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1.
Exp Mol Med ; 2024 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-38825641

RESUMO

The effects of ultraviolet (UV) radiation on brain function have previously been investigated; however, the specific neurotransmitter-mediated mechanisms responsible for UV radiation-induced neurobehavioral changes remain elusive. In this study, we aimed to explore the mechanisms underlying UV radiation-induced neurobehavioral changes. In a mouse model, we observed that UV irradiation of the skin induces deficits in hippocampal memory, synaptic plasticity, and adult neurogenesis, as well as increased dopamine levels in the skin, adrenal glands, and brain. Chronic UV exposure altered the expression of genes involved in dopaminergic neuron differentiation. Furthermore, chronic peripheral dopamine treatments resulted in memory deficits. Systemic administration of a dopamine D1/D5 receptor antagonist reversed changes in memory, synaptic plasticity, adult neurogenesis, and gene expression in UV-irradiated mice. Our findings provide converging evidence that chronic UV exposure alters dopamine levels in the central nervous system and peripheral organs, including the skin, which may underlie the observed neurobehavioral shifts, such as hippocampal memory deficits and impaired neurogenesis. This study underscores the importance of protection from UV exposure and introduces the potential of pharmacological approaches targeting dopamine receptors to counteract the adverse neurological impacts of UV exposure.

2.
J Invest Dermatol ; 2024 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-38775766

RESUMO

UV irradiation of the human skin downregulates lipid synthesis and adipokine production in subcutaneous fat. Recent evidence has suggested that UV exposure limits body weight gain in mouse models of obesity. However, the relationship between norepinephrine and UV irradiation has not been previously reported. Chronic UV exposure stimulated food intake but prevented body weight gain. Leptin, an appetite-suppressing hormone, was significantly reduced in the serum of the UV-irradiated mice. In contrast, UV irradiation induced browning of subcutaneous white adipose tissues without increasing physical activity. Notably, UV irradiation significantly increased norepinephrine levels, and the inhibition of norepinephrine production reversed the effects of chronic UV irradiation on food intake and body weight gain. In conclusion, chronic UV irradiation induces norepinephrine release, resulting in the stimulation of food intake due to the downregulation of leptin levels, but it prevents weight gain by inducing the browning process and elevating energy expenditure.

4.
Br J Nutr ; 131(7): 1105-1114, 2024 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-38016800

RESUMO

Brain ageing, the primary risk factor for cognitive impairment, occurs because of the accumulation of age-related neuropathologies. Identifying effective nutrients that increase cognitive function may help maintain brain health. Tomatoes and lemons have various bioactive functions and exert protective effects against oxidative stress, ageing and cancer. Moreover, they have been shown to enhance cognitive function. In the present study, we aimed to investigate the effects of tomato and lemon ethanolic extracts (TEE and LEE, respectively) and their possible synergistic effects on the enhancement of cognitive function and neurogenesis in aged mice. The molecular mechanisms underlying the synergistic effect of TEE and LEE were investigated. For the in vivo experiment, TEE, LEE or their mixture was orally administered to 12-month-old mice for 9 weeks. A single administration of either TEE or LEE improved cognitive function and neurogenesis in aged mice to some extent, as determined using the novel object recognition test and doublecortin immunohistochemical staining, respectively. However, a significant enhancement of cognitive function and neurogenesis in aged mice was observed after the administration of the TEE + LEE mixture, which had a synergistic effect. N-methyl-d-aspartate receptor 2B, postsynaptic density protein 95, and brain-derived neurotrophic factor (BDNF) levels and tropomyosin receptor kinase B (TrkB)/extracellular signal-regulated kinase (ERK) phosphorylation also synergistically increased after the administration of the mixture compared with those in the individual treatments. In conclusion, compared with their separate treatments, treatment with the TEE + LEE mixture synergistically improved the cognitive function, neurogenesis and synaptic plasticity in aged mice via the BDNF/TrkB/ERK signalling pathway.


