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1.
J Am Chem Soc ; 146(26): 17866-17877, 2024 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-38916547

RESUMEN

Construction of mesoporous frameworks by noncovalent bonding still remains a great challenge. Here, we report a micelle-directed nanocluster modular self-assembly approach to synthesize a novel type of two-dimensional (2-D) hydrogen-bonded mesoporous frameworks (HMFs) for the first time based on nanoscale cluster units (1.0-3.0 nm in size). In this 2-D structure, a mesoporous cluster plate with ∼100 nm in thickness and several micrometers in size can be stably formed into uniform hexagonal arrays. Meanwhile, such a porous plate consists of several (3-4) dozens of layers of ultrathin mesoporous cluster nanosheets. The size of the mesopores can be precisely controlled from 11.6 to 18.5 nm by utilizing the amphiphilic diblock copolymer micelles with tunable block lengths. Additionally, the pore configuration of the HMFs can be changed from spherical to cylindrical by manipulating the concentration of the micelles. As a general approach, various new HMFs have been achieved successfully via a modular self-assembly of nanoclusters with switchable configurations (nanoring, Keggin-type, and cubane-like) and components (titanium-oxo, polyoxometalate, and organometallic clusters). As a demonstration, the titanium-oxo cluster-based HMFs show efficient photocatalytic activity for hydrogen evolution (3.6 mmol g-1h-1), with a conversion rate about 2 times higher than that of the unassembled titanium-oxo clusters (1.5 mmol g-1h-1). This demonstrates that HMFs exhibited enhanced photocatalytic activity compared with unassembled titanium-oxo clusters units.

2.
Diabetes Metab Syndr Obes ; 17: 2065-2074, 2024.
Artículo en Inglés | MEDLINE | ID: mdl-38778907

RESUMEN

Purpose: This study aimed to investigate the glycometabolism, fat mass, and lean mass in primary aldosteronism (PA) during disease progression. Patients and Methods: Patients diagnosed with PA and healthy controls (HCs) were enrolled. A flash glucose monitoring system (FGMS) and dual-energy X-ray absorptiometry (DEXA) were used to measure glucose variability and glucose target rate along with fat mass and lean mass. Comparative analysis of FGMS- or DEXA-derived parameters along with correlation analyses between these parameters and PA progression were performed. Results: Increased glucose variability and poor glucose target rate, along with an increased proportion of truncal fat mass, and decreased proportion of appendicular lean mass, were identified in PA group compared to those in HCs. Plasma aldosterone concentration was positively correlated with glucose variability and poor glucose target rate. Plasma renin concentration was positively correlated with the proportion of truncal fat mass and lean mass, and negatively correlated with the proportion of appendicular fat mass. Aldosterone-to-renin ratio was negatively correlated with the proportion of truncal fat mass and lean mass, and positively correlated with the proportion of appendicular fat mass. Conclusion: Patients with PA presented significant differences in glycometabolism, fat mass, and lean mass compared with HCs, and these alterations correlated with PA progression.

3.
ACS Appl Mater Interfaces ; 16(19): 24691-24702, 2024 May 15.
Artículo en Inglés | MEDLINE | ID: mdl-38693896

RESUMEN

Metal/metal oxide clusters possess a higher count of unsaturated coordination sites than nanoparticles, providing multiatomic sites that single atoms do not. Encapsulating metal/metal oxide clusters within zeolites is a promising approach for synthesizing and stabilizing these clusters. The unique feature endows the metal clusters with an exceptional catalytic performance in a broad range of catalytic reactions. However, the encapsulation of stable FeOx clusters in zeolite is still challenging, which limits the application of zeolite-encapsulated FeOx clusters in catalysis. Herein, we design a modified solvent-free method to encapsulate FeOx clusters in pure siliceous MFI zeolites (Fe@MFI). It is revealed that the 0.3-0.4 nm subnanometric FeOx clusters are stably encapsulated in the 5/6-membered rings intersectional voids of the pure siliceous MFI zeolites. The encapsulated Fe@MFI catalyst with a Fe loading of 1.4 wt % demonstrates remarkable catalytic activity and recycle stability in the direct oxidation of methane, while also promoting the direct oxidation of cyclohexane, surpassing the performance of conventional zeolite-supported Fe catalysts.

