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2.
Dalton Trans ; 53(6): 2807-2814, 2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38230412

RESUMO

The research on electron transfer coupled spin transition regulating the valence state and spin state transition of metal ions is promising and challenging. Herein, we report a cyano-bridged {FeIII2FeII2} molecular square complex, {[Fe(Tp)(CN)3]2 [Fe(bnbpen)]2}(ClO4)2·8CH3OH (1·8CH3OH, bnbpen = N,N'-bis-(2-naphthylmethyl)-N,N'-bis(2-picolayl)-ethylenediamine), and its free of solvents form (1). Combined single-crystal X-ray diffraction, temperature-dependent infrared (IR) spectra, magnetic measurements, and Mössbauer spectra reveal that 1·8CH3OH and 1 exhibit reversible one-step and two-step electron transfer coupled spin transition (ETCST) with temperature change, between the low-temperature state {FeII,LS(µ-CN)FeIII,LS}2 (LS = low spin, HS = high spin) and the high-temperature state {FeIII,LS(µ-CN)FeII,HS}2, respectively.

3.
Dalton Trans ; 52(41): 15009-15016, 2023 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-37811745

RESUMO

A key challenge in the design of magnetic molecules with intramolecular charge transfer behavior is to obtain reversible magnetic bistability triggered by external stimuli. Here, we show that two dinuclear metal complexes, [(bbp)Fe(CN)3Mn(Py5Me2)]·2.5CH3OH (4) and [(bbp)Fe(CN)3Ni(Py5Me2)]·2.5CH3OH (5) (Py5Me2 = 2,6-bis(1,1-di(pyridine-2-yl)ethyl)pyridine, H2bbp = 2,6-bis(benzimidazole-2-yl)pyridine), were self-assembly synthesized by (Bu4N)2[(bbp)FeIII(CN)3] and [Mn(Py5Me2)(OH2)](ClO4)2 or [Ni(Py5Me2)(OH2)](ClO4)2, respectively. Complexes 4 and 5 exhibited intramolecular metal-to-metal charge transfer with the addition of acids or bases in solution by UV-visible spectrophotometric measurements and electrochemistry studies, and concomitant switching of the {FeIII(µ-CN)MnII/NiII} state to the {FeII(µ-CN)MnIII/NiIII} state.

4.
Aging Clin Exp Res ; 35(11): 2531-2542, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37656410

RESUMO

BACKGROUND: Long-term nursing home (NH) care helps NH residents with their daily activities and improves their quality of life, but negatively affects their independent physical activities and increases the risk of dangerous events. Dangerous events in the elderly usually occur in the conversion of walking periods when forward striding has already happened, but the body has not yet entered a completely steady walking. OBJECTIVES: Compare the gait characteristics in Chinese long-term NH residents and community-living elderly during the walking Transitional Period (TP) and Stabilization Period (SP). METHODS: 32 long-term NH residents and 33 age- and sex-matched community-living elderly were recruited. The 30-Second Chair Stand Test (30-s CST), Timed Up and Go Test (TUGT), and Modified Falls Efficacy Scale (MFES) were used to assess their body function. The Xsens MVN BIOMECH system was used to collect and analyze the gait parameters of participants. RESULTS: Compared to community-living elderly, NH residents had fewer numbers of 30-s CST, took more time to complete TUGT, and lower MEFS scores. NH residents showed slower gait speed (P < 0.001), less peak hip flexion (P = 0.022) and extension (P = 0.003), knee internal rotation (P = 0.023), and ankle plantarflexion (P = 0.001) and internal rotation (P = 0.007) angles during walking. When walking progressed from TP to SP, NH residents showed increased ankle dorsiflexion (P < 0.001), decreased hip internal rotation (P < 0.001), and community-living elderly had increased hip extension (P = 0.005) angles. CONCLUSIONS: Chinese long-term NH residents had reduced lower extremities strength and postural balance, and higher fear of falling compared to community-living elderly. Their walking performance also showed high fall risk. Besides, long-term NH residents adopted a distal strategy to propel the body forward, which may be a compensatory measure to compensate for inadequate proximal joint control from forward walking to stable walking, and long-term NH residents have reduced postural stability during this process.


