On the role of asymmetric molecular geometry in high-performance organic solar cells.

Although asymmetric molecular design has been widely demonstrated effective for organic photovoltaics (OPVs), the correlation between asymmetric molecular geometry and their optoelectronic properties is still unclear. To access this issue, we have designed and synthesized several symmetric-asymmetric non-fullerene acceptors (NFAs) pairs with identical physical and optoelectronic properties. Interestingly, we found that the asymmetric NFAs universally exhibited increased open-circuit voltage compared to their symmetric counterparts, due to the reduced non-radiative charge recombination. From our molecular-dynamic simulations, the asymmetric NFA naturally exhibits more diverse molecular interaction patterns at the donor (D):acceptor (A) interface as compared to the symmetric ones, as well as higher D:A interfacial charge-transfer state energy. Moreover, it is observed that the asymmetric structure can effectively suppress triplet state formation. These advantages enable a best efficiency of 18.80%, which is one of the champion results among binary OPVs. Therefore, this work unambiguously demonstrates the unique advantage of asymmetric molecular geometry, unveils the underlying mechanism, and highlights the manipulation of D:A interface as an important consideration for future molecular design.

Versatile Sequential Casting Processing for Highly Efficient and Stable Binary Organic Photovoltaics.

Forming an ideal bulk heterojunction (BHJ) morphology is a critical issue governing the photon to electron process in organic solar cells (OSCs). Complementary to the widely-used blend casting (BC) method for BHJ construction, sequential casting (SC) can also enable similar or even better morphology and device performance for OSCs. Here, BC and SC methods on three representative donor:acceptor (D:A) blends are utilized, that is, PM6:PC71 BM, PM6:IT-4F and PM6:L8-BO. Higher power conversion efficiencies (PCEs) in all cases by taking advantage of beneficial morphology from SC processing are achieved, and a champion PCE of 18.86% (certified as 18.44%) based on the PM6:L8-BO blend is reached, representing the record value among binary OSCs. The observations on phase separation and vertical distribution inspire the proposal of the swelling-intercalation phase-separation model to interpret the morphology evolution during SC processing. Further, the vertical phase segregation is found to deliver an improvement of device performance via affecting the charge transport and collection processes, as evidenced by the D:A-ratio-dependent photovoltaic properties. Besides, OSCs based on SC processing show advantages on device photostability and upscale fabrication. This work demonstrates the versatility and efficacy of the SC method for BHJ-based OSCs.

High-Efficiency ITO-Free Organic Photovoltaics with Superior Flexibility and Upscalability.

Developing indium-tin-oxide (ITO)-free flexible organic photovoltaics (OPVs) with upscaling capacity is of great significance for practical applications of OPVs. Unfortunately, the efficiencies of the corresponding devices lag far behind those of ITO-based rigid small-area counterparts. To address this issue, an advanced device configuration is designed and fabricated featuring a top-illuminated structure with ultrathin Ag as the transparent electrode. First, a conjugated polyelectrolyte layer, i.e., PCP-Li, is inserted to effectively connect the bottom Ag anode and the hole transport layer, achieving good photon to electron conversion. Second, charge collecting grids are deposited to suppress the increased resistance loss with the upscaling of the device area, realizing almost full retention of device efficiency from 0.06 to 1 cm2 . Third, the designed device delivers the best efficiency of 15.56% with the area of 1 cm2 on polyimide substrate, representing as the record among the ITO-free, large-area, flexible OPVs. Interestingly, the device exhibits no degradation after 100 000 bending cycles with a radius of 4 mm, which is the best result for flexible OPVs. This work provides insight into device structure design and optimization for OPVs with high efficiency, low cost, superior flexibility, and upscaling capacity, indicating the potential for the future commercialization of OPVs.

Synergistic Effects of Chlorination and Branched Alkyl Side Chain on the Photovoltaic Properties of Simple Non-Fullerene Acceptors with Quinoxaline as the Core.

