Dynamics of ligand substitution in labile cobalt complexes resolved by ultrafast T-jump

Ligand exchange of hydrated metal complexes is common in chemical and biological systems. Using the ultrafast T-jump, we examined this process, specifically the transformation of aqua cobalt (II) complexes to their fully halogenated species. The results reveal a stepwise mechanism with time scales varying from hundreds of picoseconds to nanoseconds. The dynamics are significantly faster when the structure is retained but becomes rate-limited when the octahedral-to-tetrahedral structural change bottlenecks the transformation. Evidence is presented, from bimolecular kinetics and energetics (enthalpic and entropic), for a reaction in which the ligand assists the displacement of water molecules, with the retention of the entering ligand in the activated state. The reaction time scale deviates by one to two orders of magnitude from that of ionic diffusion, suggesting the involvement of a collisional barrier between the ion and the much larger complex

Application of six sigma methodology to reduce defects of a grinding process

Six Sigma is a data-driven leadership approach using specific tools and methodologies that lead to fact-based decision making. This paper deals with the application of the Six Sigma methodology in reducing defects in a fine grinding process of an automotive company in India. The DMAIC (Define–Measure–Analyse–Improve–Control) approach has been followed here to solve the underlying problem of reducing process variation and improving the process yield. This paper explores how a manufacturing process can use a systematic methodology to move towards world-class quality level. The application of the Six Sigma methodology resulted in reduction of defects in the fine grinding process from 16.6 to 1.19%. The DMAIC methodology has had a significant financial impact on the profitability of the company in terms of reduction in scrap cost, man-hour saving on rework and increased output. A saving of approximately US$2.4 million per annum was reported from this project

Shadow kernels: A general mechanism for kernel specialization in existing operating systems

Existing operating systems share a common kernel text section amongst all processes. It is not possible to perform kernel specialization or tuning such that different applications execute text optimized for their kernel use despite the benefits of kernel specialization for performance guided optimization, exokernels, kernel fastpaths, and cheaper hardware access. Current specialization primitives involve system wide changes to kernel text, which can have adverse effects on other processes sharing the kernel due to the global side-effects. We present shadow kernels: a primitive that allows multiple kernel text sections to coexist in a contemporary operating system. By remapping kernel virtual memory on a context-switch, or for individual system calls, we specialize the kernel on a fine-grained basis. Our implementation of shadow kernels uses the Xen hypervisor so can be applied to any operating system that runs on Xen.This work was principally supported by internal funds from the Computer Laboratory at the University of Cambridge; and also by the Engineering and Physical Sciences Research Council [grant number EP/K503009/1].This is the final version of the article. It first appeared from ACM via http://dx.doi.org/10.1145/2797022.279702

What e-patients want from the doctor-patient relationship: content analysis of posts on discussion boards.

People with long-term conditions are encouraged to take control and ownership of managing their condition. Interactions between health care staff and patients become partnerships with sharing of expertise. This has changed the doctor-patient relationship and the division of roles and responsibilities that traditionally existed, but what each party expects from the other may not always be clear. Information that people with long-term conditions share on Internet discussion boards can provide useful insights into their expectations of health care staff. This paper reports on a small study about the expectations that people with a long-term condition (diabetes) have of their doctors using information gleaned from Internet discussion boards

Soroban: Attributing latency in virtualized environments

Applications running in the cloud have highly-variable response times due to the lack of perfect performance isolation from other services served by common infrastructure. In particular, response latency when executing on a loaded hypervisor or in a container is substantially higher than uncontested bare-metal performance. Whilst efforts to increase performance isolation continue, we present Soroban, a framework for attributing latency to either the cloud provider or their customer. Soroban allows cloud providers to instrument commonly used programs, such as a web server to determine, for each request, how much of the latency is due to the cloud provider, or the consumer. We apply Soroban to a HTTP server and show that it identifies when the cause of latency is due to a provider-induced activity, such as underprovisioning a host, or due to the software run by the customer.This is the author accepted manuscript. The final version is available from USENIX. via https://www.usenix.org/conference/hotcloud15/workshop-program/presentation/sne