Retraction Note: Living annulative π-extension polymerization for graphene nanoribbon synthesis.

This article has been retracted. Please see the Retraction Notice for more detail: https://doi.org/10.1038/s41586-020-2950-0 .

Living annulative π-extension polymerization for graphene nanoribbon synthesis.

The properties of graphene nanoribbons (GNRs)1-5-such as conductivity or semiconductivity, charge mobility and on/off ratio-depend greatly on their width, length and edge structure. Existing bottom-up methods used to synthesize GNRs cannot achieve control over all three of these parameters simultaneously, and length control is particularly challenging because of the nature of step-growth polymerization6-18. Here we describe a living annulative π-extension (APEX)19 polymerization technique that enables rapid and modular synthesis of GNRs, as well as control over their width, edge structure and length. In the presence of palladium/silver salts, o-chloranil and an initiator (phenanthrene or diphenylacetylene), the benzonaphthosilole monomer polymerizes in an annulative manner to furnish fjord-type GNRs. The length of these GNRs can be controlled by simply changing the initiator-to-monomer ratio, achieving the synthesis of GNR block copolymers. This method represents a type of direct C-H arylation polymerization20 and ladder polymerization21, activating two C-H bonds of polycyclic aromatic hydrocarbons and constructing one fused aromatic ring per chain propagation step.

Step-Growth Annulative π-Extension Polymerization for Synthesis of Cove-Type Graphene Nanoribbons.

Graphene nanoribbons (GNRs), nanometer-wide strips of graphene, are attracting significant attention in materials science as candidates for next-generation carbon materials. As their physical properties mainly depend on their structures, the precise synthesis of structurally well-defined GNRs is highly desirable to control their properties. Herein, we report a step-growth annulative π-extension polymerization that allows for the rapid and modular synthesis of cove-type GNRs with pyrene and/or coronene diimide repeating units. The structures and photophysical properties of the separated GNRs were confirmed by various spectroscopic analyses. In addition, gas-blow-assisted uniform on-surface self-assembly of the GNRs was accomplished.

High-throughput sequencing revealed differences of microbial community structure and diversity between healthy and diseased Caulerpa lentillifera.

BACKGROUND: Caulerpa lentillifera is one of the most important economic green macroalgae in the world. Increasing demand for consumption has led to the commercial cultivation of C. lentillifera in Japan and Vietnam in recent decades. Concomitant with the increase of C. lentillifera cultivation is a rise in disease. We hypothesise that epiphytes or other microorganisms outbreak at the C. lentillifera farm may be an important factor contributing to disease in C. lentillifera. The main aims are obtaining differences in the microbial community structure and diversity between healthy and diseased C. lentillifera and key epiphytes and other microorganisms affecting the differences through the results of high-throughput sequencing and bioinformatics analysis in the present study. RESULTS: A total of 14,050, 2479, and 941 operational taxonomic units (OTUs) were obtained from all samples using 16S rDNA, 18S rDNA, and internal transcribed spacer (ITS) high-throughput sequencing, respectively. 16S rDNA sequencing and 18S rDNA sequencing showed that microbial community diversity was higher in diseased C. lentillifera than in healthy C. lentillifera. Both PCoA results and UPGMA results indicated that the healthy and diseased algae samples have characteristically different microbial communities. The predominant prokaryotic phyla were Proteobacteria, Planctomycetes, Bacteroidetes, Cyanobacteria, Acidobacteria, Acidobacteria and Parcubacteria in all sequences. Chlorophyta was the most abundant eukaryotic phylum followed by Bacillariophyta based on 18S rDNA sequencing. Ascomycota was the dominant fungal phylum detected in healthy C. lentillifera based on ITS sequencing, whereas fungi was rare in diseased C. lentillifera, suggesting that Ascomycota was probably fungal endosymbiont in healthy C. lentillifera. There was a significantly higher abundance of Bacteroidetes, Cyanobacteria, Bacillariophyta, Ulvales and Tetraselmis in diseased C. lentillifera than in healthy C. lentillifera. Disease outbreaks significantly change carbohydrate metabolism, environmental information processing and genetic information processing of prokaryotic communities in C. lentillifera through predicted functional analyses using the Tax4Fun tool. CONCLUSIONS: Bacteroidetes, Cyanobacteria, Bacillariophyta, Ulvales and Tetraselmis outbreak at the C. lentillifera farm sites was an important factor contributing to disease in C. lentillifera.

