Nitro-, Cyano-, and Methylfuroxans,and Their Bis-Derivatives: From Green Primary to Melt-Cast Explosives

In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalpies using highly accurate multilevel procedures W2-F12 and/or W1-F12 in conjunction with the atomization energy approach and isodesmic reactions with the domain-based local pair natural orbital (DLPNO) modifications of the coupled-cluster techniques. Apart from this, we proposed reliable benchmark values of the formation enthalpies of furoxan and a number of its (azo)bis-derivatives. Additionally, we reported the previously unknown crystal structure of 3-cyano-4-nitrofuroxan. Among the monocyclic compounds, 3-nitro-4-cyclopropyl and dicyano derivatives of furoxan outperformed trinitrotoluene, a benchmark melt-cast explosive, exhibited decent thermal stability (decomposition temperature >200 °C) and insensitivity to mechanical stimuli while having notable volatility and low melting points. In turn, 4,4′-azobis-dicarbamoyl furoxan is proposed as a substitute of pentaerythritol tetranitrate, a benchmark brisant high explosive. Finally, the application prospects of 3,3′-azobis-dinitro furoxan, one of the most powerful energetic materials synthesized up to date, are limited due to the tremendously high mechanical sensitivity of this compound. Overall, the investigated derivatives of furoxan comprise multipurpose green energetic materials, including primary, secondary, melt-cast, low-sensitive explosives, and an energetic liquid.     

Modeling and testing of snow penetration

Penetration by a cone into snow is commonly used to characterize snow properties. However, the effects of the diameter and half-angle of the cone on the mechanical properties of snow have not been systematically studied. In addition, no estimation of material parameters in a physically-based model has been made such that the results from penetration provide only an index of snow properties. In this paper, modeling and experimental methods are used to examine the effects of cone geometry on the maximum penetration force and associated hardness, with penetrometers ranging from 2.5 to 4 mm in diameter, 15° to 45° in cone half-angle, and testing both fine-grained and coarse-grained snows. The material point method, in conjunction with the Drucker–Prager cap plasticity model, was used to obtain the theoretical penetration force-distance relationship. Global sensitivity studies were conducted that indicate that the cohesion accounts for 86% of the penetration force, followed distantly by friction angle which accounts for 27%. A general trend, for the simulation results was established: for a given half-angle, the penetration force increases with the increase of diameter which holds for most of the test data as well; for a given diameter, the penetration force decreases with the increase of half-angle, which holds for some of the test data. In addition, for a given half-angle, the hardness decreases with the increase of diameter; for a given diameter, the hardness decreases with the increase of half-angle. To take into consideration the uncertainty of test data, a simple interval-based metric was used to compare test data with simulation results; the comparison was satisfactory. The material parameters from the simulations can thus be considered as calibrated ones for the snow studied.     

AN EFFICIENT SEQUENTIAL DESIGN FOR SENSITIVITY EXPERIMENTS

In sensitivity experiments, the response is binary and each experimental unit has a critical stimulus level that cannot be observed directly. It is often of interest to estimate extreme quantiles of the distribution of these critical stimulus levels over the tested products. For this purpose a new sequential scheme is proposed with some commonly used models. By using the bootstrap repeated-sampling principle, reasonable prior distributions based on a historic data set are specified. Then, a Bayesian strategy for the sequential procedure is provided and the estimator is given. Further, a high order approximation for such an estimator is explored and its consistency is proven. A simulation study shows that the proposed method gives superior performances over the existing methods.     

Anion influenced self-assembly of stilbazolium derivative and acid-sensitive property of its corresponding gel

Two stilbazolium derivatives with different counter-anions (Br^?  and OH^? ) have been designed and synthesised. Different counter-anions cause different aggregation properties. The reason of this difference was investigated through concentration- and temperature-dependent ¹H NMR and IR spectra. When the counter-anion is OH^? , the stilbazolium derivative exhibits pronounced aggregation properties. The scanning electron microscope images of xerogels show the characteristic gelation morphologies of 3D fibrous network structures. X-ray diffraction and fluorescence spectroscopy studies have been carried out, and provide more information to define the molecular packing model in gelation states. Finally, the acid-sensing abilities of the xerogel film were studied.     