Assuntos
Solanum lycopersicum , Animais , Camundongos , Encéfalo/metabolismo , Fator Neurotrófico Derivado do Encéfalo/metabolismo , Cognição , Hipocampo
5.
Photodermatol Photoimmunol Photomed ; 39(6): 573-581, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37731181

RESUMO

BACKGROUND/PURPOSE: Ultraviolet (UV) radiation has both harmful and beneficial effects on human skin and health. It causes skin damage, aging, and cancer; however, it is also a primary source of vitamin D. Additionally, UV radiation can impact energy metabolism and has protective effects on several cardiovascular and metabolic disorders in mice and humans. However, the mechanisms of UV protection against these diseases have not been clearly identified. METHODS: This review summarizes the systemic effects of UV radiation on hypertension and several metabolic diseases such as obesity, diabetes, and nonalcoholic fatty liver disease (NAFLD) in mice, and we also consider the mechanisms of action of the related regulators nitric oxide (NO) and vitamin D. RESULTS: UV exposure can lower blood pressure and prevent the development of cardiovascular diseases and metabolic disorders, such as metabolic syndrome, obesity, and type 2 diabetes, primarily through mechanisms that depend on UV-induced NO. UV radiation may also effectively delay the onset of type 1 diabetes through mechanisms that rely on UV-induced vitamin D. UV-induced NO and vitamin D play roles in preventing and slowing the progression of NAFLD. CONCLUSION: UV exposure is a promising nonpharmacological intervention for cardiovascular and metabolic disorders. NO and vitamin D may play a crucial role in mediating these effects. However, further investigations are required to elucidate the exact mechanisms and determine the optimal dosage and exposure duration of UV radiation.


Assuntos
Diabetes Mellitus Tipo 2 , Hepatopatia Gordurosa não Alcoólica , Humanos , Animais , Camundongos , Vitamina D/metabolismo , Raios Ultravioleta/efeitos adversos , Óxido Nítrico , Hepatopatia Gordurosa não Alcoólica/etiologia , Hepatopatia Gordurosa não Alcoólica/prevenção & controle , Vitaminas , Obesidade
6.
Dalton Trans ; 52(24): 8198-8203, 2023 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-37283185

RESUMO

A new 2D flexible cobalt(II) framework (Co-MOF) exhibits a reversible solid-state structural transformation upon guest molecule removal/uptake. After activation, Co-MOF-α with 1D porous channels transformed into Co-MOF-ß (0D voids) accompanied by a shift in metal and carboxylate coordination modes, the rotation of organic linkers and the contraction of interstitial spaces. Gas adsorption experiments reveal that Co-MOF-ß exhibits a two-step CO2 adsorption isotherm and close-to-open (type F-IV) isotherms for C2H2, C2H4 and C2H6 at 195 K. Moreover, it shows typical type I adsorption isotherms for the above gases and the selective uptake of C2H2 over CH4 and CO2 at room temperature.

7.
World J Surg Oncol ; 21(1): 125, 2023 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-37024930

RESUMO

BACKGROUND: The randomized trials which include ACOSOG Z0011 and IBCSG 23-01 had found that the survival rates were not different in patients with cT1/2N0 and 1-2 sentinel lymph node (SLN)-positive, macro/micrometastases who underwent breast-conserving therapy, and micrometastases who underwent total mastectomy (TM), when axillary lymph node dissection (ALND) was omitted. However, for patients with cT1/2N0 and 1-2 SLN macrometastases who underwent TM; there was still insufficient evidence from clinical studies to support whether ALND can be exempted. This study aimed to investigate the risk factors of non-sentinel lymph node (nSLN) metastasis in breast cancer patients with 1-2 SLN macrometastases undergoing TM. METHODS: The clinicopathological data of 1491 breast cancer patients who underwent TM and SLNB from January 2017 to February 2022 were retrospectively analyzed. Univariate and multivariate analyses were performed to analyze the risk factors for nSLN metastasis. RESULTS: A total of 273 patients with 1-2 SLN macrometastases who underwent TM were enrolled. Postoperative pathological data showed that 35.2% patients had nSLN metastasis. The results of multivariate analysis indicated that tumor size (TS) (P = 0.002; OR: 1.051; 95% CI: 1.019-1.084) and ratio of SLN macrometastases (P = 0.0001; OR: 12.597: 95% CI: 4.302-36.890) were the independent risk factors for nSLN metastasis in breast cancer patients with 1-2 SLN macrometastases that underwent TM. The ROC curve analysis suggested that when TS ≤22 mm and ratio of SLN macrometastases ≤0.33, the incidence of nSLN metastasis could be reduced to 17.1%. CONCLUSIONS: The breast cancer patients with cT1/2N0 stage, undergoing TM and 1-2 SLN macrometastases, when the TS ≤22 mm and macrometastatic SLN does not exceed 1/3 of the total number of detected SLN, the incidence of nSLN metastasis is significantly reduced, but whether ALND can be exempted needs further exploration.


