Anomalously bright single-molecule upconversion electroluminescence.

Efficient upconversion electroluminescence is highly desirable for a broad range of optoelectronic applications, yet to date, it has been reported only for ensemble systems, while the upconversion electroluminescence efficiency remains very low for single-molecule emitters. Here we report on the observation of anomalously bright single-molecule upconversion electroluminescence, with emission efficiencies improved by more than one order of magnitude over previous studies, and even stronger than normal-bias electroluminescence. Intuitively, the improvement is achieved via engineering the energy-level alignments at the molecule-substrate interface so as to activate an efficient spin-triplet mediated upconversion electroluminescence mechanism that only involves pure carrier injection steps. We further validate the intuitive picture with the construction of delicate electroluminescence diagrams for the excitation of single-molecule electroluminescence, allowing to readily identify the prerequisite conditions for producing efficient upconversion electroluminescence. These findings provide deep insights into the microscopic mechanism of single-molecule upconversion electroluminescence and organic electroluminescence in general.

Sensitivity of Botrytis cinerea from Vineyards to Boscalid, Isofetamid, and Pydiflumetofen in Shandong Province, China.

Succinate dehydrogenase inhibitor (SDHI) fungicides are the most commonly and effectively used class of fungicides for controlling gray mold. Among them, only boscalid has been registered in China for controlling grape gray mold, whereas isofetamid and pydiflumetofen are two new SDHI fungicides that have demonstrated high efficacy against various fungal diseases. However, the sensitivity of Botrytis cinerea isolates from vineyards in China to these three fungicides is currently unknown. In this study, the sensitivity of 55 B. cinerea isolates from vineyards to boscalid, isofetamid, and pydiflumetofen was determined, with the effective concentrations for inhibiting 50% of spore germination (EC50) values ranging from 1.10 to 393, 0.0300 to 42.0, and 0.0990 to 25.5 µg ml-1, respectively. The resistance frequencies for boscalid, isofetamid, and pydiflumetofen were 60.0, 7.2, and 12.8%, respectively. Three mutations (H272R, H272Y, and P225F) were detected in the SdhB subunit, with H272R being the most prevalent (75.7%), followed by H272Y (16.2%) and P225F (8.1%). All three mutations are associated with resistance to boscalid, and of them, H272R mutants exhibited high resistance. Only P225F and H272Y mutants exhibited resistance to isofetamid and pydiflumetofen, respectively. A weakly positive cross-resistance relationship was observed between boscalid and pydiflumetofen (r = 0.38, P < 0.05). Additionally, the H272R mutants showed no significant fitness costs, whereas the remaining mutants exhibited reduced mycelial growth (P225F) and sporulation (H272Y and P225F). These results suggest that isofetamid and pydiflumetofen are effective fungicides against B. cinerea in vineyards, but appropriate rotation strategies must be implemented to reduce the selection of existing SDHI-resistant isolates.

Back focal plane imaging for light emission from a tunneling junction in a low-temperature ultrahigh-vacuum scanning tunneling microscope.

We report the design and realization of the back focal plane (BFP) imaging for the light emission from a tunnel junction in a low-temperature ultrahigh-vacuum (UHV) scanning tunneling microscope (STM). To achieve the BFP imaging in a UHV environment, a compact "all-in-one" sample holder is designed and fabricated, which allows us to integrate the sample substrate with the photon collection units that include a hemisphere solid immersion lens and an aspherical collecting lens. Such a specially designed holder enables the characterization of light emission both within and beyond the critical angle and also facilitates the optical alignment inside a UHV chamber. To test the performance of the BFP imaging system, we first measure the photoluminescence from dye-doped polystyrene beads on a thin Ag film. A double-ring pattern is observed in the BFP image, arising from two kinds of emission channels: strong surface plasmon coupled emissions around the surface plasmon resonance angle and weak transmitted fluorescence maximized at the critical angle, respectively. Such an observation also helps to determine the emission angle for each image pixel in the BFP image and, more importantly, proves the feasibility of our BFP imaging system. Furthermore, as a proof-of-principle experiment, electrically driven plasmon emissions are used to demonstrate the capability of the constructed BFP imaging system for STM induced electroluminescence measurements. A single-ring pattern is obtained in the BFP image, which reveals the generation and detection of the leakage radiation from the surface plasmon propagating on the Ag surface. Further analyses of the BFP image provide valuable information on the emission angle of the leakage radiation, the orientation of the radiating dipole, and the plasmon wavevector. The UHV-BFP imaging technique demonstrated here opens new routes for future studies on the angular distributed emission and dipole orientation of individual quantum emitters in UHV.