4.
Science ; 383(6678): 94-101, 2024 Jan 05.
Artículo en Inglés | MEDLINE | ID: mdl-38127809

RESUMEN

Copper nanoparticle-based catalysts have been extensively applied in industry, but the nanoparticles tend to sinter into larger ones in the chemical atmospheres, which is detrimental to catalyst performance. In this work, we used dealuminated Beta zeolite to support copper nanoparticles (Cu/Beta-deAl) and showed that these particles become smaller in methanol vapor at 200°C, decreasing from ~5.6 to ~2.4 nanometers in diameter, which is opposite to the general sintering phenomenon. A reverse ripening process was discovered, whereby migratable copper sites activated by methanol were trapped by silanol nests and the copper species in the nests acted as new nucleation sites for the formation of small nanoparticles. This feature reversed the general sintering channel, resulting in robust catalysts for dimethyl oxalate hydrogenation performed with supported copper nanoparticles for use in industry.

5.
Langmuir ; 39(47): 16812-16824, 2023 Nov 28.
Artículo en Inglés | MEDLINE | ID: mdl-37965918

RESUMEN

The deposition time was controlled to prepare Mn nanowires of different lengths and diameters on templates of anodic aluminum oxide (AAO) with different pore sizes. The surface of as-prepared Mn nanowires was modified with SiO2 using the sol-gel method to improve their dispersion in aqueous solution. The effects of the diameter and length of the as-prepared Mn nanowires coated with SiO2 on the relaxivity were investigated. It was found that the Mn@SiO2 nanowires have smaller diameters and a higher longitudinal relaxivity (r1) with an increased length. Mn3@SiO2 nanowires had the highest r1 value of 5.8 mM-1 s-1 among the Mn@SiO2 nanowires (Mn3 nanowires have a diameter of about 30 nm and a length of about 0.5 µm length). Additionally, the biocompatibility and in vivo imaging ability of the Mn3@SiO2 nanowires were evaluated. The Mn3@SiO2 nanowires had good cytotoxicity and biocompatibility, and the kidney of SD rats showed a positive enhancement effect during small animal imaging at 1.5 T. This study showed that the Mn3@SiO2 nanowires could potentially become contrast agents (CAs) of longitudinal relaxation time (T1).

6.
PLoS One ; 18(11): e0294152, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-37956192

RESUMEN

INTRODUCTION: Perineal extramammary paget's disease (EMPD) is characterized with high recurrence rate. Although numerous therapeutic measures for this disease have been reported so far, it is unknown whether there is significant difference in their recurrence-preventing efficiency. This study aims to compare the recurrence outcomes of reported perineal EMPD treatments. METHODS: We searched public databases of for published studies concerning perineal EMPD treatments. After screening by inclusion and exclusion criteria, we extracted the data relevant to recurrence rate, and conducted network meta-analysis (NMA) by using Bayesian random-effects approach. RESULTS: Our analysis included 29 previous studies (involving both male and female patients) and 11 treatment designs which are wide local excision (WLE), local excision (LE), Mohs micrographic surgery (MMS), radiotherapy (RT), radical vulvectomy (RV), photodynamic therapy (PDT), lasers (LS), imiquimod, and WLE+RT, WLE+PDT, WLE+LS. Comparing with WLE, the MMS showed significant advantage in reducing recurrence [OR: 0.18 (0.03-0.87)], while none of the rest treatments has statistically significant results. After removing outlier studies, MMS still has the significant advantages [OR: 0.35 (0.11-0.82)], and LE turned to be the treatment with worst performance [OR: 13 (2.50-110)]. Covariance analysis of follow-up length, gender differences, and lesion locations indicated only short follow-up time could affect the recurrence statistics, which tend to conceal the real differences. Funnel plot demonstrated there is no significant small study effect. CONCLUSION: MMS has the best performance on reducing perineal EMPD recurrence, while LE exhibits the worst capability in such regard. Recurrence-preventing abilities of other treatments have no significant difference between each other.


