Tetrathiafulvalene-acetylene scaffolding: new pi-electron systems for advanced materials

Novel extended tetrathiafulvalenes (TTFs) with hexa-2,4-diyne-1,6-diylidene spacers between the two 1,3-dithiole rings and laterally appended alkynyl moieties for one- and two-dimensional scaffolding were synthesised and investigated for their electronic properties.     

Mural inspection by vibration measurements with TV-holography

A commonly encountered problem in the conservation of historical murals is the identification of sections in the plaster that have detached from the wall and thus threaten to fall off. Commonly, walls are inspected by the acoustic response to a gentle finger-tapping (percussion method). Since this is a costly and cumbersome technique, means for a more automatic inspection are searched for. A TV-holography system of increased sensitivity in combination with acoustic excitation of the object is shown to be a new and powerful tool for monitoring of loose areas. It has the advantage of non-contact and remote operation which, for example, is extremely useful in large buildings. Principles of the method, experimental results obtained at an artificial wall in the laboratory, and a thorough comparison of results from historical sites gained by the traditional percussion method and the new technique are presented. The latter shows very good agreement in the assessment of wall quality and thus is evidence of the suitability of the optical equipment for tasks in conservation.     

Extrinsic multiecho phase-contrast SSFP: evaluation on cardiac output measurements

Multiecho phase-contrast steady-state free precession (PC-SSFP) is a recently introduced sequence for flow quantification. In this multiecho approach, a phase reference and a velocity-encoded readout were acquired at different echo times after a single excitation. In this study, the sequence is validated in vitro for stationary flow. Subsequently, the sequence was evaluated on cardiac output measurements in vivo for through-plane flow in comparison to regular single gradient echo velocity quantification [phase-contrast spoiled gradient echo (PC-GE)]. In vitro results agreed with regular flow meters (RMS 0.1 cm/s). Cardiac output measurements with multiecho PC-SSFP on 10 healthy subjects gave on average the same results as the standard PC-GE. However, the limits of repeatability of PC-SSFP were significantly larger than those of PC-GE (2 l/min and 0.5 l/min, respectively, P=.001). The multiecho approach introduced some specific problems in vivo. The difference in echo times made the velocity maps sensitive for water-fat shifts and B(0)-drifts, which in turn made velocity offset correction problematic. Also, the addition of a single bipolar gradient cancelled the flow compensated nature of the SSFP sequence. In combination with the prolonged TR, this resulted in flow artifacts caused by high and pulsatile through-plane flow, affecting repeatability. Given the significantly lower repeatability of PC-SSFP, cardiac output in turn is less reliable, thus impairing the use of multiecho PC-SSFP.     

Artifact Reduction Based on Sinogram Interpolation for the 3D Reconstruction of Nanoparticles Using Electron Tomography

Electron tomography is a well‐known technique providing a 3D characterization of the morphology and chemical composition of nanoparticles. However, several reasons hamper the acquisition of tilt series with a large number of projection images, which deteriorate the quality of the 3D reconstruction. Here, an inpainting method that is based on sinogram interpolation is proposed, which enables one to reduce artifacts in the reconstruction related to a limited tilt series of projection images. The advantages of the approach will be demonstrated for the 3D characterization of nanoparticles using phantoms and several case studies.     

Factors affecting masking release for speech in modulated noise for normal-hearing and hearing-impaired listeners

The Speech Reception Threshold for sentences in stationary noise and in several amplitude-modulated noises was measured for 8 normal-hearing listeners, 29 sensorineural hearing-impaired listeners, and 16 normal-hearing listeners with simulated hearing loss. This approach makes it possible to determine whether the reduced benefit from masker modulations, as often observed for hearing-impaired listeners, is due to a loss of signal audibility, or due to suprathreshold deficits, such as reduced spectral and temporal resolution, which were measured in four separate psychophysical tasks. Results show that the reduced masking release can only partly be accounted for by reduced audibility, and that, when considering suprathreshold deficits, the normal effects associated with a raised presentation level should be taken into account. In this perspective, reduced spectral resolution does not appear to qualify as an actual suprathreshold deficit, while reduced temporal resolution does. Temporal resolution and age are shown to be the main factors governing masking release for speech in modulated noise, accounting for more than half of the intersubject variance. Their influence appears to be related to the processing of mainly the higher stimulus frequencies. Results based on calculations of the Speech Intelligibility Index in modulated noise confirm these conclusions.     