Assuntos
Neoplasias da Mama , Linfonodo Sentinela , Humanos , Feminino , Neoplasias da Mama/patologia , Biópsia de Linfonodo Sentinela/métodos , Metástase Linfática/patologia , Estudos de Casos e Controles , Mastectomia Simples , Estudos Retrospectivos , Micrometástase de Neoplasia/patologia , Mastectomia , Axila/patologia , Linfonodo Sentinela/cirurgia , Linfonodo Sentinela/patologia , Excisão de Linfonodo/métodos , Fatores de Risco , Linfonodos/cirurgia , Linfonodos/patologia
8.
Proc Biol Sci ; 289(1989): 20221840, 2022 12 21.
Artigo em Inglês | MEDLINE | ID: mdl-36541168

RESUMO

Understanding how non-trophic social systems respond to environmental gradients is still a challenge in animal ecology, particularly in comparing changes in species composition to changes in interspecific interactions. Here, we combined long-term monitoring of mixed-species bird flocks, data on participating species' evolutionary history and traits, to test how elevation affected community assemblages and interspecific interactions in flock social networks. Elevation primarily affected flocks through reassembling interspecific associations rather than modifying community assemblages. Specifically, flock networks at higher elevations (compared to low elevations) had stronger interspecific associations (larger average weighted degree), network connectivity (enhanced network density) and fewer subnetworks. A phylogenetic and functional perspective revealed that associations between similar species weakened, whereas connections between dissimilar and/or random species were unchanged or strengthened with elevation. Likewise, network assortativity for the traits of vertical stratum and breeding period declined with elevation. The overall pattern is a change from modular networks in the lowlands, where species join flocks with other species that have matching traits, to a more open, random system at high elevations. Collectively, this rewiring of interspecific networks across elevational gradients imparts network stability and resiliency and makes mixed-species flocks less sensitive to local extinctions caused by harsh environments.


Assuntos
Altitude , Aves , Animais , Filogenia , Evolução Biológica , Ecologia
9.
ACS Catal ; 12(22): 14398-14407, 2022 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-36439036

RESUMO

The controllable divergent reactivity of 1,3-dicarbonyls is described, which enables the efficient hydro- and oxoalkylation of vinyl arenes. Both reaction pathways are initiated through the formation of polarity-reversed C-centered-radical intermediates at the active methylene center of 1,3-dicarbonyls via direct photocatalytic C-H bond transformations. The oxoalkylation of alkenes is achieved under aerobic conditions via a Cu(II)-photomediated rebound mechanism, while the corresponding hydroalkylation becomes possible under a nitrogen atmosphere by the combination of 4CzIPN and a Brønsted base. The breadth of these divergent protocols is demonstrated in the late-stage modification of drugs and natural products and by the transformation of the products to a variety of heterocycles such as pyridines, pyrroles, or furans. Moreover, the two catalytic modes can be combined synergistically for the stereoselective construction of cyclopentanol derivatives in a formal [4+1]-annulation process.

10.
Foods ; 11(21)2022 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-36360028

RESUMO

Dietary habits have a great impact on one's health, especially in cognitive decline. Tomato and lemon contain diverse bioactive compounds and possess various effects, including the enhancement of cognitive function. We observed the protective effect of tomato, lemon extract and the mixture of them on H2O2-induced cytotoxicity of PC12 cells. To measure the in vivo effect in a murine model, each extract was orally administered to forty 1-year-old mice for 6 weeks, and a novel object recognition (NOR) test was performed to observe cognitive function, and hippocampal neurogenesis was observed through a doublecortin (DCX) stain. PC12 cell death by oxidative stress was reduced by pretreating with each extract, and a synergistic reduction was observed in the mixture. Newly generated DCX-positive neurons were synergistically increased in the hippocampus by the mixture. NOR test showed a tendency to significantly improve age-related cognitive dysfunction by consuming the mixture of tomato and lemon. In conclusion, tomato and lemon extracts can reduce cellular oxidative stress and increase NOR, likely due to enhanced neurogenesis, while the mixture of the two showed synergistic anti-oxidative effects and hippocampal neurogenesis.

