Solid-State 17O NMR studies of organic and biological molecules: Recent advances and future directions

This Trends article highlights the recent advances published between 2012 and 2015 in solid-state ¹⁷O NMR for organic and biological molecules. New developments in the following areas are described: (1) new oxygen-containing functional groups, (2) metal organic frameworks, (3) pharmaceuticals, (4) probing molecular motion in organic solids, (5) dynamic nuclear polarization, and (6) paramagnetic coordination compounds. For each of these areas, the author offers his personal views on important problems to be solved and possible future directions.     

Computationally Efficient Changepoint Detection for a Range of Penalties

In the multiple changepoint setting, various search methods have been proposed, which involve optimizing either a constrained or penalized cost function over possible numbers and locations of changepoints using dynamic programming. Recent work in the penalized optimization setting has focused on developing an exact pruning-based approach that, under certain conditions, is linear in the number of data points. Such an approach naturally requires the specification of a penalty to avoid under/over-fitting. Work has been undertaken to identify the appropriate penalty choice for data-generating processes with known distributional form, but in many applications the model assumed for the data is not correct and these penalty choices are not always appropriate. To this end, we present a method that enables us to find the solution path for all choices of penalty values across a continuous range. This permits an evaluation of the various segmentations to identify a suitable penalty choice. The computational complexity of this approach can be linear in the number of data points and linear in the difference between the number of changepoints in the optimal segmentations for the smallest and largest penalty values. Supplementary materials for this article are available online.     

刮片式制冰蓄冷性能的实验研究

对刮片式动态冰浆制取系统进行实验研究,分析系统的能效比和蒸发器进出口温度、冷凝器进出口温度以及冷凝水和盐溶液流量曲线变化。研究结果表明:对制冷量为20kW的刮片式制冰装置,盐溶液有1.5℃的过冷度,随着盐溶液浓度越高其冰点越低,系统的能效系数最高达到1.9,有利于制冰蓄冷节能。     

On duality concepts in fractional programming

The paper (Part I) describes an approach to duality in fractional programming on the basis of another kind of conjugate functions. The connections to some duality concepts (the Lagrange-duality and duality concepts of Craven and Schaible) are investigated and some new proofs of strong duality theorems are given.     

Path-following barrier and penalty methods for linearly constrained problems

In the present paper some barrier and penalty methods (e.g. logarithmic barriers, SUMT, exponential penalties), which define a continuously differentiable primal and dual path, applied to linearly constrained convex problems are studied, in particular, the radius of convergence of Newton’s method depending on the barrier and penalty para-meter is estimated, Unlike using self-concordance properties the convergence bounds are derived by direct estimations of the solutions of the Newton equations. The obtained results establish parameter selection rules which guarantee the overall convergence of the considered barrier and penalty techniques with only a finite number of Newton steps at each parameter level. Moreover, the obtained estimates support scaling method which uses approximate dual multipliers as available in barrier and penalty methods     

Combined prostate diffusion tensor imaging and dynamic contrast enhanced MRI at 3T — quantitative correlation with biopsy

The purpose of this work was to compare diagnostic accuracy of Diffusion Tensor Imaging (DTI), dynamic contrast-enhanced magnetic resonance imaging (DCE MRI) and their combination in diagnosing prostate cancer. Twenty-five patients with clinical suspicion of prostate cancer underwent MRI, prior to transrectal ultrasound-guided biopsies. MRI data were correlated to biopsy results. Logistic regression models were constructed for the DTI parameters, DCE MRI parameters, and their combination. The areas under the receiver operator characteristic curves (AUC) were compared between the models. The nonparametric Wilcoxon signed rank test was used for statistical analysis. The sensitivity and specificity values were respectively 81% (74–87%) and 85% (79–90%) for DTI and 63% (55–70%) and 90% (85–94%) for DCE. The combination “DTI or DCE MRI” had 100% (97–100%) sensitivity and 77% (69–83%) specificity, while “DTI and DCE MRI” had 44% (37–52%) sensitivity and 98% (94–100%) specificity. The AUC for DTI+DCE parameters was significantly higher than that for either DTI (0.96 vs. 0.92, P=.0143) or DCE MRI parameters (0.96 vs. 0.87, P=.00187) alone. In conclusion, the combination of DTI and DCE MRI has significantly better accuracy in prostate cancer diagnosis than either technique alone.     

Anionic Conduction in Blends of Poly(Pyridinium Ethyl Methacrylate Perchloride) and Poly[Oligo(Oxyethylene) Methacrylate-Co-Acrylamide]

Abstract

Blends of poly(pyridinium ethyl methacrylate perchloride) and poly[oligo(oxyethylene) methacrylate-co-acrylamide] were prepared, and the ionic conductivity and mobility of the blends were investigated. Results indicate that both the transference of perchlorate anion and the dissociation of the polymeric salt in the comblike polyether obey the thermoactivation mechanism, and that the perchlorate anion in the blends is free.     

The Structure of a Non-Symmetric Disordered Tetramer: A Crystallographic and Solid State Multinuclear NMR Study of the Properties of 3(5)-Ethyl-5(3)-Phenyl-1H-Pyrazole

The X-ray structure and the solid-state NMR measurements, mainly ¹⁵N CPMAS of the labelled compound, allow to determine the static and dynamic properties of 3(5)-ethyl-5(3)-phenyl-1H-pyrazole. The compound is a tetramer formed by three 5-ethyl-3-phenyl-1H-pyrazole and one 3-ethyl-5-phenyl-1H-pyrazole tautomers in dynamic equilibrium with the complementary situation.     

Design,Synthesis and Structural Analysis of New Macrocycles Containing Dispiro-1,3-dioxane Units

The synthesis and the structure of new macrocycles containing semiflexible dispiro-1,3-dioxane units is reported. The structural analysis of the compounds is performed by high field NMR spectra, mass spectrometry investigations (MALDI, ESI-MS) and the solid state molecular structure obtained for two compounds by single crystal X-ray diffractometry. The dynamics of the macrocycles promoted by the flipping of the middle cyclohexane ring of the dispirane units is investigated using low temperature NMR experiments.

New macrocycles containing dispiro-1,3-dioxane units were investigated by NMR, X-ray diffractometry and mass spectrometry