TaqMan-MGB PCR Method for Rapid Detection of QoI Fungicide Resistance in Chinese Populations of Plasmopara viticola.

Grape downy mildew caused by Plasmopara viticola is one of the most devastating diseases of grapevine worldwide. Quinone outside inhibitor (QoI) fungicides are commonly used for the control of the pathogen in grape fields across China. However, their recurrent use could lead to the emergence of resistance against these compounds. Based on the most common mutation in resistant isolates, a glycine to alanine substitution at amino acid position 143 (G143A) in the cytochrome b protein, a TaqMan-MGB PCR was developed for the rapid detection of resistance to the QoI fungicide azoxystrobin in P. viticola. Specificity and sensitivity of this method showed it could specifically detect the point mutations linked with QoI resistance in P. viticola, and the detection limit was 0.2 pg. It could also quantify the resistance allele even in isolate mixtures containing as little as 5% QoI-resistant P. viticola strains. With this method, a large P. viticola population (n = 2,373) was screened, and QoI-resistant isolates were identified for the first time in China. The average frequencies of the resistant genotype from eight major-grapevine regions were up to 66%. Taken together, the results not only provide a novel tool for the rapid distinction and quantification of the QoI-resistant allele in P. viticola but also provide important references for fungicide selection and application, which will facilitate resistance management of grape downy mildew and improve grape production systems in Chinese vineyards.

Wavelike electronic energy transfer in donor-acceptor molecular systems through quantum coherence.

Quantum-coherent intermolecular energy transfer is believed to play a key role in light harvesting in photosynthesis and photovoltaics. So far, a direct, real-space demonstration of quantum coherence in donor-acceptor systems has been lacking because of the fragile quantum coherence in lossy molecular systems. Here, we precisely control the separations in well-defined donor-acceptor model systems and unveil a transition from incoherent to coherent electronic energy transfer. We monitor the fluorescence from the heterodimers with subnanometre resolution through scanning tunnelling microscopy induced luminescence. With decreasing intermolecular distance, the dipole coupling strength increases and two new emission peaks emerge: a low-intensity peak blueshifted from the donor emission, and an intense peak redshifted from the acceptor emission. Spatially resolved spectroscopic images of the redshifted emission exhibit a σ antibonding-like pattern and thus indicate a delocalized nature of the excitonic state over the whole heterodimer due to the in-phase superposition of molecular excited states. These observations suggest that the exciton can travel coherently through the whole heterodimer as a quantum-mechanical wavepacket. In our model system, the wavelike quantum-coherent transfer channel is three times more efficient than the incoherent channel.

Probing intramolecular vibronic coupling through vibronic-state imaging.

Vibronic coupling is a central issue in molecular spectroscopy. Here we investigate vibronic coupling within a single pentacene molecule in real space by imaging the spatial distribution of single-molecule electroluminescence via highly localized excitation of tunneling electrons in a controlled plasmonic junction. The observed two-spot orientation for certain vibronic-state imaging is found to be evidently different from the purely electronic 0-0 transition, rotated by 90°, which reflects the change in the transition dipole orientation from along the molecular short axis to the long axis. Such a change reveals the occurrence of strong vibronic coupling associated with a large Herzberg-Teller contribution, going beyond the conventional Franck-Condon picture. The emergence of large vibration-induced transition charges oscillating along the long axis is found to originate from the strong dynamic perturbation of the anti-symmetric vibration on those carbon atoms with large transition density populations during electronic transitions.

Sublethal Effects of Chlorantraniliprole on Spodoptera litura (Lepidoptera: Noctuidae) Moth: Implication for Attract-And-Kill Strategy.

The integrated use of plant-derived volatile attractants and synthetic insecticides in attract-and-kill programs is a useful tool for integrated pest management programs reducing pesticide input. Efficient alternative insecticides are critically needed to replace methomyl, which has been banned on cruciferous vegetables in China because it is also highly toxic to nontarget organisms. In the present study, among 15 commonly used insecticides were screened for toxicity against S. litura moths, where chlorantraniliprole, flubendiamide, and emamectin benzoate was found to have the highest levels of toxicity (LC50 of 0.56, 3.85, and 6.03 mg a.i. L-1 respectively). After exposure to the low lethal concentration LC50 of chlorantraniliprole, fecundity of the moths was substantially reduced. Egg-hatching was lower for LC20- and LC50-treated moth pairs than for untreated control pairs. Net reproductive rate (R0), intrinsic rate of increase (r), and finite rate of increase (λ) were significantly reduced in LC50♀ × LC50♂ cohorts. Larval mortality was significantly higher in subsequent generations in pairs of LC50-treated moths. Chlorantraniliprole, which was most toxic and had significant sublethal effects on moths, can be used as an alternative insecticide to methomyl in the attracticide for controlling S. litura moths, and the LC50 indicated a high potential for efficacy in the control S. litura through attract-and-kill schemes.