Asunto(s)
Enfermedad de Paget Extramamaria , Humanos , Masculino , Femenino , Enfermedad de Paget Extramamaria/cirugía , Enfermedad de Paget Extramamaria/patología , Teorema de Bayes , Metaanálisis en Red , Cirugía de Mohs/métodos , Imiquimod , Recurrencia Local de Neoplasia/patología , Estudios Retrospectivos
7.
JCO Precis Oncol ; 7: e2300389, 2023 09.
Artículo en Inglés | MEDLINE | ID: mdl-37883729

RESUMEN

PURPOSE: Surveillance after primary melanoma treatment aims to detect early signs of low-volume systemic disease. The current standard of care, surveillance imaging, is costly and difficult to access. We therefore sought to develop methylated DNA markers (MDMs) as promising alternatives for disease surveillance. METHODS: We used reduced representation bisulfite sequencing (RRBS) to identify MDMs in DNA samples obtained from metastatic melanoma, benign nevi, and normal skin tissues. The identified MDMs underwent validation in an independent cohort of tissue and buffy coat DNA samples. Subsequently, we tested the validated MDMs in the plasma DNA of patients with metastatic melanoma undergoing surveillance with total body imaging and compared them with cancer-free controls. To estimate the overall predictive accuracy of the MDMs, we used random forest modeling with bootstrap cross-validation. RESULTS: Forty MDMs demonstrated discrimination between melanoma cases and controls consisting of benign nevi and normal skin. Nine MDMs passing biological validation in tissue were run on 77 plasma samples from individuals with a history of metastatic melanoma, 49 of whom had evidence of disease detected by imaging at the time of blood draw, and 100 cancer-free controls. The cross-validated sensitivity of the panel for imaging-positive disease was 80% with a specificity of 100% in cancer-free controls, resulting in an overall AUC of 0.88 (95% CI, 0.81 to 0.96). The survival estimates for patients with melanoma who tested positive for the panel at 6 months and 1 year were 67% and 56%, respectively, while those who tested negative had survival rates of 100% and 92%. CONCLUSION: MDMs identified by RRBS demonstrate a high degree of concordance with imaging results in the plasma of patients with metastatic melanoma. Further prospective studies in larger intended use cohorts are needed to confirm these findings.


Asunto(s)
Melanoma , Nevo , Humanos , Marcadores Genéticos , Estudios Prospectivos , Melanoma/diagnóstico , Melanoma/genética , ADN
8.
Angew Chem Int Ed Engl ; 62(47): e202312377, 2023 Nov 20.
Artículo en Inglés | MEDLINE | ID: mdl-37796132

RESUMEN

The metal surfaces tend to be oxidized in air through dissociation of the O-O bond of oxygen to reduce the performances in various fields. Although several ligand modification routes have alleviated the oxidation of bulky metal surfaces, it is still a challenge for the oxidation resistance of small-size metal nanoparticles. Herein, we fixed the small-size Pd nanoparticles in tin-contained MFI zeolite crystals, where the tin acts as an electron donor to efficiently hinder the oxidation of Pd by weakening the adsorption of molecular oxygen and suppressing the O-O cleavage. This oxidation-resistant Pd catalyst exhibited superior performance in directly synthesizing hydrogen peroxide from hydrogen and oxygen, with the productivity of hydrogen peroxide at ≈10,170 mmol gPd -1 h-1 , steadily outperforming the catalysts tested previously. This work leads to the hypothesis that tin is an electron donor to realize oxidation-resistant Pd within zeolite crystals for efficient catalysis to overcome the limitation of generally supported Pd catalysts and further motivates the use of oxidation-resistant metal nanoparticles in various fields.

9.
Discov Nano ; 18(1): 136, 2023 Oct 31.
Artículo en Inglés | MEDLINE | ID: mdl-37903989

RESUMEN

A facile template method was employed to synthesize Fe nanowires of different sizes, dimensions. Comprehensive analyses were conducted to explore their morphology, structure, composition, and magnetic properties. The surface of as-prepared Fe nanowires was modified with SiO2 by sol-gel method to improve the dispersion of as-prepared Fe nanowires in aqueous solution. Furthermore, the relaxation properties, biocompatibility and in vivo imaging abilities of the Fe@SiO2 nanowires were evaluated. The study revealed that the SiO2-coated Fe nanowires functioned effectively as transverse relaxation time (T2) contrast agents (CAs). Notably, as the length of the Fe@SiO2 nanowires increased, their diameter decreased, leading to a higher the transverse relaxivity (r2) value. Our study identified that among the Fe nanowires synthesized, the Fe3@SiO2 nanowires, characterized by a diameter of around 30 nm and a length of approximately 500 nm, exhibited the highest r2 value of 59.3 mM-1 s-1. These nanowires demonstrated good biocompatibility and non-toxicity. Notably, upon conducting small animal imaging a 1.5 T with Sprague-Dawley rats, we observed a discernible negative enhancement effect in the liver. These findings indicate the promising potential of Fe@SiO2 nanowires as T2 CAs, with the possibility of tuning their size for optimized results.

