BOTPPI, a New Wittig Salt Used in the Synthesis of 12-(S)-Hydroxy-Eicosatetraenoic Acid [12-(S)-HETE]

An efficient route to (Z)-(8-benzyloxy-8-oxooct-3-en-1-yl)triphenylphosphonium iodide, or BOTPPI, is disclosed, complete with full experimental details, NMR spectra, and HRMS data. BOTPPI serves as a surrogate for (Z)-(8-methoxy-8-oxooct-3-en-1-yl)triphenylphosphonium iodide, or MOTPPI, a Wittig salt previously used in two 12-HETE syntheses. BOTPPI has the advantage over MOTPPI of being derived from a sequence for which every intermediate is UV-active and amenable to large-scale chromatographic purification. A formal asymmetric total synthesis of 12-(S)-HETE is also reported, involving a stereoselective phase-transfer catalyzed (PTC) alkylation in its key step

Centuries of Marine Radiocarbon Reservoir Age Variation Within Archaeological Mesodesma donacium Shells From Southern Peru

Mollusk shells provide brief (\u3c5 yr per shell) records of past marine conditions, including marine radiocarbon reservoir age (R) and upwelling. We report 21 14C ages and R calculations on small (~2 mg) samples from 2 Mesodesma donacium (surf clam) shells. These shells were excavated from a semi-subterranean house floor stratum 14C dated to 7625 ± 35 BP at site QJ-280, Quebrada Jaguay, southern Peru. The ranges in marine 14C ages (and thus R) from the 2 shells are 530 and 170 14C yr; R from individual aragonite samples spans 130 ± 60 to 730 ± 170 14C yr. This intrashell 14C variability suggests that 14C dating of small (time-slice much less than 1 yr) marine samples from a variable-R (i.e. variable-upwelling) environment may introduce centuries of chronometric uncertainty

UVB radiation induced effects on cells studied by FTIR spectroscopy

We have made a preliminary analysis of the results about the eVects on tumoral cell line (lymphoid T cell line Jurkat) induced by UVB radiation (dose of 310 mJ/cm^2) with and without a vegetable mixture. In the present study, we have used two techniques: Fourier transform infrared spectroscopy (FTIR) and flow cytometry. FTIR spectroscopy has the potential to provide the identiWcation of the vibrational modes of some of the major compounds (lipid, proteins and nucleic acids) without being invasive in the biomaterials. The second technique has allowed us to perform measurements of cytotoxicity and to assess the percentage of apoptosis. We already studied the induction of apoptotic process in the same cell line by UVB radiation; in particular, we looked for correspondences and correlations between FTIR spetroscopy and flow cytometry data finding three highly probable spectroscopic markers of apoptosis (Pozzi et al. in Radiat Res 168:698-705, 2007). In the present work, the results have shown significant changes in the absorbance and spectral pattern in the wavenumber protein and nucleic acids regions after the treatments

Canary in the Forest?—Tree mortality and canopy dieback of western redcedar linked to drier and warmer summers

Aim: Forest dieback is increasing from unfavourable climate conditions. Western redcedar (WRC)—a culturally, ecologically and economically important species—has recently experienced anomalously high mortality rates and partial canopy dieback. We investigated how WRC tree growth and dieback responded to climate variability and drought using tree-ring methods. Location: Pacific Northwest, USA. Taxon: Western redcedar (Thuja plicata). Methods: We collected tree cores from three tree health status groups (no canopy dieback, partial canopy dieback, and dead trees) at 11 sites in coastal (maritime climate) and interior (continental climate) WRC populations. From growth rates, we computed four growth indices that assessed the resilience to drought and estimated the year of death. Results: Warmer and drier climate conditions in May/June that extended the annual July-to- September dry season reduced radial growth in 9 of 11 sites (1975–2020). WRC trees recovered growth to pre-drought rates within 3 years when post-drought climate conditions were cooler/wetter than average. However, recovery from drought was slower or absent when warmer/drier conditions occurred during the post-drought recovery period, possibly leading to the recent and widespread mortality across the coastal population. WRC mortality was portended by 4–5 years of declining growth. Annually-resolved mortality in coastal populations predominately occurred in 2017–2018 (80% of sampled dead trees), a period that coincided with exceedingly hot temperatures and the longest regionally dry period from May to September (1970–2020). In interior populations, mortality was dispersed among years but associated with warmer and drier conditions from August to September. Main conclusions: Our findings forewarn that a warming climate and more frequent and severe summer droughts, especially in consecutive years, will likely increase the vulnerability of WRC to canopy dieback and mortality and possibly other drought-sensitive trees in one of the world\u27s largest forest carbon sinks