To date, the fused-ring electron acceptors show the best photovoltaic performances, and the development of simple non-fullerene acceptors via intramolecular noncovalent interactions can reduce synthetic costs. In this work, four simple non-fullerene acceptors with an A-D-A'-D-A configuration (QCIC1, QCIC2, QCIC3, and QCIC4) were synthesized. They contained the same conjugated backbone (A': quinoxaline; D: cyclopentadithiophene; A: dicyano-indanone) but different halogen atoms and alkyl side chains. Due to the chlorination on the end-groups and the most and/or longest branched alkyl side chains on the backbone, the blended film composed of QCIC3 and donor poly{[2,6'-4,8-di(5-ethylhexylthienyl)benzo [1,2-b : 4,5-b']dithiophene]-alt-[5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c : 4',5'-c']dithiophene-4,8-dione)]} (PBDB-T) exhibited the strongest π-π stacking and the most suitable phase-separation domains among the four blended films. Therefore, the QCIC3-based organic solar cells yielded the highest power conversion efficiency of 10.55 %. This work provides a pathway to optimize the molecular arrangements and enhance the photovoltaic property of simple electron acceptors through subtle chemical modifications.

Hierarchically micro-mesoporous ß-cyclodextrin polymers used for ultrafast removal of micropollutants from water.

Persistent organic pollutants, including plasticizers, pesticides, pharmaceuticals and endocrine disrupters, have posed a serious threat to water safety and human health. Addressing this problem calls out new materials of purifying water with high efficiency. Here, a series of cross-linked ß-cyclodextrin polymers (ß-CDPs) with hierarchically micro-mesoporous structure and high surface area were first synthesized by introducing polymer of intrinsic microporosity (PIM) and used for adsorptive removal of organic micropollutants from water. The chemical compositions and porous structures of the obtained ß-CDPs were characterized in detail. Adsorption data showed that the quasi-second-order adsorption rate constant and maximal adsorption capacity of ß-CDPs towards bisphenol A was up to 3.88 g mg-1 min-1 and 502 mg g-1, almost 2.6 and 5.7 times as large as those of the state-of-the-art porous ß-CD polymer, respectively. Further, hierarchically porous ß-CDPs also demonstrated ultrafast adsorption rates and high adsorption capacities towards various organic pollutants under the synergistic effect of micropores and mesopores. In addition, ß-CDPs were easily regenerated by simple ethanol cleaning and kept high removal ability over 5 cycles. The virtues of extraordinary adsorption ability and convenient regeneration offer ß-CDPs potential applications in water purification.

Use of propidium monoazide and increased amplicon length reduce false-positive signals in quantitative PCR for bioburden analysis.

Rapid microbiological methods (RMMs) as an alternative to conventional cultivation-based bioburden analysis are receiving increasing attention although no single technology is currently able to satisfy the needs of the health care industry. Among the RMMs, quantitative PCR (qPCR) seems particularly suited. Its implementation is, however, hampered by false-positive signals originating from free DNA in PCR reagents or from dead cells in the samples to be analysed. In this study, we assessed the capability of propidium monoazide (PMA) to inactivate exogenous DNA in PCR reagents and thus to minimise its impact in bioburden analysis. PMA is a membrane-impermeant dye that intercalates into DNA and covalently binds to it upon photoactivation leading to strong inhibition of PCR amplification. PMA is currently used mainly for treatment of microbiological samples to exclude signals from membrane-compromised cells, but is also very useful for suppression of exogenous DNA signals. In addition to testing the effect of different PMA concentrations on non-template controls and target DNA, we demonstrate the effect of amplicon length on the exclusion of background amplification. Targeting a 1,108-bp 16S rRNA gene fragment using universal bacterial primers and PCR reagents treated with 5 µM PMA resulted in complete suppression of signals from exogenous DNA within 50 cycles of amplification, while a limit of detection of 10 copies of Escherichia coli genomic DNA per PCR reaction was achieved. A combined PMA treatment of sample and PCR reagents furthermore improved the selective detection of live cells making this method appear a highly attractive RMM.

Use of image-based flow cytometry in bacterial viability analysis using fluorescent probes.

This protocol was developed to utilize imaging flow cytometry (IFCM) in combination with fluorescent dyes to both enumerate and analyze morphological features of live and dead cells in a mixed live/dead bacterial sample. The fluorescent dyes used in this protocol include 5(6)-carboxyfluorescein diacetate (CFDA), which indicates the functional activity of esterase inside viable bacterial cells, and DRAQ7, a dye that exploits membrane-compromised bacterial cells to enter and stain the cell. The live cell population stained with CFDA emits a fluorescent green color while the dead cell population stained with DRAQ7 emits a fluorescent red color, which allows the two populations to be distinctively separated by the IFCM system. Additionally, the cytometer captures a clear image of each object, which can then be analyzed for morphology features. The IFCM system is able to reliably, accurately, and precisely determine a bacterial cell concentration as long as the concentration of cells in a sample is no less than 1 × 10(3) cells/ml. The two dyes, CFDA and DRAQ7, have been demonstrated to be an effective stain combination for bacterial viability analysis.

