Evaluation of the NHS England 'Op COURAGE' High Intensity Service for military veterans with significant mental health problems.

INTRODUCTION: In November 2020, The NHS for England launched a pilot High Intensity Service (HIS) programme for treating military veterans complex mental health problems. Seven regional grants were awarded to manage the HIS, including NHS Solent, in South East England. This paper details an evaluation of the HIS, which was conducted from February 2021 to August 2022. METHODS: This mixed-methods study gained quantitative data from a specifically designed questionnaire that included a number of validated psychometric questionnaires. These were completed by either HIS staff or beneficiaries at entry and exit from the HIS, and qualitative data were gained from semi-structured interviews with the HIS staff. RESULTS: Data were sourced from 45 pre-questionnaires, 25 post programme questionnaires and 11 interviews. This evaluation identified reductions in situational stressors, symptoms and reported illnesses for veterans in crisis. There were reductions in depression, anxiety and post-traumatic stress disorder following programme exit. Staff reported that there was no notable changes in stress levels which appeared to remain high at programme exit. Staff interviews highlighted the importance of simultaneously understanding the social and psychological needs of veterans in mental health crisis. The benefits of integrating veteran staff members into military veteran health services were identified, demonstrating improvements in education around military culture in civilian services. CONCLUSIONS: The importance of collaboration between clinical and veteran staff members in veteran health services was noted, demonstrating the positive impact social care provision has on veteran's overall health and well-being. Veteran engagement with the service was advocated as a result of veterans accessing the service feeling understood. This first independent evaluation of the HIS provides a positive reflection, and adds to the limited empirical evidence exploring veteran engagement in health services.

Traditional and Dairy Products and Vegetables Dietary Patterns Are Inversely Associated with the Risk of Cataract in the Middle Age and Aged Population: A Case-Control Study.

OBJECTIVES: Cataract is one of the most common causes of visual impairment and blindness in the world. In the present study, we have been trying to investigate the relationship between major dietary patterns and cataract. DESIGN: This was a case-control study. SETTING: An ophthalmology outpatient clinic of Khatam al-Anbia Hospital, in Shoushtar city. PARTICIPANTS: 336 subjects (168 patients with cataract and 168 healthy ones), from 40 to 80 years old, were recruited. MEASUREMENTS: A socio-demographic questionnaire was used to record the demographic information. A food frequency questionnaire was used to determine the foods consumed during the last year. The principal component analysis was used to extract major dietary patterns. The possible relationship between the major dietary patterns and cataract was assessed by multivariable logistic regression models. RESULTS: We tried to eliminate the effect of cofactors. The results showed "dairy products and vegetables" dietary pattern had a negative association with cataract (OR: 0.301, 95%CI =0.137-0.658, P trend =0.002). The fourth quartile of the "traditional" dietary pattern also showed a protective role against the cataract (OR: 0.393, 95%CI =0.184-0.842, P trend = 0.036). The third and fourth quartiles of "carbohydrate and simple sugar" pattern were more related with cataract compared to the first quartile (OR: 3.574, 95%CI =1.665-7.671, and OR: 5.067, 95%CI =2.265-11.335, P trend <0.001 respectively). No significant association was found between «nuts, seeds and simple sugar" dietary pattern and cataract. CONCLUSION: It seems a dietary pattern rich in proteins and vegetables can decrease the risk of cataract in middle-aged and aged subjects.

Effect of photoperiod on growth and feed conversion of juvenile wild carp, Cyprinus carpio.

Because of the effect of photoperiod on physiological and biochemical processes in fish, this study aimed to evaluate the effect of manipulated photoperiod on growth, feed conversion and survival of wild carp, Cyprinus carpio. Fish received six photoperiod regimes (light:dark cycle) including: natural photoperiod (control), 24L:0D, 16L:8D, 12L:12D, 8L:16D and 0L:24D by the three replications. Regulated photoperiods as a 16L:8D or 12L:12D light/dark cycle significantly improved growth rate and food conversion ratio of wild carp.

