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1.
Food Chem Toxicol ; 192: 114935, 2024 Aug 14.
Article in English | MEDLINE | ID: mdl-39151875

ABSTRACT

Sodium nitrite (SN), a prevalent food preservative, is known to precipitate hepatotoxicity upon exposure. This study elucidates the hepatoprotective effects of corn oligopeptide (COP) and vitamin E (VE) against SN-induced hepatic injury in canine hepatocytes. Canine liver cells were subjected to SN to induce hepatotoxicity, followed by treatment with COP and VE. Evaluations included assays for cell viability, oxidative stress markers, apoptosis, and inflammatory cytokines. Additionally, transcriptomic and metabolomic analyses were performed to delineate the underlying molecular mechanisms. The findings demonstrated that COP and VE significantly ameliorated SN-induced cytotoxicity, oxidative stress, and apoptosis. It was evidenced by restored cell viability, enhanced antioxidant enzyme activity, reduced cytoplasmic enzyme leakage, and decreased levels of malondialdehyde and inflammatory cytokines, with COP showing superior efficacy. The RNA sequencing revealed that COP treatment suppressed the SN-activated aminoacyl-tRNA biosynthesis pathway and TGF-ß/NF-κB signaling pathways, thereby mitigating amino acid depletion, apoptosis, and inflammation. Moreover, COP treatment upregulated genes associated with protein folding, bile acid synthesis, and DNA repair. Metabolomic analysis corroborated these results, showing that COP restored amino acid levels and enhanced bile acid metabolism, alleviating SN-induced metabolic disruptions. These findings offered significant insights into the protective mechanisms of COP underscoring its prospective application in treating liver injuries.

3.
ACS Nano ; 2024 Aug 26.
Article in English | MEDLINE | ID: mdl-39185922

ABSTRACT

We have successfully fabricated single-layer (SL) 1T-VSe2/Bi2Se3 heterostructures using molecular beam epitaxy (MBE), which exhibits uniform moiré patterns on the heterostructure surface. Scanning tunneling microscopy/spectroscopy (STM/STS) reveals a notable quantum state near the Fermi energy, robust across the entire moiré lattice. This quantum state peak shifts slightly across different domain ranges, suggesting an elastic strain dependence in SL VSe2, confirmed by geometric phase analysis (GPA) simulations. Density functional theory (DFT) calculations indicate that the enhanced quantum state results from charge redistribution between the substrate and the epifilm with the orbitals of Se atoms in the deformed VSe2 playing a dominant role.

4.
Small ; : e2402752, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38822717

ABSTRACT

Surface modification of Cu current collectors (CCs) is proven to be an effective method for protecting lithium metal anodes. However, few studies have focused on the quality and efficiency of modification layers. Herein, a novel home-made filtered cathode vacuum arc (FCVA) co-deposition system with high modification efficiency, good repeatability and environmental friendliness is proposed to realize the wide range regulation of film composition, structure and performance. Through this system, ZnMgTiAl quaternary alloy films, which have good affinity with Li are successfully constructed on Cu CCs, and the fully enhanced electrochemical performances are achieved. Symmetrical cells constructed with modified CCs maintained a fairly low voltage hysteresis of only 13 mV after 2100 h at a current density of 1 mA cm-2. In addition, the capacity retention rate is as high as 75.0% after 100 cycles in the full cells. The influence of alloy films on the dynamic evolution process of constructing stable artificial solid electrolyte interphase (SEI) layer is revealed by in situ infrared (IR) spectroscopy. This work provides a promising route for designing various feasible modification films for LMBs, and it displays better industrial application prospects than the traditional chemical methods owing to the remarkable controllability and scale-up capacity.

5.
Environ Res ; 252(Pt 4): 119076, 2024 Jul 01.
Article in English | MEDLINE | ID: mdl-38710430

ABSTRACT

The large yield of anaerobic digestates and the suboptimal efficacy of nutrient slow-release severely limit its practical application. To address these issues, a new biochar based fertilizer (MAP@BRC) was developed using biogas residue biochar (BRC) to recover nitrogen and phosphorus from biogas slurry. The nutrient release patterns of MAP@BRC and mechanisms for enhancing soil fertility were studied, and it demonstrated excellent performance, with 59% total nitrogen and 50% total phosphorus nutrient release rates within 28 days. This was attributed to the coupling of the mechanism involving the dissolution of struvite skeletons and the release of biochar pores. Pot experiments showed that crop yield and water productivity were doubled in the MAP@BRC group compared with unfertilized planting. The application of MAP@BRC also improved soil nutrient levels, reduced soil acidification, increased microbial populations, and decreased soil heavy metal pollution risk. The key factors that contributed to the improvement in soil fertility by MAP@BRC were an increase in available nitrogen and the optimization of pH levels in the soil. Overall, MAP@BRC is a safe, slow-release fertilizer that exhibits biochar-fertilizer interactions and synergistic effects. This slow-release fertilizer was prepared by treating a phosphorus-rich biogas slurry with a nitrogen-rich biogas slurry, and it simultaneously addresses problems associated with livestock waste treatment and provides a promising strategy to promote zero-waste agriculture.


