Magnetic Helicity as a Predictor of the Solar Cycle.

It is well known that the polar magnetic field is at its maximum during solar minima, and that the behaviour during this time acts as a strong predictor of the strength of the following solar cycle. This relationship relies on the action of differential rotation (the Omega effect) on the poloidal field, which generates the toroidal flux observed in sunspots and active regions. We measure the helicity flux into both the northern and the southern hemispheres using a model that takes account of the Omega effect, which we apply to data sets covering a total of 60 years. We find that the helicity flux offers a strong prediction of solar activity up to five years in advance of the next solar cycle. We also hazard an early guess as to the strength of Solar Cycle 25, which we believe will be of similar amplitude and strength to Cycle 24.

Monitoring cerebral oxygenation of preterm infants using a neonatal specific sensor.

INTRODUCTION: Cerebral oxygenation (rcSO2) monitoring in preterm infants may identify periods of cerebral hypoxia or hyperoxia. We hypothesised that there was a relationship between rcSO2 values and short term outcome in infants of GA < 32weeks. METHODS: RcSO2 values were recorded for the first 48 h of life using an INVOS monitor with a neonatal sensor. The association between cranial ultrasound scan measured brain injury and rcSO2 was assessed. RESULTS: 120 infants were included. Sixty-nine percent (83) of infants had a normal outcome (no IVH, no PVL, and survival at 1 month); less than one-quarter, 22% (26), had low grade IVH 1 or 2 (moderate outcome); and 9% (11) of infants had a severe outcome (IVH ≥ 3, PVL or died before 1 month age). rcSO2 values were lower for infants GA < 28weeks when compared with those GA 28-32, p < 0.001. There was no difference in absolute rcSO2 values between the three outcome groups but a greater degree of cerebral hypoxia was associated with preterm infants who had low grade 1 or 2 IVH. CONCLUSION: Infants of GA < 28 weeks have lower cerebral oxygenation in the first 2 days of life. A greater degree of hypoxia was seen in infants with grade 1 or 2 haemorrhage. Normative ranges need to be gestation specific.

Auscultate, palpate and tap: time to re-evaluate.

AIM: To determine the accuracy of current methods of heart rate (HR) assessment. METHODS: All participants palpated a simulated pulsating umbilicus (UMB), listened to a tapping rate (TAP) and auscultated a simulated HR (AUSC). A simulated HR of 54, 88 and 128 beats per minute (bpm) was randomised for all methods. RESULTS: Twenty-nine healthcare staff participated in this study. Correct assessment of HR of 54 bpm as being within the 0-59 range occurred in 17.2% UMB, 17.2% TAP and 31% AUSC and was obtained in <10 seconds by 48.3%, 65.5% and 62.1%, respectively. A rate of 88 bpm was correctly assessed as within the 60-100 range in 82.8% UMB, 79.3% TAP and 79.3% AUSC and was obtained in <10 seconds by 55.2%, 58.6% and 55.2%, respectively. A rate of 128 bpm was identified as >100 bpm by 96.6% UMB, 93.1% TAP, and 93.1% AUSC and was obtained in <10 seconds by 51.7%, 55.2% and 62.1%, respectively. CONCLUSION: Current methods in assessing rates below 60 bpm are inaccurate and may overestimate HR. We recommend that these methods alone should not be relied upon in neonatal resuscitation and objective assessment of heart rate should be readily available at all newborn resuscitations.

Perfusion index in the preterm infant immediately after birth.

