Is part of the Bibliography
Thermoresponsive poly(2-oxazoline)s, polypeptoids, and polypeptides
- This review covers the recent advances in the emerging field of thermoresponsive polyamides or polymeric amides, i.e., poly(2-oxazoline)s, polypeptoids, and polypeptides, with a specific focus on structure–thermoresponsive property relationships, self-assembly, and applications.
Exploration of the phase diagram of liquid water in the low-temperature metastable region using synthetic fluid inclusions
- We present new experimental data of the low-temperature metastable region of liquid water derived from high-density synthetic fluid inclusions (996–916 kg m−3) in quartz. Microthermometric measurements include: (i) prograde (upon heating) and retrograde (upon cooling) liquid–vapour homogenisation. We used single ultrashort laser pulses to stimulate vapour bubble nucleation in initially monophase liquid inclusions. Water densities were calculated based on prograde homogenisation temperatures using the IAPWS-95 formulation. We found retrograde liquid–vapour homogenisation temperatures in excellent agreement with IAPWS-95. (ii) Retrograde ice nucleation. Raman spectroscopy was used to determine the nucleation of ice in the absence of the vapour bubble. Our ice nucleation data in the doubly metastable region are inconsistent with the low-temperature trend of the spinodal predicted by IAPWS-95, as liquid water with a density of 921 kg m−3 remains in a homogeneous state during cooling down to a temperature of −30.5 °C, where it is transformed into ice whose density corresponds to zero pressure. (iii) Ice melting. Ice melting temperatures of up to 6.8 °C were measured in the absence of the vapour bubble, i.e. in the negative pressure region. (iv) Spontaneous retrograde and, for the first time, prograde vapour bubble nucleation. Prograde bubble nucleation occurred upon heating at temperatures above ice melting. The occurrence of prograde and retrograde vapour bubble nucleation in the same inclusions indicates a maximum of the bubble nucleation curve in the ϱ–T plane at around 40 °C. The new experimental data represent valuable benchmarks to evaluate and further improve theoretical models describing the p–V–T properties of metastable water in the low-temperature region.
Femtosecond gas phase electron diffraction with MeV electrons
Matthew S. Robinson
- We present results on ultrafast gas electron diffraction (UGED) experiments with femtosecond resolution using the MeV electron gun at SLAC National Accelerator Laboratory. UGED is a promising method to investigate molecular dynamics in the gas phase because electron pulses can probe the structure with a high spatial resolution. Until recently, however, it was not possible for UGED to reach the relevant timescale for the motion of the nuclei during a molecular reaction. Using MeV electron pulses has allowed us to overcome the main challenges in reaching femtosecond resolution, namely delivering short electron pulses on a gas target, overcoming the effect of velocity mismatch between pump laser pulses and the probe electron pulses, and maintaining a low timing jitter. At electron kinetic energies above 3 MeV, the velocity mismatch between laser and electron pulses becomes negligible. The relativistic electrons are also less susceptible to temporal broadening due to the Coulomb force. One of the challenges of diffraction with relativistic electrons is that the small de Broglie wavelength results in very small diffraction angles. In this paper we describe the new setup and its characterization, including capturing static diffraction patterns of molecules in the gas phase, finding time-zero with sub-picosecond accuracy and first time-resolved diffraction experiments. The new device can achieve a temporal resolution of 100 fs root-mean-square, and sub-angstrom spatial resolution. The collimation of the beam is sufficient to measure the diffraction pattern, and the transverse coherence is on the order of 2 nm. Currently, the temporal resolution is limited both by the pulse duration of the electron pulse on target and by the timing jitter, while the spatial resolution is limited by the average electron beam current and the signal-to-noise ratio of the detection system. We also discuss plans for improving both the temporal resolution and the spatial resolution.
