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1.
BMC Cancer ; 24(1): 830, 2024 Jul 11.
Artigo em Inglês | MEDLINE | ID: mdl-38992606

RESUMO

OBJECTIVE: Numerous epidemiological investigations have explored the impact of body composition on the effectiveness of immune checkpoint inhibitors (ICIs) in urological malignancies (UM) patients, yielding conflicting findings. As a result, our study aims to elucidate the influence of baseline body composition on the long-term prognosis of UM patients treated with ICIs. METHODS: We employed a rigorous systematic search across various databases, including PubMed, Embase, the Cochrane Library, and Google Scholar, to identify studies meeting our inclusion criteria. Our primary endpoints of interest encompassed overall survival (OS) and progression-free survival (PFS). RESULTS: This analysis included a total of 10 articles with a combined patient cohort of 707 individuals. Our findings revealed a noteworthy association between several body composition parameters and unfavorable OS outcomes, including low psoas muscle index (PMI; HR: 3.88, p < 0.001), low skeletal muscle index (SMI; HR: 1.63, p < 0.001), sarcopenia (HR: 1.88, p < 0.001), low visceral adipose index (VAI; HR: 1.38, p = 0.018) and low subcutaneous adipose index (SAI; HR: 1.37, p = 0.018). Furthermore, our analysis demonstrated that low PMI (HR: 2.05, p = 0.006), low SMI (HR: 1.89, p = 0.002), sarcopenia (HR: 1.80, p < 0.001), and low VAI (HR:1.59, p = 0.005) were significantly correlated with inferior PFS. Conversely, SAI did not manifest a pronounced association with PFS in UM patients treated with ICIs. CONCLUSION: Collectively, our study findings underscore a substantial relationship between baseline body composition and reduced clinical efficacy in UM patients undergoing ICI therapy.


Assuntos
Composição Corporal , Inibidores de Checkpoint Imunológico , Neoplasias Urológicas , Humanos , Prognóstico , Estudos Retrospectivos , Inibidores de Checkpoint Imunológico/uso terapêutico , Neoplasias Urológicas/tratamento farmacológico , Neoplasias Urológicas/mortalidade , Neoplasias Urológicas/patologia , Imunoterapia/métodos , Masculino , Sarcopenia , Feminino , Intervalo Livre de Progressão
2.
Inorg Chem ; 2024 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-38984385

RESUMO

Efficient CO oxidation at ambient or low temperatures is essential for environmental purification and selective CO oxidation in H2, yet achieving this remains a challenge with current methodologies. In this research, we extensively evaluated the catalytic performance of phosphotungstic acid (PTA)-supported 11 M1/PTA single-atom catalysts (SACs) using density functional theory calculations across both gas phase and 12 common solvents. The Rh1/PTA, Pd1/PTA, and Pt1/PTA systems exhibit moderate CO adsorption energies, facilitating the feasibility of oxygen vacancy formation. Remarkably, the Pd1/PTA and Pt1/PTA catalysts exhibited negligible energy barriers and demonstrated exceptionally high catalytic rates, with values reaching up to (1 × 1010)11, markedly exceeding the threshold for room temperature reactions, set at 6.55 × 108. This phenomenon is attributed to a transition from the high-energy barrier processes of oxygen dissociation in O2 and N-O bond dissociation in N2O to the more efficient dissociation of H2O2. Orbital analysis and charge variations at metal sites throughout the reaction process provide deeper insights into the role of the three metal catalytic sites in CO activation. Our findings not only reveal key aspects of SACs in facilitating CO oxidation at low temperatures but also provide valuable insights for future catalytic reaction mechanism studies and environmental applications.

