Photoinduced Dynamics of a Single-Walled Carbon Nanotube with a sp3 Defect: The Importance of Excitonic Effects.

Herein, we employed linear-response time-dependent functional theory nonadiabatic dynamic simulations to explore the photoinduced exciton dynamics of a chiral single-walled carbon nanotube CNT(6,5) covalently doped with a 4-nitrobenzyl group (CNT65-NO2). The results indicate that the introduction of a sp3 defect leads to the splitting of the degenerate VBM/VBM-1 and CBM/CBM+1 states. Both the VBM upshift and the CBM downshift are responsible for the experimentally observed redshifted E11* trapping state. The simulations reveal that the photoinduced exciton relaxation dynamics completes within 500 fs, which is consistent with the experimental work. On the other hand, we also conducted the nonadiabatic carrier (electron and hole) dynamic simulations, which completely ignore the excitonic effects. The comparison demonstrates that excitonic effects are indispensable. Deep analyses show that such effects induce several dark states, which play an important role in regulating the photoinduced dynamics of CNT65-NO2. The present work demonstrates the importance of including excitonic effects in simulating photoinduced processes of carbon nanotubes. In addition, it not only rationalizes previous experiments but also provides valuable insights that will help in the future rational design of novel covalently doped carbon nanotubes with superior photoluminescent properties.

Amine- and thiol-bifunctionalized mesoporous silica material for immobilization of Pb and Cd: Characterization, efficiency, and mechanism.

In this study, a two-step functionalizing strategy by combining co-condensation with grafting procedures was employed to synthesize well-ordered Amino- and Thiol-Bifunctionalized SBA-15 (ATBS) mesoporous silica. Its physicochemical properties, performance, and mechanisms in immobilization of toxic metals Pb and Cd in water and soil were investigated. After bi-functionalization, X-ray diffractometer, transmission electron microscope, and N2 adsorption-desorption measurements confirmed that the ATBS maintained a highly-ordered mesoporous structure, large surface area and pore volume. The elemental analysis, Fourier transform infrared spectroscopy and X-ray Photoelectron Spectroscopy (XPS) evidenced the successful incorporation of amine and thiol groups into ATBS. These structure and functional characteristics of ATBS benefited Pb and Cd sorption. Sorption isotherms of Pb and Cd were better fit with Sips and Redlich-Peterson models. Sorption kinetics suggested that Pb sorption was mainly regulated by chemical reactions, whereas both diffusion process and chemical reactions were rate-regulating steps in Cd sorption. ATBS showed the maximum sorption capacities for Pb and Cd at 120 and 38 mg g-1, respectively. The sorption mechanisms revealed by XPS measurements suggested that Cd sorption was mainly attributed to thiol groups while Pb was efficiently bond to both thiol and amino groups. High and stable sorption efficiencies were attained in the pH range of 4-6, with a higher affinity towards Pb than Cd. Furthermore, its ability to immobilize Pb and Cd in soils was examined with an incubation experiment, which showed that ATBS reduced 30-56% of MgCl2-extractable Pb and Cd in a contaminated soil. The synthesized sorbent via the two-step functionalizing strategy shows high sorption efficiency towards Pb and Cd, and thus it has potential application in remediating Pb and Cd contaminated water and soils.

Arsenic accumulation and distribution in Pteris vittata fronds of different maturity: Impacts of soil As concentrations.

Arsenic (As) hyperaccumulator Pteris vittata is efficient in As uptake, translocation and accumulation, but the impacts of soil As concentrations on As accumulation and distribution in P. vittata are still unclear. The impacts of soil As (7.3, 63 and 228 mg kg-1) on plant growth and As accumulation in P. vittata after 6 months of growth were evaluated. Arsenic concentrations in the roots, midribs and pinna margin of P. vittata fronds of different maturity were determined by inductively coupled plasma mass spectrometry (ICP-MS) and scanning electron microscopy coupled with an energy dispersive spectrometer (SEM-EDS). While moderate As level at As63 didn't impact P. vittata growth, higher As at As228 decreased plant biomass by 38%. Under As stress, more As was accumulated in the senescing fronds (47%) and mature fronds (11%) than the young fronds. In senescing fronds, As concentrations in pinna margin were 2.3 times that of the midribs, consistent with As-induced necrotic symptom. Arsenic distribution based on SEM-EDS analysis revealed good correlation between Si and As in the pinnae (r = 0.49). Our data showed that As accumulation in pinna margin caused necrosis and Si may have a potential role in As detoxification in P. vittata.

Arsenic-resistance mechanisms in bacterium Leclercia adecarboxylata strain As3-1: Biochemical and genomic analyses.

