Incorporation of o-carborane into the backbone
of poly(dihexylfluorene)s drastically affects emission properties
due to an intramolecular charge-transfer state (ICT) that forms between
the fluorene and carborane moieties in the polymer backbone, which
is emissive and solvatochromic. Such polymers exhibit duel emissions
from both the ICT state and the conjugated fluorene local excited
state (LES). In order to evaluate the influence of higher degrees
of LES conjugation on the emission properties of carborane-containing
poly(dihexylfluorene)s, four random copolymers were synthesized with
different feed ratios of 2,7-dibromo-9,9-dihexylfluorene and 1,2-bis(7-bromo-9,9-dihexyl-9H-fluoren-2-yl)-closo-dicarbodecaborane.
These polymerizations were carried out through Yamamoto coupling with
greater equivalents of 2,7-dibromo-9,9-dihexylfluorene, and the photophysical
properties were compared to the homopolymer of 1,2-bis(7-bromo-9,9-dihexyl-9H-fluoren-2-yl)-closo-dicarbodecaborane.
With increasing equivalents of 2,7-dibromo-9,9-dihexylfluorene the
polymer molecular weight is increased from the homopolymer, the ground-state
absorption is red shifted, and the emission spectra show gradually
increasing LES character. Time-resolved spectroscopic methods displayed
the characteristic ICT excited-state absorption and decay for three
of the polymers, with the LES absorption and decay features increasing
in intensity with increasing fluorene character in the polymer backbone.
The polymer with the largest degree of conjugated fluorene shows excited-state
properties consistent with a linear poly(dihexylfluorene), showing
negligible ICT character. In the solid state, the intensity of the
ICT emission is enhanced as compared to the LES emission for the copolymers
with the largest degree of conjugated fluorene. Through synthetic
tuning, it is possible to produce polymers with higher molecular weights,
and overall characteristics of the non-carborane-containing analogues,
but maintain the useful properties of carborane-containing materials,
like solvatochromism, in the solid state.
Self-report data suggests a large proportion of total physical activity (PA) occurs at work. However, adults with higher levels of occupational PA may compensate by engaging in less non-occupational PA. The study aims were to 1) estimate the intensity, volume, and duration of PA in American adults that occurs at work, and 2) determine if those more active at work are less active outside of work. A cross-sectional sample of full-time employed adults (N = 510) was recruited from Georgia city and county governments in 2013–2015. Participants wore an Actigraph GT3X + accelerometer for two weeks. In 2016, for 442 participants with complete data including work schedules and self-reported job titles, accelerometer wear minutes were classified as either occupational or non-occupational, and as sedentary, LPA (light-intensity PA), or MVPA (moderate-to-vigorous intensity PA). The proportion of daily PA that occurred during work was 41.2% for total PA, 41.0% for LPA, and 39.5% for MVPA. Higher levels of occupational LPA were associated with lower levels of non-occupational LPA (r = − 0.38, P < 0.0001). However, higher levels of occupational MVPA were associated with higher levels of non-occupational MVPA (r = 0.17, P < 0.0001). These associations remained significant in a MANOVA adjusting for labor sector and other covariates. On average, employed adults get more LPA and MVPA outside of work. Adults who do more occupational MVPA do not compensate by doing less non-occupational MVPA. In contrast, adults who do more occupational LPA do compensate by doing less non-occupational LPA. Evaluations of interventions to reduce sedentary behavior should be designed to detect compensation effects.
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