11.
Medicine (Baltimore) ; 101(39): e30728, 2022 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-36181090

RESUMO

This study aimed to investigate the mechanism of warming yang and reducing turbidity decoction in the treatment of diabetic kidney disease (DKD) by network pharmacology. The active components and corresponding targets of warming yang and reducing turbidity decoction were screened through the Traditional Chinese Medicine Systems Pharmacology database, DKD-related targets were obtained from Genecard and Online Mendelian Inheritance in Man databases, and drug-disease common targets were screened through Venny online website. Then we used STRING and Cytoscape software to analyze and perform protein-protein interaction network, and used CytoNCA plug-in to perform topological analysis to screen out the core target. We used RStudio to performed gene ontology (GO) functional enrichment analysis and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analysis. One hundred one active components in warming yang and reducing turbidity decoction participated in the regulation of the body's response to foreign bodies, lipopolysaccharides, metal ions, ketone bodies, hypoxia and oxidative stress by regulating 186 targets related to DKD, and played a role in the treatment of DKD by interfering with pathways such as interfered with lipids and atherosclerosis, PI3K-Akt, fluid shear stress and atherosclerosis, AGE-RAGE and cell senescence. It was implied that warming yang and reducing turbidity decoction had the features of multi components, multi targets and multi pathways in the treatment of DKD, which might create methods and directions for further verification of the molecular mechanism of warming yang and reducing turbidity decoction.


Assuntos
Aterosclerose , Diabetes Mellitus , Nefropatias Diabéticas , Medicamentos de Ervas Chinesas , Aterosclerose/tratamento farmacológico , Diabetes Mellitus/tratamento farmacológico , Nefropatias Diabéticas/tratamento farmacológico , Medicamentos de Ervas Chinesas/farmacologia , Medicamentos de Ervas Chinesas/uso terapêutico , Humanos , Corpos Cetônicos , Lipopolissacarídeos , Medicina Tradicional Chinesa , Farmacologia em Rede , Fosfatidilinositol 3-Quinases , Proteínas Proto-Oncogênicas c-akt
12.
Animals (Basel) ; 12(18)2022 Sep 09.
Artigo em Inglês | MEDLINE | ID: mdl-36139220

RESUMO

The mud snail Cipangopaludina cathayensis is a widely distributed species in China. Particularly in Guangxi province, mud snail farming contributes significantly to the economic development. However, global warming in recent decades poses a serious threat to global aquaculture production. The rising water temperature is harmful to aquatic animals. The present study explored the effects of high temperature on the intestinal microbiota of C. cathayensis. Snail intestinal samples were collected from the control and high-temperature groups on days 3 and 7 to determine the gut microbiota composition and diversity. Gut bacterial community composition was investigated using high-throughput sequencing of the V3-V4 region of bacterial 16S rRNA genes. Our results suggested that thermal stress altered the gut microbiome structure of C. cathayensis. At the phylum level, Proteobacteria, Bacteroidetes, and Firmicutes were dominant in C. cathayensis gut microbiota. The T2 treatment (32 ± 1 °C, day 7) significantly decreased the relative abundance of Firmicutes, Actinobacteria, and Deinococcus-Thermus. In T2, the abundance of several genera of putatively beneficial bacteria (Pseudomonas, Aeromonas, Rhodobacter, and Bacteroides) decreased, whereas the abundance of Halomonas-a pathogenic bacterial genus-increased. The functional prediction results indicated that T2 treatment inhibited some carbohydrate metabolism pathways and induced certain disease-related pathways (e.g., those related to systemic lupus erythematosus, Vibrio cholerae infection, hypertrophic cardiomyopathy, and shigellosis). Thus, high temperature profoundly affected the community structure and function of C. cathayensis gut microbiota. The results provide insights into the mechanisms associated with response of C. cathayensis intestinal microbiota to global warming.

