Recent advances in automotive catalysis for NOx emission control by small-pore microporous materials.

The ever increasing demand to develop highly fuel efficient engines coincides with the need to minimize air pollution originating from the exhaust gases of internal combustion engines. Dramatically improved fuel efficiency can be achieved at air-to-fuel ratios much higher than stoichiometric. In the presence of oxygen in large excess, however, traditional three-way catalysts are unable to reduce NOx. Among the number of lean-NOx reduction technologies, selective catalytic reduction (SCR) of NOx by NH3 over Cu- and Fe-ion exchanged zeolite catalysts has been extensively studied over the past 30+ years. Despite the significant advances in developing a viable practical zeolite-based catalyst for lean NOx reduction, the insufficient hydrothermal stabilities of the zeolite structures considered cast doubts about their real-world applicability. During the past decade renewed interest in zeolite-based lean NOx reduction was spurred by the discovery of the very high activity of Cu-SSZ-13 (and the isostructural Cu-SAPO-34) in the NH3-SCR of NOx. These new, small-pore zeolite-based catalysts not only exhibited very high NOx conversion and N2 selectivity, but also exhibited exceptionally high hydrothermal stability at high temperatures. In this review we summarize the key discoveries of the past ∼5 years that led to the introduction of these catalysts into practical applications. This review first briefly discusses the structure and preparation of the CHA structure-based zeolite catalysts, and then summarizes the key learnings of the rather extensive (but not complete) characterisation work. Then we summarize the key findings of reaction kinetic studies, and provide some mechanistic details emerging from these investigations. At the end of the review we highlight some of the issues that still need to be addressed in automotive exhaust control catalysis.

(15)N2 formation and fast oxygen isotope exchange during pulsed (15)N(18)O exposure of MnOx/CeO2.

Pulsing (15)N(18)O onto an annealed 1% Mn(16)Ox/Ce(16)O2 catalyst resulted in very fast oxygen isotope exchange and (15)N2 formation at 295 K. In the 1st (15)N(18)O pulse, due to the presence of large number of surface oxygen defects, extensive (15)N2(18)O and (15)N2 formations were observed. In subsequent pulses oxygen isotope exchange dominated as a result of highly labile oxygen in the oxide.

Gender impact on electrophysiological activity of the brain.

Gender is presumed to be one of the factors causing interindividual variability in the brain's electrophysiological parameters. Our aim was to characterize the role of gender in visual evoked potentials (VEPs), event-related potentials (ERPs), visual mismatch negativity (vMMN) and the spectral characteristics of the EEG. We examined 42 healthy volunteers (21 women and 21 men, aged 20-29 years). We measured VEPs in response to pattern-reversal and motion-onset stimulation, ERPs in an oddball paradigm and vMMN in response to a combination of motion directions presented in the visual periphery. P100 peak latency for 40' reversal VEPs was significantly shorter in women than in men as determined using a non-parametric Wilcoxon signed-rank test. In addition, women showed higher relative EEG spectral power in the alpha band (p=0.023) and lower power in the theta band (p=0.004). Our results in this small but homogeneous group of subjects confirm previously reported gender influences on pattern-reversal VEPs and the EEG frequency spectrum. Gender should be taken into consideration in establishing norms on these measures. We found no statistically significant differences between women and men for any of the other stimuli presented.

Pattern and motion-related visual-evoked potentials in neuroborreliosis: follow-up study.

Visual-evoked potentials (VEPs) were used for objective testing of visual functions during treatment courses of Lyme neuroborreliosis (LNB) in adult patients in the Czech Republic. In 30 LNB patients with originally delayed VEP latencies, pattern-reversal (R-VEP) and motion onset (M-VEP) VEPs were repeatedly examined within 1 to 8 years. Six patients had Lyme optic neuritis (ON), five of them displayed prolonged latencies in both R-VEPs and M-VEPs, and one had only abnormal R-VEPs. The VEP recovery to normal latency values was in three of them. In the group of 24 LNB patients without ON, 14 patients displayed prolonged latencies only to motion stimuli, and 10 patients had abnormal latencies in both R-VEPs and M-VEPs. During the follow-up period, 7 patients displayed shortening to normal latencies. In 5 patients, VEPs latencies improved only partially, and in the remaining 12 patients, VEPs did not improve at all. This study provides objective evidence that in LNB, most of the patients without clinically manifesting ON display optic pathway involvement-predominantly magnocellular system/dorsal stream function changes. In patients with ON, however, mainly the parvocellular system is affected. About half of the patients without ON improved with a relatively long-time course of latency shortening.