Conserved and novel heat stress-responsive microRNAs were identified by deep sequencing in Saccharina japonica (Laminariales, Phaeophyta).

As a temperate-cold species, Saccharina japonica often suffers heat stress when it is transplanted to temperate and subtropical zones. Study the heat stress response and resistance mechanism of Saccharina is of great significance for understanding the acclimation to heat stress under domestication as well as for breeding new cultivars with heat stress resistance. In this study, we identified a set of heat stress-responsive miRNAs and analysed their regulation during the heat stress response. CO (control) and heat stress (HS) sRNA libraries were constructed and sequenced. Forty-nine known miRNAs and 75 novel miRNAs were identified, of which seven known and 25 novel miRNAs were expressed differentially under heat stress. Quantitative PCR of six selected miRNAs confirmed that these loci were responsive to heat stress. Thirty-nine and 712 genes were predicted to be targeted by the seven known miRNAs and 25 novel miRNAs, respectively. Gene function and pathway analyses showed that these genes probably play important roles in S. japonica heat stress tolerance. The miRNAs identified represent the first set of heat-responsive miRNAs identified from S. japonica, and their identification can help elucidate the heat stress response and resistance mechanisms in S. japonica.

Efficient Perovskite Nanograin Light-Emitting Diodes in Green-to-Blue Gamut with Co-Additive Engineering.

Perovskite nanograins exceeding the Bohr exciton diameter show great potential for high-performance light-emitting diodes (LEDs) owing to their bandgap homogeneity, spatial charge confinement, and nonlocal interaction. However, it is challenging to directly synthesize proper nanograins along with reduced crystal defects on functional substrate, and the corresponding high-efficiency perovskite LEDs (PeLEDs) have rarely been reported. In this study, crystallization modulation for perovskites with an effective co-additive system, including lithium bromide, p-fluorophenethylammonium bromide, and 18-crown-6, is performed. Furthermore, it is demonstrated that the proposed co-additive system can synergistically retard perovskite crystallization and reduce crystal defects. Consequently, high-quality perovskite nanograin solids (≈22.8 nm) are obtained with a high photoluminescence quantum yield (≈88%). These superior optical properties contribute to developing efficient green PeLEDs with a champion external quantum efficiency (EQE) of 28.4% and an average EQE of 27.1%. The co-additive system can be universally applied to mixed-halide perovskite nanograin LED, presenting a maximum EQE of 24.4%, 21.6%, 17.5%, and 11.1% for the blue device at 496, 488, 478, and 472 nm, respectively, along with a narrow spectral linewidth (17-14 nm) and stable color. These results supplement the research on high-efficiency perovskite nanograin LEDs for multicolor displays and lighting.

Comparison of transcriptome under red and blue light culture of Saccharina japonica (Phaeophyceae).

Saccharina japonica is one of the most important economic seaweeds. Several aspects such as photosynthesis in Saccharina lives are affected by blue light, the predominant light spectrum in the habitat. In this study, transcriptome profiling of S. japonica by next generation sequencing technology generated 55,102 qualified transcripts and 40.5 % transcripts were assigned to functional annotation. Expression of a large proportion of genes has been previously reported to be regulated by blue light, taking dark as control. However, by comparison among white, blue and red light, the significantly differentially expressed gene tags (DEGs) accounted for only 6.75 % of the identified sequences. It indicated that light-regulated gene expression in kelps is not a specific blue-light response. Unexpectedly, red light had more extensive effects on the transcriptomic activity than blue light did, since the most (68.4 %) DEGs were red light-regulated and only 17.5 % were specifically regulated by blue light. Some of the DEGs with the highest mRNA levels under blue light are not blue light-upregulated but red light-downregulated. The extensive regulation on gene expression under red light together with the abundant presence of phytochrome-like protein gene tags in S. japonica indicated their significant roles in the lives of brown algae. By highlighting the photosynthetic metabolism, blue light is more efficient than red light in triggering the pigment biosynthesis, light reaction and carbon fixation, revealing a molecular basis for rapid growth of kelps, since most of the time blue light is predominant in their habitat.

