Automatic assignment of absolute configuration from 1D NMR data

Opposite enantiomers exhibit different NMR properties in the presence of an external common chiral element, and a chiral molecule exhibits different NMR properties in the presence of external enantiomeric chiral elements. Automatic prediction of such differences, and comparison with experimental values, leads to the assignment of the absolute configuration. Here two cases are reported, one using a dataset of 80 chiral secondary alcohols esterified with (R)-MTPA and the corresponding 1H NMR chemical shifts and the other with 94 13C NMR chemical shifts of chiral secondary alcohols in two enantiomeric chiral solvents. For the first application, counterpropagation neural networks were trained to predict the sign of the difference between chemical shifts of opposite stereoisomers. The neural networks were trained to process the chirality code of the alcohol as the input, and to give the NMR property as the output. In the second application, similar neural networks were employed, but the property to predict was the difference of chemical shifts in the two enantiomeric solvents. For independent test sets of 20 objects, 100% correct predictions were obtained in both applications concerning the sign of the chemical shifts differences. Additionally, with the second dataset, the difference of chemical shifts in the two enantiomeric solvents was quantitatively predicted, yielding r2 0.936 for the test set between the predicted and experimental values.

Positive Solutions of the Dirichlet Problem for the One-dimensional Minkowski-Curvature Equation

We discuss existence and multiplicity of positive solutions of the Dirichlet problem for the quasilinear ordinary differential equation-(u' / root 1 - u'(2))' = f(t, u). Depending on the behaviour of f = f(t, s) near s = 0, we prove the existence of either one, or two, or three, or infinitely many positive solutions. In general, the positivity of f is not required. All results are obtained by reduction to an equivalent non-singular problem to which variational or topological methods apply in a classical fashion.

A one-dimensional prescribed curvature equation modeling the corneal shape

We prove existence, uniqueness, and stability of solutions of the prescribed curvature problem (u'/root 1 + u'(2))' = au - b/root 1 + u'(2) in [0, 1], u'(0) = u(1) = 0, for any given a > 0 and b > 0. We also develop a linear monotone iterative scheme for approximating the solution. This equation has been proposed as a model of the corneal shape in the recent paper (Okrasinski and Plociniczak in Nonlinear Anal., Real World Appl. 13:1498-1505, 2012), where a simplified version obtained by partial linearization has been investigated.

A fluorescente bicyclic Calix[4] Arene-Oxacyclophane with planar chirality: Resolution, chiroptical, properties, and absolute configuration.

A new inherently chiral calix[4]arene ICC 1 has been disclosed. The dissymmetry of 1 is generated from a chirality plane in the quinol moiety of a 1,3-bridged bicyclic calix[4]arene. ICC 1 has been resolved by enantioselective HPLC, and the chiroptical properties of both isolated antipodes (pS)-1 and (pR)-1 confirm their enantiomeric nature. The absolute configuration of the (pS)-1/(pR)-1 enantiomeric pair was established through time-dependent density functional theory (TDDFT) calculations of electronic circular dichroism (CD) spectra. (C) 2014 Elsevier Ltd. All rights reserved.

A one-dimensional prescribed curvature equation modeling the corneal shape.

We prove existence, uniqueness, and stability of solutions of the prescribed curvature problem (u'/root 1 + u'(2))' = au - b/root 1 + u'(2) in [0, 1], u'(0) = u(1) = 0, for any given a > 0 and b > 0. We also develop a linear monotone iterative scheme for approximating the solution. This equation has been proposed as a model of the corneal shape in the recent paper (Okrasinski and Plociniczak in Nonlinear Anal., Real World Appl. 13:1498-1505, 2012), where a simplified version obtained by partial linearization has been investigated.

Positive radial solutions of the Dirichlet problem for the Minkowski-Curvature equation in a ball

We study the existence and multiplicity of positive radial solutions of the Dirichlet problem for the Minkowski-curvature equation { -div(del upsilon/root 1-vertical bar del upsilon vertical bar(2)) in B-R, upsilon=0 on partial derivative B-R,B- where B-R is a ball in R-N (N >= 2). According to the behaviour off = f (r, s) near s = 0, we prove the existence of either one, two or three positive solutions. All results are obtained by reduction to an equivalent non-singular one-dimensional problem, to which variational methods can be applied in a standard way.

Optimisation of exposure parameters for spinal curvature measurements in paediatric radiography

This review aims to identify strategies to optimise radiography practice using digital technologies, for full spine studies on paediatrics focusing particularly on methods used to diagnose and measure severity of spinal curvatures. The literature search was performed on different databases (PubMed, Google Scholar and ScienceDirect) and relevant websites (e.g., American College of Radiology and International Commission on Radiological Protection) to identify guidelines and recent studies focused on dose optimisation in paediatrics using digital technologies. Plain radiography was identified as the most accurate method. The American College of Radiology (ACR) and European Commission (EC) provided two guidelines that were identified as the most relevant to the subject. The ACR guidelines were updated in 2014; however these guidelines do not provide detailed guidance on technical exposure parameters. The EC guidelines are more complete but are dedicated to screen film systems. Other studies provided reviews on the several exposure parameters that should be included for optimisation, such as tube current, tube voltage and source-to-image distance; however, only explored few of these parameters and not all of them together. One publication explored all parameters together but this was for adults only. Due to lack of literature on exposure parameters for paediatrics, more research is required to guide and harmonise practice.

Optimisation of paediatrics computed radiography for full spine curvature measurements using a phantom: a pilot study

Aim: Optimise a set of exposure factors, with the lowest effective dose, to delineate spinal curvature with the modified Cobb method in a full spine using computed radiography (CR) for a 5-year-old paediatric anthropomorphic phantom. Methods: Images were acquired by varying a set of parameters: positions (antero-posterior (AP), posteroanterior (PA) and lateral), kilo-voltage peak (kVp) (66-90), source-to-image distance (SID) (150 to 200cm), broad focus and the use of a grid (grid in/out) to analyse the impact on E and image quality (IQ). IQ was analysed applying two approaches: objective [contrast-to-noise-ratio/(CNR] and perceptual, using 5 observers. Monte-Carlo modelling was used for dose estimation. Cohen’s Kappa coefficient was used to calculate inter-observer-variability. The angle was measured using Cobb’s method on lateral projections under different imaging conditions. Results: PA promoted the lowest effective dose (0.013 mSv) compared to AP (0.048 mSv) and lateral (0.025 mSv). The exposure parameters that allowed lower dose were 200cm SID, 90 kVp, broad focus and grid out for paediatrics using an Agfa CR system. Thirty-seven images were assessed for IQ and thirty-two were classified adequate. Cobb angle measurements varied between 16°±2.9 and 19.9°±0.9. Conclusion: Cobb angle measurements can be performed using the lowest dose with a low contrast-tonoise ratio. The variation on measurements for this was ±2.9° and this is within the range of acceptable clinical error without impact on clinical diagnosis. Further work is recommended on improvement to the sample size and a more robust perceptual IQ assessment protocol for observers.