Electron transfer in photoexcited pyrrole dimers

Following on from previous experimental and theoretical work [Neville et al., Nat. Commun. 7, 11357 (2016)], we report the results of a combined electronic structure theory and quantum dynamics study of the excited state dynamics of the pyrrole dimer following excitation to its first two excited states. Employing an exciton-based analysis of the Ã(π3s/σ*) and ˜ B (π3s/3p/σ*) states, we identify an excited-state electron transfer pathway involving the coupling of the Ã(π3s/σ*) and ˜ B (π3s/3p/σ*) states and driven by N–H dissociation in the ˜ B (π3s/3p/σ*) state. This electron transfer mechanism is found to be mediated by vibronic coupling of the ˜ B state, which has a mixed π3s/3p Rydberg character at the Franck-Condon point, to a high-lying charge transfer state of the πσ* character by the N–H stretch coordinate. Motivated by these results, quantum dynamics simulations of the excited-state dynamics of the pyrrole dimer are performed using the multiconfigurational time-dependent Hartree method and a newly developed model Hamiltonian. It is predicted that the newly identified electron transfer pathway will be open following excitation to both the Ã(π3s/σ*) and ˜ B (π3s/3p/σ*) states and may be the dominant relaxation pathway in the latter case

Non-radiative relaxation dynamics of pyrrole following excitation in the range 249.5-200nm

The non-radiative relaxation dynamics of pyrrole have been investigated using time-resolved photoelectron spectroscopy and quantum dynamics simulations. Following excitation of the A2(11πσ*) state, we observe population flow out of the Franck-Condon region on a ≲50 fs timescale. Following excitation of the B2(21ππ*) state, we observe population being transferred to the A2(11πσ*) state on a <50. fs timescale and subsequently out of the Franck-Condon region, also on a <50. fs timescale. Quantum dynamics calculations suggest that population is transferred from the B2(21ππ*) state through the A2(1π3pz) state to the B1(21πσ*) state before being transferred to the A2(11πσ*) state

Fulminant Leptospirosis (Weil's disease) in an urban setting as an overlooked cause of multiorgan failure: a case report

<p>Abstract</p> <p>Introduction</p> <p>Leptospirosis has recently come to international attention as a globally important re-emerging infectious disease. Our case is unusual given the season, location and setting in which leptospirosis occurred. According to the New York City Board of Health, there were only two other cases of leptospirosis in New York City in the year that our patient was diagnosed.</p> <p>Case presentation</p> <p>A 49-year-old healthy Chinese man presented to our hospital with sepsis and multiorgan failure. The patient did not respond to antibiotics and his multiorgan failure worsened. His workup did not show any significant findings except for a positive nasopharyngeal swab result for influenza A. Later the patient developed hemoptysis with evidence of bilateral infiltrates on radiography. His status mildly improved after he was started on steroids. Eventually, a microagglutination test confirmed the presence of antibodies against <it>Leptospira icterohaemorrhagiae. </it>The patient subsequently recovered after a course of intravenous antibiotics.</p> <p>Conclusion</p> <p>The case of fulminant leptospirosis presented here should serve to alert health care providers and the general public to the clinical importance of this severe, sometimes fatal, disease. Leptospirosis should be considered early in the diagnosis of any patient with acute, non-specific febrile illness with multiorgan system involvement or high fever in a returning traveler. In addition, not only should it be considered in tropical and rural areas between late summer to early fall, but also in any location or time if the risk factors are present.</p

