Is reliability a new science? A paper from the panel session held at the 10th International Conference on Mathematical Methods in Reliability

The 10th International Conference on Mathematical Methods in Reliability, MMR 2017, held in Grenoble, France during July 3‐7, entailed a panel discussion entitled “Is reliability a new science?” with Mark Brown, Regina Liu, William Meeker, Sheldon Ross, and Nozer Singpurwalla as panelists. Bill Meeker also doubled as a chair and as a moderator of the panel. The panel discussion was spawned by the recent appearance of a book by Professor Paolo Rocchi, Docent Emeritus of IBM, titled “Reliability is a new science: Gnedenko was right” published by Springer in 2017. The panel discussion was well attended and enthusiastically received and could serve as a forerunner to other such panel discussions at future MMR conferences. This paper presents some elements from the lively debate generated by this discussion.     

SOLUBILIZATION OF HYDROCORTISONE IN LYOTROPIC LIQUID CRYSTALS

The solubilization of hydrocortisone (HC) in lamellar liquid crystals (LC) containing monoglyceride laurate (MGL) and water was studied. The maximum capacity of the 70:30 (wt/wt) MGL/water system to solubilize HC has been found to be larger than any other reported solubilization system (such as microemulsions and micelles), and exceeded 1.0 wt%.

The systems were tested by polarized light microscopy, small angle X-ray diffraction, differential scanning calorimetry and deuterium NMR. It was found that the addition of HC caused no change in the interplanar spacing of the system, and had no effect on the gel-to-LC transition temperature. However, the solubilization enlarged the quadrupole splitting of the water deuteron. These results suggest that the HC molecules are positioned in the vicinity of, or within, the polar head groups of the monoglyceride.     

Analysis of the complex formation of heparin with protamine by light scattering and analytical ultracentrifugation: implications for blood coagulation management

Heparin, a linear glycosaminoglycan, is used in different forms in anticoagulation treatment. Protamine, a highly positive charged peptide containing about 32 amino acids, acts as an antagonist for heparin to restore normal blood coagulation. The complex formation of protamine with heparin was analyzed by a combination of analytical ultracentrifugation and light scattering. Titration of heparin with protamine in blood plasma preparations results in a drastic increase of turbidity, indicating the formation of nanoscale particles. A similar increase of turbidity was observed in physiological saline solution with or without human serum albumin (HSA). Particle size analysis by analytical ultracentrifugation revealed a particle radius of approximately 30 nm for unfractionated heparin and of approximately 60 nm for low molecular weight heparin upon complexation with excess protamine, in agreement with atomic force microscopy data. In the absence of HSA, larger and more heterogeneous particles were observed. The particles obtained were found to be stable for hours. The particle formation kinetics was analyzed by light scattering at different scattering angles and was found to be complete within several minutes. The time course of particle formation suggests a condensation reaction, with sigmoidal traces for low heparin concentrations and quasi-first-order reaction for high heparin concentrations. Under all conditions, the final scattering intensity reached after several minutes was found to be proportional to the amount of heparin in the blood plasma or buffer solution, provided that excess protamine was available and no multiple scattering occurred. On the basis of a direct relation between particle concentration and the heparin concentration present before protaminization, a light scattering assay was developed which permits the quantitative analysis of the heparin concentration in blood plasma and which could complement or even replace the activated clotting time test, which is currently the most commonly used method for blood coagulation management.     

Selective detection of ¹³CHD₂ signals from a mixture of ¹³CH₃/¹³CH₂D/¹³CHD₂ methyl isotopomers in proteins

In NMR spectra of partially deuterated proteins methyl correlations are commonly observed as a combination of signals from 13CH?, 13CH?D and 13CHD? isotopomers. In a number of NMR applications, methyl groups of the 13CHD? variety are targeted because of their AX-like character and concomitant simplification of the involved relaxation mechanisms. Although complete elimination of signals from 13CH?D methyl groups can be easily achieved in such applications, if the magnetization is not transferred through deuterium nuclei, efficient suppression of usually stronger 13CH? peaks is more problematic. A pair of simple pulse-scheme elements are presented that achieve almost complete suppression of 13CH? signals in the mixtures of 13CH?/13CH?D/13CHD? methyl isotopomers of small proteins at the expense of a moderate (～20-to-40%) reduction in intensities of the targeted 13CHD? groups. The approaches described are based purely on scalar coupling (1J(CH)) evolution properties of different 13C and 1H transitions within 13CH? spin-systems and are superior to magnetization transfer through deuterons with respect to sensitivity of the detected 13CHD? methyl signals.     