Simultaneous cloud point extraction and spectrophotometric determination of carmoisine and brilliant blue FCF in food samples.

A novel simultaneous cloud point extraction method for the determination of carmoisine and brilliant blue FCF by spectrophotometry has been developed. The method is based on the cloud point extraction of carmoisine and brilliant blue FCF from aqueous solution using Triton X-100, diluting the extracted surfactant rich phase with water and measuring the absorbance at 522 and 640 nm for carmoisine and brilliant blue FCF, respectively. The effects of different parameters such as pH, concentration of surfactant and temperature on the cloud point extraction of both dyes were investigated and optimum conditions were established. Linear calibration curves were obtained in the range of 0.02-3.50 µg mL(-1) for carmoisine and 0.05-3.50 µg mL(-1) for brilliant blue FCF under optimum conditions. Detection limit based on three times the standard deviation of the blank (3S(b)) was 0.017 and 0.016 µg mL(-1) (n=10) for carmoisine and brilliant blue FCF, respectively. The relative standard deviation (RSD) for 0.1 µg mL(-1) was 4.14 and 3.30% (n=10), for carmoisine and brilliant blue FCF, respectively. The method was applied to the simultaneous determination of the dyes in different food samples.

Comparison between CUUG and UUCG tetraloops: thermodynamic stability and structural features analyzed by UV absorption and vibrational spectroscopy.

CUUG loop is one of the most frequently occurring tetraloops in bacterial 16S rRNA. This tetraloop has a high thermodynamic stability as proved by previous UV absorption and NMR experiments. Here, we present our results concerning the thermodynamic and structural features of the 10mer 5'-r(GCG-CUUG-CGC)-3', forming a highly stable CUUG tetraloop hairpin in aqueous solution, by means of several optical techniques (UV and FT-IR absorption, Raman scattering). UV melting profile of this decamer provides a high melting temperature (60.7 degrees C). A set of Raman spectra recorded at different temperatures allowed us to analyze the order-to-disorder (hairpin-to-random coil) transition. Assignment of vibrational markers led us to confirm the particular nucleoside conformation, and to get information on the base stacking and base pairing in the hairpin structure. Moreover, comparison of the data obtained from two highly stable CUUG and UUCG tetraloops containing the same nucleotides but in a different order permitted an overall discussion of their structural features on the basis of Raman marker evidences.

Solidification of a supercooled liquid in a narrow channel.

We simulate solidification in a narrow channel through the use of a phase-field model with an adaptive grid. In different regimes, we find that the solid can grow in fingerlike steady-state shapes, or become unstable, exhibiting unsteady growth. At low melt undercoolings, we find good agreement between our results, theoretical predictions, and experiment. For high undercoolings, we report evidence for a new stable steady-state finger shape which exists in experimentally accessible ranges for typical materials.

Unusual nucleotide conformations in GNRA and UNCG type tetraloop hairpins: evidence from Raman markers assignments.

High resolution NMR data on UNCG and GNRA tetraloops (where N is any of the four nucleotides and R is a purine) have shown that they contain ribonucleosides with unusual 2'-endo/anti and 3'-endo/syn conformations, in addition to the 3'-endo/anti ones which are regularly encountered in RNA chains. In the current study, Raman spectroscopy has been used to probe these nucleoside conformations and follow the order (hairpin) to disorder (random chain) structural transitions in aqueous phase in the 5-80 degreesC temperature range. Spectral evolution of GCAA and GAAA tetraloops, as formed in very short hairpins with only three G.C base pairs in their stems (T m >60 degreesC), are reported and compared with those previously published on UUCG and UACG tetraloops, for which the syn orientation of the terminal guanine as well as the 2'-endo/anti conformation of the third rC residue have been confirmed by means of vibrational marker bands. Raman data obtained as a function of temperature show that the first uracil in the UUCG tetraloop is stacked and the two middle residues (rU and rC) are in the 2'-endo/anti conformation, in agreement with the previously published NMR results. As far as the new data concerning the GNRA type tetraloops are concerned, they lead us to conclude that: (i) in both cases (GCAA and GAAA tetraloops) the adenine bases are stacked; (ii) the second rC residue in the GCAA tetraloop has a 3'-endo/anti conformation; (iii) the sugar pucker associated with the third rA residue in both tetraloops possibly undergoes a 3'-endo/2'-endo interconversion as predicted by NMR results; (iv) the stem adopts a regular A-form structure; (v) all other nucleosides of these two GNRA tetraloops possess the usual 3'-endo/anti conformation.