Subject(s)
Biofuels , Charcoal , Fertilizers , Nitrogen , Phosphorus , Soil , Fertilizers/analysis , Charcoal/chemistry , Soil/chemistry , Phosphorus/analysis , Nitrogen/analysis , Biofuels/analysis , Agriculture/methods
6.
ACS Appl Mater Interfaces ; 16(22): 28791-28797, 2024 Jun 05.
Article in English | MEDLINE | ID: mdl-38783664

ABSTRACT

Ferromagnets with a Curie temperature surpassing room temperature (RT) are highly sought after for advancing planar spintronics. The ultrathin CrTe2 is proposed as a promising two-dimensional (2D) ferromagnet with a Curie temperature above 300 K. However, its single-layer film is highly susceptible to specific external perturbations, leading to variable magnetic features depending on the environment. The magnetic ordering of single-layer CrTe2 remains a topic of debate, and experimental confirmation of ferromagnetic order at RT is still pending. In our study, we utilized molecular beam epitaxy to create a single-layer 1T-CrTe2 on bilayer graphene, demonstrating ferromagnetism above 300 K with in-plane magnetization through superconducting quantum interference devices (SQUID) measurements. Our density functional theory (DFT) calculations suggest that the ferromagnetic properties stem from epitaxial strain, which increases the distance between adjacent Cr atoms within the layer by about 1.6% and enhances the Cr-Te-Cr angle by approximately 1.6°. Due to its interaction with the graphene substrate, the magnetic moment transitions from an out-of-plane to an in-plane orientation, while electronic doping exceeds 1.5 e/u.c. Combining DFT calculations with in situ scanning tunneling microscopy (STM) characterizations allowed us to determine the configuration of the CrTe2 single layer on graphene. This discovery presents the first experimental proof of ferromagnetic order in single-layer CrTe2 with a Curie temperature above RT, laying the groundwork for future applications of CrTe2 single-layer-based spintronic devices.

7.
Nat Commun ; 15(1): 1838, 2024 Feb 28.
Article in English | MEDLINE | ID: mdl-38418810

ABSTRACT

Plastic crystals as barocaloric materials exhibit the large entropy change rivalling freon, however, the limited pressure-sensitivity and large hysteresis of phase transition hinder the colossal barocaloric effect accomplished reversibly at low pressure. Here we report reversible colossal barocaloric effect at low pressure in two-dimensional van-der-Waals alkylammonium halides. Via introducing long carbon chains in ammonium halide plastic crystals, two-dimensional structure forms in (CH3-(CH2)n-1)2NH2X (X: halogen element) with weak interlayer van-der-Waals force, which dictates interlayer expansion as large as 13% and consequently volume change as much as 12% during phase transition. Such anisotropic expansion provides sufficient space for carbon chains to undergo dramatic conformation disordering, which induces colossal entropy change with large pressure-sensitivity and small hysteresis. The record reversible colossal barocaloric effect with entropy change ΔSr ~ 400 J kg-1 K-1 at 0.08 GPa and adiabatic temperature change ΔTr ~ 11 K at 0.1 GPa highlights the design of novel barocaloric materials by engineering the dimensionality of plastic crystals.

8.
Ultrason Sonochem ; 103: 106805, 2024 Feb.
Article in English | MEDLINE | ID: mdl-38354424

ABSTRACT

This work aimed to explore low-intensity ultrasound-assisted adaptive laboratory evolution (US-ALE) of Bacillus velezensis and fermentation performance of mutant strains were investigated by nitrogen transformation metabolism. Results showed ultrasound accelerated the process of adaptive evolution and enhanced cell dry weight, amylase and protease activity of mutant strains, accompanied with the improved transformation abilities of NO-3-N to NH4+-N. Compared with original strain, the total peptide-N, peptide-N (<3 kDa) and autolytic peptide-N of mutant strains increased by the maximum 23.17%, 66.07% and 30.30%, respectively, based on ideal fermentation medium. According to the actual liquid-state fermentation of soybean meal and corn gluten meal with mutant strains, the highest peptide yields of 50.63% and 23.67% were noticed in mutant strain US-ALE-BV3, accompanied with the improved amino acid composition by bacterial autolysis technology. Thus, this study showed that low-intensity ultrasound could accelerate the process of adaptive evolution and US-ALE will provide more possibilities for modifying fermentation strains.


