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1.
J Chem Phys ; 160(16)2024 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-38647300

RESUMO

A guided ion beam tandem mass spectrometer was used to study the reactions of U+ with N2 and NO. Reaction cross sections were measured over a wide range of energy for both systems. In each reaction, UN+ is formed by an endothermic process, thereby enabling the direct measurement of the threshold energy and determination of the UN+ bond dissociation energy. For the reaction of U+ + N2, a threshold energy (E0) of 4.02 ± 0.11 eV was measured, leading to D0 (UN+) = 5.73 ± 0.11 eV. The reaction of U+ + NO yields UO+ through an exothermic, barrierless process that proceeds with 94 ± 23% efficiency at the lowest energy. Analysis of the endothermic UN+ cross section in this reaction provides E0 = 0.72 ± 0.11 eV and, therefore, D0 (UN+) = 5.78 ± 0.11 eV. Averaging the values obtained from both reactions, we report D0 (UN+) = 5.76 ± 0.13 eV as our best value (uncertainty of two standard deviations). Combined with precise literature values for the ionization energies of U and UN, we also derive D0 (UN) = 5.86 ± 0.13 eV. Both bond dissociation energies agree well with high-level theoretical treatments in the literature. The formation of UN+ in reaction of U+ with NO also exhibits a considerable increase in reaction probability above ∼3 eV. Theory suggests that this may be consistent with the formation of UN+ in excited quintet spin states, which we hypothesize are dynamically favored because the number of 5f electrons in reactants and products is conserved.

2.
Environ Pollut ; 340(Pt 2): 122828, 2024 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-37907191

RESUMO

Numerous toxic substances are directly and indirectly discharged by humans into water bodies, causing distress to the organisms living on it. 6PPD, an amino antioxidant from tires reacts with ozone to form 6PPD-Q, which has garnered global attention due to its lethal nature to various organisms. This review aims to provide an understanding of the sources, transformation, and fate of 6PPD-Q in water and the current knowledge on its effects on aquatic organisms. Furthermore, we discuss research gaps pertaining to the mechanisms by which 6PPD-Q acts within fish bodies. Previous studies have demonstrated the ubiquitous presence of 6PPD-Q in the environment, including air, water, and soil. Moreover, this compound has shown high lethality to certain fish species while not affecting others. Toxicological studies have revealed its impact on the nervous system, intestinal barrier function, cardiac function, equilibrium loss, and oxidative stress in various fish species. Additionally, exposure to 6PPD-Q has led to organ injury, lipid accumulation, and cytokine production in C. elegans and mice. Despite studies elucidating the lethal dose and effects of 6PPD-Q in fish species, the underlying mechanisms behind these symptoms remain unclear. Future studies should prioritize investigating the mechanisms underlying the lethality of 6PPD-Q in fish species to gain a better understanding of its potential effects on different organisms.


Assuntos
Aquicultura , Benzoquinonas , Peixes , Fenilenodiaminas , Água , Animais , Humanos , Camundongos , Caenorhabditis elegans , Pesqueiros , Fenilenodiaminas/química , Fenilenodiaminas/toxicidade , Benzoquinonas/química , Benzoquinonas/toxicidade , Peixes/metabolismo , Dose Letal Mediana
4.
J Microbiol Methods ; 215: 106849, 2023 12.
Artigo em Inglês | MEDLINE | ID: mdl-37907117

RESUMO

Nigrospora is a diverse genus of fungi colonizing plants through endophytic, pathogenic, or saprobic interactions. Endophytic isolates can improve growth and development of host plants, as well as their resistance to microbial pathogens, but exactly how they do so remains poorly understood. Developing a reliable transformation method is crucial to investigate these mechanisms, in particular to identify pivotal genes for specific functions that correlate with specific traits. In this study, we identified eight isolates of Nigrospora sp. internally colonizing the leaves of switchgrass plants cultivated in North Carolina. Using an Agrobacterium tumefaciens-mediated transformation approach with control and GFP-expressing vectors, we report the first successful transformation of two Nigrospora isolates. Finally, we demonstrate that wild-type and transgenic isolates both negatively impact the growth of two plant pathogens in co-culture conditions, Bipolaris maydis and Parastagonospora nodorum, responsible for the Southern Leaf Blight and Septoria Nodorum Blotch diseases, respectively. The GFP-transformed strains developed here can therefore serve as accurate reporters of spatial interactions in future studies of Nigrospora and pathogens in the plant. Finally, the transformation method we describe lays the foundation for further genetic research on the Nigrospora genus to expand our mechanistic understanding of plant-endophyte interactions.