13.
Front Microbiol ; 13: 984757, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-36003941

RESUMO

As one of the most environmentally toxic heavy metals, cadmium (Cd) has attracted the attention of researchers globally. In particular, Guangxi, a province in southwestern China, has been subjected to severe Cd pollution due to geogenic processes and anthropogenic activities. Cd can be accumulated in aquatic animals and transferred to the human body through the food chain, with potential health risks. The aim of the present study was to explore the effects of waterborne Cd exposure (0.5 mg/L and 1.5 mg/L) on the intestinal microbiota of mudsnail, Cipangopaludina cathayensis, which is favored by farmers and consumers in Guangxi. Gut bacterial community composition was investigated using high-throughput sequencing of the V3-V4 segment of the bacterial 16S rRNA gene. Our results indicated that C. cathayensis could tolerate low Cd (0.5 mg/L) stress, while Cd exposure at high doses (1.5 mg/L) exerted considerable effects on microbiota composition. At the phylum level, Proteobacteria, Bacteroidetes, and Firmicutes were the dominant phyla in the mudsnail gut microbiota. The relative abundances of Bacteroidetes increased significantly under high Cd exposure (H14) (p < 0.01), with no significant change in the low Cd exposure (L14) treatment. The dominant genera with significant differences in relative abundance were Pseudomonas, Cloacibacterium, Acinetobacter, Dechloromonas, and Rhodobacter. In addition, Cd exposure could significantly alter the pathways associated with metabolism, cellular processes, environmental information processing, genetic information processing, human diseases, and organismal systems. Notably, compared to the L14 treatment, some disease-related pathways were enriched, while some xenobiotic and organic compound biodegradation and metabolism pathways were significantly inhibited in the H14 group. Overall, Cd exposure profoundly influenced community structure and function of gut microbiota, which may in turn influence C. cathayensis gut homeostasis and health.

14.
Curr Zool ; 67(4): 431-440, 2021 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-34616940

RESUMO

Strong correlations between species diversity and climate have been widely observed, but the mechanism underlying this relationship is unclear. Here, we explored the causes of the richness-climate relationships among passerine birds in China by integrating tropical conservatism and diversification rate hypotheses using path models. We found that assemblages with higher species richness southwest of the Salween-Mekong-Pearl River Divide are phylogenetically overdispersed and have shorter mean root distances (MRDs), while species-rich regions northeast of this divide (e.g., north Hengduan Mountains-south Qinling Mountains) are phylogenetically clustered and have longer MRDs. The results of the path analyses showed that the direct effect of climatic factors on species richness was stronger than their indirect effects on species richness via phylogenetic relatedness, indicating that neither tropical conservatism nor diversification rate hypotheses can well explain the richness-climate relationship among passerines in China. However, when path analyses were conducted within subregions separately, we found that the tropical conservatism hypothesis was well supported in the southwestern Salween-Mekong-Pearl River Divide, while the diversification rate hypothesis could explain the richness-climate relationship well in the northeastern divide. We conclude that the diversity patterns of passerines in different subregions of the Eastern Himalayas-Mountains of Southwest China may be shaped by different evolutionary processes related to geological and climatic histories, which explains why the tropical conservatism or diversification rate hypothesis alone cannot fully explain the richness-climate relationships.

15.
Int J Mol Sci ; 22(3)2021 Jan 22.
Artigo em Inglês | MEDLINE | ID: mdl-33499275

RESUMO

Activin A receptor type 1C (ACVR1C), a type I transforming growth factor-ß (TGF-ß) receptor, has been implicated in sensitive skin and psoriasis and is involved in the regulation of metabolic homeostasis as well as cell proliferation and differentiation. In this study, we identified a novel role of ACVR1C in the ultraviolet (UV)-irradiation-induced reduction of epidermal lipogenesis in human skin. UV irradiation decreased ACVR1C expression and epidermal triglyceride (TG) synthesis in human skin in vivo and in primary normal human epidermal keratinocytes (NHEK) in vitro. Lipogenic genes, including genes encoding acetyl-CoA carboxylase (ACC) and sterol regulatory element binding protein-1 (SREBP1), were significantly downregulated in UV-irradiated NHEK. ACVR1C knockdown by shRNA resulted in greater decreases in SREBP1 and ACC in response to UV irradiation. Conversely, the overexpression of ACVR1C attenuated the UV-induced decreases in SREBP1 and ACC. Further mechanistic study revealed that SMAD2 phosphorylation mediated the ACVR1C-induced lipogenic gene modulation. Taken together, a decrease in ACVR1C may cause UV-induced reductions in SREBP1 and ACC as well as epidermal TG synthesis via the suppression of SMAD2 phosphorylation. ACVR1C may be a target for preventing or treating UV-induced disruptions in lipid metabolism and associated skin disorders.