Subject(s)
Bacillus , Bacillus/genetics , Amino Acids/metabolism , Peptides/metabolism , Fermentation
9.
Appl Microbiol Biotechnol ; 107(13): 4311-4321, 2023 Jul.
Article in English | MEDLINE | ID: mdl-37231160

ABSTRACT

Helium-neon (He-Ne) laser mutagenesis is widely used in microbiology and plant breeding. In this study, two frameshift mutant representative strains of Salmonella typhimurium TA97a and TA98 and two base pair substitution types TA100 and TA102 were employed as model microorganisms to assess DNA mutagenicity induced by He-Ne laser (3 J·cm-2·s-1, 632.8 nm) for 10, 20, and 30 min. The results revealed that the optimal laser application was 6 h in the mid-logarithmic growth stage. Low-power He-Ne laser for short treatment inhibited cell growth, and continued treatment stimulated the metabolism. The effects of the laser on TA98 and TA100 were the most prominent. Sequencing results from 1500 TA98 revertants showed that there were 88 insertion and deletion (InDel) types in the hisD3052 gene, of which the InDels unique to laser were 21 more than that of the control. Sequencing results from 760 TA100 revertants indicated that laser treatment created Pro (CCC) in the product of the hisG46 gene more likely to be replaced by His (CAC) or Ser (TCC) than by Leu (CTC). Two unique non-classical base substitutions, CCC → TAC and CCC → CAA, also appeared in the laser group. These findings will provide a theoretical basis for further exploration of laser mutagenesis breeding. KEY POINTS: • Salmonella typhimurium served as model organism for laser mutagenesis study. • Laser promoted the occurrence of InDels in the hisD3052 gene of TA98. • Laser promoted the occurrence of base substitution in the hisG46 gene of TA100.


Subject(s)
Mutagens , Salmonella typhimurium , Mutagens/toxicity , Salmonella typhimurium/genetics , Mutagenesis , DNA , Lasers , Mutagenicity Tests/methods
11.
J Sci Food Agric ; 103(10): 5156-5164, 2023 Aug 15.
Article in English | MEDLINE | ID: mdl-37005328

ABSTRACT

BACKGROUND: Soybean meal, a by-product of the soybean oil production industry, has a high protein content but the compact globular structure of the protein from soybean meal limits its wide application in food processing. Allicin has been found to have numerous functional properties. In this study, allicin was interacted with soy protein isolate (SPI). The functional properties of the adducts were investigated. RESULTS: Binding with allicin significantly quenched the fluorescence intensity of SPI. Static quenching was the main quenching mechanism. The stability of adducts decreased with increasing temperature. The greatest extent of binding between allicin and sulfhydryl groups (SH) of SPI was obtained at an allicin/SH molar ratio of 1:2. The amino groups of SPI did not bind with allicin covalently. Soy protein isolate was modified by allicin through covalent and non-covalent interactions. Compared with SPI, the emulsifying activity index and foaming capacity of adducts with a ratio of 3:1 were improved by 39.91% and 64.29%, respectively. Soy protein isolate-allicin adducts also exhibited obvious antibacterial effects. The minimum inhibitory concentrations (MICs) of SPI-allicin adducts on Escherichia coli and Staphylococcus aureus were 200 and 160 µg mL-1 , respectively. CONCLUSION: The interaction of allicin with SPI is beneficial for the functional properties of SPI. These adducts can be used in different food formulations as emulsifiers, foamers, and transport carriers. © 2023 Society of Chemical Industry.


