Four coordination polymers
∞
2
Ni(DMF)(L)Ln(bdc)
1.5
(Ln
=
La (
1
) and Nd (
4
)) and
∞
2
Ni
2
(DMF)
2
(L)
2
Ln
2
(bdc)
3
·CH
3
OH (Ln
=
Ce (
2
) and Pr (
3
)) were derived from a symmetrical ...salamo-based ligand (H
2
L) with Ni(OAc)
2
·4H
2
O, Ln(NO
3
)
3
·6H
2
O (Ln = La, Ce, Pr and Nd), and H
2
bdc (terephthalic acid). Coordination polymers
1
–
4
were synthesized and characterized by elemental analyses, X-ray single crystal diffraction, infrared spectroscopy and ultraviolet–visible absorption spectroscopy. Coordination polymers
1
–
4
have similar structures exhibiting two-dimensional coordination polymers with brick wall in which Ni(DMF)(L)Ln units were linked by exodentate (bdc)
2−
linker. In each unit, Ni(II) atoms adopted a slightly distorted octahedral geometry, the Ln(III) atoms were nine-coordinated, and the coordination polyhedron was a distorted tricapped trigonal prism. The crystal structure and supramolecular features were discussed in detail. At the same time, the fluorescent properties of coordination polymers
1
–
4
were also investigated.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OBVAL, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
In this paper, a salamo-based copper(
ii
) complex probe
L-Cu
2+
was synthesized, which combined with copper(
ii
) ions to form
L-Cu
2+
for the detection of S
2−
and had a good fluorescence chemical ...response. Through spectral analysis, we found that S
2−
could be identified with high sensitivity and selectivity in the presence of various anions and could be used for the detection of S
2−
by the naked eye. With the addition of S
2−
, the solution color changed from colorless to bright yellow. UV absorption, fluorescence and other characterization methods were carried out, and the mechanism of action was determined. In addition, we performed a visual inspection of H
2
S gas, and the probe
L-Cu
2+
could detect S
2−
in the gas molecules, revealing its potential application value in biology and medicine.
A highly sensitive and selective salamo-based copper(
ii
) complex probe,
L-Cu
2+
, was synthesized; it could be used for the detection of S
2−
by UV and fluorescence spectroscopies. And it also could detect S
2−
in gas molecules.
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IJS, KILJ, NUK, UL, UM, UPUK
Rhizosphere effect of nanoscale zero‐valent iron (nZVI) is crucial but little reported. Maize seeds were dressed with four nZVI concentrations (0, 1.0, 1.5, 2 g kg−1) and inoculated with arbuscular ...mycorrhizal fungus (AMF) (Funneliformis mosseae). The SEM images illuminated that excessive nZVI particles (2 g kg−1) were agglomerated on the surface of hyphae and spore, causing severe deformation and inactivation of AMF symbionts and thereafter inhibiting water uptake in maize seedlings. This restrained the scavenging effects of enzymatic (superoxide dismutase, peroxidase) and non‐enzymatic compounds (proline & malondialdehyde) on ROS, and leaf photoreduction activity and gas exchange ability (p < 0.05). Interestingly, the inoculation with AMF effectively alleviated above negative effects. In contrast, appropriate dose of nZVI, that is, ≤1.5 g kg−1, can be evenly distributed on the hyphae surface and form the ordered symbionts with AMF. This help massively to enhance hyphae growth and water and nutrient uptake. The enhanced mycorrhizal infection turned to promote rhizosphere symbiont activity and leaf Rubisco and Rubisco activase activity. Light compensation point was massively lowered, which increased photosynthetic carbon supply for AMF symbionts. Particularly, such priming effects were evidently enhanced by drought stress. Our findings provided a novel insight into functional role of nZVI in agriculture and AMF‐led green production.
Summary Statement
Proper dose of nZVI can form orderly rhizosphere symbiont with AMF, improve the Rubisco and Rubisco activity for higher assimilation rate, and promote carbon supply for AMF colonization. Yet, excessive nZVI turned to cause severe structural deformation and inactivation of AMF symbionts.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
•Two multi-nuclear Ni(II)-based complexes have been successfully prepared by the complexation of more flexible salamo-type ligand (H2L) with nickel salts of different anions.•The structure of ...tetra-nuclear complex 2 is particularly unique because the flexibility of the ligand is better, which creates conditions for the intramolecular self-assembly.
