Sustained positive behaviour change of wounded, injured and sick UK military following an adaptive adventure sports and health coaching recovery course.

INTRODUCTION: A rising trend has occurred in the physical and mental health challenges faced by recovering UK service personnel. To support these individuals, bespoke inclusive multiactivity and adventurous training courses (MAC) have been developed. This study investigated the MAC's influence on participants' ability to sustain day-to-day changes that facilitate positive mental health and psychological need satisfaction. METHODS: The 146 UK service personnel who participated in this study attended a five-day MAC 12 months ago. To investigate how the supportive experience influenced participants' lives, quantitative and qualitative data were collected via an online survey. Open-ended questioning and abductive analysis were conducted to understand mechanisms, influential aspects of the course and positive behaviour change. RESULTS: Positive behaviour changes were reported by 74% of the respondents. These changes align with positive psychological well-being (98%). Impactful elements of the course experienced by participants mostly aligned with the three basic psychological needs of autonomy (34%), competence (36%) and relatedness (61%). CONCLUSIONS: Recovery support programmes that encompass health coaching adventurous activities, such as the MAC, can initiate long-term positive behaviour change for recovering military personnel. In this specific context, the concurrence of the self-determination theory concepts that underpin the course delivery and participant outcomes is a powerful endorsement of implementation fidelity.

Measuring central-spin interaction with a spin-bath by pulsed ENDOR: Towards suppression of spin diffusion decoherence.

We present pulsed electron-nuclear double resonance (ENDOR) experiments which enable us to characterize the coupling between bismuth donor spin-qubits in Si and the surrounding spin-bath of (29)Si impurities which provides the dominant decoherence mechanism (nuclear spin diffusion) at low temperatures (< 16 K). Decoupling from the spin-bath is predicted and cluster correlation expansion simulations show near-complete suppression of spin diffusion, at optimal working points. The suppression takes the form of sharply peaked divergences of the spin diffusion coherence time, in contrast with previously identified broader regions of insensitivity to classical fluctuations. ENDOR data shows anisotropic contributions are comparatively weak, so the form of the divergences is independent of crystal orientation.

The electronic structure of the flavin cofactor in DNA photolyase.

Density functional theory is used to calculate the electronic structure of the neutral flavin radical, FADH(*), formed in the light-induced electron-transfer reaction of DNA repair in cis,syn-cyclobutane pyrimidine dimer photolyases. Using the hybrid B3LYP functional together with the double-zeta basis set EPR-II, (1)H, (13)C, (15)N, and (17)O isotropic and anisotropic hyperfine couplings are calculated and explained by reference to the electron densities of the highest occupied molecular orbital and of the unpaired spin distribution on the radical. Comparison of calculated and experimental hyperfine couplings obtained from EPR and ENDOR/TRIPLE resonance leads to a refined structure for the FAD cofactor in Escherichia coli DNA photolyase. Hydrogen bonding at N3H, O4, and N5H results in significant changes in the unpaired spin density distribution and hyperfine coupling constants. The calculated electronic structure of FADH(*) provides evidence for a superexchange-mediated electron transfer between the cyclobutane pyrimidine dimer lesion and the 7,8-dimethyl isoalloxazine moiety of the flavin cofactor via the adenine moiety.

Substrate binding to DNA photolyase studied by electron paramagnetic resonance spectroscopy.

Structural changes in Escherichia coli DNA photolyase induced by binding of a (cis,syn)-cyclobutane pyrimidine dimer (CPD) are studied by continuous-wave electron paramagnetic resonance and electron-nuclear double resonance spectroscopies, using the flavin adenine dinucleotide (FAD) cofactor in its neutral radical form as a naturally occurring electron spin probe. The electron paramagnetic resonance/electron-nuclear double resonance spectral changes are consistent with a large distance (> or =0.6 nm) between the CPD lesion and the 7,8-dimethyl isoalloxazine ring of FAD, as was predicted by recent model calculations on photolyase enzyme-substrate complexes. Small shifts of the isotropic proton hyperfine coupling constants within the FAD's isoalloxazine moiety can be understood in terms of the cofactor binding site becoming more nonpolar because of the displacement of water molecules upon CPD docking to the enzyme. Molecular orbital calculations of hyperfine couplings using density functional theory, in conjunction with an isodensity polarized continuum model, are presented to rationalize these shifts in terms of the changed polarity of the medium surrounding the FAD cofactor.

EPR, ENDOR, and TRIPLE resonance spectroscopy on the neutral flavin radical in Escherichia coli DNA photolyase.

Ultraviolet radiation promotes the formation of a cyclobutane ring between adjacent pyrimidine residues on the same DNA strand to form a pyrimidine dimer. Such dimers may be restored to their monomeric forms through the action of a light-absorbing enzyme named DNA photolyase. The redox-active cofactor involved in the light-induced electron transfer reactions of DNA repair and enzyme photoactivation is a noncovalently bound FAD. In this paper, the FAD cofactor of Escherichia coli DNA photolyase was characterized as the neutral flavin semiquinone by EPR spectroscopy at 9.68 and 94.5 GHz. From the high-frequency/high-field EPR spectrum, the principal values of the axially symmetric g-matrix of FADH(*) were extracted. Both EPR spectra show an emerging hyperfine splitting of 0.85 mT that could be assigned to the isotropic hyperfine coupling constant (hfc) of the proton at N(5). To obtain more information about the electron spin density distribution ENDOR and TRIPLE resonance spectroscopies were applied. All major proton hfc's could be measured and unambiguously assigned to molecular positions at the isoalloxazin moiety of FAD. The isotropic hfc's of the protons at C(8alpha) and C(6) are among the smallest values reported for protein-bound neutral flavin semiquinones so far, suggesting a highly restricted delocalization of the unpaired electron spin on the isoalloxazin moiety. Two further hfc's have been detected and assigned to the inequivalent protons at C(1'). Some conclusions about the geometrical arrangement of the ribityl side chain with respect to the isoalloxazin ring could be drawn: Assuming tetrahedral angles at C(1') the dihedral angle between the C(1')-C(2') bond and the 2p(z)() orbital at N(10) has been estimated to be 170.4 degrees +/- 1 degrees.

Interrupted circular suture: bleeding control during cesarean delivery in placenta previa accreta.

Rapid accumulation of blood from the placental separation site during cesarean delivery for placenta previa obscures the surgical field and quickly leads to deterioration of the patient's vital signs. We used the following technique in eight cases of intractable bleeding among 49 cesareans for placenta previa. Following failure to control the bleeding by suture at the placental separation site via the lower segment cesarean incision, the vessels were ligated using interrupted 2-3-cm sutures at 1-cm intervals in a circle around the bleeding area on the serosal surface of the uterus. The sutures were placed as deeply as possible in order to reach the endometrium. This led to a marked decrease in bleeding and allowed the small vessels to be easily identified and ligated. The amount of blood transfused and the operation time were gradually reduced as we became adept in the use of this procedure. Our experience suggests that this technique could reduce the use of hysterectomy in cesarean for placenta previa.