Ultrafast molecular dynamics of model biological systems

Femtosecond time resolved photoelectron imaging spectroscopy equipment was designed, constructed, and used to reveal the non-adiabatic dynamics of model biological systems. Indole and phenol derivatives were studied as models for eumelanin, a pigment found in humans designed to protect the body from ultraviolet radiation. The photo-dynamics of these molecules was studied after excitation with ultraviolet radiation, with particular emphasis on the effect that the hydroxyl groups have on the p * dissociative state. It was found that adding a hydroxyl group onto indole to create 5-hydroxyindole had little significant effect on the photodynamics at the excitation wavelengths studied. Adding a second hydroxyl group to phenol had a strongly marked effect only when the hydroxyl groups were in close proximity to each other, in which case it dramatically increased the relaxation rate. An ultrafast optical system, imaging photoelectron spectrometer, and software to control the hardware, and collect and analyse photoelectron data were successfully implemented and used to collect and analyse data. This system will be of use for many more years and will be the basis of much future research.Engineering and Physical Sciences Research Council (EPSRC

Following the relaxation dynamics of photoexcited aniline in the 273-266 nm region using time-resolved photoelectron imaging

Scanning tunnelling microscopy (STM) and Auger electron spectroscopy (AES) have been used to investigate the growth morphology of ultra-thin Pb films on the Ni3Al(111) face at room temperature. A previous study [K. Miśków and A. Krupski Appl Surf Sci 273, 2013, 554] using low-energy electron diffraction (LEED) and real time Auger intensity recording has demonstrated that an initial two-dimensional growth of the first Pb monolayer thick ‘wetting layer’ takes place. With further deposition and for T = 300 K, flat three atomic-layer-high islands are grown. Above 350 K, the Stranski–Krastanov growth mode was observed. In the current study, the analysis of STM measurements indicate and confirm that for coverage θ = 1.0 ML two-dimensional growth of the first Pb monolayer took place. Above θ > 1.0 ML, a three-dimensional growth of the Pb islands was observed with a strongly preferred atomic-scale ‘magic height (N),’ hexagonal shape and flat-tops. At coverage θ = 3.5 ML, only islands containing N = 3, 5, 7 and 11 atomic layers of Pb are observed. At the higher coverage θ = 5.5 ML, three types of regular hexagonal islands with side lengths of 25, 30 and 45 nm are observed. Furthermore, three different island adsorption configurations rotated by 10° ± 1° and 30° ± 6° with respect to each other were observed. After an annealing at T = 400 K of 5.5 ML of lead deposited at RT on the Ni3Al(111) the morphology of the surface changes. Post-anneal, islands of Pb are observed above the ‘wetting layer’ with an estimated average size and diameter of 768 ± 291 nm2 and 38.17 ± 6.56 nm and constant uniform height of two atomic layers (N = 2)

Time-resolved photoelectron imaging of excited state relaxation dynamics in phenol, catechol, resorcinol and hydroquinone

Time-resolved photoelectron imaging was used to investigate the dynamical evolution of the initially prepared S1 (\u3c0\u3c0*) excited state of phenol (hydroxybenzene), catechol (1,2-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene), and hydroquinone (1,4-dihydroxybenzene) following excitation at 267 nm. Our analysis was supported by ab initio calculations at the coupled-cluster and CASSCF levels of theory. In all cases, we observe rapid (<1 ps) intramolecular vibrational redistribution on the S1potential surface. In catechol, the overall S1 state lifetime was observed to be 12.1 ps, which is 1\u20132 orders of magnitude shorter than in the other three molecules studied. This may be attributed to differences in the H atom tunnelling rate under the barrier formed by a conical intersection between the S1 state and the close lying S2 (\u3c0\u3c3*) state, which is dissociative along the O\u2013H stretching coordinate. Further evidence of this S1/S2 interaction is also seen in the time-dependent anisotropy of the photoelectron angular distributions we have observed. Our data analysis was assisted by a matrix inversion method for processing photoelectron images that is significantly faster than most other previously reported approaches and is extremely quick and easy to implement.Peer reviewed: YesNRC publication: Ye

Following the excited state relaxation dynamics of indole and 5-hydroxyindole using time-resolved photoelectron spectroscopy

Time-resolved photoelectron spectroscopy was used to obtain new information about the dynamics of electronic relaxation in gas-phase indole and 5-hydroxyindole following UV excitation with femtosecond laser pulses centred at 249 nm and 273 nm. Our analysis of the data was supported by ab initio calculations at the coupled cluster and complete-active-space self-consistent-field levels. The optically bright 1La and 1Lb electronic states of 1\u3c0\u3c0* character and spectroscopically dark and dissociative 1\u3c0\u3c3* states were all found to play a role in the overall relaxation process. In both molecules we conclude that the initially excited 1La state decays non-adiabatically on a sub 100 fs timescale via two competing pathways, populating either the subsequently long-lived 1Lb state or the 1\u3c0\u3c3* state localised along the N-H coordinate, which exhibits a lifetime on the order of 1 ps. In the case of 5-hydroxyindole, we conclude that the 1\u3c0\u3c3* state localised along the O-H coordinate plays little or no role in the relaxation dynamics at the two excitation wavelengths studied.Peer reviewed: YesNRC publication: Ye

Communities as conduits of harm : A social identity analysis of appraisal, coping and justice-seeking in response to historic collective victimization