Assuntos
Ascomicetos , Panicum , Agrobacterium tumefaciens/genética , Ascomicetos/genética , Fenótipo , Transformação Genética , Folhas de Planta
5.
Antibiotics (Basel) ; 12(9)2023 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-37760667

RESUMO

Infections caused by antibiotic-resistant bacteria continue to pose a significant public health threat despite their overall decreasing numbers in the last two decades. One group of compounds fundamental to the search for new agents is low-cost natural products. In this study, we explored a group of newly synthesized novel aurone-derived triazole compounds to identify those with pharmaceutical potential as inhibitors of antibiotic-resistant Staphylococcus aureus. Using the broth microdilution method, antibacterial activities against methicillin-resistant S. aureus ATCC 43300 (MRSA) and methicillin-sensitive S. aureus ATCC 29213 (MSSA) were identified for four aurone-derived triazole compounds, AT106, AT116, AT125, and AT137, using the half-maximal inhibitory concentrations for the bacteria (IC50) and mammalian cell lines (CC50). Compounds AT125 and AT137 were identified to have pharmaceutical potential as the IC50 values against MRSA were 5.412 µM and 3.870 µM, whereas the CC50 values measured on HepG2 cells were 50.57 µM and 39.81 µM, respectively, resulting in selectivity indexes (SI) > 10. Compounds AT106 and AT116 were also selected for further study. IC50 values for these compounds were 5.439 µM and 3.178 µM, and the CC50 values were 60.33 µM and 50.87 µM, respectively; however, SI values > 10 were for MSSA only. Furthermore, none of the selected compounds showed significant hemolytic activity for human erythrocytes. We also tested the four compounds against S. aureus biofilms. Although AT116 and AT125 successfully disrupted MSSA biofilms, there was no measurable potency against MRSA biofilms. Checkerboard antibiotic assays to identify inhibitory mechanisms for these compounds indicated activity against bacterial cell membranes and cell walls, supporting the pharmaceutical potential for aurone-derived triazoles against antibiotic-resistant bacteria. Examining structure-activity relationships between the four compounds in this study and other aurone-derived triazoles in our library suggest that substitution with a halogen on either the salicyl ring or triazole aryl group along with triazoles having nitrile groups improves anti-Staphylococcal activity with the location of the functionality being very important.

6.
Sci Rep ; 13(1): 804, 2023 01 16.
Artigo em Inglês | MEDLINE | ID: mdl-36646812

RESUMO

Transport systems are crucial in many plant processes, including plant-microbe interactions. Nodule formation and function in legumes involve the expression and regulation of multiple transport proteins, and many are still uncharacterized, particularly for nitrogen transport. Amino acids originating from the nitrogen-fixing process are an essential form of nitrogen for legumes. This work evaluates the role of MtN21 (henceforth MtUMAMIT14), a putative transport system from the MtN21/EamA-like/UMAMIT family, in nodule formation and nitrogen fixation in Medicago truncatula. To dissect this transporter's role, we assessed the expression of MtUMAMIT14 using GUS staining, localized the corresponding protein in M. truncatula root and tobacco leaf cells, and investigated two independent MtUMAMIT14 mutant lines. Our results indicate that MtUMAMIT14 is localized in endosomal structures and is expressed in both the infection zone and interzone of nodules. Comparison of mutant and wild-type M. truncatula indicates MtUMAMIT14, the expression of which is dependent on the presence of NIN, DNF1, and DNF2, plays a role in nodule formation and nitrogen-fixation. While the function of the transporter is still unclear, our results connect root nodule nitrogen fixation in legumes with the UMAMIT family.