How surface reparation prevents catalytic oxidation of carbon monoxide on atomic gold at defective magnesium oxide surfaces
Jean Christophe Tremblay
- In this contribution, we study using first principles the co-adsorption and catalytic behaviors of CO and O2 on a single gold atom deposited at defective magnesium oxide surfaces. Using cluster models and point charge embedding within a density functional theory framework, we simulate the CO oxidation reaction for Au1 on differently charged oxygen vacancies of MgO(001) to rationalize its experimentally observed lack of catalytic activity. Our results show that: (1) co-adsorption is weakly supported at F0 and F2+ defects but not at F1+ sites, (2) electron redistribution from the F0 vacancy via the Au1 cluster to the adsorbed molecular oxygen weakens the O2 bond, as required for a sustainable catalytic cycle, (3) a metastable carbonate intermediate can form on defects of the F0 type, (4) only a small activation barrier exists for the highly favorable dissociation of CO2 from F0, and (5) the moderate adsorption energy of the gold atom on the F0 defect cannot prevent insertion of molecular oxygen inside the defect. Due to the lack of protection of the color centers, the surface becomes invariably repaired by the surrounding oxygen and the catalytic cycle is irreversibly broken in the first oxidation step.
Incorporation and visualization of azido-functionalized N-oleoyl serinol in Jurkat cells, mouse brain astrocytes, 3T3 fibroblasts and human brain microvascular endothelial cells
Ji Na Kong
- The synthesis and biological evaluation of azido-N-oleoyl serinol is reported. It mimicks biofunctional lipid ceramides and has shown to be capable of click reactions for cell membrane imaging in Jurkat and human brain microvascular endothelial cells.
Quantification of the push–pull effect in 2-alkylidene-4-oxothiazolidines by using NMR spectral data and barriers to rotation around the C=C bond
Dragica M. Minic
- Information about the strength of donor–acceptor interactions in push–pull alkenes is valuable, as this so-called “push–pull effect” influences their chemical reactivity and dynamic behaviour. In this paper, we discuss the applicability of NMR spectral data and barriers to rotation around the C[double bond, length as m-dash]C double bond to quantify the push–pull effect in biologically important 2-alkylidene-4-oxothiazolidines. While olefinic proton chemical shifts and differences in 13C NMR chemical shifts of the two carbons constituting the C[double bond, length as m-dash]C double bond fail to give the correct trend in the electron withdrawing ability of the substituents attached to the exocyclic carbon of the double bond, barriers to rotation prove to be a reliable quantity in providing information about the extent of donor–acceptor interactions in the push–pull systems studied. In particular all relevant kinetic data, that is the Arrhenius parameters (apparent activation energy Ea and frequency factor A) and activation parameters (ΔS‡, ΔH‡ and ΔG‡), were determined from the data of the experimentally studied configurational isomerization of (E)-9a. These results were compared to previously published related data for other two compounds, (Z)-1b and (2E,5Z)-7, showing that experimentally determined ΔG‡ values are a good indicator of the strength of push–pull character. Theoretical calculations of the rotational barriers of eight selected derivatives excellently correlate with the calculated C[double bond, length as m-dash]C bond lengths and corroborate the applicability of ΔG‡ for estimation of the strength of the push–pull effect in these and related systems.
Assessment of Climate Change Impacts on Water Resources in Three Representative Ukrainian Catchments Using Eco-Hydrological Modelling
Cathrine Fox Maule
- The information about climate change impact on river discharge is vitally important for planning adaptation measures. The future changes can affect different water-related sectors. The main goal of this study was to investigate the potential water resource changes in Ukraine, focusing on three mesoscale river catchments (Teteriv, UpperWestern Bug, and Samara) characteristic for different geographical zones. The catchment scale watershed model—Soil and Water Integrated Model (SWIM)—was setup, calibrated, and validated for the three catchments under consideration. A set of seven GCM-RCM (General Circulation Model-Regional Climate Model) coupled climate scenarios corresponding to RCPs (Representative Concentration Pathways) 4.5 and 8.5 were used to drive the hydrological catchment model. The climate projections, used in the study, were considered as three combinations of low, intermediate, and high end scenarios. Our results indicate the shifts in the seasonal distribution of runoff in all three catchments. The spring high flow occurs earlier as a result of temperature increases and earlier snowmelt. The fairly robust trend is an increase in river discharge in the winter season, and most of the scenarios show a potential decrease in river discharge in the spring.
