A Convenient Synthesis of Methyl (Z)-1-Carbamoyl-2-ethenylcyclopropanecarboxylate and (Z)-1-Carbamoyl-2-ethenylcyclopropanecarboxylic Acid

A simple method for the preparation of the title compounds via the reaction of dimethyl 2-ethenylcyclopropane-1,1-dicarboxylate with 6M ammonia in methanol is described.     

A comparison of measured room acoustics metrics using a spherical microphone array and conventional methods

The traditional microphone configuration used to measure room impulse responses (IRs) according to ISO 3382:2009 is an omnidirectional and figure-8 microphone pair. IRs measurements were taken in a 2500-seat auditorium to determine how the results from a spherical microphone array (an mh acoustics Eigenmike-em32) compare to those from the traditional microphone setup (a Brüel & Kjær Type-4192 omnidirectional microphone and a Sennheiser MKH30 figure-8 microphone). Measurements were obtained at six receiver locations, with three repetitions each in order to first evaluate repeatability. The metrics considered in this study were: reverberation time (T30), early decay time (EDT), clarity index (C80), strength (G), lateral energy fraction (J_LF) and late lateral energy level (L_J). Before calculating these quantities, the IRs were filtered to equalize the frequency response of the microphones and sound source. For the spherical array measurements, the omnidirectional (monopole) and figure-8 (dipole) patterns were extracted using beamforming. In terms of repeatability, the average standard deviation of the three measurements at each receiver location averaged across all metrics, receivers, and octave bands was found to be 0.01 just noticeable differences (JNDs). The analysis comparing the measurements from the two microphone configurations yielded differences which were less than 1 JND for the majority of metrics, with a few exceptions of EDT and C80 slightly above 1 JND. Based on this case study, these results indicate that spherical microphone arrays can be used to obtain valid room IR measurements, which will allow for the development of new metrics utilizing the higher spatial resolution made possible with spherical arrays.     

Possible Evidence of Amide Bond Formation Between Sinapinic Acid and Lysine-Containing Bacterial Proteins by Matrix-Assisted Laser Desorption/Ionization (MALDI) at 355?nm

We previously reported the apparent formation of matrix adducts of 3,5-dimethoxy-4-hydroxy-cinnamic acid (sinapinic acid or SA) via covalent attachment to disulfide bond-containing proteins (HdeA, Hde, and YbgS) from bacterial cell lysates ionized by matrix-assisted laser desorption/ionization (MALDI) time-of-flight-time-of-flight tandem mass spectrometry (TOF-TOF-MS/MS) and post-source decay (PSD). We also reported the absence of adduct formation when using ??-cyano-4-hydroxycinnamic acid (CHCA) matrix. Further mass spectrometric analysis of disulfide-intact and disulfide-reduced over-expressed HdeA and HdeB proteins from lysates of gene-inserted E. coli plasmids suggests covalent attachment of SA occurs not at cysteine residues but at lysine residues. In this revised hypothesis, the attachment of SA is preceded by formation of a solid phase ammonium carboxylate salt between SA and accessible lysine residues of the protein during sample preparation under acidic conditions. Laser irradiation at 355?nm of the dried sample spot results in equilibrium retrogradation followed by nucleophilic attack by the amine group of lysine at the carbonyl group of SA and subsequent amide bond formation and loss of water. The absence of CHCA adducts suggests that the electron-withdrawing effect of the ??-cyano group of this matrix may inhibit salt formation and/or amide bond formation. This revised hypothesis is supported by dissociative loss of SA (?224?Da) and the amide-bound SA (?206?Da) from SA-adducted HdeA and HdeB ions by MS/MS (PSD). It is proposed that cleavage of the amide-bound SA from the lysine side-chain occurs via rearrangement involving a pentacyclic transition state followed by hydrogen abstraction/migration and loss of 3-(4-hydroxy-3,5-dimethoxyphenyl)prop-2-ynal (?206?Da).     

Syntheses,structure, and reactivity of acyclic enetriyne and enetetrayne derivatives

Sonogashira coupling of buta-1,3-diynylbenzene with ((2-iodophenyl)ethynyl)trimethylsilane and 1,2-diiodobenzene led to the novel enetriyne, 1-ethynyl-2-(phenylbuta-1,3-diynyl)benzene, and enetetrayne, 1,2-bis(phenylbuta-1,3-diynyl)benzene, respectively. Solid state structural and thermal analyses are also described. In solution, 1-ethynyl-2-(phenylbuta-1,3-diynyl)benzene was found to undergo thermal Bergman cyclization to afford 2-(phenylethynyl)naphthalene.     

The cationization of synthetic polymers in matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry: Investigations of the salt‐to‐analyte ratio

Matrix‐assisted laser desorption/ionization (MALDI) is a soft ionization technique that when used to analyze synthetic polymer analytes often requires the addition of a metal cationization agent (herein termed the “salt”). The choice of both the matrix and the cationization agent needs to be taken into account when considering the polymer under study; different polymers have shown different affinities toward different cationization agents, and their selectivity can change as the matrix changes. Salt‐to‐analyte ratio (S/A) plots are used in this work to investigate the effect of the quantity of cationization agent employed in the analysis of a poly (methylmethacrylate) (PMMA) analyte with different MALDI matrices. The point at which analyte signal stops increasing with the added cationization agent is termed the “cation saturation point,” and it was found to occur around a S/A of 1. When the analyte signal after this point remains constant, it is termed an “ideal case.” The “non‐ideal case” occurs when the analyte signal decreases after the cation saturation point. The amount of matrix present (measured as the matrix‐to‐analyte molar ratio, M/A) and the use of different counterions for the salt are also found to affect the intensity of the analyte signal. In non‐ideal cases, changes in the counterion or an increase in the M/A are found to increase the analyte signal, often converting an initially observed non‐ideal case into an ideal case. Several experiments attempting to uncover the reason for observation of the non‐ideal S/A behavior are also described.