Novel preservation state of Dolerotheca (medullosalean male organ) from the Late Pennsylvanian of the Sydney Coalfield, Nova Scotia, Canada

A new preservation state for the medullosalean male organ Dolerotheca is exemplified by a detached 31-mm sideritic mold with intact coalified compression from shale from the roof of a coal seam in the Sydney Coalfield, Cape Breton Island, Nova Scotia, Canada. Clearly recognizable in the specimen is the quadripartite campanulum. Furthermore, maceration yielded significant internal information on acellular, cuticular, stomatiferous and pubescent surfaces, and prepollen sacs with grains. Stomata are rare and of the cyclocytic type. The rectangular prepollen sacs occur as doubly paired rows of sporangia that are radially arranged, and contain ellipsoidal prepollen grains 400−520 μm long and circular prepollen grains 330−460 μm in diameter. The approximate ratio of circular to ellipsoidal grains is 1:2. Regardless of shape, the prepollen grains are attributable to the genus Monoletes. The circular grains bear vestigial trilete marks. Infrared-based functional-group chemistry distinguishes between the cover-type compression state and prepollen grains on the basis of higher aliphatic and oxygenated group contents in the grains. In summary, the specimen represents a novel state of nodular preservation with intact compression.  Although the specimen is attributed to the genus Dolerotheca, specific assignment is not possible because of limited preservation and material

Lepidodendron dawsonii: functional groups and pyrolysates of compression and fossilized-cuticle (Late Asturian, Canada)

Lepidodendron dawsonii BELL 1938 is an endemic species of Late Asturian age in the Canadian Sydney Coalfield, with conspicuous elongate leaf cushions. The study specimen, 35 cm long and 10 cm wide, represents a dichotomous bough from the tree crown in which the inner part of one side is black and compression-preserved, whereas the one in contact with the entombing rock matrix is dark-amber in colour and fossilized-cuticle preserved. Only stomatal pits and cuticular details are preserved. Comparison of these preservation states, based on Fourier transform infrared (FTIR) spectrometry, and flash pyrolysis gas chromatography mass spectroscopy (Py-GC/MS), demonstrate sufficient differences in chemistry to be able to link the two preservation states with differing pathways of organic matter transformation (diagenesis). The aliphatic-hydrocarbon chains of the cuticles are comparatively shorter and more branched than the longer chains of the compressions. Py-GC/MS results support the presence of hydrocarbon markers of plant cuticles. The high abundances of C1 and -C2 alkylphenols and C1 and -C2 alkylbenzenes in pyrolysates are likely derived from maturing lignin or lignin-like biomacromolecules. We suggest comparison of L. dawsonii’s cuticles with Lepidodendron coal macerals in Chinese Permian Leping coal, and with suberinite.</p

Exhaled Eicosanoids following Bronchial Aspirin Challenge in Asthma Patients with and without Aspirin Hypersensitivity: The Pilot Study

Background. Special regulatory role of eicosanoids has been postulated in aspirin-induced asthma. Objective. To investigate effects of aspirin on exhaled breath condensate (EBC) levels of eicosanoids in patients with asthma. Methods. We determined EBC eicosanoid concentrations using gas chromatography/mass spectrometry (GC-MS) and high-performance liquid chromatography/mass spectrometry (HPLC-MS2) or both. Determinations were performed at baseline and following bronchial aspirin challenge, in two well-defined phenotypes of asthma: aspirin-sensitive and aspirin-tolerant patients. Results. Aspirin precipitated bronchial reactions in all aspirin-sensitive, but in none of aspirin-tolerant patients (ATAs). At baseline, eicosanoids profile did not differ between both asthma groups except for lipoxygenation products: 5- and 15-hydroxyeicosatetraenoic acid (5-, 15-HETE) which were higher in aspirin-induced asthma (AIA) than inaspirin-tolerant subjects. Following aspirin challenge the total levels of cysteinyl-leukotrienes (cys-LTs) remained unchanged in both groups. The dose of aspirin had an effect on magnitude of the response of the exhaled cys-LTs and prostanoids levels only in AIA subjects. Conclusion. The high baseline eicosanoid profiling of lipoxygenation products 5- and 15-HETE in EBC makes it possible to detect alterations in aspirin-sensitive asthma. Cysteinyl-leukotrienes, and eoxins levels in EBC after bronchial aspirin administration in stable asthma patients cannot be used as a reliable diagnostic index for aspirin hypersensitivity

