Manipulation of Electronic States of Pt Sites via d-Band Center Tuning for Enhanced Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells.

Expediting the torpid kinetics of the oxygen reduction reaction (ORR) at the cathode with minimal amounts of Pt under acidic conditions plays a significant role in the development of proton exchange membrane fuel cells (PEMFCs). Herein, a novel Pt-N-C system consisting of Pt single atoms and nanoparticles anchored onto the defective carbon nanofibers is proposed as a highly active ORR catalyst (denoted as Pt-N-C). Detailed characterizations together with theoretical simulations illustrate that the strong coupling effect between different Pt sites can enrich the electron density of Pt sites, modify the d-band electronic environments, and optimize the oxygen intermediate adsorption energies, ultimately leading to significantly enhanced ORR performance. Specifically, the as-designed Pt-N-C demonstrates exceptional ORR properties with a high half-wave potential of 0.84 V. Moreover, the mass activity of Pt-N-C reaches 193.8 mA gPt-1 at 0.9 V versus RHE, which is 8-fold greater than that of Pt/C, highlighting the enormously improved electrochemical properties. More impressively, when integrated into a membrane electrode assembly as cathode in an air-fed PEMFC, Pt-N-C achieved a higher maximum power density (655.1 mW cm-2) as compared to Pt/C-based batteries (376.25 mW cm-2), hinting at the practical application of Pt-N-C in PEMFCs.

Engineered Gut Symbiotic Bacterium-Mediated RNAi for Effective Control of Anopheles Mosquito Larvae.

Anopheles mosquitoes are the primary vectors for the transmission of malaria parasites, which poses a devastating burden on global public health and welfare. The recent invasion of Anopheles stephensi in Africa has made malaria eradication more challenging due to its outdoor biting behavior and widespread resistance to insecticides. To address this issue, we developed a new approach for mosquito larvae control using gut microbiota-mediated RNA interference (RNAi). We engineered a mosquito symbiotic gut bacterium, Serratia fonticola, by deleting its RNase III gene to produce double-stranded RNAs (dsRNAs) in the mosquito larval gut. We found that the engineered S. fonticola strains can stably colonize mosquito larval guts and produce dsRNAs dsMet or dsEcR to activate RNAi and effectively suppress the expression of methoprene-tolerant gene Met and ecdysone receptor gene EcR, which encode receptors for juvenile hormone and ecdysone pathways in mosquitoes, respectively. Importantly, the engineered S. fonticola strains markedly inhibit the development of A. stephensi larvae and leads to a high mortality, providing an effective dsRNA delivery system for silencing genes in insects and a novel RNAi-mediated pest control strategy. Collectively, our symbiont-mediated RNAi (smRNAi) approach offers an innovative and sustainable method for controlling mosquito larvae and provides a promising strategy for combating malaria. IMPORTANCE Mosquitoes are vectors for various diseases, imposing a significant threat to public health globally. The recent invasion of A. stephensi in Africa has made malaria eradication more challenging due to its outdoor biting behavior and widespread resistance to insecticides. RNA interference (RNAi) is a promising approach that uses dsRNA to silence specific genes in pests. This study presents the use of a gut symbiotic bacterium, Serratia fonticola, as an efficient delivery system of dsRNA for RNAi-mediated pest control. The knockout of RNase III, a dsRNA-specific endonuclease gene, in S. fonticola using CRISPR-Cas9 led to efficient dsRNA production. Engineered strains of S. fonticola can colonize the mosquito larval gut and effectively suppress the expression of two critical genes, Met and EcR, which inhibit mosquito development and cause high mortality in mosquito larvae. This study highlights the potential of exploring the mosquito microbiota as a source of dsRNA for RNAi-based pest control.

Editing of the starch synthase IIa gene led to transcriptomic and metabolomic changes and high amylose starch in barley.

In this study, a range of barley allelic mutants lost ADPG binding structure of starch synthase IIa (SSIIa) were created through targeted mutagenesis of SSIIa by RNA-guided Cas9. The transcriptomic and qRT-PCR results showed the increased mRNA expression of HvGBSSI and the decreased HvSSIIa and HvSBEI levels in ssIIa mutant grains, which were consistent with the expressions of GBSSI, SSS and SBE enzymatic activities, respectively. However, the increased expressions of HvSSI cannot effectively compensate for the loss of HvSSIIa. The metabolic pathway analysis showed that the mutation of SSIIa led to increased ADP-glucose synthesis in barley grains. The ssIIa mutant grains had two and six times amylose, and RS contents in control grains, respectively, and significantly changed starch structure and functions compared to the controls. No metabolite changes could compensate for the decrease of starch biosynthesis in the ssIIa null mutant.

