The changing incidence of childhood-onset type 1 diabetes in Wales: Effect of gender and season at diagnosis and birth.

AIMS: Determinants of the changing incidence of childhood-onset type 1 diabetes remain uncertain. We determined the recent time-trend of type 1 diabetes incidence in Wales and explored the role of vitamin D by evaluating the influence of season both at diagnosis and at birth. METHODS: Data from all Welsh paediatric units 1990-2019, and from primary care to determine ascertainment. RESULTS: Log-linear modelling indicated a non-linear secular trend in incidence with peak and subsequent decline. The peak occurred around June 2010: 31∙3 cases/year/100,000 children aged < 15y. It occurred earlier in children younger at diagnosis and earlier in boys. There were more cases in males aged <2y and >12y but more in females aged 9-10 y. More were diagnosed in winter. Also, children born in winter had less risk of future diabetes. CONCLUSIONS: The risk of developing type 1 diabetes before age 15y in Wales is no longer increasing. The data on season are consistent with a preventative role for vitamin D both during pregnancy and later childhood. Metereological Office data shows increasing hours of sunlight since 1980 likely to increase vitamin D levels with less diabetes. Additional dietary supplementation with vitamin D might further reduce the incidence of type 1 diabetes.

Effect of structured self-monitoring of blood glucose, with and without additional TeleCare support, on overall glycaemic control in non-insulin treated Type 2 diabetes: the SMBG Study, a 12-month randomized controlled trial.

AIM: To examine the impact of structured self-monitoring of blood glucose, with or without TeleCare support, on glycaemic control in people with sub-optimally controlled Type 2 diabetes. METHODS: We conducted a 12-month, multicentre, randomized controlled trial in people with established (>1 year) Type 2 diabetes not on insulin therapy, with sub-optimal glycaemic control [HbA1c ≥58 to ≤119 mmol/mol (≥7.5% to ≤13%)]. A total of 446 participants were randomized to a control group (n =151) receiving usual diabetes care, a group using structured self-monitoring of blood glucose alone (n =147) or a group using structured self-monitoring of blood glucose with additional monthly 'TeleCare' support (n =148). The primary outcome was HbA1c at 12 months. RESULTS: A total of 323 participants (72%) completed the study; 116 (77%) in the control group, 99 (67%) in the self-monitoring of blood glucose alone group and 108 (73%) in the self-monitoring of blood glucose plus TeleCare group. Compared to baseline, the mean HbA1c was lower in all groups at 12 months, with reductions of 3.3 mmol/mol (95% CI -5.71 to -0.78) or 0.3% (95% CI -0.52 to -0.07; P=0.01) in the control group, 11.4 mmol/mol (95% CI -14.11 to -8.76) or 1.1% (-1.29 to -0.81; P<0.0001) in the group using self-monitoring of blood glucose alone and 12.8 mmol/mol (95% CI -15.34 to -10.31) or 1.2% (95% CI -1.40 to -0.94; P<0.0001) in the group using self-monitoring of blood glucose plus TeleCare. This represents a reduction in HbA1c of 8.9 mmol/mol (95% CI -11.97 to -5.84) or 0.8% (95% CI -1.10 to -0.54; P≤0.0001) with structured self-monitoring of blood glucose compared to the control group. Participants with lower baseline HbA1c , shorter duration of diabetes and higher educational achievement were more likely to achieve HbA1c ≤53 mmol/mol (7.0%). CONCLUSIONS: Structured self-monitoring of blood glucose provides clinical and statistical improvements in glycaemic control in Type 2 diabetes. No additional benefit, over and above the use of structured self-monitoring of blood glucose, was observed in glycaemic control with the addition of once-monthly TeleCare support. (Clinical trial registration no.: ISRCTN21390608).

Three-dimensional kinetic Monte Carlo simulations of diamond chemical vapor deposition.