Role of latency jittering correction in motion-onset VEP amplitude decay during prolonged visual stimulation.

Visual evoked potentials to motion-onset stimulation (M-VEPs) gradually attenuate in amplitude during examination. The observed decline in averaged responses can be caused by decreases in single response magnitudes and/or increased variability in a response delays, that is, latency jittering. To illuminate the origins of the suppression of M-VEPs during stimuli repetition, we used correlation technique to estimate an upper bound of possible latency jittering of single sweeps and we evaluated the effect of its correction on the amplitudes of three M-VEP dominant peaks P1, N2 and P3. During prolonged visual motion stimulation, the variability of corrective latency shifts in the occipital region increased (r = 0.35: 0.44) and the number of single responses corresponding to the average curve declined in occipital and parietal derivations (r = -0.48: -0.62). While the P1 peak amplitude did not exhibit any time-specific behaviour, the N2 amplitude exhibited a significant decay of 29.4% that was partially reduced to 16.6% in the central occipital derivation by the latency jitter and non-correspondence corrections. The strongest attenuation (32.7%) was observed in the P3 amplitude and was less sensitive to the corrections, dropping only to 27.9%. The main part of the response suppression to repeated motion stimulation was caused by amplitude drop and represents non-stationary process that likely correspond to a fatigue model. The rise of variability in latency jitter correction and the reduction in single responses correlated with the M-VEP were significant factors associated with prolonged motion stimulation. The relation of these parameters to a hypothetical veridical response is ambiguous and can be caused by a time shift of the response or by a change of signal-to-noise ratio. Using selective averaging and latency jitter correction, the effect of response suppression was partially removed.

Visual evoked potentials to pattern, motion and cognitive stimuli in Alzheimer's disease.

The aim of our study was to verify reported visual dysfunctions of patients with Alzheimer disease with the use of several variants of VEPs and visual ERPs and to learn whether these methods can be useful in diagnostics of AD. We tested 15 patients (6 women and 9 men, aged from 58 to 87) with mild to moderate Alzheimer disease (12-23 points of Mini Mental State Examination) and 15 age, gender and education level matched controls. The examination consisted of VEPs to pattern-reversal and motion-onset stimulation (to translational and radial movement) and of visual ERPs recorded during an odd-ball test. The subjects were instructed to signalize target stimuli by pressing of a button, which enabled to evaluate also the reaction time. While pattern-reversal VEPs were comparable in patients and controls, there were significantly smaller N2 peak amplitudes of motion-onset VEPs in patients with AD (in particular in radial moving stimuli outside the central 20 deg of the visual field), which suggests a dysfunction of the motion-processing (magnocellular) system or the dorsal cortical stream. ERPs, having significantly longer latencies in patients than in controls, distinguished well both groups. However, the individual AD diagnostics based on ERPs seems to be limited by rather high inter-individual variability of the ERP latencies. The ERPs might, however, be useful in disease progress and therapy effect estimation. Electrophysiological parameters did not correlate with neuropsychological ADAS cog test (Alzheimer Disease Assessment Scale--cognitive part).

Morphological evolution of Ba(NO3)2 supported on alpha-Al2O3(0001): an in situ TEM study.

A key question for the BaO-based NOx storage/reduction catalyst system is the morphological evolution of the catalyst particles during the uptake and release of NOx. Notably, because the formed product during NOx uptake, Ba(NO3)2, requires a lattice expansion from BaO, one can anticipate that significant structural rearrangements are possible during the storage/reduction processes. Associated with the small crystallite size of high-surface area gamma-Al2O3, it is difficult to extract structural and morphological features of Ba(NO3)2 supported on gamma-Al2O3 by any direct imaging method, including transmission electron microscopy. In this work, by choosing a model system of Ba(NO3)2 particles supported on single-crystal alpha-Al2O3, we have investigated the structural and morphological features of Ba(NO3)2 as well as the formation of BaO from Ba(NO3)2 during the thermal release of NOx, using ex-situ and in-situ TEM imaging, electron diffraction, energy dispersive spectroscopy (EDS), and Wulff shape construction. We find that Ba(NO3)2 supported on alpha-Al2O3 possesses a platelet morphology, with the interface and facets being invariably the eight [111] planes. Formation of the platelet structure leads to an enlarged interface area between Ba(NO3)2 and alpha-Al2O3, indicating that the interfacial energy is lower than the Ba(NO3)2 surface free energy. In fact, Wulff shape constructions indicate that the interfacial energy is approximately 1/4 of the [111] surface free energy of Ba(NO3)2. The orientation relationship between Ba(NO3)2 and the alpha-Al2O3 is alpha-Al2O3[0001]//Ba(NO3)2[111] and alpha-Al2O3(1-210)//Ba(NO3)2(110). Thus, the results clearly demonstrate dramatic morphology changes in these materials during NOx release processes. Such changes are expected to have significant consequences for the operation of the practical NOx storage/reduction catalyst technology.