3.
J Am Chem Soc ; 145(23): 12884-12893, 2023 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-37249907

RESUMO

Lignin is the most abundant aromatic polymer from the natural and renewable lignocellulosic biomass resource. Developing highly efficient catalysts for lignin depolymerization to produce valuable monophenols with high yield and selectivity remains a desirable but challenging target in this field. Here, we design a synergistic catalyst combining atomically dispersed Mo centers and Al Lewis acid sites on a MgO substrate (Mo1Al/MgO) for the depolymerization of Eucalyptus lignin via the ß-aryl ether bond cleavage. A near-theoretical monophenol yield of 46% with an ultrahigh selectivity of 92% for coniferyl and sinapyl methyl ether, as well as good cycling durability, was achieved simultaneously by Mo1Al/MgO in an inert N2 atmosphere. First-principles calculations and control catalytic experiments confirmed the synergistic catalysis mechanism between Mo1-O5 single-atom centers and the neighboring Al Lewis acid sites with the participation of a methanol solvent. This study validates the feasibility of designing better-performing catalysts with synergistic multiactive sites for the efficient and selective disassembly of complex renewable biopolymers into highly value-added products with lower cost and greater security.

4.
J Transl Med ; 21(1): 126, 2023 02 15.
Artigo em Inglês | MEDLINE | ID: mdl-36793057

RESUMO

OBJECTIVE: Gut mycobiota plays a crucial role in benign liver diseases; however, its correlation with hepatocellular carcinoma (HCC) remains elusive. This study aimed to elucidate fungal differences in patients with HCC-associated cirrhosis compared to cirrhotic patients without HCC and healthy controls. METHODS: The 72 fecal samples from 34 HCC patients, 20 cirrhotic patients, and 18 healthy controls were collected and analyzed using ITS2 rDNA sequencing. RESULTS: Our results revealed the presence of intestinal fungal dysbiosis with significant enrichment of opportunistic pathogenic fungi such as Malassezia, Malassezia sp., Candida, and C. albicans in HCC patients compared with healthy controls and cirrhosis patients. Alpha-diversity analysis demonstrated that patients with HCC and cirrhosis showed decreased fungal diversity compared to healthy controls. Beta diversity analysis indicated that the three groups exhibited significant segregated clustering. Besides, C. albicans was found to be significantly more abundant in the HCC patients with TNM stage III-IV than those with stage I-II, in contrast to the commensal organism S. cerevisiae. We also confirmed that the HCC patients were successfully classified with an area under the curve value of 0.906 based on the fecal fungal signature. Finally, our animal experiments confirm that aberrant colonization of the intestine by C. albicans and M. furfur can promote the development of HCC. CONCLUSIONS: This study indicates that dysbiosis of the gut mycobiome might be involved in HCC development. TRIAL REGISTRATION: ChiCTR, ChiCTR2100054537. Registered 19 December 2021, http://www.chictr.org.cn/edit.aspx?pid=144550&htm=4.


Assuntos
Carcinoma Hepatocelular , Neoplasias Hepáticas , Micobioma , Animais , Saccharomyces cerevisiae , Disbiose/complicações , Disbiose/microbiologia , Candida albicans , Cirrose Hepática
5.
BMC Cancer ; 23(1): 101, 2023 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-36717809

RESUMO

BACKGROUND: Systemic inflammation is crucial for the development and progression of cancers. The advanced lung cancer inflammation index (ALI) is considered to be a better indicator of systemic inflammation than current biomarkers. However, the prognostic value of the ALI in gastrointestinal neoplasms remains unclear. We performed the first meta-analysis to explore the association between ALI and gastrointestinal oncologic outcomes to help physicians better evaluate the prognosis of those patients. METHODS: Eligible articles were retrieved using PubMed, the Cochrane Library, EMBASE, and Google Scholar by December 29, 2022. Clinical outcomes were overall survival (OS), disease-free survival (DFS), progression-free survival (PFS), and cancer-specific survival (CSS). RESULTS: A total of 18 articles with 6898 patients were included in this meta-analysis. The pooled results demonstrated that a low ALI was correlated with poor OS (HR = 1.914, 95% CI: 1.514-2.419, P < 0.001), DFS (HR = 1.631, 95% CI: 1.197-2.224, P = 0.002), and PFS (HR = 1.679, 95% CI: 1.073-2.628, P = 0.023) of patients with gastrointestinal cancers. Subgroup analysis revealed that a low ALI was associated with shorter OS (HR = 2.279, 95% CI: 1.769-2.935, P < 0.001) and DFS (HR = 1.631, 95% CI: 1.197-2.224, P = 0.002), and PFS (HR = 1.911, 95% CI: 1.517-2.408, P = 0.002) of patients with colorectal cancer. However, the ALI was not related to CSS in the patients with gastrointestinal malignancy (HR = 1.121, 95% CI: 0.694-1.812, P = 0.640). Sensitivity analysis supported the stability and dependability of the above results. CONCLUSION: The pre-treatment ALI was a useful predictor of prognosis in patients with gastrointestinal cancers.


