RESUMO
High-concentrate diet induce subacute ruminal acidosis (SARA) and cause liver damage in ruminants. It has been reported that forkhead box protein A2 (FOXA2) can enhance mitochondrial membrane potential but its function in mitochondrial dysfunction induced by high concentrate diets is still unknown. Therefore, the aim of this study was to elucidate the effect of high-concentrate (HC) diet on hepatic FOXA2 expression, mitochondrial unfolded protein response (UPRmt), mitochondrial dysfunction and oxidative stress. A total of 12 healthy mid-lactation Holstein cows were selected and randomized into 2 groups: the low concentrate (LC) diet group (concentrate:forage = 4:6) and HC diet group (concentrate:forage = 6:4). The trial lasted 21 d. The rumen fluid, blood and liver tissue were collected at the end of the experiment. The results showed that the rumen fluid pH level was reduced in the HC group and the pH was lower than 5.6 for more than 4 h/d, indicating that feeding HC diets successfully induced SARA in dairy cows. Both FOXA2 mRNA and protein abundance were significantly reduced in the liver of the HC group compared with the LC group. The activity of antioxidant enzymes (CAT, G6PDH, T-SOD, Cu/Zn SOD, Mn SOD) and mtDNA copy number in the liver tissue of the HC group decreased, while the level of H2O2 significantly increased, this increase was accompanied by a decrease in oxidative phosphorylation (OXPHOS). The balance of mitochondrial division and fusion was disrupted in the HC group, as evidenced by the decreased mRNA level of OPA1, MFN1, and MFN2 and increased mRNA level of Drp1, Fis1, and MFF. At the same time, HC diet downregulated the expression level of SIRT1, SIRT3, PGC-1α, TFAM, and Nrf 1 to inhibit mitochondrial biogenesis. The HC group induced UPRmt in liver tissue by upregulating the mRNA and protein levels of CLPP, LONP1, CHOP, Hsp10, and Hsp60. In addition, HC diet could increase the protein abundance of Bax, CytoC, Caspase 3 and Cleaved-Caspase 3, while decrease the protein abundance of Bcl-2 and the Bcl-2/Bax ratio. Overall, our study suggests that the decreased expression of FOXA2 may be related to UPRmt, mitochondrial dysfunction, oxidative stress, and apoptosis in the liver of dairy cows fed a high concentrate diet.
Assuntos
Peróxido de Hidrogênio , Doenças Mitocondriais , Animais , Feminino , Bovinos , Caspase 3/metabolismo , Peróxido de Hidrogênio/metabolismo , Proteína X Associada a bcl-2/metabolismo , Dieta/veterinária , Fígado/metabolismo , Lactação , Estresse Oxidativo , Superóxido Dismutase/metabolismo , RNA Mensageiro/metabolismo , Resposta a Proteínas não Dobradas , Doenças Mitocondriais/metabolismo , Fatores de Transcrição Forkhead/metabolismo , Leite/metabolismo , Concentração de Íons de Hidrogênio , Ração AnimalRESUMO
KEY MESSAGE: Over-expression of SlJA2 decreased the accumulation of SA, which resulted in significant physiological and gene expression changes in transgenic tobacco plants, leading to the decreased heat tolerance of transgenic tobacco. NAC family, the largest transcription factors in plants, responses to different environmental stimuli. Here, we isolated a typical NAC transcription factor (SlJA2) from tomato and got transgenic tobacco with SlJA2 over-expression. Expression of SlJA2 was induced by heat stress (42 °C), chilling stress (4 °C), drought stress, osmotic stress, abscisic acid, and salicylic acid. Over-expression of SlJA2 decreased the accumulation of salicylic acid by regulating expression of salicylic acid degradation gene under heat stress. Compared to WT plants, stomatal apertures and water loss increased in transgenic plants, and the damage of photosynthetic apparatus and chlorophyll breakdown were more serious in transgenic plants under heat stress. Meanwhile, more H2O2 and O2·- were accumulated transgenic plants and proline synthesis was restricted, which resulted in more serious oxidative damage compared to WT. qRT-PCR analysis showed that over-expression of SlJA2 could down-regulate genes involved in reactive oxygen species scavenging, proline biosynthesis, and response to heat stress. All the above results indicated that SlJA2 may be a negative regulator responded to plant's heat tolerance. Thus, this study provides new insight into roles of NAC family member in plant response to abiotic stress.