Mechanisms of dendrites occurrence during crystallization: Features of the ice crystals formation

Dendrites formation in the course of crystallization presents very general phenomenon, which is analyzed in details via the example of ice crystals growth in deionized water. Neutral molecules of water on the surface are combined into the double electric layer (DEL) of oriented dipoles; its field reorients approaching dipoles with observable radio-emission in the range of 150 kHz. The predominant attraction of oriented dipoles to points of gradients of this field induces dendrites growth from them, e.g., formation of characteristic form of snowflakes at free movement of clusters through saturated vapor in atmosphere. The constant electric field strengthens DELs' field and the growth of dendrites. Described phenomena should appear at crystallization of various substances with dipole molecules, features of radio-emission can allow the monitoring of certain processes in atmosphere and in technological processes. Crystallization of particles without constant moments can be stimulated by DELs of another nature with attraction of virtual moments of particles to gradients of fields and corresponding dendrites formation.     

Franck–Hertz effect in cathodo- and photoluminescence of wide-gap materials

A brief overview of previously obtained and novel data on the manifestations of an analogue of Franck–Hertz effect in photo- and cathodoluminescence of wide-gap inorganic materials is presented. On the example of NaCl:Tl⁺ and MgO:Cr³⁺ single crystals, the excitation processes of the luminescence of 6s² Tl⁺ ions and 3d³ Cr³⁺ ions by 5–15 keV electrons or 5–20 eV photons at 6–420 K have been studied. The rapid processes of the direct energy transfer to Tl⁺ by hot conduction electrons or to Cr³⁺ centers by hot electrons and/or hot valence holes have been separated from rapid excitonic and more inertial electron–hole processes.     

Effects of energy spread on brightness and coherence of undulator sources

The (spectral) brightness for partially transverse coherent sources such as synchrotron radiation and free‐electron laser sources can be defined as the maximum of the Wigner distribution. Then, the brightness includes information on both coherence and wavefront characteristics of the radiation field. For undulator sources, it is customary to approximate the single‐electron electric field at resonance with a Gaussian beam, leading to great simplifications. Attempts to account for the modified spatial and angular profile of the undulator radiation in the presence of detuning due to energy spread, currently build on the simplified brightness expression derived under the assumption of Gaussian beams. The influence of energy spread on undulator radiation properties is becoming important in view of diffraction‐limited rings with ultralow emittance coming on‐line. Here the effects of energy spread on the brightness of undulator radiation at resonance are discussed, as well as relevant relations with coherence properties.     

Synthesis and Post-Processing of Chemically Homogeneous Nanothreads from 2,5-Furandicarboxylic Acid**

Compared with conventional, solution-phase approaches, solid-state reaction methods can provide unique access to novel synthetic targets. Nanothreads—one-dimensional diamondoid polymers formed through the compression of small molecules—represent a new class of materials produced via solid-state reactions, however, the formation of chemically homogeneous products with targeted functionalization represents a persistent challenge. Through careful consideration of molecular precursor stacking geometry and functionalization, we report here the scalable synthesis of chemically homogeneous, functionalized nanothreads through the solid-state polymerization of 2,5-furandicarboxylic acid. The resulting product possesses high-density, pendant carboxyl functionalization along both sides of the backbone, enabling new opportunities for the post-synthetic processing and chemical modification of nanothread materials applicable to a broad range of potential applications.     

Synthesis and crystal structures of the triphenylstannyl esters of N-phthaloyl-glycine and -leucine

Triphenyltin N-phthaloylglycinate crystallizes from ethanol as a bridged, cyclic hexamer (rhombohedral R3 space group, a = 19.928(3) Å, α = 116.47(2)⁰; Z = 6) and triphenyltin N-phthaloylleucinate as a monomeric molecule (orthorhombic Pbca space group, a = 18.032(6), b = 26.992(7), c = 11.705(4) Å; Z = 8).