Nitrate and Nitrite Promote Formation of Tobacco-Specific Nitrosamines via Nitrogen Oxides Intermediates during Postcured Storage under Warm Temperature

Tobacco-specific nitrosamines (TSNAs) are carcinogenic and are present in cured tobacco leaves. This study was designed to elucidate the mechanisms of TSNAs formation under warm temperature storage conditions. Results showed that nitrogen oxides (NOx) were produced from nitrate and nitrite in a short period of time under 45 ∘ C and then reacted with alkaloids to form TSNAs. Nitrite was more effective than nitrate in promoting TSNAs formation during 45 ∘ C storage which may be due to the fact that nitrite can produce a large amount of NOx in comparison with nitrate. Presence of activated carbon effectively inhibited the TSNAs formation because of the adsorption of NOx on the activated carbon. The results indicated that TSNAs are derived from a gas/solid phase nitrosation reaction between NOx and alkaloids. Nitrate and nitrite are major contributors to the formation of TSNAs during warm temperature storage of tobacco

Changing sources and burial of organic carbon in the Chukchi Sea sediments with retreating sea ice over recent centuries

Decreasing sea ice extent in summer caused by climate change is affecting the carbon cycle of the Arctic Ocean. In this study, surface sediments across the western Arctic Ocean are investigated to characterize sources of sedimentary organic carbon (OC). Bulk organic parameters (total organic carbon, total nitrogen, &delta;13Corg and &delta;15N) combined with molecular organic biomarkers (e.g., sterols and highly branched isoprenoids (HBIs)) are applied to distinguish between sympagic, pelagic, and terrestrial OC. Furthermore, downcore profiles of these parameters were also generated from the Chukchi Sea R1 core (74&deg; N) to evaluate changes in the relative contribution of these three components of sedimentary OC over the last 200 years with decreasing sea ice. Our data evidence that from 1820s to 1930s, prevailing high and variable sea ice cover inhibited in situ primary production resulting in prominent land-derived material stored in sediments. From 1930s to 1980s, with the gradual decline of sea ice, primary production increased progressively. The ratio of sympagic and pelagic OC began to rise to account for a larger portion of sedimentary OC. Since 1980s, accelerated sea ice loss led to enhanced primary production, stabilizing over the last decades due to freshwater induced surface ocean stratification in summer.</p

CD94+ Natural Killer cells potentiate pulmonary ischemia-reperfusion injury

Pulmonary ischemia-reperfusion injury (IRI) is a major contributor to poor lung transplant outcomes. We recently demonstrated a central role of airway-centered NK cells in mediating IRI; however, there are no existing effective therapies for directly targeting NK cells in humans. We hypothesized that a depleting anti-CD94 monoclonal antibody (mAb) would provide therapeutic benefit in mouse and human models of IRI based on high levels of KLRD1 (CD94) transcripts in bronchoalveolar lavage samples from lung transplant patients. We found that CD94 is highly expressed on mouse and human NK cells, with increased expression during IRI. Anti-mouse and anti-human mAbs against CD94 showed effective NK cell depletion in mouse and human models and blunted lung damage and airway epithelial killing. In two different allogeneic orthotopic lung transplant mouse models, anti-CD94 treatment during induction reduced early lung injury and chronic inflammation relative to control therapies. Anti-CD94 did not increase donor antigen-presenting cells that could alter long-term graft acceptance. Lung transplant induction regimens incorporating anti-CD94 treatment may safely improve early clinical outcomes

Difference between Burley Tobacco and Flue-Cured Tobacco in Nitrate Accumulation and Chemical Regulation of Nitrate and TSNA Contents

Tobacco-specific nitrosamines (TSNAs) are harmful carcinogens, with nitrate as a precursor of their formation. Nitrate content is considerably higher in burley tobacco than in flue-cured tobacco, but little has been reported on the differences between types of nitrate accumulation during development. We explored nitrate accumulation prior to harvest and examined the effects of regulatory substances aimed at decreasing nitrate and TSNA accumulation. In growth experiments, nitrate accumulation in burley and flue-cured tobacco initially increased but then declined with the highest nitrate content observed during a fast-growth period. When treating tobacco crops with molybdenum (Mo) during fast growth, nitrate reductase activity in burley tobacco increased significantly, but the NO3-N content decreased. These treatments also yielded significant reductions in NO3-N and TSNA contents. Therefore, we suggest that treatment with Mo during the fast-growth period and a Mo-Gfo (Mo-glufosinate) combination at the maturity stage is an effective strategy for decreasing nitrate and TSNAs during cultivation

Nitrate and Nitrite Promote Formation of Tobacco-Specific Nitrosamines via Nitrogen Oxides Intermediates during Postcured Storage under Warm Temperature

Tobacco-specific nitrosamines (TSNAs) are carcinogenic and are present in cured tobacco leaves. This study was designed to elucidate the mechanisms of TSNAs formation under warm temperature storage conditions. Results showed that nitrogen oxides (NOx) were produced from nitrate and nitrite in a short period of time under 45°C and then reacted with alkaloids to form TSNAs. Nitrite was more effective than nitrate in promoting TSNAs formation during 45°C storage which may be due to the fact that nitrite can produce a large amount of NOx in comparison with nitrate. Presence of activated carbon effectively inhibited the TSNAs formation because of the adsorption of NOx on the activated carbon. The results indicated that TSNAs are derived from a gas/solid phase nitrosation reaction between NOx and alkaloids. Nitrate and nitrite are major contributors to the formation of TSNAs during warm temperature storage of tobacco

Umpolung reactivity of strained C–C σ-bonds without transition-metal catalysis

Abstract Umpolung is an old and important concept in organic chemistry, which significantly expands the chemical space and provides unique structures. While, previous research focused on carbonyls or imine derivatives, the umpolung reactivity of polarized C–C σ-bonds still needs to explore. Herein, we report an umpolung reaction of bicyclo[1.1.0]butanes (BCBs) with electron-deficient alkenes to construct the C(sp3)-C(sp3) bond at the electrophilic position of C–C σ-bonds in BCBs without any transition-metal catalysis. Specifically, this transformation relies on the strain-release driven bridging σ-bonds in bicyclo[1.1.0]butanes (BCBs), which are emerged as ene components, providing an efficient and straightforward synthesis route of various functionalized cyclobutenes and conjugated dienes, respectively. The synthetic utilities of this protocol are performed by several transformations. Preliminary mechanistic studies including density functional theory (DFT) calculation support the concerted Alder-ene type process of C–C σ-bond cleavage with hydrogen transfer. This work extends the umpolung reaction to C–C σ-bonds and provides high-value structural motifs