Assuntos
Expressão Gênica , Nicotiana/metabolismo , Proteínas de Plantas/metabolismo , Plantas Geneticamente Modificadas/genética , Transdução de Sinais/genética , Estresse Fisiológico/genética , Termotolerância/genética , Secas , Expressão Gênica/efeitos dos fármacos , Expressão Gênica/genética , Peróxido de Hidrogênio/metabolismo , Solanum lycopersicum/genética , Proteínas de Plantas/genética , Plantas Geneticamente Modificadas/efeitos dos fármacos , Plantas Geneticamente Modificadas/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Ácido Salicílico/farmacologia , Transdução de Sinais/efeitos dos fármacos , Estresse Fisiológico/efeitos dos fármacos , Nicotiana/efeitos dos fármacos , Nicotiana/genéticaRESUMO
SUMOylation is an important post-translational modification process that regulates different cellular functions in eukaryotes. SIZ/PIAS-type SAP and Miz1 (SIZ1) proteins exhibit SUMO E3 ligase activity, which modulates SUMOylation. However, SIZ1 in tomato has been rarely investigated. In this study, a tomato SIZ1 gene (SlSIZ1) was isolated and its molecular characteristics and role in tolerance to drought stress are described. SlSIZ1 was up-regulated by cold, sodium chloride (NaCl), polyethylene glycol (PEG), hydrogen peroxide (H2 O2 ) and abscisic acid (ABA), and the corresponding proteins were localized in the nucleus. The expression of SlSIZ1 in Arabidopsis thaliana (Arabidopsis) siz1-2 mutants partially complemented the phenotypes of dwarf, cold sensitivity and ABA hypersensitivity. SlSIZ1 also exhibited the activity of SUMO E3 ligase to promote the accumulation of SUMO conjugates. Under drought stress, the ectopic expression of SlSIZ1 in transgenic tobacco lines enhanced seed germination and reduced the accumulation of reactive oxygen species. SlSIZ1 overexpression conferred the plants with improved growth, high free proline content, minimal malondialdehyde accumulation and increased accumulation of SUMO conjugates. SlSIZ1 is a functional homolog of Arabidopsis SIZ1 with SUMO E3 ligase activity. Therefore, overexpression of SlSIZ1 enhanced the tolerance of transgenic tobacco to drought stress.
Assuntos
Adaptação Fisiológica , Secas , Nicotiana/genética , Nicotiana/fisiologia , Proteínas de Plantas/metabolismo , Solanum lycopersicum/enzimologia , Ubiquitina-Proteína Ligases/metabolismo , Ácido Abscísico/farmacologia , Adaptação Fisiológica/efeitos dos fármacos , Arabidopsis/efeitos dos fármacos , Arabidopsis/genética , Biologia Computacional , Teste de Complementação Genética , Germinação/efeitos dos fármacos , Resposta ao Choque Térmico/efeitos dos fármacos , Solanum lycopersicum/efeitos dos fármacos , Mutação/genética , Fenótipo , Plantas Geneticamente Modificadas , Transporte Proteico/efeitos dos fármacos , Espécies Reativas de Oxigênio/metabolismo , Plântula/efeitos dos fármacos , Plântula/crescimento & desenvolvimento , Transdução de Sinais/efeitos dos fármacos , Proteínas Modificadoras Pequenas Relacionadas à Ubiquitina/metabolismo , Estresse Fisiológico/efeitos dos fármacosRESUMO
To study the toxicokinetics of bakuchiol, hepatic and renal toxicity in rats after single oral administration of Psoraleae Fructus and combined with Glycyrrhizae Radix et Rhizoma, in order to provide scientific evidences for clinical safe medication use. A total of 35 SD rats were randomly divided into seven groups: vehicle (distilled water) control group, Glycyrrhizae Radix et Rhizoma group, positive control (aristolochic acid A) group, Psoraleae Fructus (40 g x kg(-1)) group( both male and female rats), Psoraleae Fructus and Glycyrrhizae Radix et Rhizoma (40 +20) g x kg(-1) group (both male and female rats). HPLC-UV method was used to determine the concentration of bakuchiol in rat plasma at different time points after single oral administration. Plasma alanine transaminase (ALT), aspartate aminotransferase (AST), blood