10.
Oral Oncol ; 146: 106568, 2023 11.
Artículo en Inglés | MEDLINE | ID: mdl-37717549

RESUMEN

OBJECTIVE: Early identification of human papillomavirus associated oropharyngeal squamous cell carcinoma (HPV(+)OPSCC) is challenging and novel biomarkers are needed. We hypothesized that a panel of methylated DNA markers (MDMs) found in HPV(+) cervical squamous cell carcinoma (CSCC) will have similar discrimination in HPV(+)OPSCC tissues. MATERIALS AND METHODS: Formalin-fixed, paraffin-embedded tissues were obtained from patients with primary HPV(+)OPSCC or HPV(+)CSCC; control tissues included normal oropharynx palatine tonsil (NOP) and cervix (NCS). Using a methylation-specific polymerase chain reaction, 21 previously validated cervical MDMs were evaluated on tissue-extracted DNA. Discrimination between case and control cervical and oropharynx tissue was assessed using area under the curve (AUC). RESULTS: 34 HPV(+)OPSCC, 36 HPV(+)CSCC, 26 NOP, and 24 NCS patients met inclusion criteria. Within HPV(+)CSCC, 18/21 (86%) of MDMs achieved an AUC ≥ 0.9 and all MDMs exhibited better than chance classifications relative to control cervical tissue (all p < 0.001). In contrast, within HPV(+)OPSCC only 5/21 (24%) MDMs achieved an AUC ≥ 0.90 but 19/21 (90%) exhibited better than chance classifications relative to control tonsil tissue (all p < 0.001). Overall, 13/21 MDMs had statistically significant lower AUCs in the oropharyngeal cohort compared to the cervical cohort, and only 1 MDM exhibited a statistically significant increase in AUC. CONCLUSIONS: Previously validated MDMs exhibited robust performance in independent HPV(+)CSCC patients. However, most of these MDMs exhibited higher discrimination for HPV(+)CSCC than for HPV(+)OPSCC. This suggests that each SCC subtype requires a unique set of MDMs for optimal discrimination. Future studies are necessary to establish an MDM panel for HPV(+)OPSCC.


Asunto(s)
Carcinoma de Células Escamosas , Neoplasias de Cabeza y Cuello , Neoplasias Orofaríngeas , Infecciones por Papillomavirus , Neoplasias del Cuello Uterino , Femenino , Humanos , Carcinoma de Células Escamosas de Cabeza y Cuello/genética , Carcinoma de Células Escamosas/patología , Virus del Papiloma Humano , Infecciones por Papillomavirus/complicaciones , Infecciones por Papillomavirus/diagnóstico , Infecciones por Papillomavirus/genética , Marcadores Genéticos , Metilación de ADN , Neoplasias del Cuello Uterino/diagnóstico , Neoplasias del Cuello Uterino/genética , Papillomaviridae/genética , Neoplasias de Cabeza y Cuello/genética
11.
Adv Sci (Weinh) ; 10(26): e2302143, 2023 09.
Artículo en Inglés | MEDLINE | ID: mdl-37401146

RESUMEN

Rationally constructing atom-precise active sites is highly important to promote their catalytic performance but still challenging. Herein, this work designs and constructs ZSM-5 supported Cu and Ag dual single atoms as a proof-of-concept catalyst (Ag1 -Cu1 /ZSM-5 hetero-SAC (single-atom catalyst)) to boost direct oxidation of methane (DOM) by H2 O2 . The Ag1 -Cu1 /ZSM-5 hetero-SAC synthesized via a modified co-adsorption strategy yields a methanol productivity of 20,115 µmol gcat -1 with 81% selectivity at 70 °C within 30 min, which surpasses most of the state-of-the-art noble metal catalysts. The characterization results prove that the synergistic interaction between silver and copper facilitates the formation of highly reactive surface hydroxyl species to activate the C-H bond as well as the activity, selectivity, and stability of DOM compared with SACs, which is the key to the enhanced catalytic performance. This work believes the atomic-level design strategy on dual-single-atom active sites should pave the way to designing advanced catalysts for methane conversion.

