Dinitration studies of 2,4,5-tribromo-3,6-dimethylphenol: the formation of an acyloin rearrangement product

Dinitration of 2,4,5-tribromo-3,6-dimethylphenol(1) gives either the tribromodinitro-compound(2) or its acyloin rearrangement product(3), depending on the reaction conditions: X-ray crystal structure analyses are reported for compounds (2) and (3).     

An unusual [4 + 4] cycloadduct from an o-quinodimethane: Characterisation and computational studies

Trapping of a pyrimidinone-derived o-quinodimethane with tetraphenylcyclopentadienone gives a mixture of the [4 + 2] and formal [4 + 4] adducts. Computational studies show that the latter arises by a sequence of [4 + 2] cycloaddition, homolysis, radical recombination to a spiro-tetrahydrofuran and Claisen rearrangement under the thermolytic conditions.     

Anion binding vs. sulfonamide deprotonation in functionalised ureas

Sulfonamide groups, commonly used as neutral hydrogen bond donors in a wide variety of anion receptors, deprotonate upon addition of certain basic anionic guests in two simple functionalised ureas.     

Gain-of-function mutational activation of human tRNA synthetase procytokine

Disease-causing mutations occur in genes for aminoacyl tRNA synthetases. That some mutations are dominant suggests a gain of function. Native tRNA synthetases, such as tyrosyl-tRNA synthetase (TyrRS) and tryptophanyl-tRNA synthetase, catalyze aminoacylation and are also procytokines that are activated by natural fragmentation. In principle, however, gain-of-function phenotypes could arise from mutational activation of synthetase procytokines. From crystal structure analysis, we hypothesized that a steric block of a critical Glu-Leu-Arg (ELR) motif in full-length TyrRS suppresses the cytokine activity of a natural fragment. To test this hypothesis, we attempted to uncover ELR in the procytokine by mutating a conserved tyrosine (Y341) that tethers ELR. Site-specific proteolytic cleavage and small-angle X-ray scattering established subtle opening of the structure by the mutation. Strikingly, four different assays demonstrated mutational activation of cytokine functions. The results prove the possibilities for constitutive gain-of-function mutations in tRNA synthetases.     

Isophthalamides and 2,6-dicarboxamidopyridines with pendant indole groups: a 'twisted' binding mode for selective fluoride recognition

Two cleft-like anion receptors have been synthesised that contain indole hydrogen-bond donors and show fluoride selectively in a DMSO-water solution with crystallographic studies showing a 'twisted' binding mode for fluoride in the solid state.     

Resonance raman and infrared spectra of ClO3 radicals in electron irradiated NaClO3

Resonance Raman and infrared absorption spectra of ClO₃ radicals have been observed from measurements of crystalline NaClO₃ irradiated at 77 K with 1.5 MeV electrons. The ClO₃ radicals occupy two sets of nonequivalent sites; radicals at one site are observed from resonance scattering using 6328 Å excitation while those at the other site are observed from resonance scattering with 5145 Å excitation. The red sensitive radicals decompose at 77 K with a half-life of ≈29 min while the green sensitive radicals are more stable at this temperature.     

Deactivation of vibrationally excited CD3H using laser-induced fluorescence

Infrared fluorescence observed after exciting to ν₆ (ν=1) of CD₃H with a Q-switched CO₂ laser yields the exponential deactivation rate constant of 0.84 ms^?1 torr^?1. Rate constants for deactivation of CD₃H by rare gases vary from 1.4 (for He) to 0.029 (for Xe) ms^?1 torr^?1.     

Analysis of trace levels of domoic acid in seawater and plankton by liquid chromatography without derivatization,using UV or mass spectrometry detection

Quantitation of trace levels of domoic acid (DA) in seawater samples usually requires labour-intensive protocols involving chemical derivatization with 9-fluorenylmethylchloroformate and liquid chromatography with fluorescence detection (FMOC–LC–FLD). Procedures based on LC–MS have been published, but time-consuming and costly solid-phase extraction pre-concentration steps are required to achieve suitable detection limits. This paper describes an alternative, simple and inexpensive LC method with ultraviolet detection (LC–UVD) for the routine analysis of trace levels of DA in seawater without the use of sample pre-concentration or derivatization steps. Qualitative confirmation of DA identity in dubious samples can be achieved by mass spectrometry (LC–MS) using the same chromatographic conditions. Addition of an ion-pairing/acidifying agent (0.15% trifluoroacetic acid) to sample extracts and the use of a gradient elution permitted the direct analysis of large sample volumes (100 μl), resulting in both high selectivity and sensitivity (limit of detection = 42 pg ml⁻¹ by LC–UVD and 15 pg ml⁻¹ by LC–MS). Same-day precision varied between 0.4 and 5%, depending on the detection method and DA concentration. Mean recoveries of spiked DA in seawater by LC–UVD were 98.8% at 0.1–10 ng ml⁻¹ and 99.8% at 50–1000 ng ml⁻¹. LC–UVD exhibited strong correlation with FMOC–LC–FLD during inter-laboratory analysis of Pseudo-nitzschia multiseries cultures containing 60–2000 ng DA ml⁻¹ (r² > 0.99), but more variable results were obtained by LC–MS (r² = 0.85). This new technique was used to confirm the presence of trace DA levels in low-toxicity Pseudo-nitzschia spp. isolates (0.2–1.6 ng ml⁻¹) and in whole-water field samples (0.3–5.8 ng ml⁻¹), even in the absence of detectable Pseudo-nitzschia spp. cells in the water column.     

Normalizers of p-subgroups in finite groups

In this paper we give a computational strategy for constructing the normalizer of a p-subgroup in a finite group. Received: 31 January 2008     

Dodecagonal quasicrystalline morphology in a poly(styrene-b-isoprene-b-styrene-b-ethylene oxide) tetrablock terpolymer

A dodecagonal quasicrystalline (QC) morphology is identified in a poly(styrene-b-isoprene-b-styrene-b-ethylene oxide) (SISO) tetrablock terpolymer based on evidence provided by transmission electron microscopy (TEM), small-angle X-ray scattering, and dynamic mechanical spectroscopy measurements. The QC state occurs at temperatures between those associated with simple hexagonal order (HEX) and the σ-phase (P4(2)/mnm), T(HEX) < T(QC) < T(σ) < T(ODT), where T(ODT) is the order-disorder transition temperature. All three morphologies are formed from spherical domains containing an O core surrounded by a shell of S that screens unfavorable segment-segment interactions with an I-rich matrix. TEM analysis reveals a QC morphology with 12-fold rotational symmetry but devoid of long-range translational order, along with locally coordinated structures consistent with dodecagonal quasicrystalline approximants. The SISO molecular architecture decouples control over the domain shape and interdomain interactions, leading to a multiplicity of packing symmetries.