Assuntos
Medicago truncatula , Nódulos Radiculares de Plantas , Nódulos Radiculares de Plantas/genética , Nódulos Radiculares de Plantas/metabolismo , Medicago truncatula/genética , Medicago truncatula/metabolismo , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Fixação de Nitrogênio/fisiologia , Proteínas de Membrana Transportadoras/genética , Proteínas de Membrana Transportadoras/metabolismo , Nitrogênio/metabolismo , Simbiose , Regulação da Expressão Gênica de Plantas
7.
Plant Signal Behav ; 17(1): 2134676, 2022 Dec 31.
Artigo em Inglês | MEDLINE | ID: mdl-36259539

RESUMO

Arbuscular mycorrhizal (AM) fungi interact with the roots of most land plants and help them to acquire various mineral resources from the soil, including potassium (K+). However, tracking K+ movement in AM symbiosis remains challenging. Recently, we reported that rubidium can be used as a proxy for K+ in mycorrhizal Medicago truncatula. In the present work, we investigated the possibility of using cesium (Cs+) as another proxy for K+ in AM symbiosis. Plants were placed in growing systems that include a separate compartment only accessible to the AM fungus Rhizophagus irregularis isolate 09 and in which various amounts of cesium chloride (0 mM, 0.5 mM, 1.5 mM, or 3.75 mM) were supplied. Plants were watered with sufficient K+ or K+-free nutrient solutions, and shoot and root biomass, fungal colonization, and K+ and Cs+ concentrations were recorded seven weeks after inoculation. Our results indicate that Cs+ accumulated in plant tissues only when K+ was present in the nutrient solution and when the highest concentration of Cs+ was used in the fungal compartment. Consequently, we conclude that Cs+ could be used as a proxy for K+ in AM symbiosis, but with serious limitations.


Assuntos
Medicago truncatula , Micorrizas , Potássio , Rubídio , Césio , Solo , Simbiose , Raízes de Plantas/microbiologia
8.
Inorg Chem ; 61(40): 15936-15952, 2022 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-36166214

RESUMO

Collision-induced dissociation (CID) of [Th,xC,xO]+, x = 3-6, with Xe is performed using a guided ion beam tandem mass spectrometer (GIBMS). Products are formed exclusively by the loss of CO ligands. Analyses of the kinetic energy-dependent CID product cross sections yield bond dissociation energies (BDEs) of (CO)x-1Th+-CO at 0 K as 1.09 ± 0.05, 0.82 ± 0.07, 0.63 ± 0.05, and 0.70 ± 0.05 eV, respectively. Different structures of [Th,xC,xO]+ were explored using various electronic structure methods, and BDEs for CO ligand loss from precursor [Th,xC,xO]+ complexes were computed. Both experimental and theoretical results corroborate that the structures of [Th,xC,xO]+, x = 3-6, formed experimentally are homoleptic thorium cation carbonyl complexes, Th+(CO)x. The nonmonotonic trend in experimental BDEs is reproduced theoretically, although ambiguities in the spin states of the x = 4-6 complexes (doublet or quartet) remain. BDEs calculated at the coupled cluster with single, double, and perturbative triple excitations (CCSD(T))/cc-pVXZ//B3LYP/cc-PVXZ (X = T and Q) level and a complete basis set (CBS) extrapolation agree reasonably well with the experimental values for all complexes. Thorium oxide ketenylidene carbonyl cations, OTh+CCO(CO)y, y = 1-4, were calculated to be the most stable structures of [Th,xC,xO]+, x = 3-6, respectively; however, these are not observed in our experiment. Potential energy profiles (PEPs) having either quartet or doublet spin calculated at the B3LYP/cc-pVQZ level suggest that the failure to observe OTh+CCO(CO)y, y = 1-4, is the result of a barrier corresponding to the C-C bond formation, making the formation of OTh+CCO(CO)y inaccessible kinetically under the present experimental conditions.

