Elucidating excited state electronic structure and intercomponent interactions in multicomponent and supramolecular systems

Rational design of supramolecular systems for application in photonic devices requires a clear understanding of both the mechanism of energy and electron transfer processes and how these processes can be manipulated. Central to achieving these goals is a detailed picture of their electronic structure and of the interaction between the constituent components. We review several approaches that have been taken towards gaining such understanding, with particular focus on the physical techniques employed. In the discussion, case studies are introduced to illustrate the key issues under consideration

Ground vs. excited state interaction in ruthenium-thienyl dyads:implications for through bond interactions in multicomponent systems

The vibrational and photophysical properties of mononuclear ruthenium(II) and ruthenium(III) polypyridyl complexes based on the ligands 2-(5'-(pyridin-2"-yl)-1'H-1',2',4'-triaz-3'-yl)-thiophene, 2-(5'-(pyrazin-2"-yl)-1'H-1',2',4'-triaz-3'-yl)-thiophene, are reported. The effect of the introduction of the non-innocent thiophene group on the properties of the triazole based ruthenium(II) complex is examined. The pH sensitive 1,2,4-triazole group, although influenced by the electron withdrawing nature of the thiophene group, does not facilitate excited state interaction of the thiophene and Ru(II) centre. Deuteriation and DFT calculations are employed to enable a deeper understanding of the interaction between the two redox-active centres and rationalise the difference between the extent of ground and excited state interaction in this simple dyad. The results obtained provide considerable evidence in support of earlier studies examining differences in ground and excited state interaction in multinuclear thiophene-bridged systems, in particular with respect to HOMO- and LUMO- mediated superexchange interaction processes.

Free-sugar, total-sugar, fibre and micronutrient intake within elite youth British soccer players: a nutritional transition from schoolboy to fulltime soccer player.

It is recommended that soccer players consume a high carbohydrate (CHO) diet to augment performance. However, growing evidence suggests that there is a link between high free-sugar (FS) intake (>5% total energy intake; TEI) and metabolic diseases. Furthermore, foods that are often high in sugar, such as processed foods, are typically lacking in nutrient quality. We therefore analysed total- and FS, dietary fibre and micronutrient intake of players from an English Premier League academy under(U) 18 (n=13); U15/16 (n=25); U13/14 (n=21) using a 7-day food diary. Data was compared to current UK dietary reference value (DRV) for free-sugar via a t-test. The U13/14s (1018 %) and U15/16s (1130 %) both consumed higher amounts of free-sugar in comparison to the UK DRV of 5% TEI 5% (P<0.01), conversely, the U18s did not exceed the DRV (513 %). Furthermore, FS intake of the U18s was significantly lower than the U13/14s and U15/16s (P<0.01). Dietary fibre was below the DRV (25g/d for U13/14 & U15/16s; 30g/d for U18s) for all squads (19.04.7; 19.68.3; 17.14.2 g/d, respectively), but not different between squads. Additionally, micronutrient reference intakes were generally met. In conclusion, we provide novel data on dietary sugar, fibre and micronutrient intake within elite youth soccer players. We report an apparent 'nutritional transition' from schoolboy to fulltime soccer player, with U18s showing a significantly lower intake of sugar in comparison to younger squads, and a similar intake of FS to the UK DRVs. Practitioners should target improving player education around sugar and fibre consumption

A Comparison of Total Food Intake at a Personalised Buffet in People with Obesity, before and 24 Months after Roux-en-Y-Gastric Bypass Surgery

Long-term reductions in the quantity of food consumed, and a shift in intake away from energy dense foods have both been implicated in the potent bariatric effects of Roux-en-Y gastric bypass (RYGB) surgery. We hypothesised that relative to pre-operative assessment, a stereotypical shift to lower intake would be observed at a personalised ad libitum buffet meal 24 months after RYGB, driven in part by decreased selection of high energy density items. At pre-operative baseline, participants (n = 14) rated their preference for 72 individual food items, each of these mapping to one of six categories encompassing high and low-fat choices in combination with sugar, complex carbohydrate or and protein. An 18-item buffet meal was created for each participant based on expressed preferences. Overall energy intake was reduced on average by 60% at the 24-month buffet meal. Reductions in intake were seen across all six food categories. Decreases in the overall intake of all individual macronutrient groups were marked and were generally proportional to reductions in total caloric intake. Patterns of preference and intake, both at baseline and at follow-up appear more idiosyncratic than has been previously suggested by verbal reporting. The data emphasise the consistency with which reductions in ad libitum food intake occur as a sequel of RYGB, this being maintained in the setting of a self-selected ad libitum buffet meal. Exploratory analysis of the data also supports prior reports of a possible relative increase in the proportional intake of protein after RYGB

White Matter Deterioration May Foreshadow Impairment of Emotional Valence Determination in Early-Stage Dementia of the Alzheimer Type