In situ growth of lead-free halide perovskites into SiO2 sub-microcapsules toward water-stable photocatalytic CO2 reduction.

Halide perovskites (HPs) are highly susceptible to heat, light, or moisture and are easily decomposed even in an ambient environment, which greatly hinders their practical applications. Herein, an in situ growth strategy is presented for implanting an inorganic lead-free HP, Cs2AgBiBr6, into SiO2 sub-microcapsules to form a Cs2AgBiBr6@SiO2 yolk-shell composite. The SiO2 sub-microcapsule endows Cs2AgBiBr6 with good thermal and light stability, as well as excellent corrosion resistance against polar solvents. Furthermore, when employed as a lead-free perovskite photocatalyst, the composite exhibits a higher visible-light-driven CO2-to-CO rate (271.76 µmol g-1 h-1) and much better stability than Cs2AgBiBr6 in water. The formation of a Cs2AgBiBr6/SiO2 heterostructure using an in situ growth method alleviates water binding on the perovskites, supported by density functional theory calculations, which is the key to an improvement in the stability of the composite. The in situ growth strategy developed here sheds light on the design and development of HP-based materials for applications involving polar solvents.

Efficiently Improved Photoluminescence in Cesium Lead Halide Perovskite Nanocrystals by Using Bis(trifluoromethane)sulfonimide.

Cesium lead halide perovskite (CsPbX3, X = Cl, Br, and I) nanocrystals (NCs) have attracted enormous attention because of their great potential for optoelectronic applications, such as light-emitting diodes (LEDs). However, the photoluminescence and surface ligands of CsPbX3 NCs have a great impact on their device applications. Herein, we report a molecular superacid of bis(trifluoromethane)sulfonimide (TFSI), which could boost the photoluminescence in the metal halide perovskite nanocrystals. In particular, the photoluminescence quantum yield (PLQY) of CsPbI3 nanocrystals could be greatly improved from 28.6% to near 100% with the superacid treatment. The improved PLQY in CsPbX3 nanocrystals is mainly contributed from the surface passivation based on the characterizations. The CsPbX3 nanocrystals were further modified with PMMA, which could greatly improve their stability while preserving high photoluminescence and good dispersion. The use of superacid combined with a polymer for improving the photoluminescence and stability in CsPbX3 provides an alternative strategy for optoelectronics.

Light-emitting field-effect transistors with EQE over 20% enabled by a dielectric-quantum dots-dielectric sandwich structure.

Emerging quantum dots (QDs) based light-emitting field-effect transistors (QLEFETs) could generate light emission with high color purity and provide facile route to tune optoelectronic properties at a low fabrication cost. Considerable efforts have been devoted to designing device structure and to understanding the underlying physics, yet the overall performance of QLEFETs remains low due to the charge/exciton loss at the interface and the large band offset of a QD layer with respect to the adjacent carrier transport layers. Here, we report highly efficient QLEFETs with an external quantum efficiency (EQE) of over 20% by employing a dielectric-QDs-dielectric (DQD) sandwich structure. Such DQD structure is used to control the carrier behavior by modulating energy band alignment, thus shifting the exciton recombination zone into the emissive layer. Also, enhanced radiative recombination is achieved by preventing the exciton loss due to presence of surface traps and the luminescence quenching induced by interfacial charge transfer. The DQD sandwiched design presents a new concept to improve the electroluminescence performance of QLEFETs, which can be transferred to other material systems and hence can facilitate exploitation of QDs in a new type of optoelectronic devices.

Correlations between shape and near infrared reflective properties of nano/micro-yttria.

