Silicon-Directed Rhenium Catalyzed Allylic Carbaminations and Oxidative Fragmentations of γ-Silyl Allylic Alcohols

A highly regioselective allylic substitution of β-silyl allylic alcohols has been achieved that provides the branched isomer as a single product. This high level of regiocontrol is achieved through the use of a vinyl silane group that can perform a Hiyama coupling providing 1,3-disubstituted allylic amines. An unusual oxidative fragmentation product was also observed at elevated temperature that appears to proceed by a Fleming–Tamao-type oxidation–elimination pathway.

Silicon-Directed Rhenium-Catalyzed Allylic Substitutions with N‑Hydroxycarbamates, N‑Hydroxysulfonamides, and Hydroxamic Acids

A rhenium-catalyzed N-selective allylic amination reaction of N-hydroxycarbamates has been developed. This reaction occurs with excellent N/O selectivity and with complete carbon selectivity on the allylic system. The reaction is tolerant of many functional groups and also proceeds with N-hydroxysulfonamides and hydroxamic acids.

Four-dimensional CT analysis of vocal cords mobility for highly focused single vocal cord irradiation

Background and Purpose: To quantify respiratory motion of the vocal cords during normal respiration using 4D-CT. The final goal is to develop a technique for single vocal cord irradiation (SVCI) in early glottic carcinoma. Sparing the non-involved cord and surrounding structures has the potential to preserve voice quality and allow re-irradiation of recurrent and second primary tumors. Material and methods: Four-dimensional CTs of 1 mm slice thickness from 10 early glottic carcinoma patients were acquired. The lateral dimensions of the air gap separating the vocal cords were measured anteriorly, at mid-level and posteriorly at each phase of the 4D-CTs. The corresponding anterior-posterior gaps were similarly measured. Cranio-caudal vocal cords movements during breathing were derived from the shifts of the arythenoids. Results: The population-averaged mean gap size ± the corresponding standard deviation due to breathing (SD_B) for the lateral gaps was 5.8 ± 0.7 mm anteriorly, 8.7 ± 0.9 mm at mid-level, and 11.0 ± 1.3 mm posteriorly. Anterior-posterior gap values were 21.7 ± 0.7 mm, while cranio-caudal shift SD_B was 0.8 mm. Conclusion: Vocal cords breathing motions were found to be small relative to their separation. Hence, breathing motion does not seem to be a limiting factor for SVCI. © 2008 Elsevier Ireland Ltd. All rights reserved.

Developing management capability within a horizontal supply chain in performance measurement deployment and evolution: A Dynamic Capabilities and Goal Theory perspective

Complex collaboration in rapidly changing business environments create challenges for management capability in Utility Horizontal Supply Chains (UHSCs) involving the deploying and evolving of performance measures. The aim of the study is twofold. First, there is a need to explore how management capability can be developed and used to deploy and evolve Performance Measurement (PM), both across a UHSC and within its constituent organisations, drawing upon a theoretical nexus of Dynamic Capability (DC) theory and complementary Goal Theory. Second, to make a contribution to knowledge by empirically building theory using these constructs to show the management motivations and behaviours within PM-based DCs. The methodology uses an interpretive theory building, multiple case based approach (n=3) as part of a USHC. The data collection methods include, interviews (n=54), focus groups (n=10), document analysis and participant observation (reflective learning logs) over a five-year period giving longitudinal data. The empirical findings lead to the development of a conceptual framework showing that management capabilities in driving PM deployment and evolution can be represented as multilevel renewal and incremental Dynamic Capabilities, which can be further understood in terms of motivation and behaviour by Goal-Theoretic constructs. In addition three interrelated cross cutting themes of management capabilities in consensus building, goal setting and resource change were identified. These management capabilities require carefully planned development and nurturing within the UHSC. 

Virtual Thrower Versus Real Goalkeeper: The Influence of Different Visual Conditions on Performance

In order to use virtual reality as a sport analysis tool, we need to be sure that an immersed athlete reacts realistically in a virtual environment. This has been validated for a real handball goalkeeper facing a virtual thrower. However, we currently ignore which visual variables induce a realistic motor behavior of the immersed handball goalkeeper. In this study, we used virtual reality to dissociate the visual information related to the movements of the player from the visual information related to the trajectory of the ball. Thus, the aim is to evaluate the relative influence of these different visual information sources on the goalkeeper's motor behavior. We tested 10 handball goalkeepers who had to predict the final position of the virtual ball in the goal when facing the following: only the throwing action of the attacking player (TA condition), only the resulting ball trajectory (BA condition), and both the throwing action of the attacking player and the resulting ball trajectory (TB condition). Here we show that performance was better in the BA and TB conditions, but contrary to expectations, performance was substantially worse in the TA condition. A significant effect of ball landing zone does, however, suggest that the relative importance between visual information from the player and the ball depends on the targeted zone in the goal. In some cases, body-based cues embedded in the throwing actions may have a minor influence on the ball trajectory and vice versa. Kinematics analysis was then combined with these results to determine why such differences occur depending on the ball landing zone and consequently how it can clarify the role of different sources of visual information on the motor behavior of an athlete immersed in a virtual environment.

Critical Nodes In Directed Networks

Critical nodes—or “middlemen”—have an essential place in both social and economic networks when considering the flow of information and trade. This paper extends the concept of critical nodes to directed networks and in doing so identify strong and weak middlemen.
Node contestability is introduced as a form of competition in networks; a duality between uncontested intermediaries and middlemen is established. The brokerage power of middlemen is formally expressed and a general algorithm is constructed to measure the brokerage power of each node from the networks adjacency matrix. Augmentations of the brokerage power measure are discussed to encapsulate relevant centrality measures. Furthermore, we extend these notions and provide measures of the competitiveness of a network.
We use these concepts to identify and measure middlemen in two empirical socio-economic networks, the elite marriage network of Renaissance Florence and Krackhardt’s advice net- work.

Clinical potential of gene-directed enzyme prodrug therapy to improve radiation therapy in prostate cancer patients

Despite the advances in prostate cancer diagnosis and treatment, current therapies are not curative in a significant proportion of patients. Gene-directed enzyme prodrug therapy (GDEPT), when combined with radiation therapy, could improve the outcome of treatment for prostate cancer, the second leading cause of cancer death in the western world. GDEPT involves the introduction of a therapeutic transgene, which can be targeted to the tumour cells. A prodrug is administered systemically and is converted to its toxic form only in those cells containing the transgene, resulting in cell kill. This review will discuss the clinical trials which have investigated the potential of GDEPT at various stages of prostate cancer progression. The advantages of using GDEPT in combination with radiotherapy will be examined, as well as some of the recent advances which enhance the potential utility of GDEPT.