Assuntos
Neoplasias Gastrointestinais , Neoplasias Pulmonares , Humanos , Prognóstico , Neoplasias Pulmonares/complicações , Neoplasias Pulmonares/diagnóstico , Neoplasias Gastrointestinais/complicações , Neoplasias Gastrointestinais/diagnóstico , Biomarcadores , Inflamação
6.
Altern Ther Health Med ; 29(8): 134-138, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37535919

RESUMO

Objective: To analyze the effect of C7-T1 extensional posterior transpedicular vertebral osteotomy (PSO) on mobility and quality of life in patients with ankylosing spondylitis (AS) and lumbar kyphosis. Methods: This study was conducted from February 2019 to February 2021 and a total of 38 patients with AS combined with kyphosis from Tianjin Union Medical Center, Tianjin, China, were selected for the study. After performing all preoperative examinations, all patients were treated with C7-T1 extensional posterior PSO osteotomy. The patients' operation and follow-up, pain degree as a Visual analogue scale (VAS) score and sagittal balance index changes before and after surgery, spinal function measured as; Bath Ankylosing Spondylitis Functional Index (BASFI) score and quality of life by Scoliosis Research Society-22 (SRS-22) score, were observed before and after surgery. Pearson correlation coefficient was used to analyze the correlation between patients' quality of life and BASFI score. Results: After surgery, the pain of the patients' back was significantly relieved, the patients' appearance and trunk balance function were significantly improved, and the symptoms related to nerve function were not significantly aggravated. No complications such as infection, internal fixation failure or spinal decompensation occurred in all patients. VAS score, kyphosis Cobb Angle and Sagittal Vertical Axis (SVA) of all patients showed P < .05 before and 1 year after surgery. BASFI score 1 year after surgery decreased significantly than that before surgery (P < .05). 1 year after surgery, body function, pain symptoms, self-image and psychological state of the patients were significantly improved, and the SRS-22 total score of the patients 1 year after surgery increased significantly than before surgery (P < 0.05). BASFI score was negatively correlated with SRS-22 score by Pearson correlation coefficient analysis (P < .05). Conclusion: C7-T1 extensional posterior PSO osteotomy has a good effect in the treatment of AS patients with lumbar kyphosis. The sagittal balance was well-restored with improvement in patients' quality of life after surgery, which makes C7-T1 osteotomy worthy of clinical application to treat patients suffering from AS combined with lumbar kyphosis.


Assuntos
Cifose , Escoliose , Espondilite Anquilosante , Humanos , Escoliose/complicações , Escoliose/cirurgia , Espondilite Anquilosante/complicações , Espondilite Anquilosante/cirurgia , Qualidade de Vida , Resultado do Tratamento , Cifose/cirurgia , Cifose/complicações , Osteotomia/efeitos adversos , Osteotomia/métodos , Dor , Estudos Retrospectivos
7.
Cancer Cell Int ; 22(1): 8, 2022 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-34991609