Subject(s)
Glycine max , Soybean Proteins , Soybean Proteins/chemistry , Glycine max/chemistry , Emulsifying Agents/chemistry , Food Handling
12.
Ultrason Sonochem ; 95: 106414, 2023 May.
Article in English | MEDLINE | ID: mdl-37098311

ABSTRACT

The effects of power ultrasound (US) pretreatment on the preparation of soy protein isolate hydrolysate (SPIH) prepared at the same degree of hydrolysis (DH) of 12 % were measured. Cylindrical power ultrasound was modified into mono-frequency (20, 28, 35, 40, 50 kHz) ultrasonic cup coupled with an agitator to make it applicable for high density SPI (soy protein isolate) solutions (14 %, w/v). A comparative study of the alterations of the hydrolysates molecular weight, hydrophobics, antioxidants and functional properties change as well as their relation were explored. The results showed that under the same DH, ultrasound pretreatment decelerated the degradation of protein molecular mass and the decrease rate of the degradation lessened with the increase of ultrasonic frequency. Meanwhile, the pretreatments improved the hydrophobics and antioxidants properties of SPIH. Both surface hydrophobicity (H0) and relative hydrophobicity (RH) of the pretreated groups increased with the decrease of ultrasonic frequency. Lowest frequency (20 kHz) ultrasound pretreatment had the most improved emulsifying properties and water holding capacities, although decrease in the viscosity and solubility were found. Most of these alterations were correspondence toward the change in hydrophobics properties and molecular mass. In conclusion, the frequency selection of ultrasound pretreatment is essential for the alteration of SPIH functional qualities prepared at the same DH.


Subject(s)
Antioxidants , Soybean Proteins , Hydrolysis , Molecular Weight , Hydrophobic and Hydrophilic Interactions , Solubility
13.
J Environ Manage ; 336: 117654, 2023 Jun 15.
Article in English | MEDLINE | ID: mdl-36870320

ABSTRACT

Dam-induced hydrological alterations and eco-environmental impacts have significant implications, however, these concern issues in large floodplain systems are less well understood. The present study shows a first attempt to adopt a quasi-three-dimensional groundwater flow modeling FEFLOW (Finite Element subsurface FLOW system) to investigate the influences of a proposed hydraulic dam on groundwater dynamics in the largest floodplain lake of the Yangtze River basin (Poyang Lake, China). The FEFLOW model was successfully constructed and has the ability to represent the hydrodynamics of floodplain groundwater flow. Model simulations indicate that, in general, the dam is likely to increase the groundwater levels across the floodplain during different hydrological phases. The responses of floodplain groundwater levels to the dam during the dry and recession phases are stronger (∼2-3 m) than the rising and flooding phases (<2 m). Under the natural condition, the floodplain groundwater may recharge the lake during the dry and recession phases, and discharge the lake during the rising and flooding phases. However, the dam regulation may alter the natural recharge-discharge patterns, forming a generally gaining condition of the floodplain groundwater. The proposed dam is most likely to reduce the groundwater flow velocity (∼<1 m/d) relative to the natural condition (up to 2 m/d) during different hydrological phases, and it may also alter the floodplain groundwater flow direction during the dry and recession phases. Additionally, the floodplain groundwater system is mainly characterized by losing state (-4.5 × 106 m3/yr) under the natural condition, while the dam-induced groundwater system exhibits an overall gaining state (9.8 × 106 m3/yr). The current research findings contribute to future water resources assessment and management by providing a foundation for assessing associated eco-environmental changes of the large lake-floodplain system.


Subject(s)
Groundwater , Lakes , Rivers , China , Hydrology
14.
Ultrason Sonochem ; 92: 106270, 2023 Jan.
Article in English | MEDLINE | ID: mdl-36543046

ABSTRACT

Low-lethality ultrasound technology has received more and more attention in regulating microorganisms of fermentation industry. Herein, two representative Ames tester strains TA97a and TA98 as model organisms were used to explore the effects of ultrasound on insertion-deletion (InDel) polymorphisms of microbial DNA and its underlying mechanisms. Results revealed that a promotion was observed in the reversion mutation of TA98 upon sonication. Sequencing results from 1752 TA98 revertants showed that there was a total of 127 InDels, of which the InDels unique to ultrasound were 36 more than that of the control. Compared with the control, ultrasound-mediated InDels of DNA displayed additional -29 bp deletion and +7 âˆ¼ +43 bp insertions of direct repeat sequences. Combined with the analysis of transcriptomics and prediction of secondary structure of single-stranded DNA from InDels core region (No. 832 âˆ¼ 915 bp) in hisD3052 gene of TA98 strain, ultrasound-mediated "thermal breathing" mechanism was proposed based on the formation of DNA hairpin structure with micro-homologous sequence. This finding implied that low-intensity ultrasound is expected to be developed a new low-lethal mutagenic technology for continuous mutagenesis.