Re-examination of the APETALA2/Ethylene-Responsive Factor Gene Family in Barley (Hordeum vulgare L.) Indicates a Role in the Regulation of Starch Synthesis.

The APETALA2/Ethylene-Responsive factor (AP2/ERF) gene family is a large plant-specific transcription factor family, which plays important roles in regulating plant growth and development. A role in starch synthesis is among the multiple functions of this family of transcription factors. Barley (Hordeum vulgare L.) is one of the most important cereals for starch production. However, there are limited data on the contribution of AP2 transcription factors in barley. In this study, we used the recently published barley genome database (Morex) to identify 185 genes of the HvAP2/ERF family. Compared with previous work, we identified 64 new genes in the HvAP2/ERF gene family and corrected some previously misannotated and duplicated genes. After phylogenetic analysis, HvAP2/ERF genes were classified into four subfamilies and 18 subgroups. Expression profiling showed different patterns of spatial and temporal expression for HvAP2/ERF genes. Most of the 12 HvAP2/ERF genes analyzed using quantitative reverse transcription-polymerase chain reaction had similar expression patterns when compared with those of starch synthase genes in barley, except for HvAP2-18 and HvERF-73. HvAP2-18 is homologous to OsRSR1, which negatively regulates the synthesis of rice starch. Luciferase reporter gene, and yeast one-hybrid assays showed that HvAP2-18 bound the promoter of AGP-S and SBE1 in vitro. Thus, HvAP2-18 might be an interesting candidate gene to further explore the mechanisms involved in the regulation of starch synthesis in barley.

Genome-wide transcriptome profiling indicates the putative mechanism underlying enhanced grain size in a wheat mutant.

Grain size is an important trait for crops. The endogenous hormones brassinosteroids (BRs) play key roles in grain size and mass. In this study, we identified an ethyl methylsulfonate (EMS) mutant wheat line, SM482gs, with increased grain size, 1000-grain weight, and protein content, but decreased starch content, compared with the levels in the wild type (WT). Comparative transcriptomic analysis of SM482gs and WT at four developmental stages [9, 15, 20, and 25 days post-anthesis (DPA)] revealed a total of 264, 267, 771, and 1038 differentially expressed genes (DEGs) at these stages. Kyoto Encyclopedia of Genes and Genomes (KEGG) database analysis showed that some DEGs from the comparison at 15 DPA were involved in the pathway of "brassinosteroid biosynthesis," and eight genes involved in BR biosynthesis and signal transduction were significantly upregulated in SM482gs during at least one stage. This indicated that the enhanced BR signaling in SM482gs might have contributed to its increased grain size via network interactions. The expression of seed storage protein (SSP)-encoding genes in SM482gs was upregulated, mostly at 15 and 20 DPA, while most of the starch synthetase genes showed lower expression in SM482gs at all stages, compared with that in WT. The expression patterns of starch synthase genes and seed storage protein-encoding genes paralleled the decreased level of starch and increased storage protein content of SM482gs, which might be related to the increased seed weight and wrinkled phenotype. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s13205-020-02579-6.

A single-base change at a splice site in Wx-A1 caused incorrect RNA splicing and gene inactivation in a wheat EMS mutant line.

KEY MESSAGE: An EMS-induced single-base mutation at a splice site caused abnormal RNA splicing and resulted in the gene inactivation and the lack of Wx-A1 protein in a wheat EMS mutant line. An EMS-mutagenized population was generated using common wheat cv. SM126 consisting of 10,600 M2 plants. One Wx-A1 null mutant was identified through analyses of 390 grains produced from 130 M2 plants using electrophoresis analyses. The Wx-A1 sequences of parental line SM126 and M2-31 mutant were determined as 2781 bp, and there was only one SNP mutation between them. The SNP was a mutation from G to A at nucleotide sequence position 2168 bp (G2168A) downstream of the start codon which was located at the splicing site within the eighth intron. All 52 cDNA transcripts were found to be incorrectly spliced and can be summarized as five types of variations. The deletion of the exon and the exclusion of intron were structural features in abnormal splicing RNA. Together with the prediction of potential splice regulatory motifs, the mutation G2168A happened within the 5' splice site of the eighth intron and destroyed the splice donor site from GU to AU, which may have brought about a barrier against correct RNA splice, and generated abnormal mRNA, which was the mechanism of the inactivation of Wx-A1 in M2-31. The lack of Wx-A1 has resulted in changes in starch properties in the M2-31 mutant, with the reduction in amylose and starch contents. The increased grains hardness was observed in M2-31, which may be related to the lower expression level of Pinb-D1 gene. As the waxy wheat foods have a lot of advantages, the null waxy genes will be widely applied in breeding waxy wheat for varied amylose contents.