Two new tri- and tetra-nuclear Ni(II)-based complexes, {NiL(EtOH)(μ-OAc)}2Ni·4EtOH (1) and Ni4L2(μ3-OMe)4(MeOH)4 (2), supported by a more flexible salamo-type ligand H2L containing coumarin functional groups have been synthesized. Complex 1 is tri-nuclear, including three Ni(II) atoms with hexa-coordinated octahedral geometries. X-ray single-crystal structure analysis revealed that complex 2 is a novel tetra-nuclear structure previously unreported, and the geometry of four Ni(II) atoms with hexa-coordinate can be regarded as octahedron. Interestingly, due to the improvement of the flexibility of salamo-type ligand H2L, complex 2 is obtained by the form of intramolecular self-assembly. Moreover, the fluorescence properties of H2L and its Ni(II)-based complexes were studied. Subsequently, the supramolecular structure, Hirshfeld surfaces analyses and DFT calculations of the two Ni(II)-based complexes have been performed.
Display omitted Two new tri- and tetra-nuclear Ni(II)-based complexes, {NiL(EtOH)(μ-OAc)}2Ni·4EtOH (1) and Ni4L2(μ3-OMe)4(MeOH)4 (2), supported by a more flexible salamo-type ligand H2L containing coumarin functional groups have been synthesized and characterized structurally. Interestingly, complex 2 is a novel tetra-nuclear structure previously unreported. The fluorescence properties, Hirshfeld surfaces analyses and DFT calculations of H2L and its Ni(II)-based complexes were studied.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Vacancy defects in the porous ZnO nanoplates facilitate separation of charge carriers, and are in favor of adsorption and activation of CO2, resulting in greatly enhanced photocatalytic activity.
...Display omitted
•Porous ZnO nanoplates with VO defects are prepared by annealing precursor in air.•Amount of vacancy defects in ZnO can be tailored by changing heating temperature.•Different amount of defects lead to different performance for CO2 photoreduction.•VO defect can facilitate the separation of photogenerated electrons and holes.•VO defect is in favor of the adsorption and activation of CO2 on ZnO surface.
Photocatalytic conversion of CO2 into hydrocarbons by utilization of the solar energy is considered a promising approach to mitigate energy crisis and the environmental issues. Since the defects in a catalyst play an important role in CO2 reduction, herein, the porous ZnO nanoplates with vacancy defects are synthesized by annealing ZnS(en)0.5 precursor in air at different temperature. The defect amount in ZnO changes with the annealing temperature, resulting in different photocatalytic activity for CO2 reduction. The related mechanism has been studied both experimentally and theoretically. Raman spectra and chemical composition of the obtained catalysts are used to determine the defects. Transient techniques are used to investigate the separation of photogenerated charge carriers. CO2 adsorption capacity for different catalysts is also measured. First-principles calculation is used to study the adsorption and activation of CO2 on the ZnO surface. We envision that this work may afford an efficient approach to develop the semiconductor photocatalysts with superior activity via defects engineering.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Mild photothermal therapy (PTT), as a new anticancer therapeutic strategy, faces big challenges of limited therapeutic accuracy and side‐effects due to uneven heat distribution. Here, near infrared ...triggered nitric oxide (NO) release nanocomposites based on bismuth sulfide (Bi2S3) nanoparticles and bis‐N‐nitroso compounds (BNN) are constructed for NO‐enhanced mild photothermal therapy. Upon 808 nm irradiation, the high photothermal conversion efficiency and on‐demand NO release are realized simultaneously. Due to the unique properties of NO, enhanced antitumor efficacy of mild PTT based on BNN‐Bi2S3 nanocomposites is achieved in vitro and in vivo. Mechanism studies reveal that the exogenous NO from BNN‐Bi2S3 could not only impair the autophagic self‐repairing ability of tumor cells in situ, but also diffuse to the surrounding cells to enhance the therapeutic effect. This work points out a strategy to overcome the difficulties in mild PTT, and has potentials for further exploitation of NO‐sensitized synergistic cancer therapy.