Subject(s)
DNA , INDEL Mutation , Ultrasonography , Mutagenesis
15.
Sci Total Environ ; 857(Pt 2): 159414, 2023 Jan 20.
Article in English | MEDLINE | ID: mdl-36244485

ABSTRACT

Groundwater behaviors in lake-floodplain systems are dynamic and complex; in particular, the role of groundwater flux in regulating lake water storage subject to strong seasonal variation is not well understood. This study addresses the contribution of groundwater flux in a large floodplain system (Poyang Lake, China), with focus on quantifying the groundwater-lake interactions at multiple time scales in high rainfall (2010) and low rainfall (2011) years using a groundwater flow model (MODFLOW). Simulated results revealed that the unconfined aquifer received approximately 8 % of the annual rainfall as groundwater recharge. Fluctuations in shallow groundwater and lake water level reflected hydraulic synchronization and hysteresis. Additionally, the diurnal variability in the groundwater-lake exchange fluxes was subject to dynamic and bidirectional patterns, and a time lag between the water exchange and rainfall was also found. For 2010 and 2011, the monthly net flux of lake infiltration into groundwater was 1.5-10.0 mm and 0.1-6.0 mm and groundwater exfiltration into lake was 1.3-9.5 mm and 0.4-2.2 mm, respectively, demonstrating a significant variation of the exchange magnitude and direction. In particular, we found that groundwater exfiltration contributed up to 55 % of lake storage change in February of 2011. The outcomes from this study indicate that groundwater can be a major component of the Poyang Lake's water balance, which suggests an important role of groundwater in regulating the lake water storage and perhaps other flood pulse systems.


Subject(s)
Groundwater , Lakes , Hydrology , Seasons , Water , China
16.
Sci Total Environ ; 853: 158558, 2022 Dec 20.
Article in English | MEDLINE | ID: mdl-36087659

ABSTRACT

Groundwater and surface water are hydrologically interconnected systems that exhibit dynamic water, heat and mass exchanges. In this study, a conceptual framework was used to investigate groundwater behaviors and associated hydrological exchanges by combining field measurements, digital filtering and analytical approaches, exemplified by a linked catchment-floodplain-lake system (Poyang Lake, China). The results show that the hydrological regime for both groundwater and surface water exhibit a seasonal variability in the lake catchment. Topographically, the lake catchment can be divided into the mountainous baseflow, ungauged lateral groundwater and floodplain groundwater that contribute to the lake storage changes. Although groundwater flow is generally from the mountainous catchment to the lake floodplain areas due to topographic effects, precipitation provides an additional input for the shallow groundwater and is expected to enhance the groundwater dynamics in terms of spatially heterogeneous responses. The estimation indicates that about 40 % of the catchment river discharge may be coming from the mountainous baseflow (~290 × 108 m3/yr) and discharged into the lake through a surface flow pathway. The ungauged groundwater-lake interaction shows the annual discharge volume is up to 10 × 108 m3/yr and associated exchange fluxes tend to be stronger during spring-summer months (23-45 m3/s) than those of autumn-winter months (9-22 m3/s). Additionally, the floodplain groundwater-lake exchange (~9.5 × 108 m3/yr) indicates that groundwater generally receives the lake water during summer months (mean flux = 110 m3/s) and discharges into the lake during other months (90 m3/s) through a subsurface pathway. This study highlights the importance of groundwater's contributions to the surface river-lake system in terms of the flux variability and different transport pathways. The outcomes of this work will benefit future water resources management and applications by providing a methodology for predicting the groundwater hydrology of large lake-catchment systems.


Subject(s)
Groundwater , Lakes , Hydrology , Rivers , Water
17.
Nanoscale ; 14(36): 13227-13235, 2022 Sep 22.
Article in English | MEDLINE | ID: mdl-36052550

ABSTRACT

The sluggish conversion reaction and the accompanying huge volume fluctuation greatly hinder the application of lithium-selenium (Li-Se) batteries. Therefore, reasonably constructing stable carbonaceous hosts with efficient electrochemically active sites is particularly essential for promoting the development of Se cathodes. Herein, a metal-organic solid derived carbon host with multiple heterogeneous NiSe2/Ni2Co/CoSe2 interfaces was fabricated via in situ selenization. The formation of multiple heterointerfaces introduced subtle atomic array distortions, which provided additional electrochemically active sites compared with single heterointerfaces. Besides, the establishment of a built-in electric field was favorable for electron transfer and the absorption of Li+, thereby accelerating the reaction kinetics. Depending on the hollow structure and the heterogeneous catalysts, Li-Se batteries with NiSe2/Ni2Co/CoSe2@Se cathodes delivered reversible capacities of 503 and 324 mA h g-1 after 900 and 2200 cycles at 1 and 12 C, respectively. This work revealed the synergistic mechanism of multiple heterostructures composed of a Ni2Co alloy and in situ derived bimetallic selenides for Se cathodes and provided new insights into the exploitation of energy storage materials.