9.
RSC Adv ; 12(35): 22639-22649, 2022 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-36105995

RESUMO

Aurones are a class of well-studied natural compounds primarily responsible for the yellow pigment in flowering plants and have been shown to have fluorescent properties as well as beneficial biological effects. Traditionally, aurones can be easily synthesized through a Knoevenagel condensation of benzofuranones with arylaldehydes. Recently, Kafle et al. unexpectedly synthesized a new aurone derivative containing a 1,2,3-triazole within its backbone. Since, 1,2,3-triazole containing structures have been shown to be useful as fluorophores with large Stokes shifts, we hypothesized that these new aurone-derived triazole compounds (ATs) could be utilized as potential fluorophores. Here we describe a newly-synthesized fluorescent compound which has potential for use as a live-cell probe, having a large Stokes shift of 118.3 ± 1.01 nm in phosphate-buffered saline with the benefit of increased fluorescence in protic environments, which is uncommon in aurone-derived fluorophores.

10.
Plant Sci ; 322: 111364, 2022 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-35760157

RESUMO

Arbuscular mycorrhizal (AM) fungi considerably improve plant nutrient acquisition, particularly phosphorus and nitrogen. Despite the physiological importance of potassium (K+) in plants, there is increasing interest in the mycorrhizal contribution to plant K+ nutrition. Yet, methods to track K+ transport are often costly and limiting evaluation opportunities. Rubidium (Rb+) is known to be transported through same pathways as K+. As such our research efforts attempt to evaluate if Rb+ could serve as a viable proxy for evaluating K+ transport in AM symbiosis. Therefore, we examined the transport of K+ in Medicago truncatula colonized by the AM fungus Rhizophagus irregularis isolate 09 having access to various concentrations of Rb+ in custom-made two-compartment systems. Plant biomass, fungal root colonization, and shoot nutrient concentrations were recorded under sufficient and limited K+ regimes. We report that AM plants displayed higher shoot Rb+ and K+ concentrations and a greater K+:Na+ ratio relative to non-colonized plants in both sufficient and limited K+ conditions. Consequently, our results indicate that Rb+ can be used as a proxy to assess the movement of K+ in AM symbiosis, and suggest the existence of a mycorrhizal uptake pathway for K+ nutrition in M. truncatula.


Assuntos
Medicago truncatula , Micorrizas , Medicago truncatula/metabolismo , Micorrizas/fisiologia , Raízes de Plantas/metabolismo , Potássio/metabolismo , Rubídio/metabolismo , Simbiose/fisiologia
11.
Mycorrhiza ; 32(3-4): 281-303, 2022 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-35511363

RESUMO

Arbuscular mycorrhizal (AM) fungi form a root endosymbiosis with many agronomically important crop species. They enhance the ability of their host to obtain nutrients from the soil and increase the tolerance to biotic and abiotic stressors. However, AM fungal species can differ in the benefits they provide to their host plants. Here, we examined the putative molecular mechanisms involved in the regulation of the physiological response of Medicago truncatula to colonization by Rhizophagus irregularis or Glomus aggregatum, which have previously been characterized as high- and low-benefit AM fungal species, respectively. Colonization with R. irregularis led to greater growth and nutrient uptake than colonization with G. aggregatum. These benefits were linked to an elevated expression in the roots of strigolactone biosynthesis genes (NSP1, NSP2, CCD7, and MAX1a), mycorrhiza-induced phosphate (PT8), ammonium (AMT2;3), and nitrate (NPF4.12) transporters and the putative ammonium transporter NIP1;5. R. irregularis also stimulated the expression of photosynthesis-related genes in the shoot and the upregulation of the sugar transporters SWEET1.2, SWEET3.3, and SWEET 12 and the lipid biosynthesis gene RAM2 in the roots. In contrast, G. aggregatum induced the expression of biotic stress defense response genes in the shoots, and several genes associated with abiotic stress in the roots. This suggests that either the host perceives colonization by G. aggregatum as pathogen attack or that G. aggregatum can prime host defense responses. Our findings highlight molecular mechanisms that host plants may use to regulate their association with high- and low-benefit arbuscular mycorrhizal symbionts.


