Theoretical Studies on the Redox-Stimulated Isomerization in Electrochromic Osmium Sulfoxide Complexes

Redox-stimulated intramolecular isomerization of the DMSO ligand in [Os­(bpy)₂(DMSO)₂]²⁺ (bpy = 2,2′-bipyridine; DMSO = dimethyl sulfoxide) was explored theoretically for better understanding the electrochromic properties of osmium sulfoxide complexes. It is found that the HOMO–LUMO gap is decreased because the electron transfer amount from DMSO1 ligand to Os center using Os–S₁ linkage is larger than that using Os–O₁ linkage, which makes the absorption of such electrochromic Os­(II) sulfoxide complexes red-shifted. Moreover, it is observed that Os–O linkage is preferred by the “hard” Os­(III) metal and the “soft” Os­(I) metal prefers Os–S linkage, compared with Os­(II). Intrinsic reaction pathway calculation results demonstrate that Os–S₁ → Os–O₁ isomerization is favored by Os­(II) oxidation, while Os–O₁ → Os–S₁ isomerization is much easier to be triggered by reduction of Os­(III) or Os­(II). In addition, DMSO2 linkage isomerization becomes much harder to proceed attributed to the increased bond-strength between DMSO2 and Os center upon Os­(II)–O₁ → Os­(II)–S₁ rearrangement, which makes only one DMSO ligand isomerized observed experimentally

Modeling Evidence of Episodic Intercontinental Long-Range Transport of Lindane

Two global atmospheric transport models for persistent toxic substances were employed to quantify the intercontinental atmospheric transport of lindane in 2005 using a recently constructed global lindane emission inventory. The focus of this numerical investigation was to identify, on an intercontinental scale, the major sources of lindane that contributed to the contamination of North America and the Arctic. Both models simulated several strong episodic trans-Pacific atmospheric transport events of lindane from its sources in Asia to the western seaboard of North America. Modeling results also detected, for the first time, an important atmospheric pathway for persistent toxic substances from Western Africa/Western Europe to the Caribbean, the southern United States, and the eastern seaboard of North America. Several episodic lindane trans-Atlantic atmospheric transport events were found from May to October. These events were associated primarily with the easterly trade winds and the African easterly wave that extends from the subtropical eastern Atlantic to the Caribbean. This atmospheric pathway for toxic chemicals has a substantial implication for the level of toxic substances in North America. Atmospheric mechanisms contributing to these transport events are briefly discussed. Multiple modeling scenarios were studied to assess the contribution of lindane sources in Europe, Asia, and North America to its fate in the Arctic. Results show that these continental contributions are season-dependent with the highest contribution from Europe in the spring

Abnormal Negative Thermal Quenching of Photoluminescence (PL) in Laser-Induced Exfoliated Black Phosphorus Quantum Dots for Applications as a Semiconductor PL Nanomaterial

Black phosphorus quantum dots (BPQDs) are promising candidates for semiconductor photoluminescence (PL) nanomaterials with the desired blue-violet emission and size-tuned optical response. Here, three prominent PL peaks were observed in the BPQDs with uniform nanosize, which were fabricated by pulsed-laser ablation of black phosphorus crystals. A sharp increase in the peak intensity was observed in the narrow temperature range of 225–250 K. This anomalous temperature dependence of the PL intensity is derived from negative thermal quenching, in which more electrons that are restricted in the intermediate states are thermally activated and excited to the lowest unoccupied molecular orbital (LUMO) with increasing temperature. The intermediate states were formed due to the defects induced by laser ablation. Consequently, the radiative transitions from LUMO to the σinner, σouter, and surface states dominate. By contrast, in the temperature ranges of 200–225 and 250–320 K, the PL intensity decreases because of normal thermal quenching, which usually occurs in conventional PL materials. The fitting result shows a nonmonotonicity similar to that in the negative thermal quenching semiconductors, reflecting the competition between normal and negative thermal quenching with changing temperature. Furthermore, the PL peak positions are blue-shifted with increasing temperature, which is associated with the stronger electron–phonon coupling and the lattice thermal expansion caused by transverse optical vibrations. The peak full width at half-maximum values broadened with temperature, which is attributed to the exciton–phonon interaction. This work is of great significance for not only a comprehensive understanding of the PL mechanism of the BPQDs but also the design of BPQDs-based optoelectrical nanodevices

The application of N-butyl Phosphorothioate Triamine and Dicyandiamide changes the soil N₂O production path