urea nitrogen (BUN), plasma creatinine (Cr), N-acetyl-ß-D-glucosaminidase (NAG) and kidney injury molecule 1 (Kim-1) were measured after administration for 24 h. The main toxicokinetics parameters of bakuchiol in rats exert significantly gender difference. When Psoraleae Fructus combination with Glycyrrhizae Radix et Rhizoma, the total area under the plasma concentration-time curve( AUC), C(max), and plasma clearance (CL) of bakuchiol were increased, respectively; CL, half-life (t½) were decreased, and T(max) were prolonged. The biochemical indicators (including ALT, AST, BUN, Cr and KIM-1 level) in different dose of Psoraleae Fructus groups, were found no statistically significant difference when compared with vehicle control group. The level of NAG in both Psoraleae Fructus and compatibility with Glycyrrhizae Radix et Rhizoma groups were significant increased (P < 0.05). There are obvious effects on toxicokinetics of bakuchiol in rats when Psoraleae Fructus combined with Glycyrrhizae Radix et Rhizoma. Renal toxicity induced by Psoraleae Fructus at high dose was observed after single oral administration and no liver damage in rats was found.
Assuntos
Glycyrrhiza/toxicidade , Rim/efeitos dos fármacos , Fígado/efeitos dos fármacos , Fenóis/toxicidade , Psoralea/toxicidade , Administração Oral , Animais , Feminino , Masculino , Fenóis/farmacocinética , Ratos , Ratos Sprague-Dawley , Rizoma/toxicidade , ToxicocinéticaRESUMO
The studies of geometrical structures, thermal stabilities, redox properties, nonlinear responses and optoelectronic properties have been carried out on a series of novel ferrocenyl (Fc) chromophores with the view of assessing their switchable and tailorable second order nonlinear optics (NLO). The use of a constant Fc donor and a 4,4'-bipyridinium acceptor and varied conjugated bridges makes it possible to systematically determine the contribution of organic connectors to chromophore nonlinear optical activities. The structures reveal that both the reduction reactions and organic connectors have a significant influence on 4,4'-bipyridinium. The potential energy surface maps along with plots of reduced density gradient mirror the thermal stabilities of the Fc-based chromophores. The first and second reductions take place preferentially at the 4,4'-bipyridinium moieties. Significantly, the reduction processes result in the molecular switches with large NLO contrast varying from zero or very small to a large value. Moreover, time-dependent density functional theory results indicate that the absorption peaks are mainly attributed to Fc to 4,4'-bipyridinium charge transfer and the mixture of intramolecular charge transfer within the two respective 4,4'-bipyridinium moieties coupled with interlayer charge transfer between the two 4,4'-bipyridinium moieties. This provides us with comprehensive information on the effect of organic connectors on the NLO properties.
RESUMO
Density functional theory (DFT) calculations and natural bond orbital (NBO) analysis were carried out to investigate the electronic structures and bonding features between the ruthenium(ii) atom and the SO2 molecule in two ruthenium-sulfur dioxide (SO2) adducts, trans-Ru(NH3)4(SO2)Cl(+) and [{SiW11O39}Ru(II)(SO2)](6-). In addition, the bonding interactions between SO2 and the metal-ruthenium fragment were determined by binding energy (ΔEabs) calculation and electronic structures. The results indicate that the η(1)-S-planar model in both trans-Ru(NH3)4(SO2)Cl(+) and [{SiW11O39}Ru(II)(SO2)](6-) are more favorable. NBO analysis of the bonding interaction between ruthenium and sulfur centers in the [{SiW11O39}Ru(II)(SO2)](6-) complex shows that it possesses a σ and a π bond. It predicts that the polyoxometalate [SiW11O39Ru](6-) can serve as a potential adsorbent for the SO2 molecule because of the strong Ru-S bond relative to Ru(NH3)4Cl(+).