Assuntos
Qualidade de Vida , Caminhada , Idoso , Humanos , Fenômenos Biomecânicos , População do Leste Asiático , Medo , Casas de Saúde , Equilíbrio Postural , Estudos de Tempo e Movimento , Caminhada/fisiologia , Caminhada/psicologia , Vida Independente , Características de Residência
5.
Phys Chem Chem Phys ; 25(29): 19422-19426, 2023 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-37455579

RESUMO

DFT calculations of reaction mechanisms in solution have always been a hot topic, especially for transition-metal-catalyzed reactions, in which the traditional DFT-D3 method has been extensively employed. The overestimation of the dispersion from the traditional DFT-D3 method leads to a quite low activation free-energy barrier, so it is worth finding a proper way to deal with the dispersion for solution systems. The solvent-solute dispersion is also important for solution systems, and thus it should be calculated together with the solute dispersion. The newly generated solute-solute dispersion energy should be shared equally with the newly formed cavity between two interacting species; therefore, only half of the solute-solute and solvent-solute dispersion terms belong to the solute molecule. The detailed treatment of dispersion correction for solution systems has been fully addressed, and this method has been confirmed with the examples of ligand exchange reactions and catalytic reactions.

6.
Front Neurol ; 14: 1195915, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37332999

RESUMO

Background: Hemiplegic shoulder pain (HSP) is a common complication in patients with stroke. The pathogenesis of HSP is complex, and muscle hypertonia, especially the hypertonia of internal rotation muscles of the shoulder, may be one of the important causes of shoulder pain. However, the relationship between muscle stiffness and HSP has not been well studied. The purpose of this study is to explore the correlations between the stiffness of internal rotation muscles and clinical symptoms in patients with HSP. Methods: A total of 20 HSP patients and 20 healthy controls were recruited for this study. The stiffness of internal rotation muscles was quantified using shear wave elastography, and Young's modulus (YM) of the pectoralis major (PM), anterior deltoid (AD), teres major ™, and latissimus dorsi (LD) were measured. Muscle hypertonia and pain intensity were evaluated using the Modified Ashworth Scale (MAS) and Visual Analog Scale (VAS), respectively. The mobility of the shoulder was evaluated using the Neer score. The correlations between muscle stiffness and the clinical scales were analyzed. Results: YM of internal rotation muscles on the paretic side was higher than that of the control group in the resting and passive stretching positions (P < 0.05). YM of internal rotation muscles on the paretic side during passive stretching was significantly higher than that at rest (P < 0.05). YM of PM, TM, and LD during passive stretching were correlated with MAS (P < 0.05). In addition, the YM of TM during passive stretching was positively correlated with VAS and negatively correlated with the Neer score (P < 0.05). Conclusion: Increased stiffness of PM, TM, and LD was observed in patients with HSP. The stiffness of TM was associated with pain intensity of the shoulder and shoulder mobility.

7.
Front Oncol ; 13: 1096955, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-37260972

RESUMO

Purpose: To explore the safety and efficacy of lenvatinib in combination with trans-arterial chemoembolization (TACE) and programmed death receptor 1 (PD-1) antibody in the treatment of unresectable recurrent hepatocellular carcinoma (urHCC). Patients and methods: The clinical data of 16 patients with unresectable recurrent hepatocellular carcinoma admitted to the Department of Liver Surgery and Liver Transplantation Center, West China Hospital, Sichuan University, and received the conversion therapy of lenvatinib + TACE + PD-1 antibody between January 2019 and January 2022 were retrospectively analyzed. Results: There were 25% (4/16) patients suffering from grade 3 adverse events and no patients suffering from grade 4 or higher adverse events. After 4 months of treatment of 16 patients, according to the modified Response Evaluation Criteria in Solid Tumors (mRECIST), two, five, three, and six cases were in complete response (CR), partial response (PR), stable disease (SD), and progressive disease (PD), respectively, and the objective response rate (ORR) was 43.8% (7/16). The 1-year overall survival (OS) rate and 1-year progression-free survival (PFS) rate were 86.2% and 46.9%, respectively. In our subgroup analysis, the ORR of patients with multiple lesions reached up to 60%, which was higher than that of patients with single lesions. Conclusions: Lenvatinib in combination with TACE and PD-1 antibody is safe and effective in the treatment of unresectable recurrent hepatocellular carcinoma.