Finite element and sensitivity analysis of thermally induced flow instabilities

This paper presents a finite element algorithm for the simulation of thermo‐hydrodynamic instabilities causing manufacturing defects in injection molding of plastic and metal powder. Mold‐filling parameters determine the flow pattern during filling, which in turn influences the quality of the final part. Insufficiently, well‐controlled operating conditions may generate inhomogeneities, empty spaces or unusable parts. An understanding of the flow behavior will enable manufacturers to reduce or even eliminate defects and improve their competitiveness. This work presents a rigorous study using numerical simulation and sensitivity analysis. The problem is modeled by the Navier–Stokes equations, the energy equation and a generalized Newtonian viscosity model. The solution algorithm is applied to a simple flow in a symmetrical gate geometry. This problem exhibits both symmetrical and non‐symmetrical solutions depending on the values taken by flow parameters. Under particular combinations of operating conditions, the flow was stable and symmetric, while some other combinations leading to large thermally induced viscosity gradients produce unstable and asymmetric flow. Based on the numerical results, a stability chart of the flow was established, identifying the boundaries between regions of stable and unstable flow in terms of the Graetz number (ratio of thermal conduction time to the convection time scale) and B, a dimensionless ratio indicating the sensitivity of viscosity to temperature changes. Sensitivities with respect to flow parameters are then computed using the continuous sensitivity equations method. We demonstrate that sensitivities are able to detect the transition between the stable and unstable flow regimes and correctly indicate how parameters should change in order to increase the stability of the flow. Copyright © 2009 John Wiley & Sons, Ltd.     

Untersuchungen zur Empfindlichkeit der β-Rückstreumethode bei der Messung dünner Auftragsschichten mit einem 11C-Spezialpräparat

Die Bestimmung dünner Auftragsschichten auf bewegten Trāgermaterialien mit der β-Rūckstreumethode hängt wesentlich von der Empfindlichkeit der Messung und der Dynamik des Prozesses ab.

In diesem Beitrag wird für spezielle Stoffe der Einfluβ der Trāgermaterialien bei Mehrschichtproblemen auf die Empfindlichkeit untersucht.     

Sensitivity enhancement and matrix effect evaluation during summation of multiple transition pairs—case studies of clopidogrel and ramiprilat

Sensitivity enhancement via summation of multiple MRM transition pairs is gaining popularity in tandem mass spectrometric assays. Numerous validation experiments describing the assays for two model substrates, clopidogrel and ramiprilat, were performed. The quantitation of clopidogrel was achieved by the summation of transition pairs m/z 322.2 to m/z 212.0 and m/z 322.2 to m/z 184.0, while that of ramiprilat was achieved by the summation of transition pairs m/z 389.2 to m/z 206.1 and m/z 389.2 to m/z156.1. The use of summation approach achieved sensitivities of >2 fold for both compounds as compared with the reported single MRM transition pair assays. The validation experiments addressed some important assay development issues, such as: (a) lack of impact of matrix effect; (b) unequivocal verification of the percentage contribution of each MRM transition pair towards sensitivity; (c) sensitivity enhancement factor achieved by summation approach of MRM transition pairs; and (d) accurate prediction of quality control samples using summation approach vs a single MRM transition pair. In summary, the appropriateness of using two MRM transition pairs for quantitation was demonstrated for both clopidogrel and ramiprilat. Additionally, pharmacokinetic application of the MRM transition pair assays using a summation approach was established for the two compounds. Copyright © 2009 John Wiley & Sons, Ltd.     

大非球面镜的郎奇检验灵敏度理论研究及仿真分析

为了研究等间距直线条光栅的周期及其他相关参数的变化对大非球面镜朗奇检验法的影响，提出了一种评估郎奇检验灵敏度大小的新方法。其检验灵敏度定义为一个光栅周期所能检测到的镜面偏差大小能力。在朗奇检验的几何原理基础上，利用光线追迹法讨论了镜面偏差与朗奇光栅周期之间的关系，并以此推导出检验灵敏度公式，计算了抛物面镜的朗奇检测灵敏度。分析结果表明，如果给定镜子的规格参数及检验光路，朗奇检验灵敏度分别随着光栅周期间隔和半通光口径的变大而减小。     

Sensitivity enhancement in structural measurements by solid state NMR through pulsed spin locking

Free induction decay (FID) signals in solid state NMR measurements performed with magic angle spinning can often be extended in time by factors on the order of 10 by a simple pulsed spin locking technique. The sensitivity of a structural measurement in which the structural information is contained in the dependence of the integrated FID amplitude on a preceding evolution period can therefore be enhanced substantially by pulsed spin locking in the signal detection period. We demonstrate sensitivity enhancements in a variety of solid state NMR techniques that are applicable to selectively isotopically labeled samples, including 13C-15N rotational echo double resonance (REDOR), 13C-13C dipolar recoupling measurements using the constant-time finite-pulse radio-frequency-driven recoupling (fpRFDR-CT) and constant-time double-quantum-filtered dipolar recoupling (CTDQFD) techniques, and torsion angle measurements using the double quantum chemical shift anisotropy (DQCSA) technique. Further, we demonstrate that the structural information in the solid state NMR data is not distorted by pulsed spin locking in the detection period.