What can single-molecule Fano resonance tell?

In this work, we showcase applications of single-molecule Fano resonance (SMFR) measurements beyond the determination of molecular excitonic energy and associated dipole orientation. We use the SMFR measurement to probe the local influence of a man-made single chlorine vacancy on the molecular transition of a single zinc phthalocyanine, which clearly reveals the lifting-up of the double degeneracy of the excited states due to defect-induced configurational changes. Furthermore, time-trace SMFR measurements at different excitation voltages are used to track the tautomerization process in a free-base phthalocyanine. Different behaviors in switching between two inner-hydrogen configurations are observed with decreasing voltages, which helps to reveal the underlying tautomerization mechanism involving both the molecular electronic excited states and vibrational excited states in the ground state.

Detection and Characterization of Carboxylic Acid Amide-Resistant Plasmopara viticola in China Using a TaqMan-MGB Real-Time PCR.

Grape production is increasing globally and so are problems with downy mildew, one of the main constraints in grape production. Downy mildew on grape is caused by Plasmopara viticola, an obligate biotrophic pathogen belonging to the oomycetes. Control of the disease is usually performed by fungicide applications, of which carboxylic acid amide (CAA) fungicides represent one of the most widely used groups of fungicides. Our previous research showed that the extensive application of CAA fungicides can result in fungicide resistance and in China, CAA-resistant isolates of P. viticola were collected from the field in 2014. To monitor the distribution and spread of CAA fungicide resistance, we developed a TaqMan-minor groove binder (MGB) real-time PCR-based method designed on a functional mutation in the PvCesA3 gene that allows efficient identification of CAA fungicide resistant and sensitive genotypes. The assay was validated on 50 isolates using Sanger sequencing and fungicide bioassays and exploited in a comprehensive survey comprising 2,227 single-sporangiophore isolates from eight major grapevine regions in China. We demonstrate that CAA fungicide resistance in P. viticola is widespread in China. On average, 53.3% of the isolates were found to be resistant, but marked differences were found between locations with percentages of resistant isolates varying from 0.3 to 96.6%. Furthermore, the frequency of CAA-resistant isolates was found to be significantly correlated with the exposure to CAA fungicides (P < 0.05). We further discussed the possibilities to apply the TaqMan-MGB real-time PCR assay to assess the frequency of fungicide-resistant P. viticola isolates in each region or vineyard, which would facilitate the correct choice of fungicide for grape downy mildew and resistance management strategies.

Electrically Driven Single-Photon Superradiance from Molecular Chains in a Plasmonic Nanocavity.

We demonstrate single-photon superradiance from artificially constructed nonbonded zinc-phthalocyanine molecular chains of up to 12 molecules. We excite the system via electron tunneling in a plasmonic nanocavity and quantitatively investigate the interaction of the localized plasmon with single-exciton superradiant states resulting from dipole-dipole coupling. Dumbbell-like patterns obtained by subnanometer resolved spectroscopic imaging disclose the coherent nature of the coupling associated with superradiant states while second-order photon correlation measurements demonstrate single-photon emission. The combination of spatially resolved spectral measurements with theoretical considerations reveals that nanocavity plasmons dramatically modify the linewidth and intensity of emission from the molecular chains, but they do not dictate the intrinsic coherence of the superradiant states. Our studies shed light on the optical properties of molecular collective states and their interaction with nanoscopically localized plasmons.

Electrically driven single-photon emission from an isolated single molecule.

Electrically driven molecular light emitters are considered to be one of the promising candidates as single-photon sources. However, it is yet to be demonstrated that electrically driven single-photon emission can indeed be generated from an isolated single molecule notwithstanding fluorescence quenching and technical challenges. Here, we report such electrically driven single-photon emission from a well-defined single molecule located inside a precisely controlled nanocavity in a scanning tunneling microscope. The effective quenching suppression and nanocavity plasmonic enhancement allow us to achieve intense and stable single-molecule electroluminescence. Second-order photon correlation measurements reveal an evident photon antibunching dip with the single-photon purity down to g (2)(0) = 0.09, unambiguously confirming the single-photon emission nature of the single-molecule electroluminescence. Furthermore, we demonstrate an ultrahigh-density array of identical single-photon emitters.Molecular emitters offer a promising solution for single-photon generation. Here, by exploiting electronic decoupling by an ultrathin dielectric spacer and emission enhancement by a resonant plasmonic nanocavity, the authors demonstrate electrically driven single-photon emission from a single molecule.