Reproducibility of the gadolinium concentration measurements and of the fitting parameters of the vascular input function in the superior sagittal sinus in a patient population

It is widely recognised that the measurement of the arterial input function (AIF) is a key issue and a major source of errors in the pharmacokinetic modelling of dynamic, contrast-enhanced magnetic resonance imaging (DCE-MRI) data, and the modality of the AIF determination is still a matter of debate. In this study we addressed the problem of the intrinsic variability of the AIF within the imaged volume of a DCE-MRI scan by systematically investigating the change in the concentration of contrast agent over time and the fit parameters of the derived vascular input function (VIF) obtained from the superior sagittal sinus (SSS) of a patient population that was scanned longitudinally during treatment for high grade glioma. From a total of 82 scanning sessions, we compared the results obtained with three different DCE-MRI protocols and between two different fitting functions. We applied a correction algorithm to the measured concentration-time curves to minimize the effect of the low temporal resolution on the VIF, and investigated the effect of this algorithm on the reproducibility. Finally, where possible, we compared the signal obtained in the SSS to the signal obtained in the middle cerebral artery. We found a good intrapatient reproducibility of both the measured gadolinium concentrations and VIF parameters, and that the variation of the parameters due to slice location within a patient was significantly lower than the intra patient variation. Intrapatient, interscan differences were significantly less marked than inter-patient differences showing a good intraclass correlation coefficient. We did encounter a MRI protocol dependence of the VIF fitting parameters. The correction algorithm significantly improved the reproducibility of the fitting parameters. These results support the idea that the use of a patient specific measured AIF, not necessarily averaged over a large volume, offers a significant benefit with respect to an external AIF or a measured cohort average AIF.     

Deviant Vocal Fold Vibration as Observed During Videokymography: The Effect on Voice Quality

Videokymographic images of deviant or irregular vocal fold vibration, including diplophonia, the transition from falsetto to modal voice, irregular vibration onset and offset, and phonation following partial laryngectomy were compared with the synchronously recorded acoustic speech signals. A clear relation was shown between videokymographic image sequences and acoustic speech signals, and the effect of irregular or incomplete vocal fold vibration patterns was recognized in the amount of perceived breathiness and roughness and by the harmonics-to-noise ratio in the speech signal. Mechanisms causing roughness are the presence of mucus, phase differences between the left and right vocal fold, and short-term frequency and amplitude modulation. It can be concluded that the use of simultaneously recorded videokymographic image sequences and speech signals contributes to the understanding of the effect of irregular vocal fold vibration on voice quality.     

Disk Noise Measurement System for Optical Disks

We developed a system to measure disk noise as a function of both radial and angular position. In order to obtain an accurate disk noise measurement, crosstalk and intersymbol interference were avoided by recording regularly repeating pit patterns and the influence of electronic and laser noise was removed by averaging techniques. We found the system’s mapping ability and its high sensitivity to be very useful in investigating disk noise phenomena in the mastering process. We used the system to assess the accuracy and reproducibility of the photopolymerization replication and Al vapor deposition processes. Also, we investigated the choice of photoresist and found that photoresists with the combination of the narrowest molecular weight distribution and the highest photo-active compound content resulted in the lowest disk noise levels. Our system can, in principle, be adapted to evaluate magneto-optical and phase change disks.     

Transition Metal Catalysis in Living Cells: Progress,Challenges, and Novel Supramolecular Solutions

The importance of transition metal catalysis is exemplified by its wide range of applications, for example in the synthesis of chemicals, natural products, and pharmaceuticals. However, one relatively new application is for carrying out new-to-nature reactions inside living cells. The complex environment of a living cell is not welcoming to transition metal catalysts, as a diverse range of biological components have the potential to inhibit or deactivate the catalyst. Here we review the current progress in the field of transition metal catalysis, and evaluation of catalysis efficiency in living cells and under biological (relevant) conditions. Catalyst poisoning is a ubiquitous problem in this field, and we propose that future research into the development of physical and kinetic protection strategies may provide a route to improve the reactivity of catalysts in cells.