Sequential decoupling of negative-energy states in Douglas-Kroll-Hess theory

Here, we review the historical development, current status, and prospects of Douglas--Kroll--Hess theory as a quantum chemical relativistic electrons-only theory.Comment: 15 page

Trapping virtual pores by crystal retro-engineering

Stable guest-free porous molecular crystals are uncommon. By contrast, organic molecular crystals with guest-occupied cavities are frequently observed, but these cavities tend to be unstable and collapse on removal of the guests—this feature has been referred to as ‘virtual porosity’. Here, we show how we have trapped the virtual porosity in an unstable low-density organic molecular crystal by introducing a second molecule that matches the size and shape of the unstable voids. We call this strategy ‘retro-engineering’ because it parallels organic retrosynthetic analysis, and it allows the metastable two-dimensional hexagonal pore structure in an organic solvate to be trapped in a binary cocrystal. Unlike the crystal with virtual porosity, the cocrystal material remains single crystalline and porous after removal of guests by heating

Forming a three-dimensional porous organic network via solid-state explosion of organic single crystals

Solid-state reaction of organic molecules holds a considerable advantage over liquid-phase processes in the manufacturing industry. However, the research progress in exploring this benefit is largely staggering, which leaves few liquid-phase systems to work with. Here, we show a synthetic protocol for the formation of a three-dimensional porous organic network via solid-state explosion of organic single crystals. The explosive reaction is realized by the Bergman reaction (cycloaromatization) of three enediyne groups on 2,3,6,7,14,15-hexaethynyl-9,10-dihydro-9,10-[1,2]benzenoanthracene. The origin of the explosion is systematically studied using single-crystal X-ray diffraction and differential scanning calorimetry, along with high-speed camera and density functional theory calculations. The results suggest that the solid-state explosion is triggered by an abrupt change in lattice energy induced by release of primer molecules in the 2,3,6,7,14,15-hexaethynyl-9,10-dihydro-9,10-[1,2]benzenoanthracene crystal lattice

Triptycene-based organic molecules of intrinsic microporosity

Four Organic Molecules of Intrinsic Microporosity (OMIMs) were prepared by fusing triptycene-based components to a biphenyl core. Due to their rigid molecular structures that cannot pack space efficiently, these OMIMs form amorphous materials with significant microporosity as demonstrated by apparent BET surface areas in the range of 515–702 m2 g–1. Bulky cyclic 1′,2′,3′,4′-tetrahydro-1′,1′,4′,4′-tetramethylbenzo units placed on the triptycene termini are especially efficient at enhancing microporosity

Tolerance to coxibs in patients with intolerance to non-steroidal anti-inflammatory drugs (NSAIDs): a systematic structured review of the literature

Adverse events triggered by non-steroidal anti-inflammatory drugs (NSAIDs) are among the most common drug-related intolerance reactions in medicine; they are possibly related to inhibition of cyclooxygenase-1. Coxibs, preferentially inhibiting cyclooxygenase-2, may therefore represent safe alternatives in patients with NSAID intolerance. We reviewed the literature in a systematic and structured manner to identify and evaluate studies on the tolerance of coxibs in patients with NSAID intolerance. We searched MEDLINE (1966–2006), the COCHRANE LIBRARY (4th Issue 2006) and EMBASE (1966–2006) up to December 9, 2006, and analysed all publications included using a predefined evaluation sheet. Symptoms and severity of adverse events to coxibs were analysed based on all articles comprising such information. Subsequently, the probability for adverse events triggered by coxibs was determined on analyses of double-blind prospective trials only. Among 3,304 patients with NSAID intolerance, 119 adverse events occurred under coxib medication. All adverse events, except two, have been allergic/urticarial in nature; none was lethal, but two were graded as life-threatening (grade 4). The two non-allergic adverse events were described as a grade 1 upper respiratory tract haemorrhage, and a grade 1 gastrointestinal symptom, respectively. In 13 double-blind prospective studies comprising a total of 591 patients with NSAID intolerance, only 13 adverse reactions to coxib provocations were observed. The triggering coxibs were rofecoxib (2/286), celecoxib (6/208), etoricoxib (4/56), and valdecoxib (1/41). This review documents the good tolerability of coxibs in patients with NSAID intolerance, for whom access to this class of drugs for short-term treatment of pain and inflammation is advantageous