the selected redesign strategies and repeat VULA method for KPIs, as defined in Step 3.
Contributions of this research are listed as follows. First, we have identified emerging research areas - SC robustness, and its counterpart, vulnerability. Second, we have developed a definition of SC robustness, operationalized it, and identified and structured the relevant elements for the design of robust SCs in the form of a research framework. With this research framework, we contribute to a better understanding of the concepts of vulnerability and robustness and related issues in food SCs. Third, we identified the relationship between contextual factors of food SCs and specific DMPs used to maintain robust SC performances: characteristics of the product and the SC environment influence the selection and use of DMPs; processes and SC networks are influenced by DMPs. Fourth, we developed specific metrics for vulnerability assessments, which serve as a basis of a VULA method. The VULA method investigates different measures of the variability of both the duration of impacts from disturbances and the fluctuations in their magnitude.
With this project, we also hope to have delivered practical insights into food SC vulnerability. First, the integrated framework for the design of robust SCs can be used to guide food companies in successful disturbance management. Second, empirical findings from case studies lead to the identification of changeable characteristics of SCs that can serve as a basis for assessing where to focus efforts to manage disturbances. Third, the VULA method can help top management to get more reliable information about the “health” of the company.
The two most important research opportunities are: First, there is a need to extend and validate our findings related to the research framework and contextual factors through further case studies related to other types of (food) products and other types of SCs. Second, there is a need to further develop and test the VULA method, e.g.: to use other indicators and statistical measures for disturbance detection and SC improvement; to define the most appropriate KPI to represent the robustness of a complete SC. We hope this thesis invites other researchers to pick up these challenges and help us further improve the robustness of (food) SCs.

Process of debonding in RC beams shear-strengthened with FRP U-strips or side strips

Reinforced concrete (RC) beams may be strengthened for shear using externally bonded fiber reinforced polymer (FRP) composites in the form of side bonding, U-jacketing or complete wrapping. The shear failure of almost all RC beams shear-strengthened with side bonded FRP and the majority of those strengthened with FRP U-jackets, is due to debonding of the FRP. The bond behavior between the externally-bonded FRP reinforcement (referred to as FRP strips for simplicity) and the concrete substrate therefore plays a crucial role in the failure process of these beams. Despite extensive research in the past decade, there is still a lack of understanding of how debonding of FRP strips in such a beam propagates and how the debonding process affects its shear behavior. This paper presents an analytical study on the progressive debonding of FRP strips in such strengthened beams. The complete debonding process is modeled and the contribution of the FRP strips to the shear capacity of the beam is quantified. The validity of the analytical solution is verified by comparing its predictions with numerical results from a finite element analysis. This analytical treatment represents a significant step forward in understanding how interaction between FRP strips, steel stirrups and concrete affects the shear resistance of RC beams shear-strengthened with FRP strips.