RESUMO

BACKGROUND: In humans, riboflavin must be obtained through intestinal absorption because it cannot be synthesized by the body. SLC52A2 encodes a membrane protein belonging to the riboflavin transporter protein family and is associated with a variety of diseases. Here, we systematically explore its relevance to multiple human tumors. METHODS: We analyzed the association of SLC52A2 with 33 tumors using publicly available databases such as TCGA and GEO. We verified the SLC52A2 expression in hepatocellular carcinoma, gastric cancer, colon cancer, and rectal cancer using immunohistochemistry. RESULTS: We report that SLC52A2 was highly expressed in almost all tumors, and the immunohistochemical results in the hepatocellular, gastric, colon, and rectal cancers were consistent with the above. SLC52A2 expression was linked to patient overall survival, disease-specific survival, progression-free interval, diagnosis, mutations, tumor mutational burden, microsatellite instability, common immune checkpoint genes, and immune cells infiltration. Enrichment analysis showed that SLC52A2 was mainly enriched in oocyte meiosis, eukaryotic ribosome biogenesis, and cell cycle. In hepatocellular carcinoma, the SLC52A2 expression is an independent prognostic factor. The SNHG3 and THUMPD3-AS1/hsa-miR-139-5p-SLC52A2 axis were identified as potential regulatory pathways in hepatocellular carcinoma. CONCLUSION: In conclusion, we have systematically described for the first time that SLC52A2 is closely associated with a variety of tumors, especially hepatocellular carcinoma.

8.
Molecules ; 27(23)2022 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-36500652

RESUMO

Since antimicrobials were banned as feed additives, coccidiostats with favorable anticoccidial action and growth promotion have been widely used in the breeding industry. The monitoring of coccidiostats in feed is necessary, while the current methods based on mass-spectrometer analysis have limited applicability and matrix effects could interfere with the results. Accordingly, in the present paper, a rapid analytical strategy for the simultaneous determination of six synthetic coccidiostats in feed using high-performance liquid chromatography coupled with diode-array detection was developed. Coccidiostats in chicken feeds were extracted with the trichloroacetic acid-acetonitrile solution. The cleanup was performed by dispersive solid-phase extraction after the optimization of the response surface methodology. The method exhibited good linearity for target coccidiostats within the range of 0.05~20 µg/mL. Recoveries for six compounds in fortified feed samples were from 67.2% to 107.2% with relative standard deviations less than 9.6%. The limit of detection was 0.2~0.3 mg/kg. The successful application of the method in commercial feed verified that it is effective and sensitive for the rapid determination of multiple coccidiostats in chicken feeds.


Assuntos
Coccidiostáticos , Animais , Cromatografia Líquida de Alta Pressão/métodos , Coccidiostáticos/química , Espectrometria de Massas em Tandem/métodos , Extração em Fase Sólida , Galinhas , Ração Animal/análise
9.
BMC Cancer ; 20(1): 1167, 2020 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-33256658

RESUMO

BACKGROUND: An increasing number of studies have focused on the association between leptin, adiponectin levels and the risk as well as the prognosis of hepatocellular carcinoma. However, the reported results are conflicting. METHODS: A meta-analysis was performed to assess the correlation between leptin, adiponectin levels and risk and prognosis of hepatocellular carcinoma (CRD42020195882). Through June 14, 2020, PubMed, Cochrane Library and EMBASE databases were searched, including references of qualifying articles. Titles, abstracts, and main texts were reviewed by at least 2 independent readers. Stata 16.0 was used to calculate statistical data. RESULTS: Thirty studies were included in this meta-analysis and results showed that hepatocellular carcinoma group had significantly higher leptin levels than the cancer-free control group (SMD = 1.83, 95% CI (1.09, 2.58), P = 0.000), the healthy control group (SMD = 4.32, 95% CI (2.41, 6.24), P = 0.000) and the cirrhosis group (SMD = 1.85, 95% CI (0.70, 3.01), P = 0.002). Hepatocellular carcinoma group had significantly higher adiponectin levels than the healthy control group (SMD = 1.57, 95% CI (0.37, 2.76), P = 0.010), but no statistical difference compared with the cancer-free control group (SMD = 0.24, 95% CI (- 0.35, 0.82), P = 0.430) and the cirrhosis group (SMD = - 0.51, 95% CI (- 1.30, 0.29), P = 0.213). The leptin rs7799039 polymorphism was associated with increased risk of hepatocellular carcinoma (G vs A: OR = 1.28, 95% CI (1.10, 1.48), P = 0.002). There were linear relationships between adiponectin levels and the risk of hepatocellular carcinoma (OR = 1.066, 95% CI (1.03, 1.11), P = 0.001). In addition, the results showed that high/positive expression of adiponectin was significantly related to lower overall survival in hepatocellular carcinoma patients (HR = 1.70, 95% CI (1.22, 2.37), P = 0.002); however, there was no significantly association between the leptin levels and overall survival (HR = 0.92, 95% CI (0.53, 1.59), P = 0.766). CONCLUSION: The study shows that high leptin levels were associated with a higher risk of hepatocellular carcinoma. Adiponectin levels were proportional to hepatocellular carcinoma risk, and were related to the poor prognosis.