Tetra-primer ARMS PCR for rapid detection and characterisation of Plasmopara viticola phenotypes resistant to carboxylic acid amide fungicides.

BACKGROUND: The occurrence of Plasmopara viticola populations resistant to carboxylic acid amide (CAA) fungicides is becoming a serious problem in the control of grapevine downy mildew worldwide. The resistance is caused by point mutations in the PvCesA3 gene. These isolates with this mutation have been detected mainly by determining the minimum inhibitory concentration of fungicides, which is always time consuming and inefficient. RESULTS: To establish a suitable method for rapid detection of the G1105S mutation in P. viticola, an efficient and simple molecular method was developed, based on tetra-primer ARMS PCR. A set of four primers were designed and optimised to distinguish the different genotypes within one step. Only 2 h was required from the sampling of symptoms to the phenotyping of fungicide resistance. Using this method, CAA-resistant P. viticola were identified for the first time in China. Also, the finding of sensitive heterozygotes indicated that the resistant allele is spreading in the population in Ziyuan. CONCLUSION: This new method proved to be useful as an early warning system for resistance outbreaks of P. viticola to CAA fungicides in the field and may be helpful in decisions concerning rotation of different fungicide groups. © 2016 Society of Chemical Industry.

Development and application of loop-mediated isothermal amplification (LAMP) for detection of Plasmopara viticola.

A rapid LAMP (loop-mediated isothermal amplification) detection method was developed on the basis of the ITS sequence of P. viticola, the major causal agent of grape downy mildew. Among the 38 fungal and oomycete species tested, DNA isolated exclusively from P. viticola resulted in a specific product after LAMP amplification. This assay had high sensitivity and was able to detect the presence of less than 33 fg of genomic DNA per 25-µL reaction within 30 min. The infected leaves may produce sporangia that serve as a secondary inoculum. The developed LAMP assay is efficient for estimating the latent infection of grape leaves by P. viticola. When combined with the rapid and simple DNA extraction method, this assay's total detection time is shortened to approximately one hour; therefore it is suitable for on-site detection of latent infection in the field. The sporangia levels in the air are strongly associated with disease severity. The LAMP method was also demonstrated to be able to estimate the level of sporangia released in the air in a certain period. This assay should make disease forecasting more accurate and rapid and should be helpful in decision-making regarding the control of grape downy mildew.

[Purification and characterization of the haemocoel insecticide Tp40 from Xenorhabdus nematophila].

OBJECTIVE: Xenorhabdus nematophila is an insect pathogen bacterium symbiotically associated with entomopathogenic nematode. The bacteria produce a number of toxins to overcome immune response of insect hosts and kill their hosts. We purified a novel haemocoel insecticidal protein from X. nematophila HB310, cloned and analysed gene sequence of this novel protein. METHODS: We isolated and purified the insecticidal protein by methods of salting out and native-PAGE from the intracellular proteins of X. nematophila HB310. We tested the virulence of the protein by direct injection into fifth-instar Galleria mellonella larvae. The protein was identified by western blotting. The gene of insecticidal protein was cloned by PCR and analyzed in GenBank. RESULTS: We purified a novel haemocoel insecticidal protein that was named as Tp40. The injectable hemocoelic potency (LD50) of Tp40 was 68.54 ng/larva against fifth-instar G. mellonella larvae. The SDS-PAGE spectrum of Tp40 only showed a single - 42kDa band. Western blotting with an antibody that was highly specific to the known Txp40 indicated that Tp40 was homologous to the known Txp40 and only existed inside cells. The nucleotide sequences of tp40 gene have been deposited in GenBank (accession number GenBank: EU095326). The size of the open reading frame of tp40 was 1107bp, encoding a peptide of 368 amino acid residues, with a theoretical molecular weight 41.5 kDa and an isoelectricpoint (IP) 8.66. The Tp40 shared 85%-99% homology of nucleotide sequences and 70%-99% amino acids with those of 13 group strains. CONCLUSION: Tp40 is high injectable virulent for G. mellonella larvae and its gene/protein sequence is highly conserved, which play a key role during the bacterium-nematode killing host insects process.