RESUMO
KEY MESSAGE: Transgenic tomato plants overexpressing LeFAD3 sense and antisense sequences were generated. Salt stress suppressed the growth of WT and antisense plants to a higher extent than that in sense plants. In this study, we investigated the role of the LeFAD3-encoding ER-type omega-3 fatty acid desaturase in salt tolerance in tomato plants. We created transgenic tomato plants by overexpressing its sense and antisense sequences under the control of the cauliflower mosaic virus 35S promoter. Based on the results of northern and western blotting as well as quantitative reverse transcription-polymerase chain reaction, sense plants expressed more desaturase than wild-type (WT) plants, whereas antisense plants expressed less desaturase than WT. Salt stress suppressed the growth of both WT and antisense plants to a higher extent than that in sense plants, which can be attributed to the fact that sense plants performed better in maintaining the integrity of the membrane system, as revealed by electron microscopy. The concomitant increase in superoxide dismutase (EC 1.15.1.1) and ascorbate peroxidase (EC 1.11.1.7) may have alleviated the photoinhibition caused by the increased level of ROS in sense plants. Our results suggest that LeFAD3 overexpression can enhance the tolerance of early seedlings to salinity stress.
Assuntos
Retículo Endoplasmático/enzimologia , Ácidos Graxos Dessaturases/metabolismo , Salinidade , Tolerância ao Sal , Plântula/enzimologia , Solanum lycopersicum/enzimologia , Solanum lycopersicum/fisiologia , Ascorbato Peroxidases/metabolismo , Condutividade Elétrica , Retículo Endoplasmático/efeitos dos fármacos , Ácidos Graxos Dessaturases/genética , Ácidos Graxos/metabolismo , Regulação da Expressão Gênica de Plantas/efeitos dos fármacos , Solanum lycopersicum/efeitos dos fármacos , Solanum lycopersicum/genética , Estresse Oxidativo/efeitos dos fármacos , Estresse Oxidativo/genética , Folhas de Planta/efeitos dos fármacos , Folhas de Planta/ultraestrutura , Plantas Geneticamente Modificadas , Tolerância ao Sal/efeitos dos fármacos , Tolerância ao Sal/genética , Plântula/efeitos dos fármacos , Plântula/fisiologia , Cloreto de Sódio/farmacologia , Estresse Fisiológico/efeitos dos fármacos , Estresse Fisiológico/genética , Superóxido Dismutase/metabolismoRESUMO
NAC (NAM-ATAF1, 2-CUC2) family members play important roles in various environmental responses. Here, we cloned a full-length NAC gene (954 bp) from Solanum lycopersicum (SlNAC1). This gene belonged to ATAF subfamily which included ATAF1 and ATAF2 of Arabidopsis thaliana. SlNAC1 expression was induced by chilling stress (4°C), heat stress (40°C), high salinity, osmotic stress and mechanical wounding. SlNAC1 transcripts were enhanced after application of abscisic acid, methyl jasmonate, salicylic acid, gibberellin, ethylene, methyl viologen and hydrogen peroxide. The seedlings of transgenic plants overexpressing SlNAC1 grew more leaves but were shorter than wild-type (WT) plants. SlNAC1 overexpression increased the chilling tolerance of tomato plants by maintaining the higher maximal photochemical efficiency of photosystem II and oxygen-evolving activities. Compared with WT plants, transgenic plants showed higher superoxide dismutase (EC 1.15.1.1) and catalase (EC 1.11.1.6) activities, which reduced levels of H2 O2 and superoxide anion radicals and promoted lower ion leakage and malondialdehyde content. The expression level of SlCBF1 in transgenic plants was also higher than that in WT plants under both normal conditions and chilling stress; this increased expression may be the main factor influencing the high chilling tolerance of transgenic plants. The results suggest that SlNAC1 plays important roles in diversiform plant-stress responses and diverse signaling pathways.