Nanocomposites based on bismuth sulfide nanoparticles and nitric oxide (NO) donors are constructed to realize simultaneous near infrared‐controlled NO release and mild photothermal therapy (PTT). The results lead to efficient tumor ablation due to the efficient dispersion of NO and the synergistic effect of NO and heat, which could overcome the drawbacks of mild PTT.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Note: P (phosphorus), W (water), + (positive or increase), – (negative or decrease).
Display omitted
•Plant facilitation was found in the intercropping system of maize and grass pea.•Facilitation ...shifted from +/+, +/0 to +/- from low to high water and P gradients.•In low P, rhizosphere soil acidification of grass pea fostered P mineralization.•Soil microbial biomass P was improved for higher productivity in +/+ facilitation.•Soil water and phosphorus availability altered interspecific facilitation model.
Plant-plant facilitation is widely studied to increase productivity and resource utilization in cereal-legume intercropping system. However, physiological and ecological mechanisms driving interspecific interaction shift along the environmental gradients is largely unknown. To clarify this issue, we first tested plant-plant facilitation along with four phosphorus (P) gradients in maize-grass pea intercropping system. Results illustrated a progressive transition of seed yield-based facilitation from mutually facilitated (+/+) to maize facilitated but grass pea as facilitator (+/-) along with low to high P gradients. Secondly, above trend was evidently enhanced when combining with drought stress gradients, in which severe drought amplified facilitative effects, whereas the magnitude of facilitation was relatively weak under well-watered condition. Interestingly, biomass-based facilitation transition did not synchronize with seed-based one, in which occurred in a broader threshold range of water and P gradients. Specifically, total yield, biomass, N and P uptake increased by 0.5%, 4.1%, 1.8% and 2.9% under the sufficient P and water availability, whereas these indicators increased by 25.3%, 18.5%, 20.5% and 21.4% in P and water deficient soils. And the total net effect was positive under all the environmental conditions. Rhizosphere interaction plays a crucial role in facilitation judgment, and the driving mechanism was associated with soil acidification and microbial community promotion under P-deficient condition. Under low soil moisture and available P, soil acidification and lower rhizosphere soil pH of intercropped maize were observed. Rhizosphere phosphatase secretion were significantly activated in P-deficient soils and accelerated the mineralization of soil organophosphorus, and the microbial biomass P was improved for stronger facilitation. Taken together, our findings confirmed the P and water driven facilitation shift along with stress gradients and highlighted the roles of rhizosphere interaction in affecting species diversity advantage. In conclusion, our work provided a relatively full picture for plant facilitation evaluation and more accurate management regarding intercropping productivity.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
•Ploidy level and drought stress affected yield and biomass distribution of wheat.•Wheat responded to mild drought by nHRS and to severe drought by HRS respectively.•Diploid and tetraploid wheat ...followed a different positive defense strategy in response to nHRS.•However, both wheat species displayed a similar negative adaptive strategy under the HRS.
Non-hydraulic root signals (nHRS) and hydraulic root signals (HRS) are important mechanisms that play a major role in determining plant productivity under drought stress. In the present study, six wheat varieties (three diploid and three tetraploid) were used to investigate the variation of yield, its components, water use efficiency (WUE) and biomass allocation under two signals. At the jointing stage, three water treatments were set up: i) well-watered control (WW, 80 % field water capacity (FC)), ii) moderate water stress (MS, 50 % FC) and iii) severe water stress (SS, 30 % FC). The results showed that around 50 % FC, wheat activated the nHRS to respond to drought. While around 30 % FC, wheat activated the HRS as a response to deeper drought. Under the operation of nHRS, the reduction of yield, aboveground biomass and WUE of diploid species was greater than that of tetraploid ones, but there were no differences under the operation of