Perturbative quantum gravity with the Immirzi parameter

We study perturbative quantum gravity in the first-order tetrad formalism. The lowest order action corresponds to Einstein-Cartan plus a parity-odd term, and is known in the literature as the Holst action. The coupling constant of the parity-odd term can be identified with the Immirzi parameter of loop quantum gravity. We compute the quantum effective action in the one-loop expansion. As in the metric second-order formulation, we find that in the case of pure gravity the theory is on-shell finite, and the running of Newton's constant and the Immirzi parameter is inessential. In the presence of fermions, the situation changes in two fundamental aspects. First, non-renormalizable logarithmic divergences appear, as usual. Second, the Immirzi parameter becomes a priori observable, and we find that it is renormalized by a four-fermion interaction generated by radiative corrections. We compute its beta function and discuss possible implications. The sign of the beta function depends on whether the Immirzi parameter is larger or smaller than one in absolute value, and the values plus or minus one are UV fixed-points (we work in Euclidean signature). Finally, we find that the Holst action is stable with respect to radiative corrections in the case of minimal coupling, up to higher order non-renormalizable interactions.Comment: v2 minor amendment

Shear Strength Parameters of Improved Peat by Chemical Stabilizer.

The present research aimed to discuss the applicability of cationic grouts in geotechnical engineering. The effects of several cationic stabilizers such as monovalent (sodium silicate), divalent (calcium oxide and calcium chloride), and trivalent (aluminum hydroxide) were investigated on shear strength improvement of tropical peat samples. The unconfined compressive strength (UCS) tests were performed after the time frame of 7, 21, and 30 days as curing time, respectively. Apart from the physicochemical characteristics of the stabilized peat, scanning electron microscopy and energy-dispersive X-ray spectroscopy tests were also carried out to study the ongoing microstructural changes. It is to be noted that the shear strength values for peat samples rose to 8, 6, 6, and 4 % of sodium silicate, calcium oxide, calcium chloride, and aluminum hydroxide, respectively. The highest observed UCS outcome is the one taken from the calcium oxide where the UCS of treated peat after 30-day curing time increased to 76 kPa. The strength changes resulted from the various cationic stabilizers can best be explained via the consideration within the mineralogical composition as well as those physicochemical changes happening in the peat

Systematic development of a self-regulation weight-management intervention for overweight adults

Background. This paper describes the systematic development of an intervention for the prevention of obesity among overweight adults. Its development was guided by the six steps of Intervention Mapping (IM), in which the establishment of program needs, objectives and methods is followed by development of the intervention and an implementation and evaluation plan. Methods. Weight gain prevention can be achieved by making small changes in dietary intake (DI) or physical activity (PA). The intervention objectives, derived from self-regulation theory, were to establish goal-oriented behaviour. They were translated into a computer-tailored Internet-delivered intervention consisting of four modules. The intervention includes strategies to target the main determinants of self-regulation, such as feedback and action planning. The first module is intended to ensure adults' commitment to preventing weight gain, choosing behaviour change and action initiation. The second and third modules are intended to evaluate behaviour change, and to adapt action and coping plans. The fourth module is intended to maintain self-regulation of body weight without use of the program. The intervention is being evaluated for its efficacy in an RCT, whose protocol is described in this paper. Primary outcomes are weight, waist circumference and skin-fold thickness. Other outcomes are DI, PA, cognitive mediators and self-regulation skills. Discussion. The IM protocol helped us integrating insights from various theories. The performance objectives and methods were guided by self-regulation theory but empirical evidence with regard to the effectiveness of theoretical methods was limited. Sometimes, feasibility issues made it necessary to deviate from the original, theory-based plans. With this paper, we provide transparency with regard to intervention development and evaluation. Trial registration. NTR1862

Is the process of delivery of an individually tailored lifestyle intervention associated with improvements in LDL cholesterol and multiple lifestyle behaviours in people with Familial Hypercholesterolemia?

