2,114 research outputs found
Transport and Spectroscopic Studies of the Effects of Fullerene Structure on the Efficiency and Lifetime of Polythiophene-based Solar Cells
Time-dependent measurements of both power conversion efficiency and
ultraviolet-visible absorption spectroscopy have been observed for solar cell
blends containing the polymer poly(3-hexylthiophene-2,5-diyl) (P3HT) with two
different functionalized C60 electron acceptor molecules: commercially
available [6,6]-phenyl C61 butyric acid methyl ester (PCBM) or [6,6]-phenyl C61
butyric acid octadecyl ester (PCBOD) produced in this laboratory. Efficiency
was found to decay with an exponential time dependence, while spectroscopic
features show saturating exponential behavior. Time constants extracted from
both types of measurements showed reasonable agreement for samples produced
from the same blend. In comparison to the PCBM samples, the stability of the
PCBOD blends was significantly enhanced, while both absorption and power
conversion efficiency were decreased.Comment: manuscript submitted to Solar Energy Materials and Solar Cell
Conformational distributions of isolated myosin motor domains encode their mechanochemical properties
Myosin motor domains perform an extraordinary diversity of biological functions despite sharing a common mechanochemical cycle. Motors are adapted to their function, in part, by tuning the thermodynamics and kinetics of steps in this cycle. However, it remains unclear how sequence encodes these differences, since biochemically distinct motors often have nearly indistinguishable crystal structures. We hypothesized that sequences produce distinct biochemical phenotypes by modulating the relative probabilities of an ensemble of conformations primed for different functional roles. To test this hypothesis, we modeled the distribution of conformations for 12 myosin motor domains by building Markov state models (MSMs) from an unprecedented two milliseconds of all-atom, explicit-solvent molecular dynamics simulations. Comparing motors reveals shifts in the balance between nucleotide-favorable and nucleotide-unfavorable P-loop conformations that predict experimentally measured duty ratios and ADP release rates better than sequence or individual structures. This result demonstrates the power of an ensemble perspective for interrogating sequence-function relationships
Selfâhealing encapsulation and controlled release of vaccine antigens from PLGA microparticles delivered by microneedle patches
There is an urgent need to reduce reliance on hypodermic injections for many vaccines to increase vaccination safety and coverage. Alternative approaches include controlled release formulations, which reduce dosing frequencies, and utilizing alternative delivery devices such as microneedle patches (MNPs). This work explores development of controlled release microparticles made of poly (lacticâcoâglycolic acid) (PLGA) that stably encapsulate various antigens though aqueous active selfâhealing encapsulation (ASE). These microparticles are incorporated into rapidâdissolving MNPs for intradermal vaccination.PLGA microparticles containing Alhydrogel are loaded with antigens separate from microparticle fabrication using ASE. This avoids antigen expsoure to many stressors. The microparticles demonstrate biâphasic release, with initial burst of soluble antigen, followed by delayed release of Alhydrogelâcomplexed antigen over approximately 2âmonths in vitro. For delivery, the microparticles are incorporated into MNPs designed with pedestals to extend functional microneedle length. These microneedles readily penetrate skin and rapidly dissolve to deposit microparticles intradermally. Microparticles remain in the tissue for extended residence, with MNPâinduced micropores resealing readily. In animal models, these patches generate robust immune responses that are comparable to conventional administration techniques. This lays the framework for a versatile vaccine delivery system that could be selfâapplied with important logistical advantages over hypodermic injections.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/147859/1/btm210103-sup-0001-supinfo.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/147859/2/btm210103_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/147859/3/btm210103.pd
A Modular Strategy for Fully Conjugated DonorâAcceptor Block Copolymers
A novel strategy for the synthesis of fully conjugated donorâacceptor block copolymers, in a single reaction step employing Stille coupling polymerization of end-functional polythiophene and AA + BB monomers, is presented. The unique donorâacceptor structure of these block copolymers provides a rich self-assembly behavior, with the first example of a fully conjugated donorâacceptor block copolymer having two separate crystalline domains being obtained
Structureâfunction relationships of fullerene esters in polymer solar cells: unexpected structural effects on lifetime and efficiency
We report both transport measurements and spectroscopic data of polymer/fullerene blend photovoltaics using a small library of fullerene esters to correlate device properties with a range of functionality and structural diversity of the ester substituent. We observe that minor structural changes can lead to significant and surprising differences in device efficiency and lifetime. For example we have found that isomeric R-groups in the fullerene ester-based devices we have studied have dramatically different efficiencies. The characteristic lifetimes derived from both transport and spectroscopic measurements are generally comparable; however, some more rapid effects in specific fullerene esters are not observed spectroscopically. It is apparent from our results that each fullerene derivative requires re-optimization to reveal the best device performance. Furthermore we conclude that a library approach is essential for evaluating the effects of structural differences in the constituent molecules and serves as important device optimization method that is not being currently employed in photovoltaic investigations