HRS. It could be argued that two different wheat species followed differentiate positive defense strategy in response to nHRS, but fell into a similar negative adaptive strategy under the HRS. The ploidy level of wheat also had a significant effect on wheat yield composition, WUE and biomass allocation model. As such, grain yield, grain number and spike weight per plant, aboveground biomass, harvest index (HI) and WUE were significantly greater in the tetraploid species than the diploids ones. In addition, the retention rate of aboveground biomass and grain decreased under the operation of nHRS and HRS. Path analysis showed that spikelet number, thousand grain weight and grain number were the main factors affecting yield formation. Grain number had the greatest direct effect on yield, while spikelet number and its grain number exerted the main effect on yield. These results were consistent under both signals.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Two new asymmetric complexes with the chemical structural formulas {Co
2
(L)(μ
2
-OH)}{Co
2
(L)(OAc)(CH
3
OH)}{Co
2
(L)(μ
2
-OCH
3
)}{Co
2
(L)(μ
2
-OAc)}⋅4CH
3
OH and Ni
2
(L)(μ
2
-OAc)(CH
3
OH)⋅CH
2
...Cl
2
⋅3CH
3
OH have been synthesized from cobalt(II) acetate, nickel(II) acetate, and a bis(salamo)-based tetraoxime ligand derived from 3-bromo-5-chlorosalicylicaldehyde and 4-tert-butyl-2,6-diformylphenol, respectively, and characterized by elemental analyses, IR, UV-vis, fluorescence spectra, and single-crystal X-ray diffraction analyses. The Co(II) complex unit cell contained four crystallographically independent and chemically different heterotrinuclear complexes (molecules A, B, C, and D). The crystal structure included eight Co(II) ions, four completely deprotonated ligand (L)
3−
moieties, one bridging hydroxide, one monodentate acetate, one bridging methoxy, one bidentate chelating acetate, one coordinated methanol, and four crystallization methanol molecules. The Ni(II) complex had a dinuclear structure. The crystal structure of the Ni(II) complex included two Ni(II) ions, one completely deprotonated ligand (L)
3−
, one bidentate bridging acetate, one coordinated methanol, one crystallized dichloromethane, and three crystallized methanol molecules. Hirshfeld surface analyses showed that the complexes are stable. Furthermore, the fluorescence quenching of the Co(II) and Ni(II) complexes with H
3
L further confirmed the above experimental results.
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BFBNIB, DOBA, GIS, IJS, IZUM, KILJ, KISLJ, NUK, PILJ, PNG, SAZU, UILJ, UKNU, UL, UM, UPUK
Two newly designed heteromultinuclear CuII4SmIII2 and CuII2TbIII bis (salamo)‐based complexes, {Cu2(L)Sm (NO3)2(μ2‐NO3)(CH3OH)}2·2CH3OH and Cu2(L)Tb (NO3)2(μ2‐NO3)Cu2(L)Tb (NO3)2(μ2‐NO3)(H2O)·CH3OH, ...were synthesized and characterized by elemental analyses, Fourier transform infrared (FT‐IR) spectra, ultraviolet–visible (UV–vis) absorption spectra, and X‐ray crystallography. The ultraviolet titration experiments exhibited that the coordination ratio of the ligand, rare earth metal, and transition metal is 1:1:2. In the CuII4SmIII2 complex, Cu1 atom has a distorted quadrilateral pyramid geometry, whereas Cu2 atom forms a slightly distorted octahedral geometry. The CuII2TbIII complex unit cell contains two crystallographically independent and chemically different heterotrinuclear complexes (Molecules A and B). In Molecule A, the Cu1 atom bears a four‐coordinated plane quadrilateral geometry, whereas the five‐coordinated Cu2 atom forms a slightly distorted tetragonal cone geometry. In Molecule B, the five‐coordinated Cu3 and Cu4 atoms possess slightly distorted tetragonal cone geometries. Noncovalent interactions like hydrogen bonding and π···π stacking interactions are operative in construction of supramolecular architectures. The CuII2TbIII complex behaves as a catalyst towards oxidative coupling of 2‐AP in MeCN medium. In addition, fluorescence properties of the ligand H4L and its CuII4SmIII2 and CuII2TbIII complexes have also been discussed.
Two newly designed heteromultinuclear CuII4SmIII2 and CuII2TbIII bis (salamo)‐based complexes, {Cu2(L)Sm (NO3)2(μ2‐NO3)(CH3OH)}2·2CH3OH and Cu2(L)Tb (NO3)2(μ2‐NO3)Cu2(L)Tb (NO3)2(μ2‐NO3)(H2O)·CH3OH, were synthesized and characterized structurally. Catalytic oxidase properties and fluorescence properties of the CuII4SmIII2 and CuII2TbIII complexes have also been discussed.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
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