Formation of the bisulfite anion (HSO3–, m/z 81) upon collision‐induced dissociation of anions derived from organic sulfonic acids

In the negative‐ion collision‐induced dissociation mass spectra of most organic sulfonates, the base peak is observed at m/z 80 for the sulfur trioxide radical anion (SO₃^–·). In contrast, the product‐ion spectra of a few sulfonates, such as cysteic acid, aminomethanesulfonate, and 2‐phenylethanesulfonate, show the base peak at m/z 81 for the bisulfite anion (HSO₃^–). An investigation with an extensive variety of sulfonates revealed that the presence of a hydrogen atom at the β‐position relative to the sulfur atom is a prerequisite for the formation of the bisulfite anion. The formation of HSO₃^– is highly favored when the atom at the β‐position is nitrogen, or the leaving neutral species is a highly conjugated molecule such as styrene or acrylic acid. Deuterium‐exchange experiments with aminomethanesulfonate demonstrated that the hydrogen for HSO₃^– formation is transferred from the β‐position. The presence of a peak at m/z 80 in the spectrum of 2‐sulfoacetic acid, in contrast to a peak at m/z 81 in that of 3‐sulfopropanoic acid, corroborated the proposed hydrogen transfer mechanism. For diacidic compounds, such as 4‐sulfobutanoic acid and cysteic acid, the m/z 81 ion can be formed by an alternative mechanism, in which the negative charge of the carboxylate moiety attacks the α‐carbon relative to the sulfur atom. Experiments conducted with deuterium‐exchanged and deuterium‐labeled analogs of sulfocarboxylic acids demonstrated that the formation of the bisulfite anion resulted either from a hydrogen transfer from the β‐carbon, or from a direct attack by the carboxylate moiety on the α‐carbon. Copyright © 2012 John Wiley & Sons, Ltd.     

Neutron activation analysis of concrete for cross-border nuclear security

The dissolution of the Soviet Union coupled with the growing sophistication of international terror organizations has brought about a desire to ensure that a sound infrastructure exists to interdict smuggled nuclear material prior to leaving its country of origin. To combat the threat of nuclear trafficking, radiation portal monitors (RPMs) are deployed around the world to intercept illicit material while in transit by passively detecting gamma and neutron radiation. Portal monitors in some locations have reported abnormally high background counts. The higher background data has been attributed, in part, to the naturally occurring radioactive materials (NORM) in the concrete surrounding the portal monitors. Higher background increases the minimum detectable activity (MDA) and can ultimately lead to more material passing through the RPMs undetected. This work employed two different neutron activation analysis (NAA) methods for the purpose of developing a process to characterize the concrete surrounding the RPMs. Thermal neutron instrumental NAA (INAA) and fast NAA (FNAA) were conducted on six samples from three different composition concrete slabs. Comparator standards and quality control materials were used to help ensure that the methods were both precise and accurate. The combination of INAA and FNAA accounted for 84–100% of the total elemental composition of the samples. Knowing the composition of the concrete will allow RPM customers to choose suitable materials prior to installation, thereby increasing the ability of the monitors to detect radiological and nuclear materials.     

Synthetic and quantum mechanical studies into the N-heterocyclic carbene catalyzed (4 + 2) cycloaddition

The N-heterocyclic carbene catalyzed (4 + 2) cycloaddition between α,β-unsaturated acid fluorides and TMS dienol ethers provides cyclohexene fused β-lactone intermediates stable below -20 °C. These can be intercepted reductively or with organolithium reagents to produce diastereomerically pure cyclohexenes (>20:1 dr) with up to four contiguous stereocenters. The mechanism has been investigated using theoretical calculations and by examining secondary kinetic isotope effects. Together these studies implicate the formation of a diastereomerically pure β-lactone intermediate by a stepwise (4 + 2) cycloaddition involving Michael addition, aldol cyclization, and lactonization.     