Disentangling the Regional Climate Impacts of Competing Vegetation Responses to Elevated Atmospheric CO<sub>2</sub>
Biophysical vegetation responses to elevated atmospheric carbon dioxide (CO(2)) affect regional hydroclimate through two competing mechanisms. Higher CO(2) increases leaf area (LAI), thereby increasing transpiration and water losses. Simultaneously, elevated CO(2) reduces stomatal conductance and transpiration, thereby increasing rootzone soil moisture. Which mechanism dominates in the future is highly uncertain, partly because these two processes are difficult to explicitly separate within dynamic vegetation models. We address this challenge by using the GISS ModelE global climate model to conduct a novel set of idealized 2ĂCO(2) sensitivity experiments to: evaluate the total vegetation biophysical contribution to regional climate change under high CO(2); and quantify the separate contributions of enhanced LAI and reduced stomatal conductance to regional hydroclimate responses. We find that increased LAI exacerbates soil moisture deficits across the subâtropics and more waterâlimited regions, but also attenuates warming by âŒ0.5â1°C in the US Southwest, Central Asia, Southeast Asia, and northern South America. Reduced stomatal conductance effects contribute âŒ1°C of summertime warming. For some regions, enhanced LAI and reduced stomatal conductance produce nonlinear and either competing or mutually amplifying hydroclimate responses. In northeastern Australia, these effects combine to exacerbate radiationâforced warming and contribute to yearâround water limitation. Conversely, at higher latitudes these combined effects result in less warming than would otherwise be predicted due to nonlinear responses. These results highlight substantial regional variation in CO(2)âdriven vegetation responses and the importance of improving model representations of these processes to better quantify regional hydroclimate impacts
Apolipoprotein E4 has extensive conformational heterogeneity in lipid-free and lipid-bound forms
The Δ4-allele variant of apolipoprotein E (ApoE4) is the strongest genetic risk factor for Alzheimer\u27s disease, although it only differs from its neutral counterpart ApoE3 by a single amino acid substitution. While ApoE4 influences the formation of plaques and neurofibrillary tangles, the structural determinants of pathogenicity remain undetermined due to limited structural information. Previous studies have led to conflicting models of the C-terminal region positioning with respect to the N-terminal domain across isoforms largely because the data are potentially confounded by the presence of heterogeneous oligomers. Here, we apply a combination of single-molecule spectroscopy and molecular dynamics simulations to construct an atomically detailed model of monomeric ApoE4 and probe the effect of lipid association. Importantly, our approach overcomes previous limitations by allowing us to work at picomolar concentrations where only the monomer is present. Our data reveal that ApoE4 is far more disordered and extended than previously thought and retains significant conformational heterogeneity after binding lipids. Comparing the proximity of the N- and C-terminal domains across the three major isoforms (ApoE4, ApoE3, and ApoE2) suggests that all maintain heterogeneous conformations in their monomeric form, with ApoE2 adopting a slightly more compact ensemble. Overall, these data provide a foundation for understanding how ApoE4 differs from nonpathogenic and protective variants of the protein
Vms1 and ANKZF1 peptidyl-tRNA hydrolases release nascent chains from stalled ribosomes
Ribosomal surveillance pathways scan for ribosomes that are transiently paused or terminally stalled owing to structural elements in mRNAs or nascent chain sequences. Some stalls in budding yeast are sensed by the GTPase Hbs1, which loads Dom34, a catalytically inactive member of the archaeo-eukaryotic release factor 1 superfamily. Hbs1âDom34 and the ATPase Rli1 dissociate stalled ribosomes into 40S and 60S subunits. However, the 60S subunits retain the peptidyl-tRNA nascent chains, which recruit the ribosome quality control complex that consists of Rqc1âRqc2âLtn1âCdc48âUfd1âNpl4. Nascent chains ubiquitylated by the E3 ubiquitin ligase Ltn1 are extracted from the 60S subunit by the ATPase Cdc48âUfd1âNpl4 and presented to the 26S proteasome for degradation. Failure to degrade the nascent chains leads to protein aggregation and proteotoxic stress in yeast and neurodegeneration in mice. Despite intensive investigations on the ribosome quality control pathway, it is not known how the tRNA is hydrolysed from the ubiquitylated nascent chain before its degradation. Here we show that the Cdc48 adaptor Vms1 is a peptidyl-tRNA hydrolase. Similar to classical eukaryotic release factor 1, Vms1 activity is dependent on a conserved catalytic glutamine. Evolutionary analysis indicates that yeast Vms1 is the founding member of a clade of eukaryotic release factor 1 homologues that we designate the Vms1-like release factor 1 clade
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