Partial flattening of the spatially extended molecular scaffold has been employed as an effective tactic to improve the device performance of a perylenediimide (PDI)-based small-molecule acceptor because the less twisted yet not completely planar molecular geometry is anticipated to improve the molecular packing and thereby attain a more suitable balance between the carrier transport ability and phase domain size. A small-molecule acceptor BF-PDI comprising four alpha-substituted PDI units attached around a 9,9'-bifluorenylidene (BF) central moiety is designed and studied in polymer solar cells. The BF group is deemed a ring-fused analogue of the tetraphenylethylene (TPE) unit. Due to the less twisted and better conjugated BF skeleton, BF-PDI displays more delocalized lowest unoccupied molecular orbital. By virtue of both the electronic and steric effects, BF-PDI is suggested to bring about superior intermolecular stacking and donor-acceptor phase separation morphology in blend films. Indeed, the experimental results show that BF-PDI displays improved charge transport ability and a higher power-conversion efficiency of 8.05% than that of TPE-PDI. Grazing-incidence wide-angle X-ray diffraction and resonant soft X-ray scattering confirm the more compact and ordered molecular packing as well as smaller domain sizes in the P3TEA/BF-PDI blend.
This study presents a comprehensive comparision between 2D and 3D hydrodynamic modeling of a pseudo-2D turbulent fluidized bed with Geldart B particle. Based on the Euler-Euler approach and the EMMS-based drag model, 2D/3D CFD models are established, their sensitivities to the restitution coefficient and the specularity coefficient are analyzed, and the 2D/3D hydrodynamic simulations are performed and compared. The simulation results show that 3D simulations are more sensitive to the restitution coefficient and the specularity coefficient than 2D simulations. At the beginning of fluidization process, 2D simulation predicts greater bubble size and higher bed expansion than 3D simulation; as a complete fluidization is achieved, 2D model exhibits higher solid concentrations in the middle transition and the upper dilute-phase regions; the fluidization process in the 2D simulation develops more quickly than that in the 3D computation. Both the 2D and 3D models could capture the global flow behavior in the bottom dense-phase region of the turbulent fluidized bed reasonably. In the middle and upper regions, however, the 2D model overestimates the solid concentration and particle velocity while the 3D simulation gives better hydrodynamic prediction. For the present pseudo-2D turbulent fluidized bed with Geldart B particle, the bottom dense-phase region resembles 2D flow and 2D simulations may be adequate; however, the middle and upper regions exhibit 3D flow and full 3D simulations are needed.
Terminally differentiated cells can be generated by lineage reprogramming, which is, however, hindered by incomplete conversion with residual initial cell identity and partial functionality. Here, we demonstrate a new reprogramming strategy by mimicking the natural regeneration route, which permits generating expandable hepatic progenitor cells and functionally competent human hepatocytes. Fibroblasts were first induced into human hepatic progenitor-like cells (hHPLCs), which could robustly expand in vitro and efficiently engraft in vivo. Moreover, hHPLCs could be efficiently induced into mature human hepatocytes (hiHeps) in vitro, whose molecular identity highly resembles primary human hepatocytes (PHHs). Most importantly, hiHeps could be generated in large quantity and were functionally competent to replace PHHs for drug-metabolism estimation, toxicity prediction and hepatitis B virus infection modeling. Our results highlight the advantages of the progenitor stage for successful lineage reprogramming. This strategy is promising for generating other mature human cell types by lineage reprogramming.
Solid fuel consumption and associated emissions from residential use are highly uncertain due to a lack of reliable statistics. In this study, we estimate solid fuel consumption and emissions from the rural residential sector in China by using data collected from a new nationwide field survey. We conducted a field survey in 2010 which covered ∼17,000 rural residential households in 183 counties in China, to obtain data for solid fuel consumption and use patterns. We then developed a Generalized Additive Model (GAM) to establish the relationship between solid fuel consumption and heating degree days (HDD), income, coal production, coal price, and vegetation coverage, respectively. The GAM was used to estimate solid fuel consumption in rural households in China at the county level. We estimated that, in 2010, 179.8Tg of coal were consumed in Chinese rural households for heating and cooking, which is 62% higher than that reported in official energy statistics. We found that large quantities of rural residential coal consumption in the North China Plain were underreported in energy statistics. For instance, estimated coal consumption in rural households in Hebei (one of most polluted provinces in China) was 20.8Tg in 2010, which is twice as high as government statistics indicate. In contrast, modeled national total consumption of crop residues (used as fuels) we found to be ∼50% lower than reported data. Combining the underlying data from the survey, the GAM and emission factors from literature, we estimate emissions from China’s rural residential sector in 2010 to be: 3.3Tg PM2.5, 0.6Tg BC, 1.2Tg OC, 2.1Tg VOC, 2.3Tg SO2, 0.4Tg NOx, 43.6Tg CO and 727.2Tg CO2, contributing to 29%, 35%, 38% and 26% of national total PM2.5, BC, OC, and CO emissions respectively. This work reveals that current emission inventories in China likely underestimate emissions from coal combustion in rural residential households due to missing coal consumption in official statistics, especially for the heavily polluted North China Plain (NCP) region. Per capita income appears to be the driving factor that results in the difference between surveyed data and official data. Residents with high income prefer commercial energy and have a higher per capita fuel consumption than lower income residents. Therefore, rural residential coal combustion may contribute even more to regional air pollution than the large contributions previously identified.