8.
Acta Physiol (Oxf) ; 238(4): e13987, 2023 08.
Artigo em Inglês | MEDLINE | ID: mdl-37183727

RESUMO

AIM: Enhanced cardiac sympathetic afferent reflex (CSAR) promotes sympathetic hyperactivation in chronic heart failure (CHF). Salusin-ß is a torsin family 2 member A (TOR2A) gene product and a cardiovascular active peptide closely associated with cardiovascular diseases. We aimed to determine the roles of salusin-ß in the paraventricular nucleus (PVN) in modulating enhanced CSAR and sympathetic hyperactivation in rats with CHF induced by coronary artery ligation and elucidate the underlying molecular mechanisms. METHODS: CSAR was evaluated based on the responses of mean arterial pressure (MAP) and renal sympathetic nerve activity (RSNA) to the epicardial administration of capsaicin in rats under anesthesia. RESULTS: Salusin-ß protein expression was upregulated in the PVN of the CHF compared with sham-operated rats. Salusin-ß microinjection into the PVN dose-dependently increased MAP and RSNA and enhanced CSAR, while anti-salusin-ß IgG exerted opposite effects. The effect of salusin-ß was inhibited by reactive oxygen species (ROS) scavenger or NAD(P)H oxidase inhibitor but promoted by superoxide dismutase inhibitor. The effect of anti-salusin-ß IgG was interdicted by nitric oxide (NO) synthase inhibitor. Furthermore, chronic salusin-ß gene knockdown in PVN attenuated CSAR, reduced sympathetic output, improved myocardial remodeling and cardiac function, decreased NAD(P)H oxidase activity and ROS levels, and increased NO levels in the CHF rats. CONCLUSION: Increased salusin-ß activity in the PVN contributes to sympathetic hyperactivation and CSAR in CHF by inhibiting NO release and stimulating NAD(P)H oxidase-ROS production. Reducing endogenous central salusin-ß expression might be a novel strategy for preventing and treating CHF in the future.


Assuntos
Insuficiência Cardíaca , Núcleo Hipotalâmico Paraventricular , Ratos , Animais , Espécies Reativas de Oxigênio/metabolismo , Núcleo Hipotalâmico Paraventricular/metabolismo , Vasos Coronários/metabolismo , Ratos Sprague-Dawley , Angiotensina II/farmacologia , Insuficiência Cardíaca/metabolismo , Reflexo/fisiologia , Sistema Nervoso Simpático , NADPH Oxidases/metabolismo , Imunoglobulina G/metabolismo , Imunoglobulina G/farmacologia , Pressão Sanguínea/fisiologia
9.
Head Face Med ; 19(1): 14, 2023 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-37038160

RESUMO

OBJECTIVE: This study aimed to study the cytokines in gingival crevicular fluid (GCF) of the teeth opposing to dental implants and 3-unit fixed partial dentures (FPDs). MATERIALS AND METHODS: A total of 74 participants were recruited for this cross-sectional study. Based on the status of lower first molars, the participants were divided into dental implants group and 3-unit FPDs group. Social index and oral hygiene were recorded. Occlusal loading was evaluated with a T-scan. GCF was sampled from the upper first molar and assessed with a commercial cytokine assay kit. RESULTS: Forty three dental implants patients and 31 3-unit FPDs patients received all of the clinical and laboratory evaluation. The dental implants group had a higher occlusion force distribution on first molars region. IL-10, IL-17, RANK had a higher mean in dental implants group and was associated with occlusion force of first molar. There was a weakly association between IL-10 and dental implants in the binary logistic regression analyses. CONCLUSIONS: In this study, the teeth opposing implants have a higher level of cytokines in the GCF than teeth opposing to 3-unit FPDs in periodontal healthy participants because of the poor osseoperception of dental implants. IL-10 might reflect a higher occlusion force in dental implants region. CLINICAL RELEVANCE: This study provided that different tooth restoration methods could influence the periodontal status of the contact teeth.