A three-dimensional kinetic Monte Carlo model has been developed to simulate the chemical vapor deposition of a diamond (100) surface under conditions used to grow single-crystal diamond (SCD), microcrystalline diamond (MCD), nanocrystalline diamond (NCD), and ultrananocrystalline diamond (UNCD) films. The model includes adsorption of CHx (x = 0, 3) species, insertion of CHy (y = 0-2) into surface dimer bonds, etching/desorption of both transient adsorbed species and lattice sidewalls, lattice incorporation, and surface migration but not defect formation or renucleation processes. A value of ∼200 kJ mol(-1) for the activation Gibbs energy, ΔG(‡) etch, for etching an adsorbed CHx species reproduces the experimental growth rate accurately. SCD and MCD growths are dominated by migration and step-edge growth, whereas in NCD and UNCD growths, migration is less and species nucleate where they land. Etching of species from the lattice sidewalls has been modelled as a function of geometry and the number of bonded neighbors of each species. Choice of appropriate parameters for the relative decrease in etch rate as a function of number of neighbors allows flat-bottomed etch pits and/or sharp-pointed etch pits to be simulated, which resemble those seen when etching diamond in H2 or O2 atmospheres. Simulation of surface defects using unetchable, immobile species reproduces other observed growth phenomena, such as needles and hillocks. The critical nucleus for new layer growth is 2 adjacent surface carbons, irrespective of the growth regime. We conclude that twinning and formation of multiple grains rather than pristine single-crystals may be a result of misoriented growth islands merging, with each island forming a grain, rather than renucleation caused by an adsorbing defect species.

A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase.

The S1((1)ππ*) state of the (dominant) syn-conformer of 2-chlorophenol (2-ClPhOH) in the gas phase has a subpicosecond lifetime, whereas the corresponding S1 states of 3- and 4-ClPhOH have lifetimes that are, respectively, ∼2 and ∼3-orders of magnitude longer. A range of experimental techniques-electronic spectroscopy, ultrafast time-resolved photoion and photoelectron spectroscopies, H Rydberg atom photofragment translational spectroscopy, velocity map imaging, and time-resolved Fourier transform infrared emission spectroscopy-as well as electronic structure calculations (of key regions of the multidimensional ground (S0) state potential energy surface (PES) and selected cuts through the first few excited singlet PESs) have been used in the quest to explain these striking differences in excited state lifetime. The intramolecular O-H···Cl hydrogen bond specific to syn-2-ClPhOH is key. It encourages partial charge transfer and preferential stabilization of the diabatic (1)πσ* potential (relative to that of the (1)ππ* state) upon stretching the C-Cl bond, with the result that initial C-Cl bond extension on the adiabatic S1 PES offers an essentially barrierless internal conversion pathway via regions of conical intersection with the S0 PES. Intramolecular hydrogen bonding is thus seen to facilitate the type of heterolytic dissociation more typically encountered in solution studies.

Reaction dynamics. Vibrational relaxation and microsolvation of DF after F-atom reactions in polar solvents.

Solvent-solute interactions influence the mechanisms of chemical reactions in solution, but the response of the solvent is often slower than the reactive event. Here, we report that exothermic reactions of fluorine (F) atoms in d3-acetonitrile and d2-dichloromethane involve efficient energy flow to vibrational motion of the deuterium fluoride (DF) product that competes with dissipation of the energy to the solvent bath, despite strong solvent coupling. Transient infrared absorption spectroscopy and molecular dynamics simulations show that after DF forms its first hydrogen bond on a subpicosecond time scale, DF vibrational relaxation and further solvent restructuring occur over more than 10 picoseconds. Characteristic dynamics of gas-phase F-atom reactions with hydrogen-containing molecules persist in polar organic solvents, and the spectral evolution of the DF products serves as a probe of solvent reorganization induced by a chemical reaction.

O2(a1Δg) + Mg, Fe, and Ca: experimental kinetics and formulation of a weak collision, multiwell master equation with spin-hopping.