Assuntos
Arabidopsis/fisiologia , Oxigênio/metabolismo , Solanum lycopersicum/genética , Fatores de Transcrição/metabolismo , Adaptação Fisiológica , Arabidopsis/genética , Temperatura Baixa , Regulação da Expressão Gênica de Plantas , Solanum lycopersicum/efeitos dos fármacos , Solanum lycopersicum/enzimologia , Solanum lycopersicum/fisiologia , Complexo de Proteína do Fotossistema II/metabolismo , Reguladores de Crescimento de Plantas/farmacologia , Folhas de Planta/efeitos dos fármacos , Folhas de Planta/enzimologia , Folhas de Planta/genética , Folhas de Planta/fisiologia , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Plantas Geneticamente Modificadas , Espécies Reativas de Oxigênio/metabolismo , Plântula/efeitos dos fármacos , Plântula/enzimologia , Plântula/genética , Plântula/fisiologia , Estresse Fisiológico , Fatores de Transcrição/genéticaRESUMO
The switchable second-order nonlinear optical (NLO) properties on two-dimensional (2D) molecules based on Lindqvist-type [Mo6O19](2-) and dithienylperfluorocyclopentene (DTE) have been investigated at density functional theory (DFT) level. The CAM-B3LYP and M06-2X functionals were employed to study the switching behavior on NLO properties by photoisomerization reaction. The ßtot value of system 2c (closed-ring form) is 15920.5 au, which is 150.1 times larger than that of the corresponding open-ring form (system 2o). The time-dependent DFT calculations predict that the charge transfer from DTE to polyoxometalate, and DTE intramolecular charge transfer in closed-ring systems effectively improve the static first hyperpolarizability. Furthermore, the Λ-shaped systems possess a larger u value than those of W-shaped systems owing to different orientation for substituent groups.
RESUMO
The electronic circular dichroism (ECD) and UV-visible absorption (UV-vis) spectra of Strandberg-type polyoxometalates (POMs) (R, R)-[(R*PO3)2M5O15](2-) (R* = CH3CH(NH3), (M = Mo, W)) have been explored using the time-dependent density functional theory (TDDFT) method. It demonstrates that the absolute configurations of chiral systems can be determined by chiroptical spectroscopic methods combined with DFT calculations. The calculated ECD spectra of the Strandberg-type molybdate were produced over the range of 3.3-6.5 eV, which are generally in agreement with the experimental spectra. In addition, the ECD spectra of (R, R)-[(R*PO3)2W5O15](2-) (R* = CH3CH(NH3)) were produced over the range of 4.5-8.5 eV. The Becke's half-and-half hybrid exchange-correlation functional (BHandHLYP) with the HF exchange fraction to 55% hybrid functional was found to well predict the excitation energies of studied systems. The origins of the ECD bands of two systems are mainly ascribed to charge-transfer (CT) transitions from oxygen atoms to metal atoms in polyanion. The results suggest that the polyanion are chiroptical chromophores. The polyanion plays a role as an optically active chromophore and contribute to the absorptions of ECD spectra. The difference of the UV-vis/ECD spectra between two systems shows that the transition metal atom significantly influences on the chiroptical properties of the studied Strandberg-type POMs.