Assuntos
Citocinas , Implantes Dentários , Humanos , Citocinas/análise , Interleucina-10/análise , Líquido do Sulco Gengival/química , Estudos Transversais , Prótese Parcial Fixa
10.
Medicine (Baltimore) ; 102(11): e33300, 2023 Mar 17.
Artigo em Inglês | MEDLINE | ID: mdl-36930130

RESUMO

BACKGROUND: Losing postural control ability and related injuries are of particular concern for elders living in the nursing home (NH). The Otago Exercise Program (OEP) is a multimodal exercise training program initially designed as an individually tailored home exercise for community-dwelling elders, but whether its movement characteristics and exercise intensity meet NH elders' needs still needs to be clarified. This study aimed to determine the effects of the OEP in enhancing postural control ability among elders in the NH. METHODS: A systematic literature search of English language databases (Cochrane Library, PubMed, EMBASE, CINAHL, and Web of Science) and Chinese language databases (China National Knowledge Infrastructure, Wanfang, and Chongqing VIP) until 15 April 2022 were performed by 2 reviewers on searching randomized controlled trial (RCT) and non-RCT. A meta-analysis was performed using Review Manager 5.3 software. Continuous data were expressed as mean difference (MD) with 95% confidence intervals (95% CI). Dichotomous data were presented as risk ratios (RRs) with 95% CI. Study methodological quality was assessed according to the Cochrane Handbook for Systematic Reviews of Interventions for RCTs and Risk Of Bias In Non-randomized Studies-of Interventions for non-RCTs by 3 reviewers. RESULTS: Nine studies with 546 participants were included in this review. Two hundred and sixty-nine participants received OEP, and 277 only had conventional exercise training. Compared to the conventional exercise training group, the NH elders in the OEP group have considerably decreased in fall risk (MD = -0.84; 95% CI = -1.17, -0.51; P < .00001) and positively increased in postural balance (MD = 5.55; 95% CI = 3.60, 7.50; P < .00001), functional mobility in short-distance (MD = -6.39; 95% CI = -8.07, -4.70; P < .00001), lower-limb muscle strength (MD = 4.32; 95% CI = 3.71, 4.93; P < .00001), and health status (risk ratio = 0.35; 95% CI = 0.18, 0.66; P = .001). CONCLUSIONS: Current evidence suggests that OEP is practical and feasible in NH. The nursing personnel can receive sufficient support for maintaining and enhancing these elders' postural control ability, especially during the COVID-19 pandemic.


Assuntos
COVID-19 , Humanos , Idoso , Exercício Físico , Terapia por Exercício , Casas de Saúde , Equilíbrio Postural , Qualidade de Vida , Ensaios Clínicos Controlados Aleatórios como Assunto
11.
Phys Chem Chem Phys ; 25(2): 913-931, 2023 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-36519338

RESUMO

DFT calculations of reaction mechanisms in solution have always been a hot topic, especially for transition-metal-catalyzed reactions. The calculation of solvation energy is performed using either the polarizable continuum model (PCM) or the universal solvation model SMD. The PCM calculation is very sensitive to the choice of atomic radii to form a cavity, where the self-consistent isodensity PCM (SCI-PCM) has been recognized as the best choice and our IDSCRF radii can provide a similar cavity. Moving from a gas-phase case to a solution case, dispersion energy and entropy should be carefully treated. The solvent-solute dispersion is also important in solution systems, and it should be calculated together with the solute dispersion. Only half of the solvent-solute dispersion energy from the PCM calculation belongs to the solute molecules to maintain a thermal equilibrium between a solute molecule and its cavity, similar to the treatment of electrostatic energy. Relative solute dispersion energy should also be shared equally with the newly formed cavity. The entropy change from a gas phase to a liquid phase is quite large, but the modern quantum chemistry programs can only calculate the gas-phase translational entropy based on the idea-gas equation. In this review, we will provide an operable method to calculate the solution translational entropy, which has been coded in our THERMO program.