Assuntos
Acetil-CoA Carboxilase/metabolismo , Receptores de Ativinas Tipo I/metabolismo , Epiderme/metabolismo , Queratinócitos/metabolismo , Proteína Smad2/metabolismo , Proteína de Ligação a Elemento Regulador de Esterol 1/metabolismo , Adulto , Diferenciação Celular , Proliferação de Células , Epiderme/efeitos da radiação , Voluntários Saudáveis , Humanos , Queratinócitos/efeitos da radiação , Metabolismo dos Lipídeos , Lipogênese/genética , Fosforilação , Interferência de RNA , Pele/metabolismo , Triglicerídeos/química , Raios Ultravioleta
17.
Molecules ; 25(19)2020 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-32977516

RESUMO

Benzosultams represent one category of multi-heteroatom heterocyclic scaffolds, which have been frequently found in pharmaceuticals, agricultural agents, and chiral catalysts. Given the diversely significant functions of these compounds in organic and medicinal chemistry, great efforts have been made to develop novel catalytic systems for the efficient construction of benzosultam motifs over the past decades. Herein, in this review, we mainly summarize the recent advances in the field of catalytic synthesis of benzosultams from 2017 to August of 2020, with an emphasis on the scopes and mechanisms of representative reactions.


Assuntos
Técnicas de Química Sintética/métodos , Sulfonamidas/química , Sulfonamidas/síntese química , Catálise , Estereoisomerismo
18.
Sci Rep ; 10(1): 10306, 2020 06 25.
Artigo em Inglês | MEDLINE | ID: mdl-32587358

RESUMO

The effects of increasing yield and quality of virus-free chewing cane seedlings and their physiological and molecular basis were studied in this study. Results showed that compared with infected seedlings (the control), the yield of chewing cane stems grown from virus-free seedlings increased by 21.81-29.93%, stem length increased by 28.66-34.49 cm, internode length increased by 2.16-2.68 cm, the single stem weight increased by 20.10-27.68%, the reducing sugar increased by 0.91-1.15% (absolute value), and sucrose increased by - 0.06-1.33% (absolute value). The decrease in sucrose content did not reach significant level, but all other parameters were reached significant level. The chlorophyll content, photosynthetic parameters such as stomatal conductance (Gs), net photosynthetic rate (Pn) and transpiration rate (Tr), the activity of photosynthetic key enzymes ribulose-1,5-bisphosphate carboxylase (Rubisco) and phosphoenolpyruvate carboxylase (PEPC), and gene (pepc, rbcS, and rbcL) expression levels were all greater in virus-free seedlings than infected seedlings. The content of superoxide anion (O2-) and malondialdehyde (MDA) in virus-free seedlings was lower than infected seedlings at the main growth stage. With increased development, the activities of the antioxidant enzymes superoxide dismutase (SOD), peroxidase (POD), and catalase (CAT) were gradually higher in virus-free seedlings than infected seedlings. Our results indicate that virus-free seedlings may improve photosynthesis efficiency and promote photosynthesis by increasing chlorophyll content, photosynthetic key enzyme activity, and the gene expression levels in leaves. By increasing the activity of antioxidant enzymes, reducing the degree of membrane lipid peroxidation, and improving the stress resistance of chewing cane, the virus-free chewing cane seedlings increased yield and quality. Our findings provide a scientific and theoretical basis for the promotion and application of virus-free chewing cane seedlings.