In Alzheimer Disease (AD), non-verbal skills often remain intact for far longer than verbally mediated processes. Four (1 female, 3 males) participants with early-stage Clinically Diagnosed Dementia of the Alzheimer Type (CDDAT) and eight neurotypicals (NTs; 4 females, 4 males) completed the emotional valence determination test (EVDT) while undergoing BOLD functional magnetic resonance imaging (fMRI). We expected CDDAT participants to perform just as well as NTs on the EVDT, and to display increased activity within the bilateral amygdala and right anterior cingulate cortex (r-ACC). We hypothesized that such activity would reflect an increased reliance on these structures to compensate for on-going neuronal loss in frontoparietal regions due to the disease. We used diffusion tensor imaging (DTI) to determine if white matter (WM) damage had occurred in frontoparietal regions as well. CDDAT participants had similar behavioral performance and no differences were observed in brain activity or connectivity patterns within the amygdalae or r-ACC. Decreased fractional anisotropy (FA) values were noted, however, for the bilateral superior longitudinal fasciculi and posterior cingulate cortex (PCC). We interpret these findings to suggest that emotional valence determination and non-verbal skill sets are largely intact at this stage of the disease, but signs foreshadowing future decline were revealed by possible WM deterioration. Understanding how non-verbal skill sets are altered, while remaining largely intact, offers new insights into how non-verbal communication may be more successfully implemented in the care of AD patients and highlights the potential role of DTI as a presymptomatic biomarker

The Effective Fragment Molecular Orbital Method for Fragments Connected by Covalent Bonds

We extend the effective fragment molecular orbital method (EFMO) into treating fragments connected by covalent bonds. The accuracy of EFMO is compared to FMO and conventional ab initio electronic structure methods for polypeptides including proteins. Errors in energy for RHF and MP2 are within 2 kcal/mol for neutral polypeptides and 6 kcal/mol for charged polypeptides similar to FMO but obtained two to five times faster. For proteins, the errors are also within a few kcal/mol of the FMO results. We developed both the RHF and MP2 gradient for EFMO. Compared to ab initio, the EFMO optimized structures had an RMSD of 0.40 and 0.44 {\AA} for RHF and MP2, respectively.Comment: Revised manuscrip

Revisiting the university front

dc.subject: Postdemocracy / Public function of the university / Governance / Knowledge society / research university / Managerialism / Academic audit / Quality contro

Molecular, spectroscopic, and magnetic properties of cobalt(II) complexes with heteroaromatic N(O)-donor ligands

New [Co(SCN)2(L)4/2] complexes, where L = b-pic (1), pyCH2OH (2), py(CH2)3OH (3), 1,2,4- triazolo[1,5-a]pyrimidine (4), [CoCl2(urotrop)2] (5), and [Co(DMIM)3]Cl2 H2O (6) where urotrop = hexamethylenetetramine and DMIM = 2,20-bis(4,5-dimethylimidazolyl) were synthesized in simple reactions of CoCl2 6H2O with ammonia thiocyanate and pyridine type ligands or urotropine and diimidazolyl ligands with cobalt(II) chloride in methanol solutions. The orthorhombic crystallization for (1), (2), and (4), the monoclinic one for (3) and (5) as well as the hexagonal one for (6) were found. The plots of the overlap population density-of-states indicated nonbonding character of the interactions between pyridine derivatives ligands and cobalt(II) ions in the complexes (1)–(4). The electronic spectra showed almost perfect octahedral complex in the case of (6). The magnetic susceptibility measurements revealed paramagnetic behavior with low values of the Curie–Weiss temperature, positive for complex (5) and negative for the other ones, although the transition to collective magnetic state at low temperatures for (4) and (5) was evidenced by an observation of antiferromagnetic coupling with Ne´el temperature of 4.5 K and the ferromagnetic one with Curie temperature of 10 K, respectively

Is Violent Radicalisation Associated with Poverty, Migration, Poor Self-Reported Health and Common Mental Disorders?

BACKGROUND: Doctors, lawyers and criminal justice agencies need methods to assess vulnerability to violent radicalization. In synergy, public health interventions aim to prevent the emergence of risk behaviours as well as prevent and treat new illness events. This paper describes a new method of assessing vulnerability to violent radicalization, and then investigates the role of previously reported causes, including poor self-reported health, anxiety and depression, adverse life events, poverty, and migration and socio-political factors. The aim is to identify foci for preventive intervention. METHODS: A cross-sectional survey of a representative population sample of men and women aged 18-45, of Muslim heritage and recruited by quota sampling by age, gender, working status, in two English cities. The main outcomes include self-reported health, symptoms of anxiety and depression (common mental disorders), and vulnerability to violent radicalization assessed by sympathies for violent protest and terrorist acts. RESULTS: 2.4% of people showed some sympathy for violent protest and terrorist acts. Sympathy was more likely to be articulated by the under 20s, those in full time education rather than employment, those born in the UK, those speaking English at home, and high earners (>£75,000 a year). People with poor self-reported health were less likely to show sympathies for violent protest and terrorism. Anxiety and depressive symptoms, adverse life events and socio-political attitudes showed no associations. CONCLUSIONS: Sympathies for violent protest and terrorism were uncommon among men and women, aged 18-45, of Muslim heritage living in two English cities. Youth, wealth, and being in education rather than employment were risk factors