Spectroscopy strategy for solid propellants quality control

In this article, we highlight generalities about solid propellants (SPs) for space launch. SP is a composition of several ingredients basically oxidizer and reducing materials in order to guarantee the combustion reaction after initialization. SPs require high level control quality analysis methods due to their energetic nature with high probability of auto-inflammation, which presents a serious safety problem, thus, the spectroscopy analysis techniques are required to promote the SPs quality control accuracy. In this article, X ray diffraction (XRD), Fourier transform infrared (FTIR), and near infrared spectroscopy (NIRs) have been introduced as substantial analysis methods on SPs. The main parameters to be determined in the process of the quality control are the crystalline structure using XRD and molecular structure and molecular identification using FTIR. While NIRs combined with chemometrics proved to be a quick and non-destructive analysis tool, it provides concise quantitative data so it has great potential to meet the SPs control quality analysis requirements.     

Diffusion of non-volatile phenolic compounds in zeolite beta and silicalite in liquid phase

The present study aims to systematically investigate the adsorption kinetics of “non-volatile” phenolic compounds with different critical diameters (p-coumaric acid, ferulic acid, sinapinic acid, p-hydroxybenzoic acid, vanillic acid, syringic acid, and vanillin) onto zeolite beta and silicalite in several solvents. In the aqueous phase, the corrected diffusivity of non-volatile phenolic compounds is 2–5 orders of magnitude smaller than that of volatile aromatic compounds with the same critical diameter. On the other hand, the corrected diffusivity in zeolite beta is on the same order of magnitude among non-volatile phenolic compounds, despite the significant difference in critical diameter of the adsorbate. This suggests that the intracrystalline diffusivity of the non-volatile adsorbate is strongly affected by its original molecular immobility, rather than by the size (narrowness) of the adsorbate and micropore aperture. Non-volatility is considered to remarkably lower the molecular mobility of adsorbate on the surface of zeolite, even in the liquid phase. In addition, the intracrystalline diffusivity of non-volatile adsorbate is strongly affected by the type of solvent, and a close correlation was found between intracrystalline diffusivity and adsorption affinity. Revelations as to the kinetic behavior of non-volatile adsorbate in zeolite are expected to supply more information on the kinetic separation of compounds in the liquid phase. The significant difference in diffusivity among non-volatile and volatile adsorbates in zeolite leads to the possibility of kinetic separation among these adsorbates.     

Copper‐Catalyzed Intramolecular Oxidative Amination of Unactivated Internal Alkenes

A copper‐catalyzed oxidative amination of unactivated internal alkenes has been developed. The Wacker‐type oxidative alkene amination reaction is traditionally catalyzed by a palladium through a mechanism involving aminopalladation and β‐hydride elimination. Replacing the precious and scarce palladium with a cheap and abundant copper for this transformation has been challenging because of the difficulty associated with the aminocupration of internal alkenes. The combination of a simple copper salt, without additional ligand, as the catalyst and Dess–Martin periodinane as the oxidant, promotes efficiently the oxidative amination of allylic carbamates and ureas bearing di‐ and trisubstituted alkenes leading to oxazolidinones and imidazolidinones. Preliminary mechanistic studies suggested a hybrid radical–organometallic mechanism involving an amidyl radical cyclization to form the key C?N bond.     

Immobilization of the Gas Signaling Molecule H2S by Radioisotopes: Detection,Quantification, and In Vivo Imaging

Hydrogen sulfide (H₂S) has multifunctional roles as a gas signaling molecule in living systems. However, the efficient detection and imaging of H₂S in live animals is very challenging. Herein, we report the first radioisotope‐based immobilization technique for the detection, quantification, and in vivo imaging of endogenous H₂S. Macrocyclic ⁶⁴Cu complexes that instantly reacted with gaseous H₂S to form insoluble ⁶⁴CuS in a highly sensitive and selective manner were prepared. The H₂S concentration in biological samples was measured by a thin‐layer radiochromatography method. When ⁶⁴Cu–cyclen was injected into mice, an elevated H₂S concentration in the inflamed paw was clearly visualized and quantified by Cerenkov luminescence and positron emission tomography (PET) imaging. PET imaging was also able to pinpoint increased H₂S levels in a millimeter‐sized infarcted lesion of the rat heart.     

