Structural elucidation of V‐type nerve agents by liquid chromatography/electrospray ionization mass spectrometry

V‐nerve agents present information‐poor spectra, both in GC‐EI‐MS and LC‐ESI‐MS/MS, with dominant fragments/product ions corresponding to the amine‐containing residue. Hence, derivatives/isomers with the same amine residue exhibit similar mass spectral patterns, leading to ambiguity in the phosphonate structure. We present a simple approach for their structural elucidation based on two complementary experiments: ESI‐MS/MS of the original compound, which provides information about the amine moiety, and ESI‐MS/MS of the phosphonic acid hydrolysis products generated by N‐iodosuccinimide, which provides ions' characteristic of the phosphonate structure. This approach enables the structural elucidation of the original V‐agents with a higher degree of certainty.     

Solving systems of polynomial equations by bounded and real homotopy

Summary The homotopy method for solving systems of polynomial equations proposed by Chow, Mallet-Paret and Yorke is modified in two ways. The first modification allows to keep the homotopy solution curves bounded, the second one to work with real polynomials when solving a system of real equations. For the first method numerical results are presented.     

Antibody recognition of chiral surfaces. Enantiomorphous crystals of leucine-leucine-tyrosine

Monoclonal antibodies were selected after immunization with crystals of the tripeptide l-leucine-l-leucine-l-tyrosine. They interact with the tripeptide crystals, but do not interact with the tripeptide molecule, with other crystalline surfaces, or with adsorbed protein. The interactions of two antibodies with crystals of l-Leu-l-Leu-l-Tyr and of its enantiomer d-Leu-d-Leu-d-Tyr were characterized in depth. Antibody 48E is stereoselective and enantioselective: it recognizes only the [011] faces of the l-Leu-l-Leu-l-Tyr crystals, and not the enantiomorphous [011] faces of d-Leu-d-Leu-d-Tyr crystals, or any other faces of either crystal. In contrast, antibody 602E is poorly stereoselective and is not enantioselective: it recognizes the crystals of both enantiomers, interacting with a number of different faces of each. The different recognition patterns are explained on the basis of the nature of the interactions and the structure of the interacting surfaces. Understanding this antibody specificity advances our general understanding of surface recognition and transfer of chiral information across biological interfaces.     

Strong light‐matter coupling between a molecular vibrational mode in a PMMA film and a low‐loss mid‐IR microcavity

Microcavity devices exhibiting strong light‐matter coupling in the mid‐infrared spectral range offer the potential to explore exciting open physical questions pertaining to energy transfer between heat and light and can lead to a new generation of efficient wavelength tunable mid‐infrared sources of coherent light based on polariton Bose‐Einstein Condensation. Vibrational transitions of organic molecules, which often have strong absorption peaks in the infrared and considerably narrower linewidths than organic excitonic resonances, can generate polaritonic states in the mid‐infrared spectral range using microcavity devices. Here, narrow linewidth polaritonic resonances are exhibited in the mid‐infrared by coupling the carbonyl stretch vibrational transition of a polymethyl methacrylate film to the photonic resonance of a low optical‐loss mid‐infrared microcavity, which consisted of two Ge/ZnS dielectric Bragg reflectors. Rabi‐splitting of 14.3 meV is observed, with a 4.4 meV polariton linewidth at anti‐crossing. The large Rabi‐splitting relative to linewidth indicates efficient impedance‐matching between the bare vibrational and photonic states, and suggests molecular‐vibration polaritons incorporated in dielectric microcavities can be an enabling step towards realizing polariton optical switching and polariton condensation in the mid‐infrared spectral range.     

Identification of G‐nerve agents at picogram levels from complex organic samples containing hydrocarbon interferences by aqueous extraction,followed by derivatization and liquid chromatography‐mass spectrometry analysis

The chromatograms obtained from the gas chromatography‐electron ionization mass spectrometric (GC‐EI‐MS) analysis of extracts containing G‐nerve agents in the presence of diesel, gasoline, etc., are dominated by hydrocarbon backgrounds that “mask” the G‐nerve agents, leading to severe difficulties in identification. This paper presents a practical solution for this challenge by transferring the G‐nerve agents from the organic phase into the aqueous phase using liquid‐liquid extraction (LLE), followed by derivatization with 2‐[(dimethylamino)methyl]phenol (2‐DMAMP), allowing ultrasensitive LC‐ESI‐MS/MS analysis of the G‐derivatives. The proposed approach enables rapid identification of trace amounts of G‐nerve agents with limits of identification (LOIs) at the pg/mL scale.     

Wave function of the quantum black hole

We show that the Wald Noether-charge entropy is canonically conjugate to the opening angle at the horizon. Using this canonical relation, we extend the Wheeler–DeWitt equation to a Schrödinger equation in the opening angle, following Carlip and Teitelboim. We solve the equation in the semiclassical approximation by using the correspondence principle and find that the solutions are minimal uncertainty wavefunctions with a continuous spectrum for the entropy and therefore also of the area of the black hole horizon. The fact that the opening angle fluctuates away from its classical value of 2π indicates that the quantum black hole is a superposition of horizonless states. The classical geometry with a horizon serves only to evaluate quantum expectation values in the strict classical limit.