12.
Medicine (Baltimore) ; 102(23): e34022, 2023 Jun 09.
Artículo en Inglés | MEDLINE | ID: mdl-37335636

RESUMEN

RATIONALE: Pheochromocytomas are a group of tumors with high genetic heterogeneity, and the clinical characteristics of rearranged during transfection (RET)-mutated pheochromocytoma with medullary spongiform kidney are rarely studied. The treatment process of 1 patient with bilateral adrenal pheochromocytoma combined with medullary sponge kidney with RET gene mutation in our department was retrospectively analyzed, and the treatment methods for this type of disease were studied and summarized in combination with relevant literature. PATIENT CONCERNS: In this case, the patient was found to have bilateral adrenal masses for 8 years due to physical examination, and intermittent dizziness and discomfort for 2 years. Imaging and related laboratory examinations suggest bilateral adrenal giant pheochromocytoma with bilateral medullary sponge kidney. RET gene testing was performed on the patient and his descendant after signing the informed consent form. DIAGNOSES: The patient was diagnosed with bilateral adrenal pheochromocytoma with a RET proto-oncogene mutation and a bilateral medullary spongy kidney. INTERVISION AND OUTCOMES: After sufficient perioperative preparation, retroperitoneal laparoscopic bilateral adrenal pheochromocytoma resection was performed by stages. The operation was successful, and hormone replacement therapy was performed after the operation, with regular follow-up. Relevant genetic testing revealed that the c.1900T > C: p.C634R mutation was detected in the patient's RET gene, which was a heterozygous missense mutation, and the mutation was also present in the son of his family. A literature analysis found that pheochromocytoma is a tumor with high genetic heterogeneity, and the RET proto-oncogene is a common pathogenic gene for bilateral adrenal pheochromocytoma. Medullary sponging of kidneys is a rare complication of this disease. LESSONS: On the basis of adequate perioperative preparation, surgical resection is the most effective and preferred treatment for this type of disease. Laparoscopic surgery is minimally invasive, safe, and effective by stages. Mutations in the RET proto-oncogene may lead to medullary spongy kidneys in multiple endocrine neoplasia 2.


Asunto(s)
Neoplasias de las Glándulas Suprarrenales , Riñón Esponjoso Medular , Neoplasia Endocrina Múltiple Tipo 2a , Feocromocitoma , Neoplasias de la Tiroides , Humanos , Feocromocitoma/diagnóstico , Feocromocitoma/genética , Feocromocitoma/cirugía , Neoplasia Endocrina Múltiple Tipo 2a/diagnóstico , Neoplasia Endocrina Múltiple Tipo 2a/genética , Neoplasia Endocrina Múltiple Tipo 2a/cirugía , Estudios Retrospectivos , Proteínas Proto-Oncogénicas c-ret/genética , Proto-Oncogenes Mas , Mutación , Neoplasias de las Glándulas Suprarrenales/diagnóstico , Neoplasias de las Glándulas Suprarrenales/genética , Neoplasias de las Glándulas Suprarrenales/cirugía , Proto-Oncogenes , Neoplasias de la Tiroides/patología
13.
Natl Sci Rev ; 10(5): nwad057, 2023 May.
Artículo en Inglés | MEDLINE | ID: mdl-37274941

RESUMEN

The spontaneous formation of self-assembly monolayer (SAM) on various substrates represents an effective strategy for interfacial engineering of optoelectronic devices. Hole-selective SAM is becoming popular among high-performance inverted perovskite solar cells (PSCs), but the presence of strong acidic anchors (such as -PO3H2) in state-of-the-art SAM is detrimental to device stability. Herein, we report for the first time that acidity-weakened boric acid can function as an alternative anchor to construct efficient SAM-based hole-selective contact (HSC) for PSCs. Theoretical calculations reveal that boric acid spontaneously chemisorbs onto indium tin oxide (ITO) surface with oxygen vacancies facilitating the adsorption progress. Spectroscopy and electrical measurements indicate that boric acid anchor significantly mitigates ITO corrosion. The excess boric acid containing molecules improves perovskite deposition and results in a coherent and well-passivated bottom interface, which boosts the fill factor (FF) performance for a variety of perovskite compositions. The optimal boric acid-anchoring HSC (MTPA-BA) can achieve power conversion efficiency close to 23% with a high FF of 85.2%. More importantly, the devices show improved stability: 90% of their initial efficiency is retained after 2400 h of storage (ISOS-D-1) or 400 h of operation (ISOS-L-1), which are 5-fold higher than those of phosphonic acid SAM-based devices. Acidity-weakened boric acid SAMs, which are friendly to ITO, exhibits well the great potential to improve the stability of the interface as well as the device.