13.
Front Bioeng Biotechnol ; 11: 1297068, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-38249798

RESUMO

Introduction: Falls and fall-related injuries in young male adults with excess weight are closely related to an increased cognitive load. Previous research mainly focuses on analyzing the postural control status of these populations performing cognitive tasks while stabilized walking progress but overlooked a specific period of walking known as gait initiation (GI). It is yet unknown the influences of cognitive load on this population's postural control status during GI. Objective: This study aimed to determine the influences of cognitive load on the center of pressure (CoP) trajectory of young male adults with excess weight during GI. Design: A controlled laboratory study. Methods: Thirty-six male undergraduate students were recruited and divided into normal-weight, overweight, and obese groups based on their body mass index (BMI). Participants' CoP parameters during GI under single and dual-task conditions were collected by two force platforms. A mixed ANOVA was utilized to detect significant differences. Results: Compared with the normal-weight group, the obese group showed significant changes in the duration and CoP parameters during sub-phases of GI, mainly reflecting prolonged duration, increased CoP path length, higher mediolateral CoP displacement amplitude, and decreased velocity of anteroposterior CoP displacement. During GI with 1-back task, significantly increased mediolateral CoP displacement amplitude occurred in the obese group. During GI with 2-back task, the obese group had increased CoP path length, higher mediolateral CoP displacement amplitude, as well as a decreased velocity of CoP displacement. Conclusion: Based on the changes in CoP parameters during GI with cognitive tasks, young male adults with excess weight, mainly obese ones, have compromised postural stability. During GI with a difficult cognitive task, obese young male adults are more susceptible to deterioration in their lateral postural balance. These findings indicate that the increased cognitive load could exacerbate obese young male adults' postural control difficulty during GI under dual-task conditions, putting them at a higher risk of experiencing incidents of falls. Based on these findings, we offer suggestions for therapists to intervene with these young male adults to ensure their safety of GI.

14.
Front Oncol ; 12: 811084, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35356224

RESUMO

Background and Aims: With changes in dietary patterns and modern lifestyles, the prevalence of metabolic syndrome (MetS) in hepatitis B virus (HBV)-associated hepatocellular carcinoma (HCC) patients is increasing. The purpose of our study is to explore the impact of MetS on the prognosis of HBV-associated HCC patients following radical hepatectomy. Methods: Data on consecutive HCC patients who underwent radical hepatectomy were prospectively obtained and retrospectively analyzed from seven medical centers in west areas of China. Propensity score matching (PSM) analysis was conducted to balance the heterogeneity between MetS-HBV-HCC group and HBV-HCC group. Surgical outcomes have been contrasted between the two groups. Results: In 984 patients, 179 (18.19%) were diagnosed with MetS. Patients in the MetS-HBV-HCC group had higher CCI score (8.7 [0.0, 12.2] vs. 0.0 [0.0, 8.7], p = 0.048) and a higher rate of severe complications (Clavien-Dindo ≥3, 7.82% vs. 4.10%, p = 0.035), to be more precise: postoperative liver failure, hydrothorax, and hyperglycemia. Patients in the MetS-HBV-HCC group tended to have worse 5-year overall survival (OS) rate (61.45% vs. 69.94%, p = 0.027) and recurrence-free survival (RFS) rate (62.57% vs. 53.66%, p = 0.030), consistent with the results of the competing risk models. Last, MetS was identified to be an independent unfavorable prognostic factor in the multivariate analysis. Conclusion: The involvement of MetS increased the risk of postoperative complications and worsens the overall survival and recurrence-free survival time, reminding us to be more prudent to face metabolic disorder among tumor patients.