Molecular weight effects on chain pull-out fracture of reinforced polymeric interfaces.

Using Brownian dynamics, we simulate the fracture of polymer interfaces reinforced by diblock connector chains. We consider the mushroom regime, where connector chains are grafted with low surface density, for the case of large pulling velocities. We find that for short chains the interface fracture toughness depends linearly on the degree of polymerization N of the connector chains, while for longer chains the dependence becomes N(3/2). Based on the geometry of the initial chain configuration, we propose a scaling argument that accounts for both short and long chain limits and the crossover between them.

Structural features of the UCCG and UGCG tetraloops in very short hairpins as evidenced by optical spectroscopy.

Structures of the UCCG and UGCG tetraloops formed in octamer ribonucleotidic hairpin sequences, i.e., 5'-r[GC(UCCG)GC]-3' and 5'-r[GC(UGCG)GC]-3', have been studied in aqueous solution by methods of optical spectroscopy. UV absorption melting profiles of these short hairpins, containing only two closing GC base pairs in the stem, are consistent with a monophasic, completely reversible order-to-disorder transition and clearly confirm their unusual structural stability (with Tm congruent with 50 degrees C). To establish structural characteristics of these tetraloops, Raman and FTIR spectroscopies have been used and vibrational conformation markers arising from the phosphate backbone and various nucleosides have been analyzed. They have been assigned on the basis of known unambiguous vibrational markers established for DNA and RNA chains. Surprisingly, they are easily transferable to short oligonucleotidic sequences. Intensities and wavenumbers of these conformation markers have been monitored in the 0-70 degrees C temperature range, i.e., in going from an ordered to a disordered structure. The main structural features of the UCCG and UGCG tetraloops are similar to those previously found in the UUCG and UACG tetraloops by means of NMR and vibrational spectroscopies, except those of the second nucleosides of the tetraloops (rC and rG, respectively) which adopt a 3'-endo/anti rather than a 2'-endo/anti conformation.

Common structural features of UUCG and UACG tetraloops in very short hairpins determined by UV absorption, Raman, IR and NMR spectroscopies.

Thermodynamic and structural properties of two UNCG tetraloops in very short hairpin octamers, 5'-r(GCUUCGGC)-3' and 5'-r(GCUACGGC)-3', have been studied by means of various physical techniques. Melting profiles of both octamers, obtained from UV absorption spectra taken as a function of temperature, are consistent with a monophasic, progressive and completely reversible order-to-disorder transition and confirm their unusual structural stability (Tm > 51 degrees C). The 1H, 13C and 31P NMR chemical shifts and coupling constants of the UACG loop nucleotides are comparable with those reported previously for UUCG loops, i.e. 2'-endo/anti conformation of the second and third nucleotide of the loop as well as the syn orientation of the ultimate guanine base and the A-type double helical conformation of the hairpin stem. Simulation of quantitative NOESY volumes shows that the UACG octamer adopts a very rigid compact structure which is well represented by an average order parameter of 0.9. Three base-pairs and four additional strong hydrogen bonds are undoubtedly responsible for such limited flexibility. Raman and infrared spectra as a function of temperature reflect the order-to-disorder transition, as well. Vibrational conformational markers in low temperature spectra of both octamers indicate the hairpin structure as the major conformer in aqueous phase. These spectra further support the structural features of most of the nucleotides involved in the tetraloops and clearly demonstrate the structural similarities of the phosphodiester backbone in both hairpins. Consequently, on the basis of all present results, one can deduce that the conformational features of the UUCG and UACG tetraloops seem to be inherent to the UNCG type tetraloops, regardless of either the nature of the tetraloop second base or the stem length.