RESUMO
The second-order nonlinear optical (NLO) properties of a series of Pt(II) dithienylethene (DTE) complexes possessing the reversible photochromic behavior have been investigated by density functional theory (DFT) combined with the analytic derivatives method. The results show that the calculated static first hyperpolarizabilities (ßtot) of the open-ring and closed-ring systems significantly increase in the range of 2.1-4.5 times through strengthening of the electron-withdrawing ability of the substituent R (R = H, CF3, NO2) and an increase of the number of thiophene rings. Moreover, there is a large enhancement of the ßtot values from the open-ring systems to the corresponding closed-ring systems. This efficient enhancement is attributed to the better delocalization of the π-electron system, the more obvious degree of charge transfer, and the larger f(os)/E(gm)(3) (f(os) is the oscillator strength, and E(gm) is the transition energy between the ground and the excited states) values in the closed forms according to the bond length alternation (BLA) and time-dependent density functional theory (TDDFT) calculations. In addition, the dispersion has less influence on the frequency-dependent first hyperpolarizabilities (ßtot(ω)) of the studied systems at the low-frequency area ω (0.000-0.040 au). Our present work would be beneficial for further theoretical and experimental studies on large second-order NLO responses of metal complexes.
Assuntos
Compostos Organoplatínicos/química , Tiofenos/química , Estrutura Molecular , Fenômenos Ópticos , Processos Fotoquímicos , Teoria QuânticaRESUMO
Ascorbic acid (AsA) plays an important role in scavenging reactive oxygen species (ROS) and reducing photoinhibition in plants, especially under stress. The function of SlGGP which encodes the key enzyme GDP-L-galactose phosphorylase in AsA synthetic pathway is relatively clear. However, there is another gene SlGGP-LIKE that encodes this enzyme in tomato, and there are few studies on it, especially under salt stress. In this study, we explored the function of this gene in tomato salt stress response using transgenic lines overexpressing SlGGP-LIKE (OE). Under normal conditions, overexpressing SlGGP-LIKE can increase the content of reduced AsA and the ratio of AsA/ DHA (dehydroascorbic acid), as well as the level of xanthophyll cycle. Under salt stress, compared with the wild-type plants (WT), the OE lines can maintain higher levels of reduced AsA. In addition, OE lines also have higher levels of reduced GSH (glutathione) and total GSH, higher ratios of AsA/DHA and GSH/oxidative GSH (GSSR), and higher level of xanthophyll cycle. Therefore, the OE lines are more tolerant to salt stress, with higher photosynthetic activity, higher antioxidative enzyme activities, higher content of D1 protein, lower production rate of ROS, and lighter membrane damage. These results indicate that overexpressing SlGGP-LIKE can enhance tomato resistance to salt stress through promoting the synthesis of AsA.
Assuntos
Solanum lycopersicum , Espécies Reativas de Oxigênio/metabolismo , Solanum lycopersicum/genética , Plantas Geneticamente Modificadas/genética , Ácido Ascórbico/metabolismo , Estresse Salino , XantofilasRESUMO
A straightforward cross-coupling of aryl thioether with aryl bromide with the aid of nickel salt, magnesium, and lithium chloride in tetrahydrofuran at ambient temperature was accomplished. The one-pot reactions proceeded efficiently via C-S bond cleavage to produce the desired biaryls in modest to good yields, avoiding the use of pregenerated or commercial organometallic reagents.
RESUMO
The static second-order nonlinear optical (NLO) properties on a series of the two-dimensional (2D) pincer Ru(II) complexes with the substituted Tpy and H(2)SCS tridentate ligands (Tpy = 2,2':6',2â³-terpyridyl and H(2)SCS = 2,6-bis(benzylaminothiocarbonyl)phenyl) have been investigated by density functional theory (DFT). Introducing different donor/acceptor substituents to two ligands has an influence on the static first hyperpolarizabilities (ß(tot)) of the 2D systems. Compared to the reference system 1 [Ru(H(2)SCS)(Tpy)](+), introducing the branches with strong electron acceptor group (p-NO(2)-phenylethynyl) to the Tpy ligand or the branches with strong electron donor group (p-NH(2)-phenylethynyl) to the H(2)SCS ligand can effectively improve the ß(tot) values. Time-dependent DFT (TDDFT) calculations indicate that the enhanced ß(tot) values of the substituted systems are dominated by the intraligand charge transfer (ILCT), metal-to-ligand charge transfer (MLCT) and ligand-to-metal charge transfer (LMCT) transitions. Furthermore, the proton abstraction plays an important role in tuning the second-order NLO response. Particularly, for system 5 bearing the branches with NO(2) groups on H(2)SCS ligand, there is a dramatic enhancement in the ß(tot) values for its deprotonated forms. The ß(tot) values of the monodeprotonated system 5-H and the dideprotonated system 5-2H (58.712 × 10(-30) and 761.803 × 10(-30) esu) are about 7.58 times and 36.4 times larger than their diprotonated system 5, respectively. The second-order NLO responses based on substituent effect and proton abstraction switch are two-dimensional in characteristic with the large off-diagonal tensor values.