15.
Z Gerontol Geriatr ; 55(8): 689-695, 2022 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-34757468

RESUMO

OBJECTIVE: Frailty has a high prevalence in elders and impairs motor ability. This study aimed to investigate the influence caused by frailty in kinematic characteristics of walking and walking strategy adjustment from static standing to stable walking. METHODS: In this study, 80 community-dwelling elders performed tests. The Kihon checklist (KCL) was used to assess frailty. The timed up and go test (TUGT) and the 30-s chair stand test (30-s CST) were used to assess balance and muscle strength. The Xsens MVN BIOMECH Awinda was used to collect walking kinematic data. RESULTS: This study included 25 robust, 30 prefrail, and 25 frail elders. The TUGT completed time (P < 0.001) and the 30-s CST completed number (P = 0.002) had statistical differences among groups. The maximum peak of knee internal rotation showed an interaction between the frailty and the walking phase (P = 0.015). The peak angle of hip adduction, hip and knee flexion, and knee and ankle internal rotation were significantly lower in frail elders than others (P < 0.05). CONCLUSION: Frailty affects the kinematic characteristics of walking, resulting in the hip, knee, and ankle flexion, hip adduction, knee and ankle internal rotation reduced. Besides, frailty has a specific negative effect on the walking strategy adjustment from static standing to stable walking.


Assuntos
Vida Independente , Equilíbrio Postural , Humanos , Idoso , Estudos de Tempo e Movimento , Caminhada
16.
Phytomedicine ; 94: 153793, 2022 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-34736000

RESUMO

ETHNOPHARMACOLOGICAL RELEVANCE: Uvangoletin is a dihydrochalcone extracted from the traditional Chinese medicinal plant Sarcandra glabra. Previous research has showed that uvangoletin could induce leukemia cell death. However, the anticancer effect of uvangoletin on hepatocellular carcinoma (HCC) has not been clarified. AIM OF THE STUDY: This study aimed to investigate the anti-cancer effects of uvangoletin on HCC and to explore its underlying mechanisms. MATERIALS AND METHODS: We measured the anticancer activities of uvangoletin both in vitro and in vivo by MTT assay and HepG2 xenograft model. The effects of uvangoletin on apoptosis, autophagy, migration and invasion were also determined. Apoptosis was evaluated by flow cytometry method. Autophagy was assessed by immunofluorescence assay. Cell migration and invasion ability were validated by wound healing assay and cultrex® 96 well cell migration/invasion assay. The expression level of relevant proteins and pathways were examined by western blot. RESULTS: The results of MTT assay and HepG2 xenograft model showed that uvangoletin could inhibit HCC cells proliferation in vitro and in vivo. Uvangoletin could induce HepG2 cell apoptosis as evidence by the increased expression of cleaved caspase 3, caspase 8 and Bax while decreased Bcl-2 expression. Wound healing assay and transwell assay showed that uvangoletin inhibited HepG2 cells migration and invasion and reduced vimentin, MMP9, MMP2 expression. Uvangoletin also promoted autophagy in HepG2 cells as confirmed by the accumulation of GFP-LC3 puncta. Autophagy inhibitors like 3-MA or CQ could suppress uvangoletin-induced apoptosis. Importantly, uvangoletin-induced anti-EMT effect was also attenuated after autophagy inhibitors added in. Mechanistically, the expressions of p-JNK, p-ERK, p-p38, p-AKT, p-p70S6k and p-mTOR were significantly decreased after uvangoletin treatment. CONCLUSION: Our results showed that uvangoletin could induce apoptotic and autophagic cell death, inhibit cell proliferation and metastasis on HepG2 cells through Akt/mTOR, MAPK and TGFß/Smad2 signal pathways.