AIM: To evaluate PI in preterm infants during the first 10 min of life. DESIGN/METHODS: An observational study was conducted in the delivery room on preterm infants (less than 32 week gestation). PI values were obtained from a pre ductal saturation probe placed on the right wrist. Analysis was performed on the first 10 min of data to investigate the correlation of PI with gestational age, heart rate, blood pressure, and lactate values. RESULTS: 33 infants with a median gestational age of 29 wks (IQR, 26-30 wks) and median birth weight of 1205 g (IQR, 925-1520 g) were included for analysis. The overall median PI value for the first 10 min was 1.3 (IQR, 0.86-1.68). There was no significant correlation found between delivery room PI and gestational age(r=0.28, 95% CI: -0.09, 0.59), lactate levels (r=-0.25, 95% CI: -0.62, 0.18) and blood pressure values (r=-0.18, 95% CI: -0.46, 0.20). An average correlation value of r=-0.417 (95% CI: - 0.531, -0.253) was found between PI and heart rate values. There was no statistical difference between the median of the median PI value over the first 5 min of life compared to the second 5 min (p=0.22). Variability, as quantified by the IQR, was higher in the first 5 min compared to the second 5 min: median of 0.5(IQR, 0.27, 0.92) vs 0.2(IQR, 0.10, 0.30) (p<0.00). CONCLUSIONS: Delivery room PI values are easily obtained, however, have significant variability over the first 5 min of life and may add little to delivery room assessment.

Quantitative or qualitative carbon dioxide monitoring for manual ventilation: a mannequin study.

AIM: To compare the effectiveness of an in-line EtCO2 detector (DET) and a quantitative EtCO2 detector (CAP), both attached to a t-piece resuscitator, during PPV via a face mask. METHODS: Paediatric trainees were randomly assigned to determine the method of PPV they commenced with (No device (ND), DET or CAP). Participants used each method for 2 min. Participants were video-recorded to determine the amount of effective ventilations delivered with each method. RESULTS: Twenty-three paediatric trainees provided a total of 6035 ventilations, and 91.2% were deemed effective. The percentages of median effective ventilations with the ND, the DET and the CAP were 91.0%, 93.0% and 94.0%, respectively. Fourteen (61%) of the trainees indicated a preference for the DET method, 8 (35%) for the CAP method, and 1 (4%) of the trainees indicated a preference for the ND method. Capnography was the most effective method per patient. CONCLUSION: There was no adverse effect with the addition of EtCO2 detectors. Trainees favoured methods of EtCO2 monitoring during ventilation. The NeoStat device was the preferred device by the majority. The greatest efficacy was achieved with the capnography device. Capnography may enhance face mask ventilation.

A review of carbon dioxide monitoring in preterm newborns in the delivery room.

INTRODUCTION: The physiologic adaptation to extra uterine life during the immediate neonatal period is unique. Many newborns require assistance in this adaptive process. Recent evidence now supports titrating oxygen to guide resuscitation but no guidance is provided on utilizing exhaled CO2 measurements. AIM: To review the current evidence relating to the use of CO2 monitoring in preterm newborns in the delivery room. METHODS: Search was performed using the Cochrane Central Register of Controlled Trials, MEDLINE (1966-2014) and PREMEDLINE, EMBASE (1980-2014), CINAHL (1982-2014), Web of Science (1975-2014) and the Oxford Database of Perinatal Trials. RESULTS: The search revealed 21 articles relating to CO2 detection, either quantitative or qualitative, in the newborn infant. The majority of these were observational studies, eight relating to CO2 detection as a means of confirming correct endotracheal tube placement in the newborn infant. The other indication is for mask ventilation, and there is one randomized control trial and four observational studies of CO2 detection during mask ventilation. The overall recommendation for CO2 detection for both clinical uses in the delivery suite is level B. DISCUSSION: CO2 detection may be of particular benefit for preterm infants in the delivery suite. However there is a need for further research into CO2 detection, in particular capnography, as a means of confirming effective PPV in neonatal resuscitation.

Efficacy and user preference of two CO2 detectors in an infant mannequin randomized crossover trial.

Assessment of effective ventilation in neonatal mask ventilation can be difficult. This study aims to determine whether manual ventilation with a T-piece resuscitator containing an inline CO2 detector (either a Pedi-Cap® CO2 detector or a Neo-StatCO2

Structures of the chain metaphosphates NaM(PO3)3 (M = Ca or Sr).