Assuntos
Adiponectina/metabolismo , Carcinoma Hepatocelular/sangue , Leptina/metabolismo , Neoplasias Hepáticas/sangue , Carcinoma Hepatocelular/mortalidade , Carcinoma Hepatocelular/patologia , Humanos , Neoplasias Hepáticas/mortalidade , Neoplasias Hepáticas/patologia , Prognóstico , Análise de Sobrevida
10.
Clin Exp Rheumatol ; 38(6): 1238-1246, 2020.
Artigo em Inglês | MEDLINE | ID: mdl-32662402

RESUMO

OBJECTIVES: Initial studies investigating peripheral levels of leptin and soluble leptin receptor (LepR) in systemic lupus erythematosus (SLE) patients have generated a number of controversial results. Thus, we conducted a meta-analysis to evaluate the circulating leptin level, soluble LepR level and related gene polymorphism in SLE patients. METHODS: We performed a meta-analysis comparing the circulating leptin level, LepR level and their gene polymorphism in patients with SLE to controls, and evaluate the relationship between leptin levels, LepR levels and SLE disease activity. Pubmed, Embase, Cochrane, CNKI, WanFang and VIP databases were searched systematically with no restriction to languages and years (up to Feb. 2020). Stata v. 14.0 was used to calculate statistical data. RESULTS: 34 articles involving 7337 SLE patients and 6866 healthy controls were included in this meta-analysis. Compared with the controls, SLE patients had a significantly higher level of leptin, in particular for active SLE patients, regardless of sample size, source, or assay method. The elevated leptin level was only found in the female SLE group, but not in the male SLE group. Apart from the South American subgroup, other ethnicity subgroups showed significantly higher levels of leptin in SLE patients. A marginally lower level of LepR in SLE patients was also observed. The LepR gene rs1137101 variant (i.e. AG+GG) was borderline significantly associated with the increased risk of SLE. CONCLUSIONS: Our meta-analysis revealed thta SLE patients had an elevated leptin level and decreased LepR level. LepR gene rs1137101 mutation might be associated with increased susceptibility to SLE.


Assuntos
Leptina , Lúpus Eritematoso Sistêmico , Receptores para Leptina , Feminino , Predisposição Genética para Doença , Humanos , Leptina/sangue , Leptina/genética , Lúpus Eritematoso Sistêmico/sangue , Lúpus Eritematoso Sistêmico/diagnóstico , Lúpus Eritematoso Sistêmico/genética , Masculino , Pacientes , Polimorfismo Genético , Receptores para Leptina/sangue , Receptores para Leptina/genética
11.
Br J Neurosurg ; 34(4): 419-422, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32297527

RESUMO

Purpose of the article: To investigate the correlation between C7 slope and cervical lordosis in patients after expansive open-door laminoplasty (EOLP).Material and methods: We retrospectively analyzed 57 patients who underwent EOLP between June 2013 and January 2017 in the Department of Spinal Surgery of our hospital. The operation time, intraoperative blood loss and follow-up time were recorded. The C7 slope, C2-7 sagittal vertical axis, and C2-7 Cobb angle were measured anteroposterior radiograph of the cervical spine preoperatively and postoperatively. All patients were divided into two groups according to the preoperative C7 slope (C7 slope ≤20° group and C7 slope >20° group).Results: The amount of intraoperative bleeding was 220.2 ± 180.9ml, and the operation time was 143.4 ± 51.2min. The average follow-up time was 24.9 ± 10.3months (range12-48 months). The C2-7 Cobb angle was 13.49 ± 10.46°at the final follow-up, which was significantly lower than that preoperatively (p = .026). But, The C7 slope and C2-7 sagittal vertical axis showed no significant difference between preoperatively and postoperatively. Preoperative and postoperative C7 slope and C2-7 Cobb angle were positively correlated to age and significant difference was observed. In the group of C7 slope >20°, significant difference was observed in term of the change of the C2-7 Cobb angle and C2-7SVA postoperatively (p = .009 and p= .020). However, there was no statistically significant difference detected in these two parameters in the group of C7 slope ≤20°.Conclusion: This study indicated that C7 slope could be used as an indicator of the change in the curvature of the cervical spine after EOLP. The loss of cervical curvature after surgery was prone to occur when C7 slope was greater than 20°, which should be noted in clinical practice.