18.
ACS Appl Mater Interfaces ; 14(32): 36700-36710, 2022 Aug 17.
Article in English | MEDLINE | ID: mdl-35938596

ABSTRACT

A novel hexaazatrinaphthylene-based (HATN) azo polymer (PAH) was synthesized from a newly designed tri-nitro compound trinitrodiquinoxalino[2,3-a:2',3'-c]phenazine (HATNTN) through a Zn-induced reductive homocoupling reaction and used as a cathode material for lithium-ion batteries (LIBs). The integration of redox-active HATN units and azo linkages can improve the specific capacity, rate performance, and cycling stability of the PAH cathode. The control LIBs were assembled from HATNTN, in which HATNTN can be electrochemically reduced to an HATN-based azo polymer. Compared with the HATNTN cathode, the PAH cathode delivers higher specific capacities with much-improved cycling stability (97 mA h g-1 capacity retention after 1500 cycles at 500 mA g-1, which is around 28 times that of the HATNTN cathode) and considerably better rate performance (118 mA h g-1 at 2000 mA g-1, which is around 90 times that of the HATNTN cathode), simultaneously. This work provides a chemical polymerization strategy to construct extended π-conjugated azo polymers with multiple redox centers from nitro compounds for developing high-performance LIBs.

19.
Article in English | MEDLINE | ID: mdl-35954621

ABSTRACT

The baseflow of the Yellow River is vital and important for water resource management and for understanding the hydrological cycle and ecohydrology setting in this arid and semi-arid basin. This study uses a Lyne and Hollick digital filtering technique to investigate the behaviors of the baseflow and the baseflow index in the upper reaches of the Yellow River Basin (China). The observed streamflow discharges along the river were used to analyze the baseflow trend, persistence, and periodic characteristics during the period of 1950-2000. The results show that the average baseflow and BFI in the upper reaches of the Yellow River exhibit a decreasing trend and will continue to decline in the future. Generally, the annual average baseflow and BFI for the most upstream areas of the Yellow River show little difference, while the baseflow and BFI exhibit significant differences for the downstream areas. The filtered annual baseflow varied between 128 × 108 m3/year and 193 × 108 m3/year for the Yellow River. The BFI ranged from 0.54 to 0.65, with an average of 0.60. This indicates that on average, 60% of the long-term streamflow is likely controlled by groundwater discharge and shallow subsurface flow. Statistics show that two periodic variations were observed in the baseflow evolution process. The results indicate that on average, the first and second main cycles of baseflow behaviors occur at 28 years and 12-17 years, respectively. Correspondingly, the estimation indicates that the abrupt change points tend to appear in the 1960s, the 1980s, and the 1990s. An improved understanding of baseflow behaviors can help guide future strategies to manage the river regime, its water resources, and water quality.


Subject(s)
Groundwater , Water Movements , China , Environmental Monitoring , Rivers
20.
JACS Au ; 2(4): 853-864, 2022 Apr 25.
Article in English | MEDLINE | ID: mdl-35557757

ABSTRACT

Photosensitized energy transfer (EnT) phenomena occur frequently in a variety of photophysical and photochemical processes and have traditionally been treated with the donor-acceptor distance-dependent Förster and Dexter models. However, incorrect arguments and formulae were employed by ignoring energy resonance conditions and the selection rules of the state-to-state transition in special cases, especially for the sensitive intramolecular EnT of lanthanide complexes. Herein, we proposed an innovative model of energy-degeneracy-crossing-controlled EnT, which can be experimentally confirmed by time-resolved two-dimensional photoluminescence measurements. The computationally determined energy resonance region provides the most effective channel to achieve metal-to-ligand EnT beyond the distance-dependent model and sensitively bifurcates into symmetry-allowed or -forbidden channels for some representative europium antenna complexes. The outcomes of the multidisciplinary treatment contribute to a complementary EnT model that can be tuned by introducing a phosphorescence modulator and altering the antenna-related parameters of the ligand-centered energy level of the 3ππ* state and its spin-orbit coupling for the 3ππ* → S0 * transition through mechanism-guided crystal engineering and should motivate further development of mechanistic models and applications.

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