Microbial arsenic transformation is important in As biogeochemical cycles in the environment. In this study, a new As-resistant bacterial strain Leclercia adecarboxylata As3-1 was isolated and its associated mechanisms in As resistance and detoxification were evaluated based on genome sequencing and gene annotations. After subjecting strain As3-1 to medium containing arsenate (AsV), AsV reduction occurred and an AsV-enhanced bacterial growth was observed. Strain As3-1 lacked arsenite (AsIII) oxidation ability and displayed lower AsIII resistance than AsV, probably due to its higher AsIII accumulation. Polymerase chain reaction and phylogenetic analysis showed that strain As3-1 harbored a typical AsV reductase gene (arsC) on the plasmids. Genome sequencing and gene annotations identified four operons phoUpstBACS, arsHRBC, arsCRDABC and ttrRSBCA, with 8 additional genes outside the operons that might have involved in As resistance and detoxification in strain As3-1. These included 5 arsC genes explaining why strain As3-1 tolerated high AsV concentrations. Besides ArsC, TtrB, TtrC and TtrA proteins could also be involved in AsV reduction and consequent energy acquisition for bacterial growth. Our data provided a new example of diverse As-regulating systems and AsV-enhanced growth without ArrA in bacteria. The information helps to understand the role of As in selecting microbial systems that can transform and utilize As.

Efficient arsenate reduction by As-resistant bacterium Bacillus sp. strain PVR-YHB1-1: Characterization and genome analysis.

Arsenate (AsV) reduction in bacteria is essential to alleviate their arsenic (As) toxicity. We isolated a Bacillus strain PVR-YHB1-1 from the roots of As-hyperaccumulator Pteris vittata. The strain was efficient in reducing AsV to arsenite (AsIII), but the associated mechanisms were unclear. Here, we investigated its As resistance and reduction behaviors and associated genes at genome level. Results showed that the strain tolerated up to 20 mM AsV. When grown in 1 mM AsV, 96% AsV was reduced to AsIII in 48 h, with its AsV reduction ability being positively correlated to bacterial biomass. Two ars operons arsRacr3arsCDA and arsRKacr3arsC for As metabolisms were identified based on draft genome sequencing and gene annotations. Our data suggested that both operons might have attributed to efficient As resistance and AsV reduction in PVR-YHB1-1, providing clues to better understand As transformation in bacteria and their roles in As transformation in the environment.

Heterologous Expression of Pteris vittata Arsenite Antiporter PvACR3;1 Reduces Arsenic Accumulation in Plant Shoots.

Arsenic (As) is a toxic carcinogen so it is crucial to decrease As accumulation in crops to reduce its risk to human health. Arsenite (AsIII) antiporter ACR3 protein is critical for As metabolism in organisms, but it is lost in flowering plants. Here, a novel ACR3 gene from As-hyperaccumulator Pteris vittata, PvACR3;1, was cloned and expressed in Saccharomyces cerevisiae (yeast), Arabidopsis thaliana (model plant), and Nicotiana tabacum (tobacco). Yeast experiments showed that PvACR3;1 functioned as an AsIII-antiporter to mediate AsIII efflux to an external medium. At 5 µM AsIII, PvACR3;1 transgenic Arabidopsis accumulated 14-29% higher As in the roots and 55-61% lower As in the shoots compared to WT control, showing lower As translocation. Besides, transgenic tobacco under 5 µM AsIII or AsV also showed similar results, indicating that expressing PvACR3;1 gene increased As retention in plant roots. Moreover, observation of PvACR3;1-green fluorescent protein fusions in transgenic Arabidopsis showed that PvACR3;1 protein localized to the vacuolar membrane, indicating that PvACR3;1 mediated AsIII sequestration into vacuoles, consistent with increased root As. In addition, soil experiments showed ∼22% lower As in the shoots of transgenic tobacco than control. Thus, our study provides a potential strategy to limit As accumulation in plant shoots, representing the first report to decrease As translocation by sequestrating AsIII into vacuoles, shedding light on engineering low-As crops to improve food safety.

Bacteria from the rhizosphere and tissues of As-hyperaccumulator Pteris vittata and their role in arsenic transformation.

Arsenic (As)-resistant bacteria are abundant in the rhizosphere and tissues of As-hyperaccumulator Pteris vittata. However, little is known about their roles in As transformation and As uptake in P. vittata. In this study, the impacts of P. vittata tissue extracts with or without surface sterilization on As transformation in solutions containing 100 µg L-1 AsIII or AsV were investigated. After 48 h incubation, the sterilized and unsterilized root extracts resulted in 45% and 73% oxidation of AsIII, indicating a role of both rhizobacteria and endobacteria. In contrast, AsV reduction was only found in rhizome and frond extracts at 3.7-24% of AsV. A total of 37 strains were isolated from the tissue extracts, which are classified into 18 species based on morphology and 16S rRNA. Phylogenic analysis showed that ∼44% isolates were Firmicutes and others were Proteobacteria except for one strain belonging to Bacteroidetes. While most endobacteria were Firmicutes, most rhizobacteria were Proteobacteria. All isolated bacteria belonged to AsV reducers except for an As-sensitive strain and one AsIII- oxidizer PVR-YHB6-1. Since As transformation was not observed in solutions after filtrating or boiling, we concluded that both rhizobacteria and endobacteria were involved in As transformation in the rhizosphere and tissues of P. vittata.