Assuntos
Laminoplastia , Lordose , Vértebras Cervicais/diagnóstico por imagem , Vértebras Cervicais/cirurgia , Humanos , Laminoplastia/efeitos adversos , Lordose/diagnóstico por imagem , Lordose/cirurgia , Estudos Retrospectivos , Resultado do Tratamento
12.
Microb Pathog ; 132: 188-192, 2019 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-31039390

RESUMO

The pathogenesis and development of ankylosing spondylitis (AS) is concealed and complicated. In recent years, alterations in gut microbiota of AS patients have been largely investigated, although the underlying mechanisms remain unclear. This article reviews the recent studies on changes of gut microbiota in AS patients, and discusses the possible correlation between intestinal dysbiosis and AS development from aspects including genetic factor HLA-B27, mucosal immune responses and the depression accompanying AS.


Assuntos
Disbiose/imunologia , Disbiose/microbiologia , Espondilite Anquilosante/imunologia , Espondilite Anquilosante/microbiologia , Citocinas/metabolismo , Disbiose/complicações , Microbioma Gastrointestinal , Antígeno HLA-B27/imunologia , Humanos , Imunidade nas Mucosas , Imunoglobulina A , Inflamação/imunologia , Intestinos/imunologia , Intestinos/microbiologia , Espondilite Anquilosante/complicações
14.
Inorg Chem ; 58(8): 5221-5229, 2019 04 15.
Artigo em Inglês | MEDLINE | ID: mdl-30920211

RESUMO

In general, reduction of N2O by CO is first performed by N2O decomposition over a catalyst surface to release N2 and form an active oxygen species, and subsequently CO is oxidized by the active oxygen species to produce CO2. However, the strong adsorption behavior of CO on the catalyst surface usually inhibits adsorption and decomposition of N2O, which leads to a low activity or poisoning of catalysts. In the present paper, a Mars-van Krevelen (MvK) [correction] mechanism has been probed based on a series of phosphotungstic acid (PTA) supported single-atom catalysts (SACs), M1/PTA (M = Fe, Co, Mn, Rh, Ru, Ir, Os, Pt, and Pd). Although the calculated adsorption energy of CO is exceedingly higher than N2O for our studied systems, the adsorbed CO could react with the surface oxygen atom of the PTA support through the MvK mechanism to form an oxygen vacancy on the PTA surface. N2O acts as an oxygen donor to replenish the PTA support and release N2 in the whole reaction process. This proposed reaction mechanism avoids competitive adsorption and poisoning of the catalyst caused by CO. The calculated adsorption energy, oxygen vacancy formation energy, and the free energy profiles show that the catalytic activity of Pd1/PTA, Rh1/PTA, and Pt1/PTA SACs is quite high, especially for Pt1/PTA and Pd1/PTA systems. Meanwhile, molecular geometry and electronic structure analysis along the favorable reaction pathway indicates that the metal single atom not only plays the role of adsorbing CO and activating surface atoms of the PTA support but also works as an electron transfer media in the whole reaction process. We expect that the present calculated results could provide some clues for the search for appropriate catalyst for reduction of N2O to N2 by CO at low temperature.