<p>Abstract</p> <p>Background</p> <p>More insight in the association between reach, dose and fidelity of intervention components and effects is needed. In the current study, we aimed to evaluate reach, dose and fidelity of an individually tailored lifestyle intervention in people with Familial Hypercholesterolemia (FH) and the association between intervention dose and changes in LDL-Cholesterol (LDL-C), and multiple lifestyle behaviours at 12-months follow-up.</p> <p>Methods</p> <p>Participants (n = 181) randomly allocated to the intervention group received the PRO-FIT intervention consisting of computer-tailored lifestyle advice (<it>PRO-FIT*advice</it>) and counselling (face-to-face and telephone booster calls) using Motivational Interviewing (MI). According to a process evaluation plan, intervention reach, dose delivered and received, and MI fidelity were assessed using the recruitment database, website/counselling logs and the Motivational Interviewing Treatment Integrity (MITI 3.1.1.) code. Regression analyses were conducted to explore differences between participant and non-participant characteristics, and the association between intervention dose and change in LDL-C, and multiple lifestyle behaviours.</p> <p>Results</p> <p>A 34% (n = 181) representative proportion of the intended intervention group was reached during the recruitment phase; participants did not differ from non-participants (n = 623) on age, gender and LDL-C levels. Of the participants, 95% received a <it>PRO-FIT*advice</it> log on account, of which 49% actually logged on and completed at least one advice module. Nearly all participants received a face-to-face counselling session and on average, 4.2 telephone booster calls were delivered. None of the face-to-face sessions were implemented according to MI guidelines. Overall, weak non-significant positive associations were found between intervention dose and LDL-C and lifestyle behaviours.</p> <p>Conclusions</p> <p>Implementation of the PRO-FIT intervention in practice appears feasible, particularly <it>PRO-FIT*advice</it>, since it can be relative easily implemented with a high dose delivered. However, only less than half of the intervention group received the complete intervention-package as intended. Strategies to let participants optimally engage in using web-based computer-tailored interventions like <it>PRO-FIT*advice</it> are needed. Further, more emphasis should be put on more extensive MI training and monitoring/supervision.</p> <p>Trial registration</p> <p>NTR1899 at ww.trialregister.nl.</p

Study of Women, Infant feeding, and Type 2 diabetes mellitus after GDM pregnancy (SWIFT), a prospective cohort study: methodology and design

<p>Abstract</p> <p>Background</p> <p>Women with history of gestational diabetes mellitus (GDM) are at higher risk of developing type 2 diabetes within 5 years after delivery. Evidence that lactation duration influences incident type 2 diabetes after GDM pregnancy is based on one retrospective study reporting a null association. The Study of Women, Infant Feeding and Type 2 Diabetes after GDM pregnancy (SWIFT) is a prospective cohort study of postpartum women with recent GDM within the Kaiser Permanente Northern California (KPNC) integrated health care system. The primary goal of SWIFT is to assess whether prolonged, intensive lactation as compared to formula feeding reduces the 2-year incidence of type 2 diabetes mellitus among women with GDM. The study also examines whether lactation intensity and duration have persistent favorable effects on blood glucose, insulin resistance, and adiposity during the 2-year postpartum period. This report describes the design and methods implemented for this study to obtain the clinical, biochemical, anthropometric, and behavioral measurements during the recruitment and follow-up phases.</p> <p>Methods</p> <p>SWIFT is a prospective, observational cohort study enrolling and following over 1, 000 postpartum women diagnosed with GDM during pregnancy within KPNC. The study enrolled women at 6-9 weeks postpartum (baseline) who had been diagnosed by standard GDM criteria, aged 20-45 years, delivered a singleton, term (greater than or equal to 35 weeks gestation) live birth, were not using medications affecting glucose tolerance, and not planning another pregnancy or moving out of the area within the next 2 years. Participants who are free of type 2 diabetes and other serious medical conditions at baseline are screened for type 2 diabetes annually within the first 2 years after delivery. Recruitment began in September 2008 and ends in December 2011. Data are being collected through pregnancy and early postpartum telephone interviews, self-administered monthly mailed questionnaires (3-11 months postpartum), a telephone interview at 6 months, and annual in-person examinations at which a 75 g 2-hour OGTT is conducted, anthropometric measurements are obtained, and self- and interviewer-administered questionnaires are completed.</p> <p>Discussion</p> <p>This is the first, large prospective, community-based study involving a racially and ethnically diverse cohort of women with recent GDM that rigorously assesses lactation intensity and duration and examines their relationship to incident type 2 diabetes while accounting for numerous potential confounders not assessed previously.</p