Effects of sudden walking perturbations on neuromuscular reflex activity and three-dimensional motion of the trunk in healthy controls and back pain symptomatic subjects
Back pain patients (BPP) show delayed muscle onset, increased co-contractions, and variability as response to quasi-static sudden trunk loading in comparison to healthy controls (H). However, it is unclear whether these results can validly be transferred to suddenly applied walking perturbations, an automated but more functional and complex movement pattern. There is an evident need to develop research-based strategies for the rehabilitation of back pain. Therefore, the investigation of differences in trunk stability between H and BPP in functional movements is of primary interest in order to define suitable intervention regimes. The purpose of this study was to analyse neuromuscular reflex activity as well as three-dimensional trunk kinematics between H and BPP during walking perturbations.
Eighty H (31m/49f;29±9yrs;174±10cm;71±13kg) and 14 BPP (6m/8f;30±8yrs;171±10cm;67±14kg) walked (1m/s) on a split-belt treadmill while 15 right-sided perturbations (belt decelerating, 40m/s2, 50ms duration; 200ms after heel contact) were randomly applied. Trunk muscle activity was assessed using a 12-lead EMG set-up. Trunk kinematics were measured using a 3-segment-model consisting of 12 markers (upper thoracic (UTA), lower thoracic (LTA), lumbar area (LA)). EMG-RMS ([%],0-200ms after perturbation) was calculated and normalized to the RMS of unperturbed gait. Latency (TON;ms) and time to maximum activity (TMAX;ms) were analysed. Total motion amplitude (ROM;[°]) and mean angle (Amean;[°]) for extension-flexion, lateral flexion and rotation were calculated (whole stride cycle; 0-200ms after perturbation) for each of the three segments during unperturbed and perturbed gait. For ROM only, perturbed was normalized to unperturbed step [%] for the whole stride as well as the 200ms after perturbation. Data were analysed descriptively followed by a student´s t-test to account for group differences. Co-contraction was analyzed between ventral and dorsal muscles (V:R) as well as side right:side left ratio (Sright:Sleft). The coefficient of variation (CV;%) was calculated (EMG-RMS;ROM) to evaluate variability between the 15 perturbations for all groups. With respect to unequal distribution of participants to groups, an additional matched-group analysis was conducted. Fourteen healthy controls out of group H were sex-, age- and anthropometrically matched (group Hmatched) to the BPP.
No group differences were observed for EMG-RMS or CV analysis (EMG/ROM) (p>0.025). Co-contraction analysis revealed no differences for V:R and Srigth:Sleft between the groups (p>0.025). BPP showed an increased TON and TMAX, being significant for Mm. rectus abdominus (p = 0.019) and erector spinae T9/L3 (p = 0.005/p = 0.015). ROM analysis over the unperturbed stride cycle revealed no differences between groups (p>0.025). Normalization of perturbed to unperturbed step lead to significant differences for the lumbar segment (LA) in lateral flexion with BPP showing higher normalized ROM compared to Hmatched (p = 0.02). BPP showed a significant higher flexed posture (UTA (p = 0.02); LTA (p = 0.004)) during normal walking (Amean). Trunk posture (Amean) during perturbation showed higher trunk extension values in LTA segments for H/Hmatched compared to BPP (p = 0.003). Matched group (BPP vs. Hmatched) analysis did not show any systematic changes of all results between groups.
BPP present impaired muscle response times and trunk posture, especially in the sagittal and transversal planes, compared to H. This could indicate reduced trunk stability and higher loading during gait perturbations.
