Die Carbonylierung acyclischer Diaminocarbene

Das Dissertationsprojekt befasst sich mit dem synthetischen Potential acyclischer Diaminocarbene (aDACs; Verbindungen des Typs (R2N)2C:) und prüft dabei insbesondere deren Reaktivität gegenüber Kohlenmonoxid (CO). Grundlage des Vorhabens ist eine Aufsehen erregende Beobachtung von SIEMELING et al. (Chem. Sci., 2010, 1, 697): Der Prototyp der aDACs, das Bis(diisopropylamino)carben, ist in der Lage CO zu aktivieren. Dabei wird zunächst ein intermediäres Keten des Typs (R2N)2C=C=O generiert, das in Folge einer intramolekularen Reaktion ein stabiles β-Lactamderivat ausbildet. Eine Sensation, schließlich ging man in der Fachwelt bis dato davon aus, dass cyclische und acyclische Diaminocarbene für derartige Reaktionen nicht elektrophil genug seien. Ziel der vorliegenden Arbeit war eine systematische Auslotung der aDAC-Reaktivität gegenüber CO. Im Rahmen der durchgeführten Untersuchungen ist es gelungen, das Feld der literaturbekannten aDACs von 12 auf 19 zu erweitern. Die Carbene, ihre Formamidiniumsalz-Vorstufen, sowie die korrespondierenden Carben–Metallkomplexe konnten in den meisten Fällen vollständig charakterisiert werden. Es konnte gezeigt werden, dass manche Isopropyl-substituierten aDACs in inertem Lösemittel einer β-Umlagerung unterliegen sowie, dass eine solche intramolekulare Reaktivität innerhalb dieser Substanzklasse nicht trivial ist: Zum Teil ganz ähnlich substituierte aDACs sind in Lösung unbegrenzt haltbar. Die Reaktivität gegenüber CO konnte an etwa einem Dutzend aDACs studiert werden. Lediglich in einem Fall zeigte sich das Carben inert. In einem sterisch überfrachteten Fall entstand in einer regio- und stereoselektiven Folgereaktion ein biologisch aktives bicyclisches β-Lactamderivat. In den meisten Fällen ergaben sich betainische Oxyallylspezies des Typs [(R2N)2C]2CO als intermolekulare Folgeprodukte. Die mechanistische Scheidelinie zwischen intra- und intermolekularer Keten-Folgereaktion konnte anhand der Carbonylierung sterisch ganz ähnlich substituierter aDACs aufgezeigt werden. Die gewonnenen Erkenntnisse liefern deutliche Hinweise darauf, dass das chemische Verhalten der aDACs gegenüber CO eher durch feinste elektronische Unterschiede als durch den sterischen Anspruch der Carben-Substituenten beeinflusst wird. Mit Hilfe von In-Situ-IR-Spektroskopie gelang es in manchen Fällen, bei denen eine Isolierung der Carbonylierungsprodukte nicht glückte, die Generierung hochreaktiver Oxyallylspezies zu belegen. Weiterhin konnte im Zuge der In-Situ-IR-Studien das zuvor nur postulierte Diaminoketen als primäres Carbonylierungsprodukt dingfest gemacht werden (ν(C=C=O) = 2085 1/cm): Es handelt sich hierbei um den ersten experimentellen Nachweis eines Diaminoketens überhaupt.

BioJADE: A Design and Simulation Tool for Synthetic Biological Systems

The next generations of both biological engineering and computer engineering demand that control be exerted at the molecular level. Creating, characterizing and controlling synthetic biological systems may provide us with the ability to build cells that are capable of a plethora of activities, from computation to synthesizing nanostructures. To develop these systems, we must have a set of tools not only for synthesizing systems, but also designing and simulating them. The BioJADE project provides a comprehensive, extensible design and simulation platform for synthetic biology. BioJADE is a graphical design tool built in Java, utilizing a database back end, and supports a range of simulations using an XML communication protocol. BioJADE currently supports a library of over 100 parts with which it can compile designs into actual DNA, and then generate synthesis instructions to build the physical parts. The BioJADE project contributes several tools to Synthetic Biology. BioJADE in itself is a powerful tool for synthetic biology designers. Additionally, we developed and now make use of a centralized BioBricks repository, which enables the sharing of BioBrick components between researchers, and vastly reduces the barriers to entry for aspiring Synthetic Biologists.