Solid-state (23)Na and (31)P magic-angle spinning nuclear magnetic resonance spectroscopy and X-ray crystallography have been used to study the structures of the chain metaphosphates NaCa(PO(3))(3) and NaSr(PO(3))(3). The compounds are isostructural and crystallise in space group P(-1) with the following parameters: NaCa(PO(3))(3), a = 6.711 A, b = 6.934 A, c = 7.619 A, alpha = 83.44 degrees , beta = 81.41 degrees , gamma = 82.80 degrees ; NaSr(PO(3))(3)a = 6.805 A, b = 7.133 A, c = 7.720 A and alpha = 83.71 degrees , beta = 80.48 degrees , gamma = 82.87 degrees . Both structures contain anionic metaphosphate chains of (PO(3))(n) (n) with ionic contacts to Na(+) ions in distorted octahedral sites and Ca(2+) (or Sr(2+)) in distorted dodecahedral sites. (31)P and (23)Na NMR are entirely consistent with the crystallographic data and an empirical method for assigning (31)P resonances to particular crystallographically unique P atoms is described.

Reaction of o-phenylenediamine with diacetyl monoxime: characterisation of the product by solid-state 13C and 15N MAS NMR.

2,3-dimethylquinoxaline (DMQ) and dimethylglyoxime (DMGH2) form a 1:1 hydrogen-bonded complex in the solid state, which is completely dissociated in methanol solution. There are small differences in solid-state 13C shifts between the separated components DMQ and DMGH2 and the complex. The changes in 15N solid-state chemical shifts are more significant: the hydrogen bond imparting a low frequency shift of ca 19 ppm. The effect of direct protonation on the DMQ solid-state 15N shifts was measured, and the experimental 15N data correlated with those from GIAO molecular orbital (MO) calculations.

Thermodynamic origin of cis/trans isomers of a proline-containing beta-turn model dipeptide in aqueous solution: a combined variable temperature 1H-NMR, two-dimensional 1H,1H gradient enhanced nuclear Overhauser effect spectroscopy (NOESY), one-dimensional steady-state intermolecular 13C,1H NOE, and molecular dynamics study.

The cis/trans conformational equilibrium of the two Ac-Pro isomers of the beta-turn model dipeptide [13C]-Ac-L-Pro-D-Ala-NHMe, 98% 13C enriched at the acetyl carbonyl atom, was investigated by the use of variable temperature gradient enhanced 1H-nmr, two-dimensional (2D) 1H,1H nuclear Overhauser effect spectroscopy (NOESY), 13C,1H one-dimensional steady-state intermolecular NOE, and molecular dynamics calculations. The temperature dependence of the cis/trans Ala(NH) protons are in the region expected for random-coil peptides in H2O (delta delta/delta T = -9.0 and -8.9 ppb for the cis and trans isomers, respectively). The trans NH(CH3) proton indicates smaller temperature dependence (delta delta/delta T approximately -4.8 ppb) than that of the cis isomer (-7.5 ppb). 2D 1H,1H NOESY experiments at 273 K demonstrate significant NOEs between ProH alpha-AlaNH and AlaNH-NH(R) for the trans isomer. The experimental NOE data, coupled with computational analysis, can be interpreted by assuming that the trans isomer most likely adopts an ensemble of folded conformations. The C-CONH(CH3) fragment exhibits significant conformational flexibility; however, a low-energy conformer resembles closely the beta II-turn folded conformations of the x-ray structure of the related model peptide trans-BuCO-L-Pro-Me-D-Ala-NHMe. On the contrary, the cis isomer adopts open conformations. Steady-state intermolecular solute-solvent (H2O) 13C,1H NOE indicates that the water accessibility of the acetyl carbonyl carbons is nearly the same for both isomers. This is consistent with rapid fluctuations of the conformational ensemble and the absence of a highly shielded acetyl oxygen from the bulk solvent. Variable temperature 1H-nmr studies of the cis/trans conformational equilibrium indicate that the trans form is enthalpically favored (delta H degree = -5.14 kJ mole-1) and entropically (delta S degree = -5.47 J.K-1.mole-1) disfavored relative to the cis form. This demonstrates that, in the absence of strongly stabilizing sequence-specific interresidue interactions involving side chains and/or charged terminal groups, the thermodynamic difference of the cis/trans isomers is due to the combined effect of intramolecular and intermolecular (hydration) induced conformational changes.