RESUMO
The direct cross-couplings of aryl sulfonium salts with aryl halides could be achieved by using nickel as a reaction catalyst. The reactions proceeded efficiently via C-S bond activation in the presence of magnesium turnings and lithium chloride in THF at ambient temperature to afford the corresponding biaryls in moderate to good yields, potentially serving as an attractive alternative to conventional cross-coupling reactions employing preprepared organometallic reagents.
RESUMO
A second-order nonlinear optical (NLO) molecular switching with redox has been investigated in the present paper. The static first hyperpolarizabilities of 5-(BMes(2))-5'-(NPh(2))-2,2'-bipyridine (BNbpy) containing three-coordinate organoboron, Pt(II) chelate complex Pt(BNbpy)Ph(2), and their reduced forms have been calculated by density functional theory (DFT) combined with the analytic derivatives method. There is an enhancement of static first hyperpolarizabilities in the reduced form according to the calculations. That is, the ß(vec) value of one-electron-reduced form is ~7 times as large as that of neutral form BNbpy; the ß(vec) values of one- and two-electron-reduced forms are ~3 and ~4 times as large as that of neutral form Pt(BNbpy)Ph(2), respectively. In particular, the ß(vec) value of two-electron-reduced form (3)Pt(BNbpy)Ph(2)(2-) is 1349 × 10(-30) esu, ~286 times larger than its neutral form. Moreover, the component ß(z) value of the metal chelate complex Pt(BNbpy)Ph(2) is 25 × 10(-30) esu, which is ~14 times as large as that of ligand BNbpy; the corresponding F(-)/CN(-) compounds show a decrease in ß(x) values compared with the case of the ligand and Pt(II) complex. Analyses of geometries, density of states (DOS), and time-dependent DFT (TDDFT) calculations reveal that the one-electron reduction promotes the molecular conjugation in the x-axis and intensifies the interaction between the metal Pt(II) and ligand and then results in an enhancement of the static first hyperpolarizability, whereas the binding of F(-)/CN(-) to the B atom turns off the p(π)-π* conjugation and has no effect on the conjugation of bipyridine, which leads to a decreasing ß value in the x-axis.
Assuntos
2,2'-Dipiridil/química , Quelantes/química , Platina/química , Teoria Quântica , 2,2'-Dipiridil/análogos & derivados , Estrutura Molecular , OxirreduçãoRESUMO
Two isostructural MOFs with coordination of different halogen ions (Cl- and Br-), namely NNU-17 and NNU-18, were utilized to reveal the influence of different electron-withdrawing halogen anions on ECR performance. The performance difference between them mainly originates from the different abilities of adsorption and activation of CO2 by halogen ions.
RESUMO
Five examples of bis(pyrazolyl)borate Ni(ii) complexes 2-5, exhibiting C-HNi interactions, were readily prepared from the reactions of K[BBN(3-R1-4-R2-pz)2] with Ni(ii) precursors (Ni(acac)2 or NiCl2(PPh3)2) in dichloromethane or toluene. When R1 = R2 = H, complex 2a with square-planar geometry around the Ni centre and showing an unusual C-HNi anagostic interaction was obtained. In contrast, when R1 = Me, R2 = H or R1 = Me, R2 = Br, tetrahedral complexes 3 or 4 were formed preferentially with strong C-HNi agostic interactions, respectively. Additionally, some differences in the formation and transformation of 3 and 4 were also found including a 1,2-borotropic shift during the formation of 3 and a further geometrical transformation from tetrahedral 3 to square-planar 2b by the second 1,2-borotropic shift under continuous heating; in contrast, no ligand change and further conversion were found in 4. When the more hindered 3-iPr-substituted ligand 1d was introduced in the reaction, the hydrolysis and cleavage of one B-N bond in the ligand occurred, leading to the singly hydroxo-bridged complex 5. The experimental and theoretical results indicate that the preference to form a thermodynamically stable complex and then balancing with orbital energy should be the intrinsic reason for the reaction selectivity.