14.
Gynecol Oncol ; 174: 11-20, 2023 07.
Artículo en Inglés | MEDLINE | ID: mdl-37141817

RESUMEN

OBJECTIVE: Alterations in DNA methylation are early events in endometrial cancer (EC) development and may have utility in EC detection via tampon-collected vaginal fluid. METHODS: For discovery, DNA from frozen EC, benign endometrium (BE), and benign cervicovaginal (BCV) tissues underwent reduced representation bisulfite sequencing (RRBS) to identify differentially methylated regions (DMRs). Candidate DMRs were selected based on receiver operating characteristic (ROC) discrimination, methylation level fold-change between cancers and controls, and absence of background CpG methylation. Methylated DNA marker (MDM) validation was performed using qMSP on DNA from independent EC and BE FFPE tissue sets. Women ≥45 years of age with abnormal uterine bleeding (AUB) or postmenopausal bleeding (PMB) or any age with biopsy-proven EC self-collected vaginal fluid using a tampon prior to clinically indicated endometrial sampling or hysterectomy. Vaginal fluid DNA was assayed by qMSP for EC-associated MDMs. Random forest modeling analysis was performed to generate predictive probability of underlying disease; results were 500-fold in-silico cross-validated. RESULTS: Thirty-three candidate MDMs met performance criteria in tissue. For the tampon pilot, 100 EC cases were frequency matched by menopausal status and tampon collection date to 92 BE controls. A 28-MDM panel highly discriminated between EC and BE (96% (95%CI 89-99%) specificity; 76% (66-84%) sensitivity (AUC 0.88). In PBS/EDTA tampon buffer, the panel yielded 96% (95% CI 87-99%) specificity and 82% (70-91%) sensitivity (AUC 0.91). CONCLUSION: Next generation methylome sequencing, stringent filtering criteria, and independent validation yielded excellent candidate MDMs for EC. EC-associated MDMs performed with promisingly high sensitivity and specificity in tampon-collected vaginal fluid; PBS-based tampon buffer with added EDTA improved sensitivity. Larger tampon-based EC MDM testing studies are warranted.


Asunto(s)
Neoplasias Endometriales , Humanos , Femenino , Marcadores Genéticos , Ácido Edético/metabolismo , Neoplasias Endometriales/diagnóstico , Neoplasias Endometriales/genética , Neoplasias Endometriales/metabolismo , Endometrio/metabolismo , ADN , Metilación de ADN
15.
Materials (Basel) ; 16(10)2023 May 19.
Artículo en Inglés | MEDLINE | ID: mdl-37241462

RESUMEN

In this work, PDA@BN-TiO2 nanohybrid particles were incorporated chemically into a zinc-phosphating solution to form a robust, low-temperature phosphate-silane coating on Q235 steel specimens. The morphology and surface modification of the coating was characterized by X-Ray Diffraction (XRD), X-ray Spectroscopy (XPS), Fourier-transform infrared spectroscopy (FT-IR), and Scanning electron microscopy (SEM). Results demonstrate that the incorporation of PDA@BN-TiO2 nanohybrids produced a higher number of nucleation sites and reduced grain size with a denser, more robust, and more corrosion-resistant phosphate coating compared to pure coating. The coating weight results showed that the PBT-0.3 sample achieved the densest and most uniform coating (38.2 g/m2). The potentiodynamic polarization results showed that the PDA@BN-TiO2 nanohybrid particles increased phosphate-silane films' homogeneity and anti-corrosive capabilities. The 0.3 g/L sample exhibits the best performance with an electric current density of 1.95 × 10-5 A/cm2, an order of magnitude lower than that of the pure coatings. Electrochemical impedance spectroscopy revealed that PDA@BN-TiO2 nanohybrids provided the greatest corrosion resistance compared to pure coatings. The corrosion time for copper sulfate in samples containing PDA@BN/TiO2 prolonged to 285 s, a significantly higher amount of time than the corrosion time found in pure samples.

