Nitrone [2]rotaxanes: Simultaneous chemical protection and electrochemical activation of a functional group

We report on the use of the hydrogen bond accepting properties of neutral nitrone moieties to prepare benzylic-amide-macrocycle-containing [2]rotaxanes in yields as high as 70 %. X-Ray crystallography shows the presence of up to four intercomponent hydrogen bonds between the amide groups of the macrocycle and the two nitrone groups of the thread. Dynamic 1H NMR studies of the rates of macrocycle pirouetting in nonpolar solutions indicate that amide-nitrone hydrogen bonds are particularly strong, ~1.3 and ~0.2 kcal mol-1 stronger than similar amide-ester and amide-amide interactions, respectively. In addition to polarizing the N-O bond through hydrogen bonding, the rotaxane structure affects the chemistry of the nitrone groups in two significant ways: The intercomponent hydrogen bonding activates the nitrone groups to electrochemical reduction, a one electron reduction of the rotaxane being stablized by a remarkable 400 mV (8.1 kcal mol-1) with respect to the same process in the thread; encapsulation, however, protects the same functional groups from chemical reduction with an external reagent (and slows down electron transfer to and from the electroactive groups in cyclicvoltammetry experiments). Mechanical interlocking with a hydrogen bonding molecular sheath thus provides a route to an encapsulated polarized functional group and radical anions of significant kinetic and thermodynamic stability.

Practical improvements to simultaneous computation of multi-view geometry and radial lens distortion

This paper discusses practical issues related to the use of the division model for lens distortion in multi-view geometry computation. A data normalisation strategy is presented, which has been absent from previous discussions on the topic. The convergence properties of the Rectangular Quadric Eigenvalue Problem solution for computing division model distortion are examined. It is shown that the existing method can require more than 1000 iterations when dealing with severe distortion. A method is presented for accelerating convergence to less than 10 iterations for any amount of distortion. The new method is shown to produce equivalent or better results than the existing method with up to two orders of magnitude reduction in iterations. Through detailed simulation it is found that the number of data points used to compute geometry and lens distortion has a strong influence on convergence speed and solution accuracy. It is recommended that more than the minimal number of data points be used when computing geometry using a robust estimator such as RANSAC. Adding two to four extra samples improves the convergence rate and accuracy sufficiently to compensate for the increased number of samples required by the RANSAC process.

Simultaneous voltammetric determination of three herbicides in food and water samples with the aid of chemometrics

Differential pulse stripping voltammetry method(DPSV) was applied to the determination of three herbicides, ametryn, cyanatryn, and dimethametryn. It was found that their voltammograms overlapped strongly, and it is difficult to determine these compounds individually from their mixtures. With the aid of chemometrics, classical least squares(CLS), principal component regression(PCR) and partial least squares(PLS), voltammogram resolution and quantitative analysis of the synthetic mixtures of the three compounds were successfully performed. The proposed method was also applied to the analysis of some real samples with satisfactory results.

Outdoor simultaneous localisation and mapping using RatSLAM

In this paper an existing method for indoor Simultaneous Localisation and Mapping (SLAM) is extended to operate in large outdoor environments using an omnidirectional camera as its principal external sensor. The method, RatSLAM, is based upon computational models of the area in the rat brain that maintains the rodent’s idea of its position in the world. The system uses the visual appearance of different locations to build hybrid spatial-topological maps of places it has experienced that facilitate relocalisation and path planning. A large dataset was acquired from a dynamic campus environment and used to verify the system’s ability to construct representations of the world and simultaneously use these representations to maintain localisation.

Towards semantic search and inference in electronic medical records : an approach using concept-based information retrieval

For more than a decade research in the field of context aware computing has aimed to find ways to exploit situational information that can be detected by mobile computing and sensor technologies. The goal is to provide people with new and improved applications, enhanced functionality and better use experience (Dey, 2001). Early applications focused on representing or computing on physical parameters, such as showing your location and the location of people or things around you. Such applications might show where the next bus is, which of your friends is in the vicinity and so on. With the advent of social networking software and microblogging sites such as Facebook and Twitter, recommender systems and so on context-aware computing is moving towards mining the social web in order to provide better representations and understanding of context, including social context. In this paper we begin by recapping different theoretical framings of context. We then discuss the problem of context- aware computing from a design perspective.

PySSM : a Python module for Bayesian inference of linear Gaussian state space models

PySSM is a Python package that has been developed for the analysis of time series using linear Gaussian state space models (SSM). PySSM is easy to use; models can be set up quickly and efficiently and a variety of different settings are available to the user. It also takes advantage of scientific libraries Numpy and Scipy and other high level features of the Python language. PySSM is also used as a platform for interfacing between optimised and parallelised Fortran routines. These Fortran routines heavily utilise Basic Linear Algebra (BLAS) and Linear Algebra Package (LAPACK) functions for maximum performance. PySSM contains classes for filtering, classical smoothing as well as simulation smoothing.