Determination of the relative NH proton lifetimes of the peptide analogue viomycin in aqueous solution by NMR-based diffusion measurement.

In aqueous solution, exchanging peptide NH protons experience two environments, that of the peptide itself with a relatively slow diffusion coefficient and that of the water solvent with a faster diffusion coefficient. Although in slow exchange on the NMR chemical shift timescale, the magnetic field gradient dependence of the NH peak intensities in an experiment used to measure diffusion coefficients reflects the relative time periods spent in the two environments and this allows the determination of the relative solvent accessibility of exchangeable protons in peptides or proteins. To test this approach, the magnetic field gradient dependent intensities of the chemically shifted amide and amine NH protons of the peptide antibiotic viomycin have been measured using the high resolution longitudinal-eddy-current-delay (LED) NMR method incorporating solvent water peak elimination by non-excitation. The NH resonances of viomycin have been assigned previously and their relative exchange rates determined. Here, the gradient dependence of each NH proton intensity is reported, and these, after a bi- exponential least squares fitting, yield the fractional lifetimes of the protons spent in the peptide and water environments during the diffusion period of the experiment.

13C- and 57Fe-NMR studies of the Fe-C-O unit of heme proteins and synthetic model compounds in solution: comparison with IR vibrational frequencies and X-ray structural data.

13C- and 57Fe-NMR spectra of several carbon monoxide hemoprotein models with varying polar and steric effects of the distal organic superstructure, constraints of the proximal side, and solvent polarity are reported. The 13C shieldings of heme models cover a 4.0 ppm range that is extended to 7.0 ppm when several hemoglobin CO and myoglobin CO species at different pHs are included. Both heme models and heme proteins obey a similar excellent linear delta(13C) versus nu(C-O) relationship that is primarily due to modulation of pi backbonding from Fe d pi to the CO pi* orbital by the distal pocket polar interactions. There is no direct correlation between delta(13C) and Fe-C-O geometry. The poor monotonic relation between delta(13C) and nu(Fe-C) indicates that the iron-carbon pi bonding is not a primary factor influencing delta(13C) and delta(57Fe). The delta(57Fe) was found to be extremely sensitive to deformation of the porphyrin geometry, and increased shielding by more than 600 ppm with increased ruffling was observed for various heme models of known X-ray structures.

The effects of atropisomerism and porphyrin deformation on 57Fe shieldings in superstructured hemoprotein models.

57Fe NMR chemical shifts of superstructured heme model compounds have been found to be extremely sensitive to atropisomerism and deformation (ruffling) of the porphyrin geometry.

13C CP/MAS NMR Studies of Hemoprotein Models with and without an Axial Hindered Base: (13)C Shielding Tensors and Comparison with Hemoproteins and X-ray Structural Data.

13C cross-polarization magic-angle-spinning (CP/MAS) NMR spectra of several carbonmonoxide (93-99% (13)C enriched) hemoprotein models with 1,2-dimethylimidazole (1,2-diMeIm) and 1-methylimidazole (1-MeIm) as axial ligands are reported. This enables the (13)CO spinning sideband manifold to be measured and hence the principal components of the (13)CO chemical shift tensor to be obtained. Negative polar interactions in the binding pocket of the cap porphyrin model and inhibition of Fe-->CO back-donation result in a reduction in shielding anisotropy; on the contrary, positive distal polar interactions result in an increase in the shielding anisotropy and asymmetry parameter in some models. It appears that the axial hindered base 1,2-dimethylimidazole has little direct effect on the local geometry at the CO site, despite higher rates of CO desorption being observed for such complexes. This suggests that the mechanism by which steric interactions are released for the 1,2-diMeIm complexes compared to 1-MeIm complexes does not involve a significant increase in bending of the Fe-C-O unit. The asymmetry of the shielding tensor of all the heme model compounds studied is smaller than that found for horse myoglobin and rabbit hemoglobin.

Detection of aldehydes and their conjugated hydroperoxydiene precursors in thermally-stressed culinary oils and fats: investigations using high resolution proton NMR spectroscopy.