The first excited electronic state of molecular oxygen, O(2)(a(1)Δ(g)), is formed in the upper atmosphere by the photolysis of O(3). Its lifetime is over 70 min above 75 km, so that during the day its concentration is about 30 times greater than that of O(3). In order to explore its potential reactivity with atmospheric constituents produced by meteoric ablation, the reactions of Mg, Fe, and Ca with O(2)(a) were studied in a fast flow tube, where the metal atoms were produced either by thermal evaporation (Ca and Mg) or by pulsed laser ablation of a metal target (Fe), and detected by laser induced fluorescence spectroscopy. O(2)(a) was produced by bubbling a flow of Cl(2) through chilled alkaline H(2)O(2), and its absolute concentration determined from its optical emission at 1270 nm (O(2)(a(1)Δ(g) - X(3)Σ(g) (-)). The following results were obtained at 296 K: k(Mg + O(2)(a) + N(2) → MgO(2) + N(2)) = (1.8 ± 0.2) × 10(-30) cm(6) molecule(-2) s(-1); k(Fe + O(2)(a) → FeO + O) = (1.1 ± 0.1) × 10(-13) cm(3) molecule(-1) s(-1); k(Ca + O(2)(a) + N(2) → CaO(2) + N(2)) = (2.9 ± 0.2) × 10(-28) cm(6) molecule(-2) s(-1); and k(Ca + O(2)(a) → CaO + O) = (2.7 ± 1.0) × 10(-12) cm(3) molecule(-1) s(-1). The total uncertainty in these rate coefficients, which mostly arises from the systematic uncertainty in the O(2)(a) concentration, is estimated to be ±40%. Mg + O(2)(a) occurs exclusively by association on the singlet surface, producing MgO(2)((1)A(1)), with a pressure dependent rate coefficient. Fe + O(2)(a), on the other hand, shows pressure independent kinetics. FeO + O is produced with a probability of only ∼0.1%. There is no evidence for an association complex, suggesting that this reaction proceeds mostly by near-resonant electronic energy transfer to Fe(a(5)F) + O(2)(X). The reaction of Ca + O(2)(a) occurs in an intermediate regime with two competing pressure dependent channels: (1) a recombination to produce CaO(2)((1)A(1)), and (2) a singlet∕triplet non-adiabatic hopping channel leading to CaO + O((3)P). In order to interpret the Ca + O(2)(a) results, we utilized density functional theory along with multireference and explicitly correlated CCSD(T)-F12 electronic structure calculations to examine the lowest lying singlet and triplet surfaces. In addition to mapping stationary points, we used a genetic algorithm to locate minimum energy crossing points between the two surfaces. Simulations of the Ca + O(2)(a) kinetics were then carried out using a combination of both standard and non-adiabatic Rice-Ramsperger-Kassel-Marcus (RRKM) theory implemented within a weak collision, multiwell master equation model. In terms of atmospheric significance, only in the case of Ca does reaction with O(2)(a) compete with O(3) during the daytime between 85 and 110 km.

Prevalence of ketoacidosis at diagnosis of childhood onset Type 1 diabetes in Wales from 1991 to 2009 and effect of a publicity campaign.

AIMS: To determine the proportion of cases of childhood Type 1 diabetes that present with ketoacidosis and any temporal trend. To assess the impact of a publicity campaign promoting earlier diagnosis. METHODS: We used an all-Wales register of incident cases with data on 2046 children from 1991 to 2009. The proportion with ketoacidosis at diagnosis was compared with the Yorkshire Childhood Diabetes Register. On World Diabetes Day posters were sent to every pharmacy, school and general practitioner surgery across Wales and radio interviews given. A questionnaire survey was conducted in Gwent to assess penetrance of the campaign. RESULTS: Annually, in 1991-2009 the proportion presenting with ketoacidosis varied between 20% and 33% (mean 25%) with no change over time. Similar proportions occurred in Yorkshire. Ketoacidosis was more common before age 5 years (37% of cases) than at age 5-9 years (20%) or 10-14 years (23%) (P < 0.001). From November 2006-2007 30% of cases presented with ketoacidosis and from November 2007-2008 25% cases presented with ketoacidosis. After the campaign (November 2008-2009) 26% presented with ketoacidosis (P = 0.72). The information had reached a low proportion of families. General practitioners referred immediately cases that presented to them. CONCLUSIONS: Over 20 years in Wales there has been no change in the proportion of children with Type 1 diabetes initially presenting with ketoacidosis. This presentation occurs in a higher proportion of new cases aged under 5 years. Publicity to increase awareness did not reduce the proportion with ketoacidosis at diagnosis in Wales. We need to get the educational message through to parents to reduce ketoacidosis at presentation.

Solution behavior of iron(III) and iron(II) porphyrins in DMSO and reaction with superoxide. Effect of neighboring positive charge on thermodynamics, kinetics and nature of iron-(su)peroxo product.