16.
Small ; 19(32): e2301178, 2023 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-37066750

RESUMEN

Pt-based supported materials, a widely used electrocatalyst for hydrogen evolution reaction (HER), often experience unavoidable electron loss, resulting in a mismatching of electronic structure and HER behavior. Here, a Pt/WO3 catalyst consisting of Pt species strongly coupled with defective WO3 polycrystalline nanorods is rationally designed. The electronic structure engineering of Pt sites on WO3 can be systematically regulated, and so that the optimal electron-rich Pt sites on Pt/WO3 -600 present an excellent HER activity with only 8 mV overpotential at 10 mA cm-2 . Particularly, the mass activity reaches 7015 mA mg-1 at the overpotential of 50 mV, up to 26-fold higher than that of the commercial Pt/C. The combination of experimental and theoretical results demonstrates that the O vacancies of WO3 effectively mitigate the tendency of electron transfer from Pt sites to WO3 , so that the d-band center could reach an appropriate level relative to Fermi level, endowing it with a suitable Δ G H ∗ $\Delta {G_{{{\rm{H}}^ * }}}$ . This work identifies the influence of the electronic structure on catalytic activity.

17.
Transl Androl Urol ; 12(3): 425-432, 2023 Mar 31.
Artículo en Inglés | MEDLINE | ID: mdl-37032752

RESUMEN

Background: As the novel serum biomarkers, it has not been clearly clarified that the diagnostic accuracy of prostate health index (PHI) and prostate health index density (PHID) are superior to that of percentage free prostate-specific antigen (%fPSA) in detection of clinically significant prostate cancer (csPCa), especially in the gray zone. Therefore, this study aimed to compare the diagnostic value of PHI, PHID, and %fPSA for csPCa in the patients with prostate-specific antigen (PSA) >4 ng/mL and those with PSA within 4-10 ng/mL. Methods: In this study, the serum samples and clinicopathological features were prospectively obtained from the patients who underwent prostate biopsy between September 2019 and December 2020. According to the inclusion criteria, the patients with total PSA (tPSA) >4 ng/mL, prostate magnetic resonance imaging or ultrasound clearly suggesting an occupying lesion were enrolled in this study. The patients with Gleason score ≥7 indicated csPCa. The receiver operating characteristic curves and the area under the curve (AUC) values were used to assess the diagnostic performance. Results: Among the 296 patients (mean age 67.5 years, median tPSA 7.94 ng/mL) included in this study, there were 54 in the csPCa group (mean age 70.4 years, median tPSA 11.0 ng/mL) and 242 in the non-csPCa group (mean age 66.8 years, median tPSA 7.67 ng/mL). Based on the PSA level, there were 198 patients with PSA within the gray zone, which included 40 patients in the csPCa group and 158 in the non-csPCa group. In all patients, the sensitivity of PHID for detecting csPCa was 96.30%, and the specificity was 33.06% with the cut-off value of 0.51. Moreover, both PHID and PHI did better in the diagnosis of csPCa (AUC: 0.880 and 0.867, respectively) compared with other PSA derivative markers. Similarly, in the patients with PSA level in the gray zone, the diagnostic accuracy of PHID and PHI in predicting csPCa (AUC: 0.788 and 0.777, respectively) were better than other PSA derivative markers. Conclusions: PHID presented the better diagnostic accuracy in predicting csPCa in patients with PSA in the gray zone than other PSA derivative markers, which could be a promising biomarker for making the biopsy strategy.

18.
Adv Mater ; 35(25): e2208504, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-37014632

RESUMEN

Precise determination of the structure-property relationship of zeolite-based metal catalysts is critical for the development toward practical applications. However, the scarcity of real-space imaging of zeolite-based low-atomic-number (LAN) metal materials due to the electron-beam sensitivity of zeolites has led to continuous debates regarding the exact LAN metal configurations. Here, a low-damage high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging technique is employed for direct visualization and determination of LAN metal (Cu) species in ZSM-5 zeolite frameworks. The structures of the Cu species are revealed based on the microscopy evidence and also proved by the complementary spectroscopy results. The correlation between the characteristic Cu size in Cu/ZSM-5 catalysts and their direct oxidation of methane to methanol reaction properties is unveiled. As a result, the mono-Cu species stably anchored by Al pairs inside the zeolite channels are identified as the key structure for higher C1 oxygenates yield and methanol selectivity for direct oxidation of methane. Meanwhile, the local topological flexibility of the rigid zeolite frameworks induced by the Cu agglomeration in the channels is also revealed. This work exemplifies the combination of microscopy imaging and spectroscopy characterization serves as a complete arsenal for revealing structure-property relationships of the supported metal-zeolite catalysts.