Assuntos
Saccharum/fisiologia , Plântula/crescimento & desenvolvimento , Clorofila/análise , Qualidade dos Alimentos , Interações Hospedeiro-Patógeno/fisiologia , Peroxidação de Lipídeos , Malondialdeído/análise , Lipídeos de Membrana/metabolismo , Vírus do Mosaico/patogenicidade , Fotossíntese , Folhas de Planta/metabolismo , Proteínas de Plantas/metabolismo , Transpiração Vegetal , Saccharum/química , Saccharum/virologia , Plântula/química , Plântula/metabolismo , Plântula/virologia , Sacarose/análise , Superóxidos/análise
19.
Acc Chem Res ; 53(5): 1066-1083, 2020 05 19.
Artigo em Inglês | MEDLINE | ID: mdl-32286794

RESUMO

Nitrogen-centered radicals (NCRs) are a versatile class of highly reactive species that have a longer history than the classical carbon-based radicals in synthetic chemistry. Depending on the N-hybridization and substitution patterns, NCRs can serve as electrophiles or nucleophiles to undergo various radical transformations. Despite their power, progress in nitrogen-radical chemistry is still slow compared with the popularity of carbon radicals, and their considerable synthetic potential has been largely underexplored, which is, as concluded by Zard, mainly hampered by "a dearth of convenient access to these species and a lack of awareness pertaining to their reactivity".Over the past decade, visible-light photoredox catalysis has been established as a powerful toolbox that synthetic chemists can use to generate a diverse range of radical intermediates from native organic functional groups via a single electron transfer process or energy transfer under mild reaction conditions. This catalytic strategy typically obviates the need for external stoichiometric activation reagents or toxic initiators and often enables traditionally inaccessible ionic chemical reactions. On the basis of our long-standing interest in nitrogen chemistry and catalysis, we have emphasized the use of visible-light photoredox catalysis as a tactic to discover and develop novel methods for generating NCRs in a controlled fashion and synthetic applications. In this Account, we describe our recent advances in the development of visible-light-driven photoredox-catalyzed generation of NCRs and their synthetic applications.Inspired by the natural biological proton-coupled electron transfer (PCET) process, we first developed a strategy of visible-light-driven photoredox-catalyzed oxidative deprotonation electron transfer to activate the N-H bonds of hydrazones, benzamides, and sulfonamides to give the corresponding NCRs under mild reaction conditions. With these reactive species, we then achieved a range of 5-exo and 6-endo radical cyclizations as well as cascade reactions in a highly regioselective manner, providing access to a variety of potentially useful nitrogen heterocycles. To further expand the repertoire of possible reactions of NCRs, we also revealed that iminyl radicals, derived from O-acyl cycloalkanone oxime esters, can undergo facile ring-opening C-C bond cleavage to give cyanoalkyl radicals. These newly formed radical species can further undergo a variety of C-C bond-forming reactions to allow the synthesis of diverse distally functionalized alkyl nitriles. Stimulated by these studies, we further developed a wide variety of visible-light-driven copper-catalyzed radical cross-coupling reactions of cyanoalkyl radicals. Because of their inherent highly reactive and transient properties, the strategy of heteroatom-centered radical catalysis is still largely underexplored in organic synthesis. Building on our understanding of the fundamental chemistry of NCRs, we also developed for the first time the concept of NCR covalent catalysis, which involves the use of in situ-photogenerated NCRs to activate allyl sulfones, vinylcyclopropanes, and N-tosyl vinylaziridines. This catalytic strategy has thus enabled efficient difunctionalization of various alkenes and late-stage modification of complex biologically active molecules.In this Account, we describe a panoramic picture of our recent contributions since 2014 to the development and application of the visible-light-driven photoredox systems in the field of NCR chemistry. These studies provide not only efficient methods for the synthesis of functionally rich molecules but also some insight into the exploration of new reactivity or reaction modes of NCRs.

20.
Org Lett ; 22(6): 2470-2475, 2020 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-32125860

RESUMO

A visible light photoredox-promoted and nitrogen radical catalyzed [3 + 2] cyclization of vinylcyclopropanes and N-tosyl vinylaziridines with alkenes is developed. Key to the success of this process is the use of the readily tunable hydrazone as a nitrogen radical catalyst. Preliminary mechanism studies suggest that the photogenerated nitrogen radical undergoes reversible radical addition to the vinylcyclopropanes and N-tosyl vinylaziridines to enable their ring-opening C-C and C-N bond cleavage and ensuing cyclization with alkenes.

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