Dipolar pathways in multi-spin and multi-dimensional dipolar EPR spectroscopy.

Dipolar electron paramagnetic resonance (EPR) experiments, such as double electron-electron resonance (DEER), measure distributions of nanometer-scale distances between unpaired electrons, which provide valuable information for structural characterization of proteins and other macromolecular systems. We present an extension to our previously published general model based on dipolar pathways valid for multi-dimensional dipolar EPR experiments with more than two spin-1/2 labels. We examine the 4-pulse DEER and TRIER experiments in terms of dipolar pathways and show experimental results confirming the theoretical predictions. This extension to the dipolar pathways model allows the analysis of previously challenging datasets and the extraction of multivariate distance distributions.

Computing distance distributions from dipolar evolution data with overtones: RIDME spectroscopy with Gd(iii)-based spin labels.

Extraction of distance distributions between high-spin paramagnetic centers from relaxation induced dipolar modulation enhancement (RIDME) data is affected by the presence of overtones of dipolar frequencies. As previously proposed, we account for these overtones by using a modified kernel function in Tikhonov regularization analysis. This paper analyzes the performance of such an approach on a series of model compounds with the Gd(iii)-PyMTA complex serving as paramagnetic high-spin label. We describe the calibration of the overtone coefficients for the RIDME kernel, demonstrate the accuracy of distance distributions obtained with this approach, and show that for our series of Gd-rulers RIDME technique provides more accurate distance distributions than Gd(iii)-Gd(iii) double electron-electron resonance (DEER). The analysis of RIDME data including harmonic overtones can be performed using the MATLAB-based program OvertoneAnalysis, which is available as open-source software from the web page of ETH Zurich. This approach opens a perspective for the routine use of the RIDME technique with high-spin labels in structural biology and structural studies of other soft matter.

Quantification and compensation of the influence of pulse transients on symmetry-based recoupling sequences.

Deviations of amplitude and phase of radio-frequency pulses from the desired values, can have a severe impact on the performance of multiple-pulse sequences in NMR spectroscopy. A particular problem are pulse transients that appear every time there is a discontinuity in amplitude or phase. Based on a Floquet description using pulses with arbitrarily shaped amplitudes and phases we present a systematic study of the influence of pulse transients on symmetry-based pulse sequences in solid-state NMR under magic-angle spinning. This treatment explains the dependence of the experimentally observed transfer efficiency on the details of experimental setups. In addition, three approaches are compared which have the aim to re-establish highly efficient recoupling. We demonstrate that the application of transient-compensated pulses as basic elements of symmetry-based sequences leads to a significantly improved robustness of the experiments with respect to variations in the experimental setup.

PDA and smartphone use by individuals with moderate-to-severe memory impairment: application of a theory-driven training programme.

We describe a structured, theory-driven training programme for individuals with moderate-to-severe memory impairment in the use of emerging commercial technology. We demonstrate its application to 10 individuals with memory impairment from a variety of aetiologies. A within-subject, ABAB multi-case experimental design was used to evaluate the impact of personal digital assistant or smartphone use on day-to-day memory functioning at baseline, immediately post-intervention, at return to baseline, and at short-term follow-up (range = 3-8 months). An errorless fading-of-cues protocol enabled all participants to acquire the skill set necessary to operate their PDA or smartphone independently. All 10 individuals showed robust improvement in day-to-day functioning post-intervention as quantified across a number of ecologically valid questionnaire and task-based measures. This was further corroborated by family members with whom six of the participants resided. These findings demonstrate that individuals with moderate-to-severe memory impairment can acquire the skills necessary to independently, flexibly and broadly apply commercial technology to support their everyday memory functioning. Moreover the findings confirm that the gap between individuals with memory impairment and potent emerging technology can be closed by the application of a systematic theory-driven training programme.

Exploratory factor analysis of neuropsychological tests and their relationship to the Brown-Peterson task.

The interference condition of the Brown-Peterson task and the auditory consonant trigrams test was designed to evaluate working memory in that it required a division of attentional processes to complete two cognitive tasks. However, the specific cognitive functions contributing to the performance of this interference task have yet to be determined. The objective of this study was to determine what other tasks are comparable to the Brown-Peterson task and conduct an exploratory factor analysis that included the measures from the Brown-Peterson task and other neuropsychological measures. A neuropsychological battery was administered to younger participants (n=107, mean age=20.83) and older participants (n=93, mean age=70.14). Factor analysis yielded a two-factor solution. Performance after the intervening serial subtraction task loaded on an auditory/visual working memory and complex attention factor and had common loadings with working memory subtests of the WAIS-III and the spatial span subtest of the WMS-III. Results suggest that the performance after the intervening serial subtraction task evaluates dual information processing, complex attention, and working memory.

Explicit and objective scoring criteria for the taylor complex figure test.

The Rey and Taylor figures are two constructional and visual memory tests used interchangeably. The purpose of this study was to develop a scoring system for the Taylor figure based on the explicit guidelines established by Meyers and Meyers (1995) for the Rey figure. Younger (n = 97; mean age = 21 years) and older (n = 61; mean age = 72 years) participants' performance on the Taylor figure was scored according to the proposed scoring system and the original scoring system devised by Taylor (1989). Both scoring systems yielded comparable scores on the Taylor figure as well as comparable patterns of validity and good interrater reliabilities (0.85-0.98). Although the present system does not further improve scoring reliability, it renders both tests similar in methodology and simplifies training to evaluate the two figures. The present study also reveals the limitations of the use of the Taylor and the Rey in test-retest situations but suggests that administering the Taylor first would improve the comparability of the two figures in a test-retest situation.

Comparing the Rey and Taylor complex figures: a test-retest study in young and older adults.

The Rey and Taylor figures, two visual perception and memory tests, are not equivalent in terms of their difficulty. The purpose of this study was to examine factors such as age, gender, order of administration, copy time, and copy score that could account for the variability in recall performance. Copy score was shown to be the best overall predictor of recall. Younger participants recalled more units than older participants on both complex figures. Furthermore, older participants appeared to benefit more from the presentation of the Taylor figure first compared to when they were presented with the Rey figure first. The present findings reveal the importance of test order and provide equations that can be used to facilitate the comparison of scores derived from the two figures in test-retest situations.