Assuntos
Carcinoma Hepatocelular , Neoplasias Hepáticas , Apoptose , Autofagia , Carcinoma Hepatocelular/tratamento farmacológico , Linhagem Celular Tumoral , Proliferação de Células , Medicamentos de Ervas Chinesas , Células Hep G2 , Humanos , Neoplasias Hepáticas/tratamento farmacológico
17.
Dalton Trans ; 50(46): 17328-17337, 2021 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-34787614

RESUMO

Six Dy(III) single-ion magnets (SIMs) [Dy(n-OMe-bbpen)X] were synthesized by a solvothermal reaction with three positional isomers (ortho, meta, and para) of ligands n-OMe-H2bbpen and dysprosium halides DyX3, (n-OMe-H2bbpen = N,N'-bis(2-hydroxy-n-methoxybenzyl)-N,N'-bis(2-methylpyridyl)ethylenediamine; n = 3, X = Cl, 1; n = 3, X = Br, 2; n = 4, X = Cl, 3; n = 4, X = Br, 4; n = 5, X = Cl, 5; n = 5, X = Br, 6). Dynamic magnetic measurements revealed that the six complexes possess notably different effective barriers of magnetic reversal: 872.0 K (1), 1210.1 K (2), 137.9 K (3), 602.6 K (4), 907.0 K (5) and 1216.7 K (6). 6 showed the best performance as SIMs among the six Dy(III) complexes. Moreover, the magnetic hysteresis loops of 6 remained open at 21 K. The crystal structures indicate the switching of local symmetry around Dy(III) ion, aroused by the variation in intermolecular interactions and steric effects. This switch is primarily correlated with the distinction of magnetic properties. In addition, ab initio calculations confirmed that the different electrostatic potential around Dy(III) ion stemming from the electronic effect of the OMe-substituted group is another factor leading to the distinction in magnetic properties. This work warns us that when designing ligands for Dy-SIMs, the effect of positional isomerism on magnetic performance must be considered, which is one of the factors that can easily be overlooked.

18.
Int J Mol Sci ; 22(22)2021 Nov 12.
Artigo em Inglês | MEDLINE | ID: mdl-34830140

RESUMO

The smut fungus Ustilago esculenta infects Zizania latifolia and induces stem expansion to form a unique vegetable named Jiaobai. Although previous studies have demonstrated that hormonal control is essential for triggering stem swelling, the role of hormones synthesized by Z. latifolia and U. esculenta and the underlying molecular mechanism are not yet clear. To study the mechanism that triggers swollen stem formation, we analyzed the gene expression pattern of both interacting organisms during the initial trigger of culm gall formation, at which time the infective hyphae also propagated extensively and penetrated host stem cells. Transcriptional analysis indicated that abundant genes involving fungal pathogenicity and plant resistance were reprogrammed to maintain the subtle balance between the parasite and host. In addition, the expression of genes involved in auxin biosynthesis of U. esculenta obviously decreased during stem swelling, while a large number of genes related to the synthesis, metabolism and signal transduction of hormones of the host plant were stimulated and showed specific expression patterns, particularly, the expression of ZlYUCCA9 (a flavin monooxygenase, the key enzyme in indole-3-acetic acid (IAA) biosynthesis pathway) increased significantly. Simultaneously, the content of IAA increased significantly, while the contents of cytokinin and gibberellin showed the opposite trend. We speculated that auxin produced by the host plant, rather than the fungus, triggers stem swelling. Furthermore, from the differently expressed genes, two candidate Cys2-His2 (C2H2) zinc finger proteins, GME3058_g and GME5963_g, were identified from U. esculenta, which may conduct fungus growth and infection at the initial stage of stem-gall formation.


