7 research outputs found
Microstructural control suppresses thermal activation of electron transport at room temperature in polymer transistors
Recent demonstrations of inverted thermal activation of charge mobility in polymer field-effect transistors have excited the interest in transport regimes not limited by thermal barriers. However, rationalization of the limiting factors to access such regimes is still lacking. An improved understanding in this area is critical for development of new materials, establishing processing guidelines, and broadening of the range of applications. Here we show that precise processing of a diketopyrrolopyrrole-tetrafluorobenzene-based electron transporting copolymer results in single crystal-like and voltage-independent mobility with vanishing activation energy above 280 K. Key factors are uniaxial chain alignment and thermal annealing at temperatures within the melting endotherm of films. Experimental and computational evidences converge toward a picture of electrons being delocalized within crystalline domains of increased size. Residual energy barriers introduced by disordered regions are bypassed in the direction of molecular alignment by a more efficient interconnection of the ordered domains following the annealing process
Every Atom Counts: Elucidating the Fundamental Impact of Structural Change in Conjugated Polymers for Organic Photovoltaics
As many conjugated polymer-based
organic photovoltaic (OPV) materials
provide substantial solar power conversion efficiencies (as high as
13%), it is important to develop a deeper understanding of how the
primary repeat unit structures impact device performance. In this
work, we have varied the group 14 atom (C, Si, Ge) at the center of
a bithiophene fused ring to elucidate the impact of a minimal repeat
unit structure change on the optical, transport, and morphological
properties, which ultimately control device performance. Careful polymerization
and polymer purification produced three “one-atom change”
donor–acceptor conjugated alternating copolymers with similar
molecular weights and dispersities. DFT calculation, absorption spectroscopy,
and high-temperature solution <sup>1</sup>H nuclear magnetic resonance
(NMR) results indicate that poly(dithienosilole-<i>alt</i>-thienopyrrolodione), P(DTS-TPD), and poly(dithienogermole-<i>alt</i>-thienopyrrolodione), P(DTG-TPD) exhibit different rotational
conformations when compared to poly(cyclopentadithiophene-<i>alt</i>-thienopyrrolodione), P(DTC-TPD). Solid-state <sup>1</sup>H MAS NMR experiments reveal that the greater probability of the
anticonformation in P(DTS-TPD) and P(DTG-TPD) prevail in the solid
phase. The conformational variation seen in solution and solid-state
NMR in turn affects the polymer stacking and intermolecular interaction.
Two-dimension <sup>1</sup>H-<sup>1</sup>H DQ-SQ NMR correlation spectra
shows aromatic–aromatic correlations for P(DTS-TPD) and P(DTG-TPD),
which on the other hand is absent for P(DTC-TPD). In a thin-film interchain
packing study using grazing incidence wide-angle X-ray scattering
(GIWAXS), we observe the π-face of the conjugated backbones
of P(DTC-TPD) aligned edge-on to the substrate, whereas in contrast
the π-faces of P(DTS-TPD) and P(DTG-TPD) align parallel to the
surface. These differences in polymer conformations and backbone orientations
lead to variations in the OPV performance of blends with the fullerene
PC<sub>71</sub>BM, with the device containing P(DTC-TPD):PCBM having
a lower fill factor and a lower power conversion efficiency. Ultrafast
transient absorption spectroscopy shows the P(DTC-TPD):PCBM blend
to have a more pronounced triplet formation from bimolecular recombination
of initially separated charges. With a combination of sub-bandgap
external quantum efficiency measurements and DFT calculations, we
present evidence that the greater charge recombination loss is the
result of a lower lying triplet energy level for P(DTC-TPD), leading
to a higher rate of recombination and lower OPV device performance.
Importantly, this study ties ultimate photovoltaic performance to
morphological features in the active films that are induced from the
processing solution and are a result of minimal one-atom differences
in polymer repeat unit structure
Increase in the use of inhaled nitric oxide in neonatal intensive care units in England: a retrospective population study
Objective To describe temporal changes in inhaled nitric oxide (iNO) use in English neonatal units between 2010 and 2015.Design Retrospective analysis using data extracted from the National Neonatal Research Database.Setting All National Health Service neonatal units in England.Patients Infants of all gestational ages born 2010–2015 admitted to a neonatal unit and received intensive care.Main outcome measures Proportion of infants who received iNO; age at initiation and duration of iNO use.Results 4.9% (6346/129 883) of infants received iNO; 31% (1959/6346) were born <29 weeks, 18% (1152/6346) 29–33 weeks and 51% (3235/6346)>34 weeks of gestation. Between epoch 1 (2010–2011) and epoch 3 (2014–2015), there was (1) an increase in the proportion of infants receiving iNO: <29 weeks (4.9% vs 15.9%); 29–33 weeks (1.1% vs 4.8%); >34 weeks (4.5% vs 5.0%), (2) increase in postnatal age at iNO initiation: <29 weeks 10 days vs 18 days; 29–33 weeks 2 days vs 10 days, (iii) reduction in iNO duration: <29 weeks (3 days vs 2 days); 29–33 weeks (2 days vs 1 day).Conclusions Between 2010 and 2015, there was an increase in the use of iNO among infants admitted to English neonatal units. This was most notable among the most premature infants with an almost fourfold increase. Given the cost of iNO therapy, limited evidence of efficacy in preterm infants and potential for harm, we suggest that exposure to iNO should be limited, ideally to infants included in research studies (either observational or randomised placebo-controlled trial) or within a protocolised pathway. Development of consensus guidelines may also help standardise practice
Sunlight exposure exerts immunomodulatory effects to reduce multiple sclerosis severity
Multiple sclerosis (MS) disease risk is associated with reduced sunexposure. This study assessed the relationship between measures of sun exposure (vitamin D [vitD], latitude) and MS severity in the setting of two multicenter cohort studies (n(NationMS) = 946, n(BIONAT) = 990). Additionally, effect-modification by medication and photosensitivity-associated MC1R variants was assessed. High serum vitD was associated with a reduced MS severity score (MSSS), reduced risk for relapses, and lower disability accumulation over time. Low latitude was associated with higher vitD, lower MSSS, fewer gadolinium-enhancing lesions, and lower disability accumulation. The association of latitude with disability was lacking in IFN-beta-treated patients. In carriers of MC1R:rs1805008(T), who reported increased sensitivity toward sunlight, lower latitude was associated with higher MRI activity, whereas for noncarriers there was less MRI activity at lower latitudes. In a further exploratory approach, the effect of ultraviolet (UV)-phototherapy on the transcriptome of immune cells of MS patients was assessed using samples from an earlier study. Phototherapy induced a vitD and type I IFN signature that was most apparent in monocytes but that could also be detected in B and T cells. In summary, our study suggests benefidal effects of sun exposure on established MS, as demonstrated by a correlative network between the three factors: Latitude, vitD, and disease severity. However, sun exposure might be detrimental for photosensitive patients. Furthermore, a direct induction of type I IFNs through sun exposure could be another mechanism of UV-mediated immune-modulation in MS