15.
Inorg Chem ; 58(12): 7852-7862, 2019 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-31141350

RESUMO

Molecular geometry, electronic structure, and possible reaction mechanism of a series of mono-transition-metal-substituted Keggin-type polyoxometalate (POM)-dinitrogen complexes [PW11O39M(N2)] n- (M = Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Tc, Ru, Rh, Pd, Ag, Cd, W, Re, Os, Ir, Pt, Au, and Hg) have been investigated by using density functional theory (DFT) calculations with M06L functional. The calculated adsorption energy of N2 molecule, N-N bond length, N-N stretching frequency, and the NBO charge on the coordinated N2 moiety indicate that MoII-, TcII-, WII-, ReII-, and OsII-POM complexes are significant for binding and activation of the inert N2 molecule. The degree of the N2 activation can be classified into the "moderately activated" category according to Tuczek's sense [ J. Comput. Chem. 2006 , 27 , 1278 ]. Electronic structure and NBO analysis indicate that the terminal N atom of the coordinated N2 molecule in these POM-dinitrogen complexes possesses more negative charge relative to the bridge N atom because Jahn-Teller distorted effects lead to an effective orbital mixture between σ2s* orbital of N2 and d z2 orbital of transition metal center. And the mono-lacunary Keggin-type POM ligand with five oxygen donor atoms serves as a strong electron donor to the bivalent metal center. Meanwhile, a catalytic cycle for direct conversion of N2 into NH3 has been systematically investigated based on a Re-POM complex along distal, alternating, and enzymatic pathways. The calculated free energy profile of the three catalytic cycles indicates that the distal mechanism is the favorable pathway in the presence of proton and electron donors.

16.
Environ Sci Technol ; 53(21): 12893-12903, 2019 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-31595750

RESUMO

In the present paper, the mechanisms of N2O reduction by H2 were systemically examined over various polyoxometalate-supported single-atom catalysts (SACs) M1/PTA (M = Fe, Co, Mn, Ru, Rh, Os, Ir, and Pt; PTA = [PW12O40]3-) by means of density functional theory calculations. Among these M1/PTA SACs, Os1/PTA SAC possesses high activity for N2O reduction by H2 with a relatively low rate-determining barrier. The favorable catalytic pathway involves the first and second N2O decomposition over the Os1/PTA SAC and hydrogenation of the key species after the second N2O decomposition. Molecular geometry and electronic structure analyses along the favorable reaction pathway indicate that a strong charge-transfer cooperative effect of metal and support effectively improves the catalytic activity of Os1/PTA SAC. The isolated Os atom not only plays the role of adsorption and activation of the N2O molecule but also works as an electron transfer medium in the whole reaction process. Meanwhile, the PTA support with very high redox stability has also been proven to be capable of transporting the electron to promote the whole reaction. We expect that our computation results can provide ideas for designing new SACs for N2O reduction by using H2 selective catalytic reduction technology.


Assuntos
Teoria da Densidade Funcional , Adsorção , Catálise , Hidrogenação , Ácido Fosfotúngstico
17.
Phys Chem Chem Phys ; 21(19): 9975-9986, 2019 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-31041984

RESUMO

Density functional theory (DFT) calculations have been employed to probe the reaction mechanism of NO reduction with CO over a Cu1/PMA (PMA is the phosphomolybdate, Cs3PMo12O40) single-atom catalyst (SAC). Several important aspects of the catalytic system were addressed, including the generation of oxygen vacancies (Ov), formation of N2O2 intermediates, scission of the N-O bond of N2O2 intermediates to form N2O or N2, and decomposition of N2O to form N2. Unlike most previous theoretical studies, which tend to explore the reaction mechanism of polyoxometalate (POM) systems based on the isolated anionic unit, here, we build a model of the catalytic system with neutral species by introduction of counter cations to model the solid structure of the Cu1/PMA SAC. The major findings of our present study are: (1) CO adsorption on Cu sites leads to the formation of cationic Cu carbonyl species; (2) the Oc atom at the surface of the PMA support can easily react with the adsorbed CO to generate a Cu-Ov pair; (3) the Cu-Ov pair embedded on PMA is found to be the active site, not only for the formation of N2O2* by the reaction of two NO molecules via an Eley-Rideal pathway but also for the decomposition of N2O to form N2; (4) the adsorption of a NO molecule on the Cu-Ov pair with a bridging model results in charge transfer from the Cu atom to the π* antibonding orbital of the NO molecule; (5) IR spectroscopy of the key intermediates has been identified based on our DFT calculations; and (6) the Cu atom serves as an electron acceptor in Ov formation steps and an electron donor in N2O2 decomposition steps, and thus represents an electron reservoir. These results suggest that the POM-supported SAC with the cheaper Cu element is an efficient catalyst for the reaction between CO and NO.