Experimental Markets for Product Concepts

Market prices are well known to efficiently collect and aggregate diverse information regarding the value of commodities and assets. The role of markets has been particularly suitable to pricing financial securities. This article provides an alternative application of the pricing mechanism to marketing research - using pseudo-securities markets to measure preferences over new product concepts. Surveys, focus groups, concept tests and conjoint studies are methods traditionally used to measure individual and aggregate preferences. Unfortunately, these methods can be biased, costly and time-consuming to conduct. The present research is motivated by the desire to efficiently measure preferences and more accurately predict new product success, based on the efficiency and incentive-compatibility of security trading markets. The article describes a novel market research method, pro-vides insight into why the method should work, and compares the results of several trading experiments against other methodologies such as concept testing and conjoint analysis.

A FRAMEWORK FOR ACHIEVING LIFECYCLE VALUE IN AEROSPACE PRODUCT DEVELOPMENT

Creation of lifecycle value - a balance of performance with cost and other attributes - represents a challenge for the development of aerospace products in the twenty-first century. This paper examines the concept of lifecycle value that stems from existing approaches of value management and analysis, lifecycle costing, and systems engineering. To ascertain common characteristics of lifecycle value creation, case studies were done for four aircraft programs: F/A- 18E/F, JAS 39 Gripen, F-16C/D, and B-777. A lifecycle value creation framework is introduced, comprised of three phases: value identification, value proposition, value delivery. Based upon observed practices in the four case studies, six value creation attributes were identified. Capability maturity models for the six attributes and three value creation phases are presented. The resulting framework represents a starting point for programs seeking to create lifecycle value for aerospace products.

Lifecycle Value Framework for Tactical Aircraft Product Development

Due to a dramatic reduction in defense procurement, the benchmark for developing new defense systems today is performance at an affordable cost. In an attempt to encircle a more holistic perspective of value, lifecycle value has evolved as a concept within the Lean Aerospace Initiative, LAI. The implication of this is development of products incorporating lifecycle and long-term focus instead of a shortsighted cost cutting focus. The interest to reduce total cost of ownership while still improving performance, availability, and sustainability, other dimensions taken into account within the lifecycle value approach, falls well within this context. Several factors prevent enterprises from having a holistic perspective during product development. Some important aspects are increased complexity of the products and significant technological uncertainty. The combination of complexity in system design and the limits of individual human comprehension typically prevent a best value solution to be envisioned. The purpose of this research was to examine relative contributions in product development and determine factors that significantly promote abilities to consider and achieve lifecycle value. This paper contributes a maturity matrix based on important practices and lessons learned through extensive interview based case studies of three tactical aircraft programs, including experiences from more than 100 interviews.

Measuring Value in Product Development

“What is value in product development?” is the key question of this paper. The answer is critical to the creation of lean in product development. By knowing how much value is added by product development (PD) activities, decisions can be more rationally made about how to allocate resources, such as time and money.

Output from the 1998 Product Development Value Stream Workshop: A Framework for Understanding Information Flow in the Product Development Process

The descriptions below and the attached diagrams are outputs of the 1998 LAI Product Development Focus Team workshop on the Value Chain in Product Development. A working group at that workshop was asked to model the product development process: in terms of the phases of product development and their interfaces, boundaries and outputs. Their work has proven to be generally useful to LAI researchers and industry members, and so is formalized here.

Strategies for Lean Product Development

The essence of lean is very simple, but from a research and implementation point of view overwhelming. Lean is the search for perfection through the elimination of waste and the insertion of practices that contribute to reduction in cost and schedule while improving performance of products. This concept of lean has wide applicability to a large range of processes, people and organizations, from concept design to the factory floor, from the laborer to the upper management, from the customer to the developer. Progress has been made in implementing and raising the awareness of lean practices at the factory floor. However, the level of implementation and education in other areas, like product development, is very low.

Value Creation in Product Development

-Definitions -Value concepts -Value creation framework -Value creation and product development

Value Stream Analysis and Mapping for Product Development

This paper explores the concept of Value Stream Analysis and Mapping (VSA/M) as applied to Product Development (PD) efforts. Value Stream Analysis and Mapping is a method of business process improvement. The application of VSA/M began in the manufacturing community. PD efforts provide a different setting for the use of VSA/M. Site visits were made to nine major U.S. aerospace organizations. Interviews, discussions, and participatory events were used to gather data on (1) the sophistication of the tools used in PD process improvement efforts, (2) the lean context of the use of the tools, and (3) success of the efforts. It was found that all three factors were strongly correlated, suggesting success depends on both good tools and lean context. Finally, a general VSA/M method for PD activities is proposed. The method uses modified process mapping tools to analyze and improve process.