The solution behavior of iron(III) and iron(II) complexes of 5(4),10(4),15(4),20(4)-tetra-tert-butyl-5,10,15,20-tetraphenylporphyrin (H(2)tBuTPP) and the reaction with superoxide (KO(2)) in DMSO have been studied in detail. Applying temperature and pressure dependent NMR studies, the thermodynamics of the low-spin/high-spin equilibrium between bis- and mono-DMSO Fe(II) forms have been quantified (K(DMSO) = 0.082 ± 0.002 at 298.2 K, ΔH° = +36 ± 1 kJ mol(-1), ΔS° = +101 ± 4 J K(-1) mol(-1), ΔV° = +16 ± 2 cm(3) mol(-1)). This is a key activation step for substitution and inner-sphere electron transfer. The superoxide binding constant to the iron(II) form of the studied porphyrin complex was found to be (9 ± 0.5) × 10(3) M(-1), and does not change significantly in the presence of the externally added crown ether in DMSO (11 ± 4) × 10(3) M(-1). The rate constants for the superoxide binding (k(on) = (1.30 ± 0.01) × 10(5) M(-1) s(-1)) and release (k(off) = 11.6 ± 0.7 s(-1)) are not affected by the presence of the external crown ether in solution. The resulting iron(II)-superoxide adduct has been characterized (mass spectrometry, EPR, high-pressure UV/Vis spectroscopy) and upon controlled addition of a proton source it regenerates the starting iron(II) complex. Based on DFT calculations, the reaction product without neighboring positive charge has iron(II)-superoxo character in both high-spin side-on and low-spin end-on forms. The results are compared to those obtained for the analogous complex with covalently attached crown ether, and more general conclusions regarding the spin-state equilibrium of iron(II) porphyrins, their reaction with superoxide and the electronic structure of the product species are drawn.

Oxygen-containing gas-phase diatomic trications and tetracations: ReO(z+), NbO(z+) and HfO(z+) (z=3, 4).

Three oxygen-containing gas-phase diatomic trications ReO(3+), NbO(3+) and HfO(3+) as well as the diatomic tetracation NbO(4+) have been observed by mass spectrometry at non-integer m/z values. These unusual triply charged molecular ion species, together with the corresponding diatomic dications ReO(2+), NbO(2+) and HfO(2+), were produced by energetic, high-current oxygen ((16)O(-)) ion beam sputtering of rhenium, niobium and hafnium metal samples, respectively, whose surfaces were dynamically oxidized by oxygen primary ion incorporation. In addition, NbO(z+) (z≤ 4) were generated by intense femtosecond laser excitation and photofragmentation (Coulomb explosion) of Nb(x)O(y) clusters and were detected through Time-of-Flight Mass Spectrometry (TOF). Our experimental results confirm previous reports on the detection of NbO(4+), NbO(3+), NbO(2+), HfO(3+) and HfO(2+) with Atom Probe mass spectrometry, whereas ReO(3+) and ReO(2+) apparently had not been observed before. In addition, these multiply charged molecular ions have been studied theoretically for the first time. Ab initio calculations of their electronic structures show that the diatomic trications ReO(3+), NbO(3+) and HfO(3+) are long-lived metastable gas-phase species, with bond lengths of 1.61 Å, 1.62 Å and 1.86 Å, respectively. They present large potential barriers with respect to dissociation of more than 2.7 eV. The corresponding diatomic dications are thermochemically stable molecules with very large dissociation energies (>3.5 eV). Our calculations predict the diatomic tetracation ReO(4+) to be a metastable ion species in the gas phase. We compute a potential barrier toward fragmentation of 0.6 eV; its formation requires a quadruple adiabatic ionization energy of 85.7 eV. Even though our calculations show that NbO(4+) is a weakly bound (dissociation barrier ∼0.1 eV) metastable molecule, it is here identified via linear time-of-flight mass spectrometry.

Diabetes, metformin and lactic acidosis.