Influence of physiological changes of glycaemia on VEPs and visual ERPs.

Since hypoglycemia is known to influence cognitive functions, we checked whether the physiological changes in glycemia (after fasting or exertion) can explain the rather high intra-individual variability of event-related potentials (ERPs). Besides the ERPs to "change in coherence of a moving pattern" with reaction time (RT) recording, binocular pattern reversal VEPs and motion-onset VEPs (to linear and radial motion) were also examined in 14 healthy subjects prior to and after 24-h fasting that decreased glycemia from 5.3 to 3.9 mmol/l on the average. We only found one significant change in the latencies and amplitudes of VEPs and ERPs (with no change of RT). The N160 peak in the motion-onset VEPs to radial (expansive) motion (EM-VEPs) showed a larger amplitude at lower glycemia. For evaluation of the exertion influence, we tested glycemia prior to and after 90 min long exercise -- bicycle ergometry with the load set to 2 W/kg in women and 2.5 W/kg in men (average age-related values for W170/kg index). The changes of glycemia to exertion were, however, less distinct than those to fasting. We conclude that in healthy subjects the glycemia decrease due to 24-h fasting or intensive time-limited exercise never reaches the critical value to change the VEP, ERPs and RTs.

Visual event-related potentials to moving stimuli: normative data.

Visual cognitive responses (P300) to moving stimuli were tested in 36 subjects with the aim to find the normal range of P300 parameters. Concomitantly, the circadian intra-individual variability of the P300 was studied in a subgroup of 6 subjects. Visual stimuli consisted of either coherent (frequent stimulus) or non-coherent motion (random stimulus). The oddball paradigm was applied for recording cognitive responses. P300 to rare stimuli had an average latency of 447.3 +/- 46.6 ms and amplitude of 12.9 +/- 6.0 microV. The average reaction time was in the range from 322 to 611 ms and there was no correlation between the reaction time and P300 latency. We did not find any significant circadian changes of the P300 parameters in the 6 subjects tested four times during the same day. Cognitive (event-related) responses (P300) displayed distinctly greater inter-individual variability (S.D. of 50 ms) when compared with pattern-reversal and motion-onset VEPs (S.D. of 6.0 ms and 14 ms, respectively). For this reason, the clinical use of P300 elicited by this kind of visual stimuli seems to be rather restricted and the evaluation of its intra-individual changes is preferable.

Electrophysiological testing of dyslexia.

We enlarged our previous study (Kubová Z. et al. Physiol Res 1995;44:87-89) giving an evidence about magnocellular pathway involvement (delayed motion-onset visual evoked potentials (M-VEPs)) in 70% of dyslexic children. In the new group presented here, only 48% of 25 dyslexics displayed prolonged latencies of cortical responses to motion stimuli. However, there was no correlation of this defect with the used quantification of the reading skills (reading quotients). No significant EEG frequency spectrum changes were found. 10 subjects from the former group, who were re-examined 4 years after the previous study at the mean age of 14 years, exhibited significant shortening of the M-VEP latencies compared to the original values. Also in control subjects a distinct improvement in magnocellular pathway function was proved (in M-VEP re-examination after 4 years). These results document rather late maturation of the magnocellular pathway, which is evident mainly in dyslexic children. In both groups of dyslexics an effect of colour in moving stimuli was also tested to verify the reported effect of light wavelengths onto the magnocellular pathway function. However, no latency differences among grey, green, pink, yellow and blue stimuli were observed.