Coupling of attention and saccades when viewing scenes with central and peripheral degradation
- Degrading real-world scenes in the central or the peripheral visual field yields a characteristic pattern: Mean saccade amplitudes increase with central and decrease with peripheral degradation. Does this pattern reflect corresponding modulations of selective attention? If so, the observed saccade amplitude pattern should reflect more focused attention in the central region with peripheral degradation and an attentional bias toward the periphery with central degradation. To investigate this hypothesis, we measured the detectability of peripheral (Experiment 1) or central targets (Experiment 2) during scene viewing when low or high spatial frequencies were gaze-contingently filtered in the central or the peripheral visual field. Relative to an unfiltered control condition, peripheral filtering induced a decrease of the detection probability for peripheral but not for central targets (tunnel vision). Central filtering decreased the detectability of central but not of peripheral targets. Additional post hoc analyses are compatible with the interpretation that saccade amplitudes and direction are computed in partial independence. Our experimental results indicate that task-induced modulations of saccade amplitudes reflect attentional modulations.
Molekulare Charakterisierung des Centrosom-assoziierten Proteins CP91 in Dictyostelium discoideum
- Das Dictyostelium-Centrosom ist ein Modell für acentrioläre Centrosomen. Es besteht aus einer dreischichtigen Kernstruktur und ist von einer Corona umgeben, welche Nukleationskomplexe für Mikrotubuli beinhaltet. Die Verdoppelung der Kernstruktur wird einmal pro Zellzyklus am Übergang der G2 zur M-Phase gestartet. Durch eine Proteomanalyse isolierter Centrosomen konnte CP91 identifiziert werden, ein 91 kDa großes Coiled-Coil Protein, das in der centrosomalen Kernstruktur lokalisiert. GFP-CP91 zeigte fast keine Mobilität in FRAP-Experimenten während der Interphase, was darauf hindeutet, dass es sich bei CP91 um eine Strukturkomponente des Centrosoms handelt. In der Mitose hingegen dissoziieren das GFP-CP91 als auch das endogene CP91 ab und fehlen an den Spindelpolen von der späten Prophase bis zur Anaphase. Dieses Verhalten korreliert mit dem Verschwinden der zentralen Schicht der Kernstruktur zu Beginn der Centrosomenverdopplung. Somit ist CP91 mit großer Wahrscheinlichkeit ein Bestandteil dieser Schicht. CP91-Fragmente der N-terminalen bzw. C-terminalen Domäne (GFP-CP91 N-Terminus, GFP-CP91 C-Terminus) lokalisieren als GFP-Fusionsproteine exprimiert auch am Centrosom, zeigen aber nicht die gleiche mitotische Verteilung des Volllängenproteins. Das CP91-Fragment der zentralen Coiled-Coil Domäne (GFP-CP91cc) lokalisiert als GFP-Fusionsprotein exprimiert, als ein diffuser cytosolische Cluster, in der Nähe des Centrosoms. Es zeigt eine partiell ähnliche mitotische Verteilung wie das Volllängenprotein. Dies lässt eine regulatorische Domäne innerhalb der Coiled-Coil Domäne vermuten. Die Expression der GFP-Fusionsproteine unterdrückt die Expression des endogenen CP91 und bringt überzählige Centrosomen hervor. Dies war auch eine markante Eigenschaft nach der Unterexpression von CP91 durch RNAi. Zusätzlich zeigte sich in CP91-RNAi Zellen eine stark erhöhte Ploidie verursacht durch schwere Defekte in der Chromosomensegregation verbunden mit einer erhöhten Zellgröße und Defekten im Abschnürungsprozess während der Cytokinese. Die Unterexpression von CP91 durch RNAi hatte auch einen direkten Einfluss auf die Menge an den centrosomalen Proteinen CP39, CP55 und CEP192 und dem Centromerprotein Cenp68 in der Interphase. Die Ergebnisse deuten darauf hin, dass CP91 eine zentrale centrosomale Kernkomponente ist und für den Zusammenhalt der beiden äußeren Schichten der Kernstruktur benötigt wird. Zudem spielt CP91 eine wichtige Rolle für eine ordnungsgemäße Centrosomenbiogenese und, unabhängig davon, bei dem Abschnürungsprozess der Tochterzellen während der Cytokinese.