High field (400 and 600 MHz) proton NMR spectroscopy has been employed to investigate the thermally-induced autoxidation of glycerol-bound polyunsaturated fatty acids present in intact culinary frying oils and fats. Heating of these materials at 180 degrees C for periods of 30, 60 and 90 min. generated a variety of peroxidation products, notably aldehydes (alkanals, trans-2-alkenals and alka-2,4-dienals) and their conjugated hydroperoxydiene precursors. Since such aldehydes appear to be absorbed into the systemic circulation from the gut in vivo, the toxicological significance of their production during standard frying practices is discussed.

Generation of lipid peroxidation products in culinary oils and fats during episodes of thermal stressing: a high field 1H NMR study.

The oxidative deterioration of glycerol-bound polyunsaturated fatty acids (PUFAs) in culinary oils and fats during episodes of heating associated with normal usage (30-90 min at 180 degrees C) has been monitored by high field 1H NMR spectroscopy. Thermal stressing of PUFA-rich culinary oils generated high levels of n-alkanals, trans-2-alkenals, alka-2,4-dienals and 4-hydroxy-trans-2-alkenals via decomposition of their conjugated hydroperoxydiene precursors, whereas only low concentrations of selected aldehydes were produced in oils with a low PUFA content, lard and dripping when subjected to the above heating episodes. Samples of repeatedly used, PUFA-rich culinary oils obtained from restaurants also contained high levels of each class of aldehyde. The dietary, physiological and toxicological ramifications of the results obtained are discussed.

A comparative evaluation of the metabolic profiles of normal and inflammatory knee-joint synovial fluids by high resolution proton NMR spectroscopy.

High resolution 1H NMR spectroscopy has been employed to investigate the metabolic profile of healthy human knee-joint synovial fluid (SF) and the biochemical data acquired have been compared with those of matched serum, and inflammatory knee-joint SF samples. Results obtained indicate that the healthy human knee-joint has a hypoxic status (high lactate level when expressed relative to that of paired serum) that is milder than that of the inflamed human knee-joint. Moreover, normal SF differs from that of inflammatory SF in that it contains little or no NMR-detectable lipoprotein-associated fatty acids and 'acute-phase' glycoproteins, an observation reflecting the limited passage of these macromolecules from plasma into the synovial space in healthy subjects.

Generation of substance P carbamate in neutral aqueous solution. Relevance to inflammatory joint diseases.

High-field proton (1H) nuclear magnetic resonance (NMR) spectroscopy has been employed to evaluate the formation of substance P carbamate in aqueous solution. Equilibration of substance P with physiologically relevant concentrations of bicarbonate (2.50 x 10(-2) mol.dm-3) at pH 7.00 generated a new multiplet signal centred at 4.13 ppm in its NMR spectrum, characteristic of the alpha-proton of peptide carbamate species. High-field 1H NMR spectroscopy also demonstrated that the model dipeptide, Arg-Gly, formed a carbamate in neutral aqueous solutions containing 2.50 x 10(-2) mol.dm-3 HCO3-. The physiological significance of these results is discussed in view of the central roles of vasoactive neuropeptides in human joint diseases and the hypercapnic environment of the inflamed rheumatoid joint.

The efficacy and sedative profile of astemizole and cetirizine in the treatment of grass pollen hayfever in general practice.

The antihistamines astemizole and cetirizine were compared for the treatment of grass pollen hayfever in 158 patients who received either astemizole (10 mg od) or cetirizine (10 mg od) for a four week period in a randomised double-blind, double-dummy, parallel group, comparative assessment. Patients visited their general practitioner (GP) on three occasions and at each visit the GP made an assessment of the severity of individual hayfever symptoms. Patients recorded daily throughout the study the severity of their hayfever symptoms and their level of daytime sedation on visual analogue scales in a diary card. The primary measure of efficacy was the overall symptom visual analogue scores recorded daily by the patients. The results demonstrate that these two antihistamines are equally effective treatments for hayfever, in terms of magnitude of symptom relief, speed of onset of symptom improvement and lack of sedative effect.