Value Stream Analysis and Mapping for Product Development

This paper explores the concept of Value Stream Analysis and Mapping (VSA/M) as applied to Product Development (PD) efforts. Value Stream Analysis and Mapping is a method of business process improvement. The application of VSA/M began in the manufacturing community. PD efforts provide a different setting for the use of VSA/M. Site visits were made to nine major U.S. aerospace organizations. Interviews, discussions, and participatory events were used to gather data on (1) the sophistication of the tools used in PD process improvement efforts, (2) the lean context of the use of the tools, and (3) success of the efforts. It was found that all three factors were strongly correlated, suggesting success depends on both good tools and lean context. Finally, a general VSA/M method for PD activities is proposed. The method uses modified process mapping tools to analyze and improve process.

Measuring Value in Product Development

“What is value in product development?” is the key question of this paper. The answer is critical to the creation of lean in product development. By knowing how much value is added by product development (PD) activities, decisions can be more rationally made about how to allocate resources, such as time and money. In order to apply the principles of Lean Thinking and remove waste from the product development system, value must be precisely defined. Unfortunately, value is a complex entity that is composed of many dimensions and has thus far eluded definition on a local level. For this reason, research has been initiated on “Measuring Value in Product Development.” This paper serves as an introduction to this research. It presents the current understanding of value in PD, the critical questions involved, and a specific research design to guide the development of a methodology for measuring value. Work in PD value currently focuses on either high-level perspectives on value, or detailed looks at the attributes that value might have locally in the PD process. Models that attempt to capture value in PD are reviewed. These methods, however, do not capture the depth necessary to allow for application. A methodology is needed to evaluate activities on a local level to determine the amount of value they add and their sensitivity with respect to performance, cost, time, and risk. Two conceptual tools are proposed. The first is a conceptual framework for value creation in PD, referred to here as the Value Creation Model. The second tool is the Value-Activity Map, which shows the relationships between specific activities and value attributes. These maps will allow a better understanding of the development of value in PD, will facilitate comparison of value development between separate projects, and will provide the information necessary to adapt process analysis tools (such as DSM) to consider value. The key questions that this research entails are: · What are the primary attributes of lifecycle value within PD? · How can one model the creation of value in a specific PD process? · Can a useful methodology be developed to quantify value in PD processes? · What are the tools necessary for application? · What PD metrics will be integrated with the necessary tools? The research milestones are: · Collection of value attributes and activities (September, 200) · Development of methodology of value-activity association (October, 2000) · Testing and refinement of the methodology (January, 2001) · Tool Development (March, 2001) · Present findings at July INCOSE conference (April, 2001) · Deliver thesis that captures a formalized methodology for defining value in PD (including LEM data sheets) (June, 2001) The research design aims for the development of two primary deliverables: a methodology to guide the incorporation of value, and a product development tool that will allow direct application.

Optimizing Product Line Designs: Efficient Methods and Comparisons

We compare a broad range of optimal product line design methods. The comparisons take advantage of recent advances that make it possible to identify the optimal solution to problems that are too large for complete enumeration. Several of the methods perform surprisingly well, including Simulated Annealing, Product-Swapping and Genetic Algorithms. The Product-Swapping heuristic is remarkable for its simplicity. The performance of this heuristic suggests that the optimal product line design problem may be far easier to solve in practice than indicated by complexity theory.

Informed recommender: basing recommendations on consumer product reviews

Recommender systems attempt to predict items in which a user might be interested, given some information about the user's and items' profiles. Most existing recommender systems use content-based or collaborative filtering methods or hybrid methods that combine both techniques (see the sidebar for more details). We created Informed Recommender to address the problem of using consumer opinion about products, expressed online in free-form text, to generate product recommendations. Informed recommender uses prioritized consumer product reviews to make recommendations. Using text-mining techniques, it maps each piece of each review comment automatically into an ontology

Recommender System Based on Consumer Product Reviews

Consumer reviews, opinions and shared experiences in the use of a product is a powerful source of information about consumer preferences that can be used in recommender systems. Despite the importance and value of such information, there is no comprehensive mechanism that formalizes the opinions selection and retrieval process and the utilization of retrieved opinions due to the difficulty of extracting information from text data. In this paper, a new recommender system that is built on consumer product reviews is proposed. A prioritizing mechanism is developed for the system. The proposed approach is illustrated using the case study of a recommender system for digital cameras