This study aims to explore the effect of nitrification inhibitor combined with urease inhibitor on soil N2O emission under different nitrogen application depths. We carried out a soil column simulation test under 25°C. The combination of 1% N-butyl Phosphorothioate Triamine (NBPT) and 5% Dicyandiamide (DCD) was added to the soil. Anaerobically digested pig slurry (ADPS) was used as a nitrogen source and applied to four soil depths (soil surface (0 cm), 5 cm, 10 cm, and 15 cm, respectively). It was found that the inhibitory effects of NBPT and DCD on the soil N2O emission were significantly affected by different nitrogen application depths. When the ADPS was applied at 15 cm, 10 cm, and on the soil surface, the combination of 1% NBPT and 5% DCD could inhibit soil N2O emission by 46.1%, 21.7%, and 34.6%, respectively. Redundancy analysis (RDA) showed that the addition of inhibitors changed the microbial paths of soil N2O production. The dominant microbial path of soil N2O production after adding inhibitors was from ammonia oxidation dominated by AOB-amoA to denitrification dominated by nirS and nirK.</p

Table_3_Search for Nutritional Fitness Traits in a Biological Pest Control Agent Harmonia axyridis Using Comparative Transcriptomics.XLS

Harmonia axyridis is an important natural predator used in the biological control of insect pests. Vitellogenin (Vg) supplementation to artificial diet can improve fecundity of H. axyridis, however, the effects of Vg on physiology of H. axyridis at the molecular level is unclear. This study investigated the effects of Vg on the physiology (digestive enzyme activities) and transcriptome patterns by feeding H. axyridis adults with treatment (artificial diet with Vg supplement) and control (artificial diet supplemented with bovine serum albumin (BSA). The transcriptome sequencing yielded 43.94 Gb of clean data, and 3,946 differentially expressed genes (DEGs) – including 93 upregulated and 3,853 downregulated genes between the treatment and control. Six DEGs related to development and digestive enzyme were chosen for quantitative real-time PCR (qRT-PCR) to validate the accuracy of the RNA-seq results and confirmed that the transcriptome analysis yielded reliable results. The Vg supplement has increased activities of digestive enzymes and related genes expression in H. axyridis. The transcript level of digestive enzyme genes (apolipoprotein D and phosphoenolpyruvate carboxykinase) were much higher in adults fed on diet supplemented with Vg compared with that of the control.</p

Table_4_Search for Nutritional Fitness Traits in a Biological Pest Control Agent Harmonia axyridis Using Comparative Transcriptomics.XLS

Harmonia axyridis is an important natural predator used in the biological control of insect pests. Vitellogenin (Vg) supplementation to artificial diet can improve fecundity of H. axyridis, however, the effects of Vg on physiology of H. axyridis at the molecular level is unclear. This study investigated the effects of Vg on the physiology (digestive enzyme activities) and transcriptome patterns by feeding H. axyridis adults with treatment (artificial diet with Vg supplement) and control (artificial diet supplemented with bovine serum albumin (BSA). The transcriptome sequencing yielded 43.94 Gb of clean data, and 3,946 differentially expressed genes (DEGs) – including 93 upregulated and 3,853 downregulated genes between the treatment and control. Six DEGs related to development and digestive enzyme were chosen for quantitative real-time PCR (qRT-PCR) to validate the accuracy of the RNA-seq results and confirmed that the transcriptome analysis yielded reliable results. The Vg supplement has increased activities of digestive enzymes and related genes expression in H. axyridis. The transcript level of digestive enzyme genes (apolipoprotein D and phosphoenolpyruvate carboxykinase) were much higher in adults fed on diet supplemented with Vg compared with that of the control.</p

Nutrigenomics in <i>Arma chinensis</i>: Transcriptome Analysis of <i>Arma chinensis</i> Fed on Artificial Diet and Chinese Oak Silk Moth <i>Antheraea pernyi</i> Pupae