Social identity approach (SIA) research shows that commu- nity members often work together to support survivors of collective victimization and rectify social injustices. How- ever, complexities arise when community members have been involved in perpetrating these injustices. While many communities are unaware of their role in fostering victimi- zation, others actively deny their role and responsibility to restore justice. We explore these processes by investigating experiences of community violence and collective justice- seeking among Albanian survivors of dictatorial crimes. Sur- vivors (N = 27) were interviewed, and data were analysed using theoretical thematic analysis guided by the SIA. The analysis reveals the diverse ways communities can become harmful ‘Social Curses’. First, communities in their various forms became effective perpetrators of fear and control (e.g., exclusion and/or withholding ingroup privileges) dur- ing the dictatorship because of the close relationship between communities and their members. Second, commu- nities caused harm by refusing to accept responsibility for the crimes, and by undermining attempts at collective action to address injustices. This lack of collective accountability also fosters survivors' feelings of exclusion and undermines their hope for systematic change. Implica- tions for SIA processes relating to health/wellbeing (both Social Cure and Curse) are discussed. We also discuss impli- cations for understanding collective action and victimhood.Peer reviewe

Too many shades of grey : photometrically and spectrally mismatched targets and backgrounds in printed acuity tests for infants and young children

Purpose: Acuity tests for infants and young children use preferential looking methods that require a perceptual match of brightness and color between grey background and target spatial average. As a first step in exploring this matching, this article measures photometric and colorimetric matches in these acuity tests. Methods: The luminance, uniformity, contrast, and color spectra of Teller Acuity Cards, Keeler Acuity Cards for Infants, and Lea Paddles under ambient, warm, and cold lighting, and of grey-emulating patterns on four digital displays, were measured. Five normal adults’ acuities were tested at 10 m observationally. Results: Luminance and spectral mismatches between target and background were found for the printed tests (Weber contrasts of 0.3% [Teller Acuity Cards], −1.7% [Keeler Acuity Cards for Infants], and −26% [Lea Paddles]). Lighting condition had little effect on contrast, and all printed tests and digital displays met established adult test luminance and uniformity standards. Digital display grey backgrounds had very similar luminance and color whether generated by a checkerboard, vertical grating, or horizontal grating. Improbably good psychophysical acuities (better than −0.300 logMAR: (logarithm of the minimum angle of resolution)) were recorded from adults using the printed tests at 10 m, but not using the digital test Peekaboo Vision. Conclusions: Perceptible contrast between target and background could lead to an incorrectly measured, excessively good acuity. It is not clear whether the luminance and spectral contrasts described here have clinically meaningful consequences for the target patient group, but they may be avoidable using digital tests. Translational Relevance: Current clinical infant acuity tests present photometric mismatches that may return inaccurate testing results

The effects of symmetry and rigidity on non-adiabatic dynamics in tertiary amines:a time-resolved photoelectron velocity-map imaging study of the cage-amine ABCO

The non-adiabatic relaxation dynamics of the tertiary cage-amine azabicyclo[2.2.2]octane (ABCO, also known as quinuclidine) have been investigated following 3p Rydberg excitation at 201 nm using femtosecond time-resolved photoelectron imaging (TRPEI). The aim of the study was to investigate the influence of the rigid and symmetric cage structure found in ABCO on the general non-adiabatic relaxation processes commonly seen in other tertiary aliphatic amines (TAAs). Our data is compared with TRPEI results very recently obtained for several structurally less rigid TAA systems [J. O. F. Thompson et al., Chem. Sci., 2016, 7, 1826–1839] and helps to confirm many of the previously reported findings. The experimental results for ABCO in the short-time (<1 ps) regime strongly support earlier conclusions suggesting that planarization about the N-atom is not a prerequisite for efficient 3p–3s internal conversion. Additionally, individual photoelectron peaks within our ABCO data show no temporal shifts in energy. As confirmed by our supporting quantum mechanical calculations, this demonstrates that neither internal conversion within the 3p manifold or significant conformational re-organization are possible in the ABCO system. This result therefore lends strong additional support to the active presence of such dynamical effects in other, less conformationally restricted TAA species, where photoelectron peak shifts are commonly observed. Finally, the extremely long (>1 ns) 3s Rydberg state lifetime seen in ABCO (relative to other TAA systems at similar excitation energies) serves to illustrate the large influence of symmetry and conformational rigidity on intramolecular vibrational redistribution processes previously implicated in mediating this aspect of the overall relaxation dynamics

Dysregulation of glucocorticoid metabolism in murine obesity: comparable effects of leptin resistance and deficiency

In obese humans, metabolism of glucocorticoids by 11β-hydroxysteroid dehydrogenase type 1 (11β-HSD1) and A-ring reduction (by 5α- and 5β-reductases) is dysregulated in a tissue specific manner. These changes have been recapitulated in leptin resistant obese Zucker rats but were not observed in high-fat fed Wistar rats. Recent data from mouse models suggest that such discrepancies may reflect differences in leptin signalling. We therefore compared glucocorticoid metabolism in murine models of leptin deficiency and resistance. Male ob/ob and db/db mice and their respective littermate controls (n=10–12/group) were studied at the age of 12 weeks. Enzyme activities and mRNA expression were quantified in snap-frozen tissues. The patterns of altered pathways of steroid metabolism in obesity were similar in ob/ob and db/db mice. In liver, 5β-reductase activity and mRNA were increased and 11β-HSD1 decreased in obese mice, whereas 5α-reductase 1 (5αR1) mRNA was not altered. In visceral adipose depots, 5β-reductase was not expressed, 11β-HSD1 activity was increased and 5αR1 mRNA was not altered in obesity. By contrast, in subcutaneous adipose tissue 11β-HSD1 and 5αR1 mRNA were decreased. Systematic differences were not found between ob/ob and db/db murine models of obesity, suggesting that variations in leptin signalling through the short splice variant of the Ob receptor do not contribute to dysregulation of glucocorticoid metabolism