Assuntos
Basidiomycota/genética , Resistência à Doença/genética , Perfilação da Expressão Gênica/métodos , Doenças das Plantas/genética , Tumores de Planta/genética , Poaceae/genética , Sequência de Aminoácidos , Basidiomycota/metabolismo , Basidiomycota/patogenicidade , Proteínas Fúngicas/classificação , Proteínas Fúngicas/genética , Proteínas Fúngicas/metabolismo , Regulação Fúngica da Expressão Gênica , Regulação da Expressão Gênica de Plantas , Interações Hospedeiro-Patógeno/genética , Hifas/genética , Hifas/metabolismo , Hifas/patogenicidade , Ácidos Indolacéticos/metabolismo , Oxigenases/genética , Oxigenases/metabolismo , Filogenia , Doenças das Plantas/microbiologia , Reguladores de Crescimento de Plantas/biossíntese , Proteínas de Plantas/classificação , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Caules de Planta/genética , Caules de Planta/metabolismo , Caules de Planta/microbiologia , Tumores de Planta/microbiologia , Poaceae/metabolismo , Poaceae/microbiologia , Homologia de Sequência de Aminoácidos , Virulência/genética
19.
Microorganisms ; 8(3)2020 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-32143469

RESUMO

The growth of a large number of poisonous plants is an indicator of grassland degradation. Releasing allelochemicals through root exudates is one of the strategies with which poisonous plants affect neighboring plants in nature. Arbuscular mycorrhizal fungi (AMF) can form a mutualistic symbiosis with most of the higher plants. However, the manner of interaction between root exudates of poisonous plants and AMF on neighboring herbage in grasslands remains poorly understood. Stellera chamaejasme L., a common poisonous plant with approved allelopathy, is widely distributed with the dominant grass of Leymus chinensis in the degradeds of Northern China. In this study, we investigated the addition of S. chamaejasme root exudates (SRE), the inoculation of AMF, and their interaction on the growth and tissue nitrogen contents of L. chinensis, the characteristics of rhizosphere AMF, and soil physicochemical properties. Results showed that SRE had significant effects on ramet number, aboveground biomass, and total nitrogen of L. chinensis in a concentration dependent manner. Additionally, SRE had a significant negative effect on the rate of mycorrhiza infection and spore density of the AMF. Meanwhile, the addition of SRE significantly affected soil pH, electrical conductivity, available nitrogen (AN), available phosphorus (AP), total nitrogen (TN), and total carbon (TC) contents; while neither inoculation of AMF itself nor the interaction of AMF with SRE significantly affected the growth of L. chinensis. The interaction between AMF and SRE dramatically changed the pH, AP, and TC of rhizosphere soil. Therefore, we suggested SRE of S. chamaejasme affected the growth of L. chinensis by altering soil pH and nutrient availability. AMF could change the effect of SRE on soil nutrients and have the potential to regulate the allelopathic effects of S. chamaejasme and the interspecific interaction between the two plant species. We have provided new evidence for the allelopathic mechanism of S. chamaejasme and the regulation effects of AMF on the interspecific relationship between poisonous plants and neighboring plants. Our findings reveal the complex interplay between the root exudates of poisonous plants and rhizosphere AMF in regulating population growth and dynamics of neighboring plants in degraded grassland ecosystems.

20.
Spectrochim Acta A Mol Biomol Spectrosc ; 204: 340-347, 2018 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-29957412

RESUMO

In past two decades, lots of bidentate Pt(II) complexes are developed as potential organic light emitting diodes due to their simple synthetic process. The relative low quantum efficiency is one of the major blocks for their applications. Two new heteroleptic Pt(II) complexes bearing an n-hexyloxy substituted phenyllepidine-based ligand and either a picolinate (pic) (1) or acetylacetonate (acac) (2) ancillary ligand are synthesized as orange-red-emitter by Wawrzinek and coauthors. The quantum efficiency of 2 is much larger than that of 1 indicating that the variation of ancillary ligand has a great effect on the performance. Inspired by it, other two new bidentate Pt(II) complexes are theoretically designed with the same primary ligand along with pyrazolone (pzl) (3) or N-substituted carbazole (NCaz) (4) ancillary ligand. The phosphorescent properties are explored by density functional theory (DFT) and time dependent DFT (TDDFT) methods with the ultimate goal to explore the influence of ancillary ligand. Moreover, the emission rule is confirmed. Finally, the quantum yield is estimated according to the radiative rate constant (kr) and nonradiative rate constant (knr). The smaller knr is the vital item to determine the high quantum yield.

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