Thermodynamic and structural properties of r(ACC) as revealed by ultraviolet electronic absorption, circular dichroism, 1H-NMR spectroscopy and Monte Carlo simulations.

UV absorption, circular dichroism (CD) and 1H NMR, associated with Monte Carlo (MC) molecular structure simulations have been applied to the study of the trinucleoside diphosphate: r(ACC). The MC study which has been conducted as a function of temperature, is based on random variations of the nucleotide conformational angles, i.e. phosphodiester chain torsional angles and sugar pucker pseudorotational angles. All of the chemical bond lengths and valence angles remained fixed during the structural simulation, except those of the sugar pucker. Six different initial structures have been selected in order to explore the molecular conformational space as completely as possible. This simulation procedure led to distinct families of equilibrium conformations at 283, 298 and 318 K. The thermodynamical parameters such as variations in entropy, enthalpy and also melting temperature (delta SX0, delta HX0 and Tm) of the stacking (X) equilibrium were obtained from UV absorption and circular dichroism (CD) spectra recorded over a 80K temperature range. Chemical shifts (delta), vicinal coupling constants (3Jk,l), and cross-relaxation rate (sigma k,l) of trimers were measured at 400.13 MHz over a range of concentrations (2-13 mM) and temperatures (283-333K). Least-squares fitting of the experimental chemical shifts to simple models of association (A) and stacking equilibria allowed separation of the variations in the delta values (delta delta X and delta delta A) due to either phenomenon. The three NMR data sets (delta delta X, 3Jk,l, and sigma k,l) were then evaluated for the minima conformers obtained with the MC stimulations. Theoretical values of delta delta X were estimated using the results of an ab initio study while the coupling constant data were simulated with Karplus-type equations. Finally, the relaxation data were simulated from the distance matrices using treatment for cases of both slow conformational exchange accompanied by rapid small-amplitude fluctuations about the minima structures. A consistent picture of the large amplitude deformations (torsional angle variation) of these trimers has emerged from the present study. Optimized conformational blends at 283,296 and 318K were obtained by least-squares fitting of the experimental data to the theoretical ones, while considering the populations as adjustable parameters. As it would be expected, the right-handed helical conformation (A-RNA type) is found to be the major stacked species, in the temperature range of 283 to 318K. Limited evidence for bulged structures has been obtained, whereas novel reverse-stacked and half-stacked conformers also presented theoretical data compatible with the NMR observables of aqueous r(ACC).

Vibrational mode analysis of guanine by neutron inelastic scattering.

The low-temperature neutron inelastic spectrum of guanine has been measured. In order to assign the intense peaks observed in this spectrum, a normal mode analysis has been performed, using the Wilson GF-method. The theoretical treatment is based on a non-redundant set of internal coordinates, and a simplified valence force-field approximation. Only the fundamentals have been considered for simulating the internal vibrational mode spectrum. The calculations account for the spectral shape as well as the main observed peaks.

Interpretation of DNA vibrational spectra by normal coordinate analysis.

1. In the following article we undertake a brief review of the most prominent DNA vibrational markers as observed experimentally by Raman and i.r. spectroscopies on polynucleotides and explain how a simplified valence force field can account for the evolution of the DNA vibrational spectra. 2. Our discussion made as a review of our previous investigations on the interpretation of DNA vibration modes, is based on some of the most characteristic and structure dependent DNA vibrational markers.

Interpretation of DNA vibration modes: III--The behaviour of the sugar pucker vibration modes as a function of its pseudorotation parameters.

A systematic study of the sugar pucker characteristic vibration modes as a function of its geometrical conformations, has been performed. The present investigation is based on the Wilson GF method and a non-redundant valence force field. The calculated results allow to assign the modes arising mainly from the sugar motions and present in quasi whole vibrational spectra related to the right or left-handed double-helices (i.e., 1050 cm-1, 960 cm-1 and 890 cm-1). Moreover, the conformation dependent modes as those at 860 cm-1 and around 810 cm-1 (A form) as well as the one located around 830 cm-1 (B form) are interpreted by the present investigation. The possibility of the interaction of the latter modes with the phosphate group motions along the DNA double-helical chains are also discussed.