Synergistic effects of sodium chloride, glucose, and temperature on biofilm formation by Listeria monocytogenes serotype 1/2a and 4b strains.

Biofilm formation by Listeria monocytogenes is generally associated with its persistence in the food-processing environment. Serotype 1/2a strains make up more than 50% of the total isolates recovered from food and the environment, while serotype 4b strains are most often associated with major outbreaks of human listeriosis. Using a microplate assay with crystal violet staining, we examined biofilm formation by 18 strains of each serotype in tryptic soy broth with varying concentrations of glucose (from 0.25% to 10.0%, wt/vol), sodium chloride (from 0.5% to 7.0%, wt/vol) and ethanol (from 1% to 5.0%, vol/vol), and at different temperatures (22.5 degrees C, 30 degrees C, and 37 degrees C). A synergistic effect on biofilm formation was observed for glucose, sodium chloride, and temperature. The serotype 1/2a strains generally formed higher-density biofilms than the 4b strains under most conditions tested. Interestingly, most serotype 4b strains had a higher growth rate than the 1/2a strains, suggesting that the growth rate may not be directly related to the capacity for biofilm formation. Crystal violet was found to stain both bacterial cells and biofilm matrix material. The enhancement in biofilm formation by environmental factors was apparently due to the production of extracellular polymeric substances instead of the accumulation of viable biofilm cells.

Competition of Listeria monocytogenes serotype 1/2a and 4b strains in mixed-culture biofilms.

The majority of Listeria monocytogenes isolates recovered from foods and the environment are strains of serogroup 1/2, especially serotypes 1/2a and 1/2b. However, serotype 4b strains cause the majority of human listeriosis outbreaks. Our investigation of L. monocytogenes biofilms used a simulated food-processing system that consisted of repeated cycles of growth, sanitation treatment, and starvation to determine the competitive fitness of strains of serotypes 1/2a and 4b in pure and mixed-culture biofilms. Selective enumeration of strains of a certain serotype in mixed-culture biofilms on stainless steel coupons was accomplished by using serotype-specific quantitative PCR and propidium monoazide treatment to prevent amplification of extracellular DNA or DNA from dead cells. The results showed that the serotype 1/2a strains tested were generally more efficient at forming biofilms and predominated in the mixed-culture biofilms. The growth and survival of strains of one serotype were not inhibited by strains of the other serotype in mixed-culture biofilms. However, we found that a cocktail of serotype 4b strains survived and grew significantly better in mixed-culture biofilms containing a specific strain of serotype 1/2a (strain SK1387), with final cell densities averaging 0.5 log(10) CFU/cm(2) higher than without the serotype 1/2a strain. The methodology used in this study contributed to our understanding of how environmental stresses and microbial competition influence the survival and growth of L. monocytogenes in pure and mixed-culture biofilms.

Escherichia coli O157:H7 strains isolated from environmental sources differ significantly in acetic acid resistance compared with human outbreak strains.

A number of studies on the influence of acid on Escherichia coli O157:H7 have shown considerable strain differences, but limited information has been reported to compare the acid resistance based on the different sources of E. coli O157:H7 isolates. The purpose of this study was to determine the survival of E. coli O157:H7 strains isolated from five sources (foods, bovine carcasses, bovine feces, water, and human) in 400 mM acetic acid solutions under conditions that are typical of acidified foods. The isolates from bovine carcasses, feces, and water survived acetic acid treatment at pH 3.3 and 30 degrees C significantly (P < or = 0.05) better than did any food or human isolates. However, resistance to acetic acid significantly increased as temperature decreased to 15 degrees C for a given pH, with little (P > or = 0.05) difference among the different isolation sources. All groups of E. coli O157:H7 strains showed more than 1.8- to 4.5-log reduction at pH 3.3 and 30 degrees C after 25 min. Significantly reduced (less than 1-log reduction) lethality for all E. coli O157:H7 strain mixtures was observed when pH increased to 3.7 or 4.3, with little difference in acetic acid resistance among the groups. The addition of glutamate to the acetic acid solution or anaerobic incubation provided the best protection compared with the above conditions for all groups of isolates. These results suggest that temperature, pH, and atmospheric conditions are key factors in establishing strategies for improving the safety of acidified foods.