Oil sands (OS) are an important type of heavy oil deposit, for which operations in Alberta, Canada, were recently found to be a large source of secondary organic aerosol (SOA). However, SOA formation from the OS mining, processing, and subsequent tailings, especially in the presence of NOx, remains unclear. Here, photooxidation experiments for OS-related precursors under high-NOx conditions were performed using an oxidation flow reactor, in which similar to 95% of peroxy radicals (RO2) react with NO. The SOA yields under high-NOx conditions were found to be lower than yields under low-NOx conditions for all precursors, which is likely due to the higher volatilities of the products from the RO2 + NO pathway compared with RO2 + HO2. The SOA yields under high-NOx conditions show a strong dependence on pre-existing surface area (not observed in previous low-NOx experiments), again attributed to the higher product volatilities. Comparing the mass spectra of SOA formed from different precursors, we conclude that the fraction of m/z > 80 (F-80) can be used as a parameter to separate different types of SOA in the region. In addition, particle-phase organic nitrate was found to be an important component (9-23%) of OS SOA formed under high-NOx conditions. These results have implications for better understanding the atmospheric processing of OS emissions.
The current uncertainties in the reactivity and atmospheric persistence of particle-associated chemicals present a challenge for the prediction of long-range transport and deposition of emerging chemicals such as organophosphate flame retardants, which are ubiquitous in the global environment. Here, the OH-initiated heterogeneous oxidation kinetics of organophosphate flame retardants (OPFRs) coated on inert (NH4)(2)SO4 and redox-active FeSO4 particles were systematically determined as a function of relative humidity (RH). The derived reaction rate constants for the heterogeneous loss of tricresyl phosphate (TCP; k(TCP)) and tris(2-butoxyethyl) phosphate (TBEP; k(TBEP)) were in the range of (2.69-3.57) X 10(-12) and (3.06-5.55) x 10(-12) cm(3) molecules(-1) s(-1) respectively, depending on the RH and coexisting Fe(II) content. The k(TCP), (coated on (NH4)(2)SO4) was relatively constant over the investigated RH range while k(TBEP) was enhanced by up to 19% with increasing RH. For both OPFRs, the presence of Fe(II) enhanced their k by up to 53% over inert (NH4)(2)SO4. These enhancement effects (RH and Fe(II)) were attributed to fundamental changes in the organic phase state (higher RH lowered particle viscosity) and Fenton type chemistry which resulted in the formation of reactive oxygen species, respectively. Such findings serve to emphasize the importance of ambient RH, the phase state of particle-bound organics in general, and the presence of coexisting metallic species for an accurate description of the degradation kinetics and aging of particulate OPFRs in models used to evaluate their atmospheric persistence.
Soil organic matter (SOM) play an important role in soil ecology and global carbon dynamic. As one of the most sever and irreversible land use change, urbanization could alter the regional carbon storage and composition pattern. However how urbanization influence on SOM is still unclear. In this study, we collected soil samples from highly urbanized area of Beijing, China and explore the quantity and quality variations of SOM by using fluorescence spectroscopy in combine with parallel factor analysis (PARAFAC). The results shown that the soil physic-chemical properties were shaped by urbanization. Comparing to nature soil, moisture content, total organic carbon and total nitrogen in urban and rural soil significantly decreased. The fluorescence spectrum demonstrated that SOM quality was also altered by urbanization induced environmental changes. Five fluorescent compounds in SOM was identified by PARAFAC model and three of them was assigned to humic-like substances. The fluorescence intensity of humic-like substances in nature land was significantly higher than of rural and urban land, meanwhile microbial related substance accumulated in urban land in comparison with rural and nature land. The multivariate analyses further reveal the relationship between soil physic-chemical properties and SOM composition. These results suggest that urbanization could not only decrease the SOM quantity but also change the SOM composition. The SOM loss caused by urbanization was mainly consist of humic-like substance loss. Besides urbanization also stimulate the accumulation of microbial related substance in SOM which highlight the importance of microorganism is SOM dynamic.