Interpretation of DNA vibration modes: IV--A single-helical approach to assign the phosphate-backbone contribution to the vibrational spectra in A and B conformations.

A calculated approach based on the Higgs method for assigning the vibration modes of an infinite helicoidal polymeric chain has been performed on the basis of a reliable valence force field. The calculated results allowed the phosphate-backbone marker modes of the A and B forms, to be interpreted. In the dynamic models used, the bases have been omitted and no interchain interaction was considered. The calculation can also interprete quite satisfactorily the characteristic Raman peaks and infrared bands in the 1250-700 cm-1 spectral region arising from the sugar or sugar-phosphate association and reproduce their evolution upon the B----A DNA conformational transition. They clearly show that the phosphate-backbone modes in the above mentioned spectral region constitute the optical branches of the phonon dispersion curves with no detectable variation in the first Brillouin-zone.

Particular behavior of the adenine and guanine ring-breathing modes upon the DNA conformational transitions.

Harmonic dynamics calculations performed on the deoxyguanosine (dG) and deoxyadenosine (dA) residues, based on a reliable force field, show that the breathing motions of both guanine and adenine residues are involved in two different vibration modes (750-500 cm-1 spectral region). The calculated results reveal a strong coupling of these modes with the sugar pucker motions. This effect has been verified for the dG residue by the Raman spectra of polyd(G-C). As far as the dA residue is concerned, the particular behavior of the adenine residue breathing mode predicted by these calculations, has been confirmed by Raman spectra of polyd(A-T) undergoing a B----Z conformational transition.

Interpretation of DNA vibration modes. II--The adenosine and thymidine residues involved in oligonucleotides and polynucleotides.

Normal coordinate analysis of the adenosine and thymidine residues involved in the right- and left-handed conformations of oligonucleotides and polynucleotides has been performed. The valence force field, employed in this work, allowed recently to reproduce the vibrational spectra of 2'-deoxythymidine and 2'-deoxyadenosine. The calculated wavenumbers based on a non-redundant set of internal coordinates have been compared to the Raman and infrared peak positions arising from A, B, C, D and Z conformations, in the 1550-1250 cm-1 and 800-600 cm-1 spectral regions: i.e. characteristic of adenosine and thymidine residues. Moreover, a systematic study has been performed on the evolution of the vibrational wavenumbers as a function of the glycosidic angle (chi) and the sugar pucker conformation.

Normal coordinate analysis of 2'-deoxythymidine and 2'-deoxyadenosine.

The proposed valence force field allows us to reproduce the vibration modes of 2'-deoxythymidine and 2'-deoxyadenosine. The present calculations are based on the Wilson GF-method and a non-redundant set of symmetrical coordinates. The calculated wavenumbers have been compared to the available Raman and infrared peak positions observed in solid, amorphous or aqueous samples. Moreover, the results obtained with the present force field allow us to assign some of the characteristic vibration modes for the thymidine and adenosine residues involved in DNA double-helical chains.

Interpretation of DNA vibration modes: I--The guanosine and cytidine residues involved in poly(dG-dC).poly(dG-dC) and d(CG)3.d(CG)3.

A normal coordinate analysis has been carried out on guanosine and cytidine residues appearing in oligo and polynucleotides by using a simplified valence force field that allows the vibrational spectra of 5'-dGMP and 2'-deoxycytidine molecules to be reproduced. The role of both C2'-endo and C3'-endo conformations on sugar pucker, as well as that of glycosidic torsion angle (X), on several characteristic vibration modes of these residues have been studied. The present calculations based on a non-redundant set of internal coordinates preserving the harmonic approximation of the potential field, allows us to explain quite satisfactorily the modifications of the vibrational spectra in the 1550-1250 cm-1 and 785-500 cm-1 regions, when the right----left-handed conformational transition occurs.