OBJECTIVE: Metformin has long been thought to cause lactic acidosis (LA) but evidence from various sources has led researchers to question a direct causative relationship. We assessed the relationship of metformin prescription and other factors to the incidence of LA. METHODS: All cases of LA at a single hospital were identified from laboratory lactate measurements. We compared patients classified as Cohen and Woods class A and B, patients with and without diabetes, and those taking metformin or not. RESULTS: LA was more common than in published analyses based on hospital coding of diagnoses. The incidence of LA was greater in diabetes than in the nondiabetic population but with no further increase in patients taking metformin. Lactate levels were no greater in patients on metformin than in patients with type 2 diabetes not on metformin even if patients with acute cardiorespiratory disturbance (Cohen and Woods class A) were excluded. Acidosis was greater in diabetes (hydrogen ion 94·9 ± 4·6 vs 83·2 ± 2·3 10(-9) m, P = 0·027) but factors besides lactate contributed. Acute cardiorespiratory illness, acute renal impairment and sepsis were the most common of the recognized precipitating factors. Age (P = 0·01), acute renal failure (P = 0·015) and sepsis (P = 0·005) were associated with mortality. CONCLUSIONS: Diabetes rather than metformin therapy is the major risk factor for the development of LA. Lactic acidosis occurs in association with acute illness particularly in diabetes. Current guidance for the prevention of lactic acidosis may overemphasize the role of metformin.

Mediation by illness perceptions of the effect of personality and health threat communication on coping with the diagnosis of diabetes.

OBJECTIVES: (1) To examine the relationship of personality traits and diabetes health threat communication (DHTC) to the coping strategies of newly diagnosed diabetes patients; (2) to determine to what extent these postulated effects are mediated by illness representations (IRs). DESIGN: A longitudinal prospective study based on the common sense model. METHODS: Patients were assessed shortly after diagnosis and 2 years after the diagnosis of diabetes. Personality traits (Mini-markers) were assessed at baseline. The DHTC Questionnaire was completed at baseline and 2 years. The Revised Illness Perception Questionnaire and the coping orientation to problems experienced were completed at 2 years. Mediation by IRs of the potential influence of personality and DHTC on coping behaviour was assessed by the method of Baron and Kenny. RESULTS: Multiple regression analyses showed that educational level, agreeableness, openness/intellect, conscientiousness, and perceptions of a more reassuring health message since diagnosis were related to more adaptive coping (e.g., active coping, planning). The association of openness and perceived reassuring health message with active coping showed complete mediation by illness coherence and personal control. Openness led to seeking emotional support mediated by perceived personal control. Coherence associated with (partial mediation) the relation of openness to planning. Similarly, personal control and coherence mediated the relation of openness to positive reinterpretation and growth (PRG). Agreeableness had a direct relationship with active coping and PRG but led to planning and seeking instrumental support mediated by perceived treatment effectiveness. Perceptions of a threatening health message were associated with seeking instrumental and emotional support and this was mediated by symptom perception but threat had a direct relationship with planning. CONCLUSIONS: Both personality traits and health threat communication predict the way individuals cope with diabetes. The relationships of these factors are largely mediated through measurable IRs. The results suggest targets for intervention to achieve greater problem-focused coping.

Use of cystatin C-based estimations of glomerular filtration rate in patients with type 2 diabetes.

AIMS/HYPOTHESIS: The Modification of Diet in Renal Disease (MDRD) equation has recognised limitations when using estimated GFR in persons at risk of chronic kidney disease. Equations based on cystatin C provide an alternative method. We compared performance of the MDRD equation with a selection of cystatin C-based formulae for estimation of GFR in normoalbuminuric patients with type 2 diabetes. METHODS: Estimated GFR was calculated using the MDRD equation and the cystatin C formulae proposed by several investigator teams. Isotopic GFR was measured using plasma clearance of (51)Cr-EDTA. RESULTS: We studied 106 participants, of whom 83 (78%) were men with the following characteristics, mean (SD): age 61 (9) years, HbA(1c) 7.10 (1.27)%, creatinine 89.0 (12.7) micromol/l, cystatin C 0.859 (0.234) mg/l and isotopic GFR 104.5 (20.1) ml min(-1) 1.73 m(-2). MDRD estimated GFR was 77.4 (13.6) ml min(-1) 1.73 m(-2) (p < 0.05 for difference from isotopic GFR). Cystatin C-based calculations of estimated GFR were: Perkins 124.5 (31.8), Rule 90.0 (30.0), Stevens (age) 96.0 (30.4) and Stevens (creatinine) 85.6 (19.0) ml min(-1) 1.73 m(-2) (p < 0.05 for difference with isotopic GFR). For Arnal's, MacIsaac's and Tan's formulae cystatin-C estimated GFR were 101.7 (34.8), 102.1 (27.0) and 101.6 (27.8) ml min(-1) 1.73 m(-2), respectively (p = NS for difference with isotopic GFR). Cystatin C-based formulae were less biased and, with the exception of Perkins' formula, more accurate to within 10% of isotopic GFR than MDRD. CONCLUSIONS/INTERPRETATION: Performance of cystatin C equations was superior to MDRD in normoalbuminuric patients with type 2 diabetes. These results support further evaluation of cystatin C for estimation of GFR in persons at risk of chronic kidney disease.