Assuntos
Compostos de Amônio , Medicago truncatula , Micorrizas , Compostos de Amônio/metabolismo , Medicago truncatula/microbiologia , Micorrizas/fisiologia , Raízes de Plantas/microbiologia , Simbiose/fisiologia , Transcriptoma
12.
Phys Chem Chem Phys ; 24(2): 842-853, 2022 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-34908066

RESUMO

Collision-induced dissociation (CID) of [Th,2C,2O]+ with Xe is performed using a guided ion beam tandem mass spectrometer (GIBMS). The only products observed are ThCO+ and Th+ by sequential loss of CO ligands. The experimental findings and theoretical calculations support that the structure of [Th,2C,2O]+ is the bent homoleptic thorium dicarbonyl cation, Th+(CO)2, having quartet spin, which is both thermodynamically and kinetically stable enough in the gas phase to be observed in our GIBMS instrument. Analysis of the kinetic energy-dependent cross sections for this CID reaction yields the first experimental determination of the bond dissociation energy (BDE) of (CO)Th+-CO at 0 K as 1.05 ± 0.09 eV. A theoretical BDE calculated at the CCSD(T) level with cc-pVXZ (X = T and Q) basis sets and a complete basis set (CBS) extrapolation is in very good agreement with the experimental result. Although the doublet spin bent thorium oxide ketenylidene cation, OTh+CCO, is calculated to be the most thermodynamically stable structure, it is not observed in our experiment where [Th,2C,2O]+ is formed by association of Th+ and CO in a direct current discharge flow tube (DC/FT) ion source. Potential energy profiles of both quartet and doublet spin are constructed to elucidate the isomerization mechanism of Th+(CO)2 to OTh+CCO. The failure to observe OTh+CCO is attributed to a barrier associated with C-C bond formation, which makes OTh+CCO kinetically inaccessible under our experimental conditions. Chemical bonding patterns in low-lying states of linear and bent Th+(CO)2 and OTh+CCO isomers are also investigated.

13.
J Exp Bot ; 73(5): 1288-1300, 2022 03 02.
Artigo em Inglês | MEDLINE | ID: mdl-34791191

RESUMO

Most land plants symbiotically interact with soil-borne fungi to ensure nutrient acquisition and tolerance to various environmental stressors. Among these symbioses, arbuscular mycorrhizal and ectomycorrhizal associations can be found in a large proportion of plants, including many crops. Split-root assays are widely used in plant research to study local and systemic signaling responses triggered by local treatments, including nutrient availability, interaction with soil microbes, or abiotic stresses. However, split-root approaches have only been occasionally used to tackle these questions with regard to mycorrhizal symbioses. This review compiles and discusses split-root assays developed to study arbuscular mycorrhizal and ectomycorrhizal symbioses, with a particular emphasis on colonization by multiple beneficial symbionts, systemic resistance induced by mycorrhizal fungi, water and nutrient transport from fungi to colonized plants, and host photosynthate allocation from the host to fungal symbionts. In addition, we highlight how the use of split-root assays could result in a better understanding of mycorrhizal symbioses, particularly for a broader range of essential nutrients, and for multipartite interactions.


Assuntos
Micorrizas , Micorrizas/fisiologia , Nitrogênio , Raízes de Plantas/microbiologia , Plantas/microbiologia , Solo , Simbiose
14.
Front Plant Sci ; 12: 780454, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34956276

RESUMO

Maximizing the function of indigenous arbuscular mycorrhizal (AM) fungi by choosing specific crop genotypes offers one of the few untapped opportunities to improve the sustainability of agriculture. In this study, the differences in mycorrhizal responsiveness (MR) in plant growth and shoot phosphorus (P) content among cotton (Gossypium spp. L.) genotypes from different release dates were compared and then the relationships between MR and P uptake-related traits were determined. The experimental design in a greenhouse included 24 genotypes released from 1950 to present in Xinjiang Province, inoculation with or without AM fungi, and P levels (15 and 150 mg P kg-1 added as KH2PO4). Results showed that the modern cotton genotypes exhibited a higher degree of mycorrhizal colonization, the hyphal length density (HLD), and mycorrhizae-induced changes in shoot growth than the old genotypes when inoculated with indigenous AM fungi at both the P levels. Moreover, MR was highly correlated with the HLD at low P levels and the HLD may provide useful insights for future cotton breeding aimed at delivering crop genotypes that can benefit more from AM fungi.