Kinetics and stereochemistry of hydrolysis of an N-(phenylacetyl)-α-hydroxyglycine ester catalyzed by serine β-lactamases and dd-peptidases

The α-hydroxydepsipeptide 3-carboxyphenyl N-(phenylacetyl)-α-hydroxyglycinate () is a quite effective substrate of serine β-lactamases and low molecular mass dd-peptidases. The class C P99 and ampC β-lactamases catalyze the hydrolysis of both enantiomers of , although they show a strong preference for one of them. The class A TEM-2 and class D OXA-1 β-lactamases and the Streptomyces R61 and Actinomadura R39 dd-peptidases catalyze hydrolysis of only one enantiomer of at any significant rate. Experiments show that all of the above enzymes strongly prefer the same enantiomer, a surprising result since β-lactamases usually prefer l(S) enantiomers and dd-peptidases d(R). Product analysis, employing peptidylglycine α-amidating lyase, showed that the preferred enantiomer is d(R). Thus, it is the β-lactamases that have switched preference rather than the dd-peptidases. Molecular modeling of the P99 β-lactamase active site suggests that the α-hydroxyl of may interact with conserved Asn and Lys residues. Both α-hydroxy and α-amido substituents on a glycine ester substrate can therefore enhance its productive interaction with the β-lactamase active site, although their effects are not additive; this may also be true for inhibitors.     

Cyclization of peptoids by formation of boronate esters

Introduction of conformational constraints into peptoids (N-substituted oligoglycines) will enable new applications in molecular recognition and self-assembly. Peptoids that contain both a phenylboronic acid side chain and a vicinal diol cyclize by intramolecular condensation to form boronate esters. A fluorescent indicator of free boronic acid was used to assay esterification. A galactose moiety 2 to 5 monomer units away from a boronic acid side chain in a peptoid reacts with the boronic acid in competition with the indicator. The intramolecular reaction predominates in each case, with 80-90% of the peptoid cyclized. When the diol is a simple 2,3-dihydroxypropyl group, esterification is less favored but still appreciable.     

Ligand effects on hydrogen atom transfer from hydrocarbons to three-coordinate iron imides

A new β-diketiminate ligand with 2,4,6-tri(phenyl)phenyl N-substituents provides protective bulk around the metal without exposing any weak C-H bonds. This ligand improves the stability of reactive iron(III) imido complexes with Fe═NAd and Fe═NMes functional groups (Ad = 1-adamantyl; Mes = mesityl). The new ligand gives iron(III) imido complexes that are significantly more reactive toward 1,4-cyclohexadiene than the previously reported 2,6-diisopropylphenyl diketiminate variants. Analysis of X-ray crystal structures implicates Fe═N-C bending, a longer Fe═N bond, and greater access to the metal as potential reasons for the increase in C-H bond activation rates.     

Quartic force field predictions of the fundamental vibrational frequencies and spectroscopic constants of the cations HOCO+ and DOCO+

Only one fundamental vibrational frequency of protonated carbon dioxide (HOCO(+)) has been experimentally observed in the gas phase: the ν(1) O-H stretch. Utilizing quartic force fields defined from CCSD(T)/aug-cc-pVXZ (X = T,Q,5) complete basis set limit extrapolated energies modified to include corrections for core correlation and scalar relativistic effects coupled to vibrational perturbation theory and vibrational configuration interaction computations, we are predicting the full set of gas phase fundamental vibrational frequencies of HOCO(+). Our prediction of ν(1) is within less than 1 cm(-1) of the experimental value. Our computations also include predictions of the gas phase fundamental vibrational frequencies of the deuterated form of the cation, DOCO(+). Additionally, other spectroscopic constants for both systems are reported as part of this study, and a search for a cis-HOCO(+) minimum found no such stationary point on the potential surface indicating that only the trans isomer is stable.     

Total synthesis of hapalindoles J and U

The total synthesis of D,L-hapalindoles J and U has been accomplished. Hapalindole J was prepared in 11% overall yield over 11 synthetic steps and hapalindole U was prepared in 25% overall yield over 13 synthetic steps from commercially available materials. The route employs a novel silyl ether-based strategy for accessing the 6:5:6:6 ring system of the hapalindoles rapidly and in good yields.