Characterization of conformers and dimers of antithrombin by capillary electrophoresis-quadrupole-time-of-flight mass spectrometry

Antithrombin (AT) is a plasma glycoprotein which possesses anticoagulant and anti-inflammatory properties. AT exhibits various forms, among which are native, latent and heterodimeric ones. We studied the potential of capillary electrophoresis-mass spectrometry (CE-MS) using a sheath liquid interface, electrospray ionization (ESI), and a quadrupole-time-of-flight (Q-TOF) mass spectrometer to separate and quantify the different AT forms. For CE separation, a neutral polyvinyl alcohol (PVA) coated capillary was employed. The protein conformation was preserved by using a background electrolyte (BGE) at physiological pH. A sheath liquid of isopropanol-water 50:50 (v/v) with 14 mM ammonium acetate delivered at a flow rate of 120 μL h⁻¹ resulted in optimal signal intensities. Each AT form exhibited a specific mass spectrum, allowing unambiguous distinction. Several co-injection experiments proved that latent AT had a higher electrophoretic mobility (μ_ep) than native AT, and that these conformers could associate to form a heterodimer during the CE analysis. The developed CE-MS method enabled the detection and quantitation of latent and heterodimeric forms in a commercial AT preparation stored at room temperature for three weeks.     

A convenient guideline to determine if two Y‐STR profiles are from the same lineage

Y chromosome STR loci are used in forensics primarily for identification purposes by determining the male lineages. The Henan province in China has established a large Y‐STR (>200 000 profiles) database for criminal investigations. A large proportion of the Y‐STR profiles in the database were generated using either the Applied Biosystems Yfiler^? or Yfiler^? Plus PCR Amplification kits. The additional loci in the Yfiler Plus kit as compared to the Yfiler kit results in a concomitant cumulative mutation rate increase across the loci. Therefore, in those cases when two profiles have one to a few mismatched loci, it is difficult to determine if they are from the same lineage. In this study, 7405 unrelated male profiles were manually selected from the database. Analysis showed higher power of discrimination than the corresponding Yfiler haplotypes. Further, the distributions of the number of mismatched loci and the mismatched steps were generated for father‐son, grandfather‐grandson, uncle‐nephew, and cousins (i.e. one, two, three, and four meioses, respectively) by exhaustive pairwise comparison of the unrelated profiles using a dynamic programming approach. The same distributions were generated for unrelated pairs with mutation rates of the loci. With the distributions, the false negative and false positive rates were determined. Two Yfiler profiles with ≤2 mismatched loci or ≤2 steps are more likely from the same lineage than unrelated lineages, and two Yfiler Plus profiles with ≤4 mismatched loci or ≤5 mismatched steps are more likely from the same lineage.     

Mixed‐mode chromatography integrated with high‐performance liquid chromatography for protein analysis and separation: Using bovine serum albumin and lysozyme as the model target

A type of mixed‐mode chromatography was integrated with high‐performance liquid chromatography for protein analysis and separation. The chromatographic behavior was tested using bovine serum albumin and lysozyme as model proteins. For the mixed‐mode column, the silica beads were activated with γ‐(2,3‐epoxypropoxy)‐propytrimethoxysilane and coupled with 4‐mercaptopyridine as the functional ligand. The effects of pH, salt, and the organic solvent conditions of the mobile phase on the retention behavior were studied, which provided valuable clues for separation strategy. When eluted with a suitable pH gradient, salt concentration gradient, and acetonitrile content gradient, the separation behavior of bovine serum albumin and lysozyme could be controlled by altering the conditions of the mobile phase. The results indicated this type of chromatography might be a useful method for protein analysis and separation.     

Visible Light Activation of Boronic Esters Enables Efficient Photoredox C(sp2)–C(sp3) Cross‐Couplings in Flow

We report herein a new method for the photoredox activation of boronic esters. Using these reagents, an efficient and high‐throughput continuous flow process was developed to perform a dual iridium‐ and nickel‐catalyzed C(sp²)–C(sp³) coupling by circumventing solubility issues associated with potassium trifluoroborate salts. Formation of an adduct with a pyridine‐derived Lewis base was found to be essential for the photoredox activation of the boronic esters. Based on these results we were able to develop a further simplified visible light mediated C(sp²)–C(sp³) coupling method using boronic esters and cyano heteroarenes under flow conditions.     

Diastereo‐ and Enantioselective Copper(I)‐Catalyzed Intermolecular [3+2] Cycloaddition of Azomethine Ylides with β‐Trifluoromethyl β,β‐Disubstituted Enones

Reported herein is an asymmetric [3+2] cycloaddition reaction of azomethine ylides with β‐trifluoromethyl β,β‐disubstituted enones, a reaction which is enabled by a Ming‐Phos‐derived copper(I) catalyst (Ming‐Phos=chiral sulfinamide monophosphines, Figure 2 ). This method provides scalable and efficient access to the highly substituted pyrrolidines with a trifluoromethylated, all‐carbon quaternary stereocenter in good yields with up to greater than 20:1 d.r. and 98 % ee. The reaction has a broad substrate scope and tolerates a wide range of functional groups.