Yttria nanorods, nanoflakes and microshperes have been prepared via solvothermal and homogeneous precipitation methods followed by further calcining treatment, without any catalysts, templates, or substrates, in which yttrium nitrate was used as the yttrium source, sodium hydroxide and urea as the precipitators. The results show that the reflectivity of nano-yttria has significant correlations with its nanostructures. In contrast, Y2O3 microshperes possess about 90% reflectivity in the NIR region, which can be applied in energy saving and military camouflage etc.

Preparation and tunable luminescent characteristics of SiO2 coated ZnO:LiAc nanoparticles.

ZnO:LiAc nanopaticles were successfully synthesized though a colloidal-sol technique in nonaqueous solution under ultrasonic irradiation. The luminescent characteristics from blue to red can be tunable by varying [Li]/[Zn] ratios. The possible reason of tunable luminescent characteristics can be attributed to the increase of density of oxygen vacancies caused by Li+ adsorbed in the surface of magic-sized ZnO nanocrystals based on XRD, zeta potential and XPS results. What's more, it is found that SiO2 shell coated on ZnO:LiAc nanoparticles can improve the surface property of ZnO nanoparticles and enhance the PL emission intensity and optical stability. Due to its excellent luminescent characteristic and optical stability, as-prepared SiO2 coated ZnO:LiAc nanoparticles may be a promising candidate for some applications in high-efficiency low-voltage phosphor, solar cells and biological luminescent labels.

ZnO-ZnS QDs interfacial heterostructure for drug and food delivery application: enhancement of the binding affinities of flavonoid aglycones to bovine serum albumin.

Zero-dimensional nanostructures are green nanomaterials that have recently attracted increasing attention. However, very little information is available on whether or not these heterostructures affect drug transport in blood. In current work, flavonoid aglycones were studied for their affinities for bovine serum albumin (BSA) in the presence and absence of zinc oxide-zinc sulfide quantum dots (ZnO-ZnS QDs) in vitro. The fluorescence intensity of BSA decreased remarkably with increasing concentration of ZnO-ZnS QDs, resulting in an obvious red-shift of the maximum emission of BSA from 340 to 348 nm. The magnitudes of binding constants in the presence of QDs ranged from 10(4) to 10(6) L/mol, and the number of binding sites per BSA molecule (n) was determined as 1.12 ± 0.17. Although ZnO-ZnS QDs significantly increased the affinities for BSA of myricetin, luteolin, gallocatechin gallate, tectorigenin, and formononetin, they barely affected the binding affinities of flavone, (-)-epicatechin gallate, and quercetin. FROM THE CLINICAL EDITOR: Serum albumins are major transport proteins in blood that reversibly bind fatty acids, amino acids, drugs, and inorganic ions, which interactions have important effects on the distribution, free concentration, and metabolism of drugs in blood. In this research nine flavonoid aglycones were studied for their affinities for bovine serum albumin (BSA). Interestingly it was found that presence of ZnO-ZnS QDs significantly increased the affinities of BSA for several of these aglycones.

An ultrasensitive molybdenum-based double-heterojunction phototransistor.

Two-dimensional (2D) materials are promising for next-generation photo detection because of their exceptional properties such as a strong interaction with light, electronic and optical properties that depend on the number of layers, and the ability to form hybrid structures. However, the intrinsic detection ability of 2D material-based photodetectors is low due to their atomic thickness. Photogating is widely used to improve the responsivity of devices, which usually generates large noise current, resulting in limited detectivity. Here, we report a molybdenum-based phototransistor with MoS2 channel and α-MoO3-x contact electrodes. The device works in a photo-induced barrier-lowering (PIBL) mechanism and its double heterojunctions between the channel and the electrodes can provide positive feedback to each other. As a result, a detectivity of 9.8 × 1016 cm Hz1/2 W-1 has been achieved. The proposed double heterojunction PIBL mechanism adds to the techniques available for the fabrication of 2D material-based phototransistors with an ultrahigh photosensitivity.

Solution-Processed Double-Junction Quantum-Dot Light-Emitting Diodes with an EQE of Over 40.