19.
World J Surg Oncol ; 21(1): 83, 2023 Mar 07.
Artículo en Inglés | MEDLINE | ID: mdl-36882854

RESUMEN

PURPOSE: The study aimed to construct a predictive model for clinically significant prostate cancer (csPCa) and investigate its clinical efficacy to reduce unnecessary prostate biopsies. METHODS: A total of 847 patients from institute 1 were included in cohort 1 for model development. Cohort 2 included a total of 208 patients from institute 2 for external validation of the model. The data obtained were used for retrospective analysis. The results of magnetic resonance imaging were obtained using Prostate Imaging Reporting and Data System version 2.1 (PI-RADS v2.1). Univariate and multivariate analyses were performed to determine significant predictors of csPCa. The diagnostic performances were compared using the receiver operating characteristic (ROC) curve and decision curve analyses. RESULTS: Age, prostate-specific antigen density (PSAD), and PI-RADS v2.1 scores were used as predictors of the model. In the development cohort, the areas under the ROC curve (AUC) for csPCa about age, PSAD, PI-RADS v2.1 scores, and the model were 0.675, 0.823, 0.875, and 0.938, respectively. In the external validation cohort, the AUC values predicted by the four were 0.619, 0.811, 0.863, and 0.914, respectively. Decision curve analysis revealed that the clear net benefit of the model was higher than PI-RADS v2.1 scores and PSAD. The model significantly reduced unnecessary prostate biopsies within the risk threshold of > 10%. CONCLUSIONS: In both internal and external validation, the model constructed by combining age, PSAD, and PI-RADS v2.1 scores exhibited excellent clinical efficacy and can be utilized to reduce unnecessary prostate biopsies.


Asunto(s)
Imágenes de Resonancia Magnética Multiparamétrica , Neoplasias de la Próstata , Masculino , Humanos , Neoplasias de la Próstata/diagnóstico por imagen , Imagen por Resonancia Magnética , Antígeno Prostático Específico , Estudios Retrospectivos
20.
BMC Urol ; 23(1): 47, 2023 Mar 29.
Artículo en Inglés | MEDLINE | ID: mdl-36991447

RESUMEN

BACKGROUND: Dealing with the giant pheochromocytomas (maximum diameter ≥ 6 cm) has long been a tough challenge for urologists. We introduced a new retroperitoneoscopic adrenalectomy method modified with renal-rotation techniques to treat giant pheochromocytomas. METHODS: 28 diagnosed patients were prospectively recruited as the intervention group. Meanwhile, by referring to the historical records in our database, matched patients who had undergone routine retroperitoneoscopic adrenalectomy (RA), transperitoneal laparoscopic adrenalectomy (TA), or open adrenalectomy (OA) for giant pheochromocytomas were selected as controls. Perioperative and follow-up data were collected for comparative assessment. RESULTS: Among all the groups, the intervention group had the minimal bleeding volume (28.93 ± 25.94 ml, p < 0.05), the least intraoperative blood pressure variation (59.11 ± 25.68 mmHg, p < 0.05), the shortest operation time (115.32 ± 30.69 min, p < 0.05), the lowest postoperative ICU admission rates (7.14%, p < 0.05), and shortest drainage time length (2.57 ± 0.50 days, p < 0.05). Besides, compared with TA and OA groups, intervention group was also characterized by lower pain scores (3.21 ± 0.63, p < 0.05), less postoperative complications (p < 0.05), earlier diet initiation time (1.32 ± 0.48 postoperative days, p < 0.05) and ambulation time (2.68 ± 0.48 postoperative days, p < 0.05). Follow-up blood pressure and metanephrine and normetanephrine levels in all intervention group patients remained normal. CONCLUSION: Compared with RA, TA, and OA, retroperitoneoscopic adrenalectomy with renal-rotation techniques is a more feasible, efficient, and secure surgical treatment for giant pheochromocytomas. TRIAL REGISTRATION: This study has been prospectively registered on the Chinese Clinical Trial Registry website (ChiCTR2200059953, date of first registration: 14/05/2022).


Asunto(s)
Neoplasias de las Glándulas Suprarrenales , Laparoscopía , Feocromocitoma , Humanos , Neoplasias de las Glándulas Suprarrenales/cirugía , Adrenalectomía/métodos , Laparoscopía/métodos , Feocromocitoma/cirugía , Complicaciones Posoperatorias/cirugía , Estudios Retrospectivos
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