The importance of health belief models in determining self-care behaviour in diabetes.

Patients' self-care behaviours have a major role in diabetes management. Diabetes education provides the required knowledge, but despite this, self-care is often suboptimal. The degree to which patients follow advice as regards the various self-care behaviours is determined by their health beliefs (Illness Representations or Personal Models) of diabetes. Psychometric studies have tried to categorize and measure the beliefs about illness that influence patients to adhere to treatment recommendations in diabetes. Various models have been proposed to explain the relationship between beliefs and behaviour. Leventhal's Self-Regulatory Model, which takes account of the emotional as well as the objective rational response to illness, currently seems to offer the best system for identifying the determinants of patient self-care behaviour. A review of interventions indicates those based on psychological theory offer professionals the best chance of maximizing their patients' contribution to diabetes self-management and achieving improved outcomes, both glycaemic and psychosocial. Studies designed specifically to modify illness representations are now being undertaken. This brief review aims to summarize developments in this area of psychological theory over the last 20 years and the implications for promoting better self-care behaviour in diabetes.

Performance of the revised '175' Modification of Diet in Renal Disease equation in patients with type 2 diabetes.

AIMS/HYPOTHESIS: Estimation of GFR (eGFR) is recommended for the assessment of kidney function in all patients with diabetes. We studied performance of the traditional '186' Modification of Diet in Renal Disease (MDRD) equation, and the 2005 revised '175' MDRD equation in patients with type 2 diabetes. METHODS: Two hundred and ninety-three mainly normoalbuminuric (267/293) patients were recruited. Patients were classified as having mild renal impairment (group 1, GFR <90 ml min(-1) 1.73 m(-2)) or normal renal function (group 2, GFR >or=90 ml min(-1) 1.73 m(-2)). eGFR was calculated by the traditional 186 MDRD equation using traditional creatinine values and the revised 175 MDRD equation using isotope dilution mass spectrometry-standardised creatinine values. Isotopic GFR was measured by the four-sample plasma clearance of (51)Cr-EDTA. RESULTS: For patients in group 1, mean +/- SD isotopic (51)Cr-EDTA GFR (iGFR) was 83.8 +/- 4.3 ml min(-1) 1.73 m(-2), and eGFR was 73.2 +/- 11.9 and 75.8 +/- 13.7 ml min(-1) 1.73 m(-2) using the 186 and 175 MDRD equations, respectively. Method bias was -10.6 with the 186 MDRD and -7.9 ml min(-1) 1.73 m(-2) (p < 0.05) with the 175 MDRD equation. In group 2, iGFR was 119.4 +/- 20.2 ml min(-1) 1.73 m(-2), and eGFR was 92.3 +/- 18.6 and 97.5 +/- 21.6 ml min(-1) 1.73 m(-2) using the 186 and 175 MDRD equations, respectively. Method bias was -27.1 with the 186 MDRD equation and -21.9 ml min(-1) 1.73 m(-2) (p < 0.05) with the 175 MDRD equation. CONCLUSIONS/INTERPRETATION: In patients newly diagnosed with type 2 diabetes, the revised 175 MDRD equation was less biased than the traditional 186 MDRD equation. Despite a continued tendency to underestimate isotopically measured GFR, use of standardised creatinine values is a positive step towards improved estimation of GFR.

An investigation of the molecular geometry and electronic structure of nitryl chloride by a combination of rotational spectroscopy and ab initio calculations.