Despite the rapid development in quantum-dot light-emitting diodes (QD-LEDs) with a single junction, it remains a big challenge to make tandem QD-LEDs with high performance. Here, we report solution-processed double-junction tandem QD-LEDs with a high external quantum efficiency of 42.2% and a high current efficiency of 183.3 cd A-1, which are comparable to those of the best vacuum-deposited tandem organic LEDs. Such high-efficiency devices are achieved by interface engineering of fully optimized single light-emitting units, which improves carriers' transport/injection balance and suppresses exciton quenching induced by ZnO, and design of an effective interconnecting layer consisting of poly(4-butylphenyl-diphenylamine) (poly-TPD)-mixed poly(9-vinylcarbazole) (PVK)/poly(3,4-ethylenedioxythiophene):polystyrene sulfonate/polyethylenimine ethoxylated-modified ZnO.

Evidence for line width and carrier screening effects on excitonic valley relaxation in 2D semiconductors.

Monolayers of transition metal dichalcogenides (TMDC) have recently emerged as excellent platforms for exploiting new physics and applications relying on electronic valley degrees of freedom in two-dimensional (2D) systems. Here, we demonstrate that Coulomb screening by 2D carriers plays a critical role in excitonic valley pseudospin relaxation processes in naturally carrier-doped WSe2 monolayers (1L-WSe2). The exciton valley relaxation times were examined using polarization- and time-resolved photoluminescence spectroscopy at temperatures ranging from 10 to 160 K. We show that the temperature-dependent exciton valley relaxation times in 1L-WSe2 under various exciton and carrier densities can be understood using a unified framework of intervalley exciton scattering via momentum-dependent long-range electron-hole exchange interactions screened by 2D carriers that depend on the carrier density and the exciton linewidth. Moreover, the developed framework was successfully applied to engineer the valley polarization of excitons in 1L-WSe2. These findings may facilitate the development of TMDC-based opto-valleytronic devices.

Highly stable perovskite solar cells with an all-carbon hole transport layer.

Nano-carbon materials (carbon nanotubes, graphene, and graphene oxide) have potential application for photovoltaics because of their excellent optical and electronic properties. Here, we demonstrate that a single-walled carbon nanotubes/graphene oxide buffer layer greatly improves the photovoltaic performance of organo-lead iodide perovskite solar cells. The carbon nanotubes/graphene oxide buffer layer works as an efficient hole transport/electron blocking layer. The photovoltaic conversion efficiency of 13.3% was achieved in the organo-lead iodide perovskite solar cell due to the complementary properties of carbon nanotubes and graphene oxide. Furthermore, the great improvement of photovoltaic performance stability in the perovskite solar cells using carbon nanotubes/graphene oxide/polymethyl methacrylate was demonstrated in comparison with that using a typical organic hole transport layer of 2,2',7,7'-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9'-spirobifluorene.

Distribution, function and evolution characterization of microsatellite in Sargassum thunbergii (Fucales, Phaeophyta) transcriptome and their application in marker development.

Using transcriptome data to mine microsatellite and develop markers has growingly become prevalent. However, characterizing the possible function of microsatellite is relatively rare. In this study, we explored microsatellites in the transcriptome of the brown alga Sargassum thunbergii and characterized the frequencies, distribution, function and evolution, and developed primers to validate these microsatellites. Our results showed that Tri-nucleotide is the most abundant, followed by di- and mono-nucleotide. The length of microsatellite was significantly affected by the repeat motif size. The density of microsatellite in the CDS region is significantly lower than that in the UTR region. The annotation of the transcripts containing microsatellite showed that 573 transcripts have GO terms and can be categorized into 42 groups. Pathways enrichment showed that microsatellites were significantly overrepresented in the genes involved in pathways such as Ubiquitin mediated proteolysis, RNA degradation, Spliceosome, etc. Primers flanking 961 microsatellite loci were designed, and among the 30 pairs of primer selected randomly for availability test, 23 were proved to be efficient. These findings provided new insight into the function and evolution of microsatellite in transcriptome, and the identified microsatellite loci within the annotated gene will be useful for developing functional markers in S. thunbergii.