15.
Inorg Chem ; 60(14): 10426-10438, 2021 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-34213318

RESUMO

Threshold collision-induced dissociation (TCID) of the thorium monocarbonyl cation, ThCO+, with xenon is performed using a guided ion beam tandem mass spectrometer. The only product observed is Th+ resulting from loss of the CO ligand. Analysis of the kinetic energy-dependent cross sections for this CID reaction yields the first experimental determination of the bond dissociation energy (BDE) of Th+-CO at 0 K as 0.94 ± 0.06 eV. Calculated BDEs at the CCSD(T) level of theory with cc-pVXZ (X = T and Q) basis sets and a complete basis set (CBS) extrapolation are in good agreement with the experimental result. The Feller-Peterson-Dixon composite coupled-cluster methodology was also applied on both ThCO+ and ThCO, with contributions up to CCSDT(Q) and a four-component treatment of spin-orbit coupling effects. The final 0 K Th+-CO BDE of 0.94 ± 0.04 eV is in excellent agreement with the current experimental result. The ionization energy of ThCO, as well as the atomization energies and heats of formation for both ThCO and ThCO+, is reported at this same level of theory. Complete potential energy profiles of both quartet and doublet spin are also constructed to elucidate the mechanism for the formation and interconversion of different isomers of [Th,O,C]+. Chemical bonding patterns in low-lying states of ThCO+ and potential energy curves for ThCO+ dissociation are also investigated.

16.
J Phys Chem A ; 124(16): 3090-3100, 2020 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-32227848

RESUMO

Threshold collision-induced dissociation of Th(OH)3+(H2O)n (n = 1-4) with xenon was performed using a guided ion beam tandem mass spectrometer. The primary dissociation pathway for all complexes is a loss of a single water molecule followed by the sequential loss of additional water molecules at higher collision energies. The data were analyzed using a statistical model after accounting for lifetime effects and reactant internal and kinetic energy distributions to obtain 0 K bond dissociation energies (BDEs). These were also converted using rigid rotor/harmonic oscillator approximations to yield thermodynamic values at room temperature. The 0 K BDEs of H2O ligands to Th(OH)3+ (IV) are experimentally determined for the first time as 106 ± 6, 89 ± 6, 76 ± 4, and 51 ± 4 kJ/mol for the first, second, third, and fourth water ligand added. These values agree reasonably well with values calculated at the B3LYP, B3PW91, and PBE0 levels of theory with aug-cc-pVQZ basis sets, whereas B3LYP-GD3BJ, MP2, and CCSD(T) single point energies with (without) counterpoise corrections systematically overestimate the bond energies by about 15 (20), 19 (25), and (18) kJ/mol, respectively.

17.
Chem Sci ; 12(1): 239-246, 2020 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-34163592

RESUMO

Heparanase (HPA) is a critical enzyme involved in the remodeling of the extracellular matrix (ECM), and its elevated expression has been linked with diseases such as various types of cancer and inflammation. The detection of heparanase enzymatic activity holds tremendous value in the study of the cellular microenvironment, and search of molecular therapeutics targeting heparanase, however, no structurally defined probes are available for the detection of heparanase activity. Here we present the development of the first ultrasensitive fluorogenic small-molecule probe for heparanase enzymatic activity via tuning the electronic effect of the substrate. The probe exhibits a 756-fold fluorescence turn-on response in the presence of human heparanase, allowing one-step detection of heparanase activity in real-time with a picomolar detection limit. The high sensitivity and robustness of the probe are exemplified in a high-throughput screening assay for heparanase inhibitors.