18.
Sheng Wu Yi Xue Gong Cheng Xue Za Zhi ; 34(2): 271-277, 2017 04 25.
Artigo em Zh | MEDLINE | ID: mdl-29745585

RESUMO

A new one-time registration method was developed in this research for hand-eye calibration of a surgical robot to simplify the operation process and reduce the preparation time. And a new and practical method is introduced in this research to optimize the end-tool parameters of the surgical robot based on analysis of the error sources in this registration method. In the process with one-time registration method, firstly a marker on the end-tool of the robot was recognized by a fixed binocular camera, and then the orientation and position of the marker were calculated based on the joint parameters of the robot. Secondly the relationship between the camera coordinate system and the robot base coordinate system could be established to complete the hand-eye calibration. Because of manufacturing and assembly errors of robot end-tool, an error equation was established with the transformation matrix between the robot end coordinate system and the robot end-tool coordinate system as the variable. Numerical optimization was employed to optimize end-tool parameters of the robot. The experimental results showed that the one-time registration method could significantly improve the efficiency of the robot hand-eye calibration compared with the existing methods. The parameter optimization method could significantly improve the absolute positioning accuracy of the one-time registration method. The absolute positioning accuracy of the one-time registration method can meet the requirements of the clinical surgery.

20.
Gene ; 894: 147942, 2024 Feb 05.
Artigo em Inglês | MEDLINE | ID: mdl-37935322

RESUMO

BACKGROUND: Postmenopausal osteoporosis (PMOP) is related to the elevated risk of fracture in postmenopausal women. Thus, to effectively predict the occurrence of PMOP, we explored a novel gene signature for the prediction of PMOP risk. METHODS: The WGCNA analysis was conducted to identify the PMOP-related gene modules based on the data from GEO database (GSE56116 and GSE100609). The "limma" R package was applied for screening differentially expressed genes (DEGs) based on the data from GSE100609 dataset. Next, LASSO Cox algorithm were applied to identify valuable PMOP-related risk genes and construct a risk score model. GSEA was then conducted to analyze potential signaling pathways between high-risk (HR) score and low-risk (LR) score groups. RESULTS: A novel risk model with five PMOP-related risk genes (SCUBE3, TNNC1, SPON1, SEPT12 and ULBP1) was developed for predicting PMOP risk status. RT-qPCR and western blot assays validated that compared to postmenopausal non-osteoporosis (non-PMOP) patients, SCUBE3, ULBP1, SEPT12 levels were obviously elevated, and TNNC1 and SPON1 levels were reduced in blood samples from PMOP patients. Additionally, PMOP-related pathways such as MAPK signaling pathway, PI3K-Akt signaling pathway and HIF-1 signaling pathway were significantly activated in the HR-score group compared to the LR-score group. The circRNA-gene-miRNA and gene-transcription factor networks showed that 533 miRNAs, 13 circRNAs and 40 TFs might be involved in regulating the expression level of these five PMOP-related genes. CONCLUSION: Collectively, we developed a PMOP-related gene signature based on SCUBE3, TNNC1, SPON1, SEPT12 and ULBP1 genes, and higher risk score indicated higher risk suffering from PMOP.


Assuntos
MicroRNAs , Osteoporose Pós-Menopausa , Humanos , Feminino , Osteoporose Pós-Menopausa/genética , Fosfatidilinositol 3-Quinases/genética , Fosfatidilinositol 3-Quinases/metabolismo , Redes Reguladoras de Genes , MicroRNAs/genética , Transdução de Sinais/genética , Proteínas de Ligação ao Cálcio/genética
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