The ground-state rotational spectra of the six isotopomers (16)O(2) (14)N(35)Cl, (16)O(2) (14)N(37)Cl, (18)O(16)O(14)N(35)Cl, (18)O(2) (14)N(35)Cl, (16)O(2) (15)N(35)Cl, and (16)O(2) (15)N(37)Cl of nitryl chloride were observed with a pulsed-jet, Fourier-transform microwave spectrometer to give rotational constants, Cl and (14)N nuclear quadrupole coupling, and spin-rotation coupling constants. These spectroscopic constants were interpreted to give r(0), r(s), and r(m) ((2)) versions of the molecular geometry and information about the electronic redistribution at N when nitryl chloride is formed from NO(2) and a Cl atom. The r(m) ((2)) geometry has r(N-Cl)=1.8405(6) A, r(N-O)=1.1929(2) A, and the angle ONO=131.42(4) degrees , while the corresponding quantities for the r(s) geometry are 1.8489 A, 1.1940 A, and 131.73 degrees , respectively. Electronic structure calculations at CCSD(T)cc-pVXZ (X=T, Q, or 5) levels of theory were carried out to give a r(e) geometry, vibration-rotation corrections to equilibrium rotational constants, and values of the (35)Cl and (14)N nuclear hyperfine (quadrupole and spin-rotation) coupling constants in good agreement with experiment. The equilibrium geometry at the CCSD(T)/cc-pV5Z level of theory has r(N-Cl)=1.8441 A, r(N-O)=1.1925 A and the angle ONO=131.80 degrees . The observed rotational constants were corrected for the vibration-rotation effects calculated ab initio to yield semiempirical equilibrium constants which were then fitted to give the following semiempirical equilibrium geometry: r(N-Cl)=1.8467(2) A, r(N-O)=1.1916(1) A, and the angle ONO=131.78(3) degrees .

The development of personal models of diabetes in the first 2 years after diagnosis: a prospective longitudinal study.

AIMS: Personal models of diabetes comprise beliefs about symptoms, treatment effectiveness, consequences and emotional responses to possible future complications. They are associated with, and influence, self-care behaviour. Little work has examined potential influences on the development and maintenance of personal models. The aims of this study were: (i) to assess changes in personal models over 2 years from diagnosis of diabetes; and (ii) to examine the relative contributions of health threat communication (at diagnosis, since diagnosis, during follow-up care) and personality to personal models of diabetes 2 years post-diagnosis. METHODS: Newly diagnosed patients were interviewed at diagnosis (< 3 months; time 1) and 6 months (time 2), 1 year (time 3) and 2 years (time 4) after diagnosis. Data were available for 158 patients at time 1 (32 Type 1 patients and 126 Type 2 patients), 147 at time 2, 142 at time 3 and 138 at time 4. RESULTS: Perceptions of symptoms, consequences, course and control of diabetes remained stable over time. Emotional responses decreased and illness coherence (perceived understanding) increased over time. Health threat communication was a stronger predictor of personal models than personality. Emotional responses to diabetes 2 years after diagnosis were predicted by perceptions of a threatening health message (at diagnosis 18%, at follow-up 5%). Health threat communication predicted perceptions of serious consequences (at diagnosis 5%, at follow-up 9%). Perceptions of a reassuring message during follow-up were related to beliefs of treatment effectiveness (26%). CONCLUSIONS: The communication of information and the way it is perceived is an important determinant of the patient's view of their diabetes. The initial effects of the education process at diagnosis persisted 2 years after diagnosis.

The influence of health threat communication and personality traits on personal models of diabetes in newly diagnosed diabetic patients.