<div><p>Background</p><p>The insect predator, <i>Arma chinensis</i>, is capable of effectively controlling many pests, such as Colorado potato beetle, cotton bollworm, and mirid bugs. Our previous study demonstrated several life history parameters were diminished for <i>A. chinensis</i> reared on an artificial diet compared to a natural food source like the Chinese oak silk moth pupae. The molecular mechanisms underlying the nutritive impact of the artificial diet on <i>A. chinensis</i> health are unclear. So we utilized transcriptome information to better understand the impact of the artificial diet on <i>A. chinensis</i> at the molecular level.</p> <p>Methodology/Principal Findings</p><p>Illumina HiSeq2000 was used to sequence 4.79 and 4.70 Gb of the transcriptome from pupae-fed and artificial diet-fed <i>A. chinensis</i> libraries, respectively, and a <i>de novo</i> transcriptome assembly was performed (Trinity short read assembler). This resulted in 112,029 and 98,724 contigs, clustered into 54,083 and 54,169 unigenes for pupae-fed and diet-fed <i>A. chinensis,</i> respectively. Unigenes from each sample’s assembly underwent sequence splicing and redundancy removal to acquire non-redundant unigenes. We obtained 55,189 unigenes of <i>A. chinensis</i>, including 12,046 distinct clusters and 43,143 distinct singletons. Unigene sequences were aligned by BLASTx to nr, Swiss-Prot, KEGG and COG (E-value <10⁻⁵), and further aligned by BLASTn to nt (E-value <10⁻⁵), retrieving proteins of highest sequence similarity with the given unigenes along with their protein functional annotations. Totally, 22,964, 7,898, 18,069, 15,416, 8,066 and 5,341 unigenes were annotated in nr, nt, Swiss-Prot, KEGG, COG and GO, respectively. We compared gene expression variations and found thousands of genes were differentially expressed between pupae-fed and diet-fed <i>A. chinensis</i>.</p> <p>Conclusions/Significance</p><p>Our study provides abundant genomic data and offers comprehensive sequence information for studying <i>A. chinensis</i>. Additionally, the physiological roles of the differentially expressed genes enable us to predict effects of some dietary ingredients and subsequently propose formulation improvements to artificial diets.</p> </div

Strong Coupling of Plasmonic Nanorods with a MoSe₂ Monolayer in the Near-Infrared Shortwave Region

Strong room-temperature light–matter coupling between quantum emitters and plasmonic nanoparticles is a central issue in nanophotonics. However, few studies have reported on the coherent states in the near-infrared shortwave region (NIR-I). In this study, a hybrid system composed of a single gold nanorod (Au NR) and a MoSe2 monolayer was constructed. By tuning the length-to-diameter ratio of the single-anisotropy Au NR to match the exciton energy of MoSe2 at 1.57 eV (791 nm), Rabi splitting of up to 75 meV was obtained via the dark-field scattering spectrum. Moreover, theoretical calculations using the finite-difference time-domain method were obtained and found to correspond with the experimental spectral results. This is attributed to the mode volume reduction and localized electric field distribution at the NIR-I resonance peak. These results facilitate obtaining and manipulating strong room-temperature light–matter couplings in the NIR-I region

Additional file 6: of De novo transcriptome sequencing and analysis of Coccinella septempunctata L. in non-diapause, diapause and diapause-terminated states to identify diapause-associated genes

S6-The primer of qRT-PCR. (XLSX 10.3 kb

Effect of culture residence time on substrate uptake and storage by a pure culture of Thiothrix (CT3 strain) under continuous or batch feeding

A pure culture of the filamentous bacterium Thiothrix, strain CT3, was aerobically cultured in a chemostat under continuous acetate feeding at three different culture residence times (RT 6, 12 or 22 d) and the same volumetric organic load rate (OLR 0.12 gCOD/L/d). Cells cultured at decreasing RT in the chemostat had an increasing transient response to acetate spikes in batch tests. The maximum specific acetate removal rate increased from 25 to 185 mgCOD/gCOD/h, corresponding to a 1.8 to 8.1 fold higher respective steady-state rate in the chemostat. The transient response was mainly due to acetate storage in the form of poly(3-hydroxybutyrate) (PHB), whereas no growth response was observed at any RT. Interestingly, even though the storage rate also decreased as the RT increased, the storage yield increased from 0.41 to 0.50 COD/COD. This finding does not support the traditional view that storage plays a more important role as the transient response increases. The transient response of the steady-state cells was much lower than in cells cultured under periodic feeding (at 6 d RT, from 82 to 247 mgCOD/gCOD/h), with the latter cells showing both storage and growth responses. On the other hand, even though steady-state cells had no growth response and their storage rate was also less, steady-state cells showed a higher storage yield than cells cultured under dynamic feeding. This suggests that in Thiothrix strain CT3, the growth response is triggered by periodic feeding, whereas the storage response is a constitutive mechanism, independent from previous acclimation to transient conditions