18.
RSC Adv ; 10(73): 45180-45188, 2020 Dec 17.
Artigo em Inglês | MEDLINE | ID: mdl-35516280

RESUMO

Hydrogen sulfide detection and sensing is an area of interest from both an environmental and a biological perspective. While many methods are currently available, the most sensitive and biologically applicable ones are fluorescence based. In general, these fluorescent probes are based upon large, high-molecular weight, well-characterized fluorescent scaffolds that are synthetically demanding to prepare and difficult to tune and modify. In this study, we have reported a new reduction-based, rationally designed and synthesized turn-on fluorescent probe (Z)-2-(4'-azidobenzylidene)-5-fluorobenzofuran-3(2H)-one (6g) utilizing a low molecular weight aurone fluorophore. During these studies, the modular nature of the synthesis was used to quickly overcome problems with solubility, overlap of excitation of the probe and reduced product, and rate of reaction, resulting in a final compound that is efficient and sensitive for the detection of hydrogen sulfide. The limitation of slow reaction and the reduced fluorescence in a biologically relevent medium was solved by employing cationic surfactant cetyltrimethyl ammonium bromide (CTAB). The probe features a high fluorescence enhancement, fast response (10-30 min), and good sensitivity (1 µm) and selectivity for hydrogen sulfide.

19.
J Phys Chem A ; 123(28): 5893-5905, 2019 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-31264866

RESUMO

The kinetic energy dependences of the reactions of ThO+, ThO2+, and OThOD+ with D2O, ThO2+ with D2, and OThOD+ with Xe were studied using guided ion beam tandem mass spectrometry. Exothermic formation of OThOD+ is the dominant process observed in reactions of both ThO+ and ThO2+ with D2O. Minor products formed in endothermic reactions include ThO2+, DThO+, and ThO2D2+. OThOD+ is also formed in the reaction of ThO2+ with D2 but in an endothermic process. Collision-induced dissociation (CID) of OThOD+ with Xe leads to endothermic loss of the hydroxide ligand. OThOD+ reacts further with D2O to form the associative complex ThO3D3+, which is long-lived before dissociating back to the reactants. The OThOD+-D2O bond energy of the associative complex is measured to be 2.96 ± 0.05 eV by modeling the kinetic energy-dependent cross section for association using a phase space theory model that rigorously conserves angular momentum. By comparison with theory, this bond energy identifies the ThO3D3+ species as the trihydroxide cation, Th(OD)3+. From the endothermic reactions and CID of OThOD+ with Xe, the OTh+-D, OTh+-O, and OTh+-OD bond dissociation energies (BDEs) are measured to be 2.33 ± 0.24, 4.66 ± 0.15, and 6.00 ± 0.17 eV, respectively. All four of these BDEs are experimentally determined for the first time and agree reasonably well with values calculated at the B3LYP, B3PW91, and PBE0 levels of theory with cc-pVQZ basis sets. Complete potential energy surfaces for all reactions were calculated at the B3LYP/cc-pVTZ level and elucidate the mechanisms for all processes observed.

20.
J Chem Phys ; 151(3): 034304, 2019 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-31325947

RESUMO

Kinetic-energy dependent reactions of Th+ with N2 and NO are studied using a guided ion beam tandem mass spectrometer. The formation of ThO+ in the reaction of Th+ with NO is observed to be exothermic and barrierless with a reaction efficiency at low energies of 0.91 ± 0.18. Formation of ThN+ in the reactions of Th+ with N2 and NO is endothermic in both cases. The kinetic-energy dependent cross sections for formation of this product ion were evaluated to determine a 0 K bond dissociation energy (BDE) of D0(Th+-N) = 6.51 ± 0.08 eV, the first direct measurement of this BDE. Additionally, the reactions were explored by quantum chemical calculations, including a full Feller-Peterson-Dixon composite approach with correlation contributions up to CCSDTQ for ThN and ThN+, as well as more approximate CCSD(T) calculations where a semiempirical model was used to estimate spin-orbit energy contributions. The ThN+ BDE is found to be larger than those of the transition metal congeners, TiN+ along with estimated values for ZrN+ and HfN+, believed to be a result of the actinide contraction.

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