BACKGROUND: Personal models of diabetes, i.e. patients' beliefs about symptoms, treatment effectiveness, consequences (impact on life, seriousness) and emotional response to possible short- and long-term complications, have been associated with diabetes self-care behaviours. Little work has examined potential determinants of personal models. AIMS: To examine the influence of health threat communication and personality traits on personal models in newly diagnosed patients. METHODS: Newly diagnosed patients (n = 158; 32 Type 1 and 126 Type 2) completed the Big Five Personality Inventory, Diabetes Health Threat Communication Questionnaire (DHTCQ), Personal Models of Diabetes Interview-Adapted (PMDI) and Illness Perception Questionnaire-Revised (IPQ-R). RESULTS: Emotional responses to diabetes (PMDI) were associated with perceptions of a more threatening health message (22% explained variance), less emotional stability (5%) and the presence of dependent children (3%). Emotional representations (IPQ-R) were associated with a threatening health message (6%) and less emotional stability (15%). An adverse view of consequences (PMDI) was predicted by a more threatening/less reassuring health message (15%), less emotional stability (6%) and Type 1 diabetes (4%). Consequences (IPQ-R) were predicted by perceptions of a more threatening health message (20%), being less agreeable/cooperative (7%) and having dependent children (4%). Treatment effectiveness beliefs (PMDI) were associated with perceptions of a more reassuring health message (31%), younger age (3%) and more openness/intellect (2%). CONCLUSIONS: Personal models of diabetes are influenced by health threat communication, demographic and personality factors. These findings support the concept of tailoring health messages to the needs of individual patients and provide information on factors to be taken into account in the education process.

Towards comprehensive population-based screening for diabetic retinopathy: operation of the North Wales diabetic retinopathy screening programme using a central patient register and various screening methods.

OBJECTIVES: To examine whether population-based retinopathy screening using a central diabetes register and employing various screening methods can achieve a high degree of population coverage to meet National Screening Committee (NSC) targets. To identify the main barriers to achieving comprehensive population coverage. To analyse referrals to ophthalmology and their outcome as a measure of previously unmet need. To assess the influence of modality of screening. SETTING: Three local health board areas in North Wales. METHODS: Establishment of a district diabetes register to hold records of all patients and subserve call-recall of general practitioner (GP) sole-care patients for screening by optometrists or digital photography. Hospital attenders were screened in diabetic clinic by direct ophthalmoscopy. Data were collected for years 1 and 2 of operation of the scheme. RESULTS: The system held a screening record for 86% of diabetic patients after year 1 and 93% after year 2. Failure to attend was the major barrier to comprehensive population screening, but this improved in year 2 (P<0.001). Both optometrists and photography identified substantial unmet need: 1% of all GP sole-care patients required immediate laser treatment. Photography was more sensitive than optometrist screening, but the additional retinopathy identified was mostly minor not requiring treatment. CONCLUSIONS: Lack of screening is much more important than modality of screening as a cause of missed sight-threatening retinopathy. A central, district-based patient register system identifies those patients not screened for further follow-up and can produce a high level of population coverage, close to NSC targets. Such schemes are needed, particularly to support primary care diabetes management.

The effect of oral folic acid on glutathione, glycaemia and lipids in Type 2 diabetes.

Plasma homocysteine is an established risk factor for vascular disease and precursor of the anti-oxidant glutathione. This study was designed to investigate the relationship of changes in homocysteine (Hcy) induced by oral folate to glutathione and measures of glycaemia and lipid metabolism in Type 2 diabetes (T2DM). Twenty-seven patients (26 male, 1 female, aged 48-68 years) with T2DM and microalbuminuria were treated with folic acid 10 mg daily for 3 months. During the study, diastolic blood pressure (p=0.04), HbA1c (p=0.04), serum triglycerides (p=0.04) and serum total/HDL-cholesterol ratio (p=0.004) all increased and serum HDL-cholesterol fell (p=0.006). The increased red cell folate correlated with a reduction in microalbuminuria (p=0.001). Overall, plasma glutathione increased (p=0.016) despite reduction in its precursor Hcy (p<0.001). Change in glutathione correlated inversely with change in HbA1c (p<0.02), total cholesterol (p=0.003) and triglycerides (p<0.02) and positively with HDL-cholesterol (p=0.033). Increase in glutathione correlated with levels of vitamin B6 (p<0.05). Metformin treatment protected against the rise in blood pressure (BP) (p=0.02), independently of changes in plasma glutathione. In summary, oral folic acid supplementation in T2DM reduced plasma Hcy and increased glutathione levels. HbA1c, triglycerides and HDL-cholesterol deteriorated during the trial: their levels correlated inversely with changes in glutathione. The increase in glutathione may depend on an adequate supply of B6, as changes in glutathione correlated with vitamin B6 levels. Reduced Hcy and increased glutathione may both mediate improvement in vascular function and outcome. Some aspects of the response to folate may be different in patients on metformin.