A series of oxahelicenes composed of ortho/meta-annulated benzene/pyridine and 2H-pyran rings were synthesized on the basis of the cobalt(I)-mediated (or rhodium(I)- or nickel(0)-mediated) double, triple, or quadruple [2+2+2] cycloisomerization of branched aromatic hexa-, nona-, or dodecaynes, thus allowing the construction of 6, 9, or 12 rings in a single operation. The use of a flow reactor was found to be beneficial for the multicyclization reactions. The stereogenic centers present in some of the oligoynes steered the helical folding in such a way that the final oxa[9]-, [13]-, [17]- and [19]helicenes were obtained in both enantiomerically and diastereomerically pure form. Specifically, the oxa[19]helicenes beat the current record in the length of a helicene backbone. Single-molecule conductivity was studied by the mechanically controllable break-junction method with a pyridooxa[9]helicene.
As eries of oxahelicenes composed of ortho/metaannulated benzene/pyridine and 2H-pyran rings were synthesized on the basis of the cobalt(I)-mediated (or rhodium(I)-or nickel(0)-mediated) double,t riple,o rq uadruple [2+ +2+ +2] cycloisomerization of branched aromatic hexa-, nona-, or dodecaynes,thus allowing the construction of 6, 9, or 12 rings in asingle operation. The use of aflow reactor was found to be beneficial for the multicyclization reactions.T he stereogenic centers present in some of the oligoyness teered the helical folding in such aw ay that the final oxa[9]-, [13]-, [17]-and [19]helicenes were obtained in both enantiomerically and diastereomerically pure form. Specifically,t he oxa-[19]helicenes beat the current recordinthe length of ahelicene backbone.S ingle-molecule conductivity was studied by the mechanically controllable break-junction method with ap yridooxa[9]helicene.
Presence of an air pocket and its size play an important role in survival of victims buried in the avalanche snow. Even small air pockets facilitate breathing. We hypothesize that the size of the air pocket significantly affects the airflow resistance and work of breathing. The aims of the study are (1) to investigate the effect of the presence of an air pocket on gas exchange and work of breathing in subjects breathing into the simulated avalanche snow and (2) to test whether it is possible to breathe with no air pocket. The prospective interventional double-blinded study involved 12 male volunteers, from which 10 completed the whole protocol. Each volunteer underwent two phases of the experiment in a random order: phase “AP”—breathing into the snow with a one-liter air pocket, and phase “NP”—breathing into the snow with no air pocket. Physiological parameters, fractions of oxygen and carbon dioxide in the airways and work of breathing expressed as pressure-time product were recorded continuously. The main finding of the study is that it is possible to breath in the avalanche snow even with no air pocket (0 L volume), but breathing under this condition is associated with significantly increased work of breathing. The significant differences were initially observed for end-tidal values of the respiratory gases (EtO2 and EtCO2) and peripheral oxygen saturation (SpO2) between AP and NP phases, whereas significant differences in inspiratory fractions occurred much later (for FIO2) or never (for FICO2). The limiting factor in no air pocket conditions is excessive increase in work of breathing that induces increase in metabolism accompanied by higher oxygen consumption and carbon dioxide production. The presence of even a small air pocket reduces significantly the work of breathing.
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