RESUMO
Ascorbate (AsA) is very important in scavenging reactive oxygen species in plants. AsA can reduce photoinhibition by xanthophyll cycle to dissipate excess excitation energy. GGP is an important enzyme in AsA biosynthesis pathway in higher plants. In this study, we cloned a gene, SlGGP-LIKE, that has the same function but different sequence compared with SlGGP. The function of SlGGP-LIKE gene in response to oxidative stress was investigated using transgenic tobacco plants overexpressed SlGGP-LIKE under methyl viologen treatment. After oxidative stress treatment, transgenic tobacco lines exhibited higher levels of reduced AsA content and APX activity than WT plants. Under oxidative stress, transgenic tobacco plants accumulated less ROS and exhibited lower degrees of REC and MDA. Consequently, relatively higher levels of Pn, Fv/Fm, de-epoxidation status of xanthophyll cycle and D1 protein were maintained in transgenic tobacco plants. Hence, overexpression of SlGGP-LIKE gene enhances AsA biosynthesis and can alleviate the photoinhibition of PSII under oxidative stress.
Assuntos
Adaptação Fisiológica/genética , Genes de Plantas , Nicotiana/fisiologia , Estresse Oxidativo/efeitos dos fármacos , Paraquat/toxicidade , Solanum lycopersicum/genética , Sequência de Aminoácidos , Ascorbato Peroxidases/metabolismo , Ácido Ascórbico/metabolismo , Regulação da Expressão Gênica de Plantas/efeitos dos fármacos , Peróxido de Hidrogênio/metabolismo , Luz , Malondialdeído/metabolismo , Proteínas de Plantas/química , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Plantas Geneticamente Modificadas , Transporte Proteico/efeitos dos fármacos , Alinhamento de Sequência , Frações Subcelulares/metabolismo , Superóxidos/metabolismo , Nicotiana/efeitos dos fármacos , Nicotiana/genética , Nicotiana/efeitos da radiação , Xantofilas/metabolismo , Zeaxantinas/metabolismoRESUMO
Plants are always exposed to abiotic and biotic stresses which can adversely affect their growth and development. As an important antioxidant, AsA plays a vital role in plant defence against damage caused by stresses. In this study, we cloned a tomato GDP-L-galactose phosphorylase-like (SlGGP-LIKE) gene and investigated its role in resistance to abiotic and biotic stresses by using antisense transgenic (AS) tomato lines. The AsA content in AS plants was lower than that in WT plants. Under chilling stress, the growth of AS plants was inhibited significantly, and they yielded higher levels of ROS, REC and MDA but demonstrated weaker APX activity than that shown by WT plants. Additionally, the declined values of Pn, Fv/Fm, oxidisable P700, and D1 protein content of PSII in AS lines were significant. Furthermore, the effect on xanthophyll cycle of AS plants was more severe than that on WT plants, and the ratio of zeaxanthin (Z)/(V + A + Z) and (Z + 0.5 A)/(V + A + Z) in AS lines was lower than that in WT plants. In spite of chilling stress, under Pseudomonas syringae pv.tomato (Pst) DC3000 strain infection, AS plants showed lesser bacterial cell growth and dead cells than those shown by WT plants. This finding indicated that AS plants demonstrated stronger resistance against pathogenic infection. Results suggest that SlGGP-LIKE gene played an important role in plant defence against chilling stress and pathogenic infection.