Fokker-Planck quantum master equation for mixed quantum-semiclassical dynamics.

We revisit Caldeira-Leggett's quantum master equation representing mixed quantum-classical theory, but with limited applications. Proposed is a Fokker-Planck quantum master equation theory, with a generic bi-exponential correlation function description on semiclassical Brownian oscillators' environments. The new theory has caustic terms that bridge between the quantum description on primary systems and the semiclassical or quasi-classical description on environments. Various parametrization schemes, both analytical and numerical, for the generic bi-exponential environment bath correlation functions are proposed and scrutinized. The Fokker-Planck quantum master equation theory is of the same numerical cost as the original Caldeira-Leggett's approach but acquires a significantly broadened validity and accuracy range, as illustrated against the exact dynamics on model systems in quantum Brownian oscillators' environments, at moderately low temperatures.

Minimum-exponents ansatz for molecular dynamics and quantum dissipation.

A unified theory for minimum exponential-term ansatzes on bath correlation functions is proposed for numerically efficient and physically insightful treatments of non-Markovian environment influence on quantum systems. For a general Brownian oscillator bath of frequency Ω and friction ζ, the minimum ansatz results in the correlation function a bi-exponential form, with the effective Ω¯ and friction ζ¯ being temperature dependent and satisfying Ω¯/Ω=(ζ¯/ζ)1/2=r¯BO/rBO≤ 1, where r¯BO=ζ¯/(2Ω¯) and rBO=ζ/(2Ω). The maximum value of r¯BO=rBO can effectively be reached when kBT≥ 0.8Ω. The bi-exponential correlation function can further reduce to single-exponential form, in both the diffusion (rBO≫1) limit and the pre-diffusion region that could occur when rBO≥ 2. These are remarkable results that could be tested experimentally. Moreover, the impact of the present work on the efficient and accuracy controllable evaluation of non-Markovian quantum dissipation dynamics is also demonstrated.

Optimizing hierarchical equations of motion for quantum dissipation and quantifying quantum bath effects on quantum transfer mechanisms.

We present an optimized hierarchical equations of motion theory for quantum dissipation in multiple Brownian oscillators bath environment, followed by a mechanistic study on a model donor-bridge-acceptor system. We show that the optimal hierarchy construction, via the memory-frequency decomposition for any specified Brownian oscillators bath, is generally achievable through a universal pre-screening search. The algorithm goes by identifying the candidates for the best be just some selected Padé spectrum decomposition based schemes, together with a priori accuracy control criterions on the sole approximation, the white-noise residue ansatz, involved in the hierarchical construction. Beside the universal screening search, we also analytically identify the best for the case of Drude dissipation and that for the Brownian oscillators environment without strongly underdamped bath vibrations. For the mechanistic study, we quantify the quantum nature of bath influence and further address the issue of localization versus delocalization. Proposed are a reduced system entropy measure and a state-resolved constructive versus destructive interference measure. Their performances on quantifying the correlated system-environment coherence are exemplified in conjunction with the optimized hierarchical equations of motion evaluation of the model system dynamics, at some representing bath parameters and temperatures. Analysis also reveals the localization to delocalization transition as temperature decreases.

Optimized hierarchical equations of motion theory for Drude dissipation and efficient implementation to nonlinear spectroscopies.

Hierarchical equations of motion theory for Drude dissipation is optimized, with a convenient convergence criterion proposed in advance of numerical propagations. The theoretical construction is on the basis of a Padé spectrum decomposition that has been qualified to be the best sum-over-poles scheme for quantum distribution function. The resulting hierarchical dynamics under the a priori convergence criterion are exemplified with a benchmark spin-boson system, and also the transient absorption and related coherent two-dimensional spectroscopy of a model exciton dimer system. We combine the present theory with several advanced techniques such as the block hierarchical dynamics in mixed Heisenberg-Schrödinger picture and the on-the-fly filtering algorithm for the efficient evaluation of third-order optical response functions.

Biexponential theory of Drude dissipation via hierarchical quantum master equation.

A nonperturbative quantum dissipation theory is developed based on an optimal construction of biexponential Drude bath correlation function for its influence on the system dynamics. It is an advanced hierarchical quantum master equation approach, aiming at a numerically efficient non-Markovian quantum dissipation propagator, with the support of a convenient criterion to estimate in advance its accuracy for general systems. Compared to its low level, single-exponential counterpart [R. X. Xu et al., J. Chem. Phys. 131, 214111 (2009)], the present theory remarkably improves the applicability range over all-parameter space, as tested critically with electron transfer and frequency-dispersed transient absorption of exciton dimer model systems.