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1.
Anal Chem ; 96(11): 4479-4486, 2024 Mar 19.
Artículo en Inglés | MEDLINE | ID: mdl-38454359

RESUMEN

Metal-organic gels (MOGs) are a new type of intelligent soft material, which are bridged by metal ions and organic ligands through noncovalent interactions. In this paper, we prepared highly stable P-MOGs, using the classical organic electrochemiluminescence (ECL) luminescence meso-tetra(4-carboxyphenyl)porphine as the organic ligand and Fe3+ as the metal ion. Surprisingly, P-MOGs can stably output ECL signals at a low potential. We introduced P-MOGs into the ECL resonance energy transfer strategy (ECL-RET) and constructed a quenched ECL immunosensor for the detection of the SARS-CoV-2 nucleocapsid protein (SARS-CoV-2-N). In the ECL-RET system, P-MOGs were used as energy donors, and Au@Cu2O@Fe3O4 were selected as energy acceptors. The ultraviolet-visible spectrum of Au@Cu2O@Fe3O4 partially overlaps with the ECL spectrum of P-MOGs, which can effectively touch off the ECL-RET behavior between the donors and receptors. Under the ideal experimental situation, the linear detection range of the SARS-CoV-2-N concentration was 10 fg/mL to 100 ng/mL, and the limit of detection was 1.5 fg/mL. This work has broad application prospects for porphyrin-MOGs in ECL sensing.


Asunto(s)
Técnicas Biosensibles , COVID-19 , Nanopartículas del Metal , Humanos , Mediciones Luminiscentes , SARS-CoV-2 , Técnicas Electroquímicas , Límite de Detección , Inmunoensayo , COVID-19/diagnóstico , Geles , Proteínas de la Nucleocápside
2.
Anal Chem ; 96(21): 8390-8398, 2024 May 28.
Artículo en Inglés | MEDLINE | ID: mdl-38716680

RESUMEN

In this work, a microfluidic immunosensor chip was developed by incorporating microfluidic technology with electrochemiluminescence (ECL) for sensitive detection of human epidermal growth factor receptor-2 (HER2). The immunosensor chip can achieve robust reproducibility in mass production by integrating multiple detection units in a series. Notably, nanoscale materials can be better adapted to microfluidic systems, greatly enhancing the accuracy of the immunosensor chip. Ag@Au NCs closed by glutathione (GSH) were introduced in the ECL microfluidic immunosensor system with excellent and stable ECL performance. The synthesized CeO2-Au was applied as a coreaction promoter in the ECL signal amplification system, which made the result of HER2 detection more reliable. In addition, the designed microfluidic immunosensor chip integrated the biosensing system into a microchip, realizing rapid and accurate detection of HER2 by its high throughput and low usage. The developed short peptide ligand NARKFKG (NRK) achieved an effective connection between the antibody and nanocarrier for improving the detection efficiency of the sensor. The immunosensor chip had better storage stability and sensitivity than traditional detection methods, with a wide detection range from 10 fg·mL-1 to 100 ng·mL-1 and a low detection limit (LOD) of 3.29 fg·mL-1. In general, a microfluidic immunosensor platform was successfully constructed, providing a new idea for breast cancer (BC) clinical detection.


Asunto(s)
Técnicas Biosensibles , Técnicas Electroquímicas , Electrodos , Oro , Mediciones Luminiscentes , Nanopartículas del Metal , Receptor ErbB-2 , Plata , Humanos , Receptor ErbB-2/análisis , Receptor ErbB-2/inmunología , Nanopartículas del Metal/química , Técnicas Electroquímicas/métodos , Plata/química , Técnicas Biosensibles/métodos , Oro/química , Inmunoensayo/métodos , Técnicas Analíticas Microfluídicas/instrumentación , Límite de Detección , Cerio/química
3.
Anal Chem ; 96(12): 4969-4977, 2024 Mar 26.
Artículo en Inglés | MEDLINE | ID: mdl-38486396

RESUMEN

Metal nanoclusters (Me NCs) have become a research hotspot in the field of electrochemiluminescence (ECL) sensing analysis. This is primarily attributed to their excellent luminescent properties and biocompatibility along with their easy synthesis and labeling characteristics. At present, the application of Me NCs in ECL mainly focuses on precious metals, whose high cost, to some extent, limits their widespread application. In this work, Cu NCs with cathode ECL emissions in persulfate (S2O82-) were prepared as signal probes using glutathione as ligands, which exhibited stable luminescence signals and high ECL efficiency. At the same time, CaMnO3 was introduced as a co-reaction promoter to increase the ECL responses of Cu NCs, thereby further expanding their application potential in biochemical analysis. Specifically, the reversible conversion of Mn3+/Mn4+ greatly promoted the generation of sulfate radicals (SO4•-), providing a guarantee for improving the luminescence signals of Cu NCs. Furthermore, a short peptide (NARKFYKGC) was introduced to enable the fixation of antibodies to specific targets, preventing the occupancy of antigen-binding sites (Fab fragments). Therefore, the sensitivity of the biosensor could be significantly enhanced by releasing additional Fab fragments. Considering the approaches discussed above, the constructed biosensor could achieve sensitive detection of CD44 over a broad range (10 fg/mL-100 ng/mL), with an ultralow detection limit of 3.55 fg/mL (S/N = 3), which had valuable implications for the application of nonprecious Me NCs in biosensing analysis.


Asunto(s)
Técnicas Biosensibles , Nanopartículas del Metal , Cobre/química , Mediciones Luminiscentes , Luminiscencia , Fragmentos Fab de Inmunoglobulinas , Técnicas Electroquímicas , Límite de Detección , Nanopartículas del Metal/química
4.
Anal Chem ; 96(4): 1678-1685, 2024 01 30.
Artículo en Inglés | MEDLINE | ID: mdl-38215346

RESUMEN

In this paper, an electrochemiluminescence (ECL) immunosensor for ultrasensitive detection of CA19-9 was constructed using ternary compound CdSSe nanoparticles as ECL emitter. The immunosensor employs Cu2S and gold-doped diindium trioxide (Au-In2O3) nanocubes as coreaction accelerators to achieve a double-amplification strategy. In general, a hexagonal maple leaf-shaped Cu2S with a large surface area was selected as the template, and the in situ growth of CdSSe on its surface was achieved using a hydrothermal method. The presence of Cu2S not only inhibited the aggregation of CdSSe nanoparticles to reduce their surface energy but also acted as an ECL cathode coreaction promoter, facilitating the generation of SO4•-. Consequently, the ECL intensity of CdSSe was significantly enhanced, and the reduction potential was significantly lower. In addition, the template method was employed to synthesize Au-In2O3 nanocubes, which offers the advantage of directly connecting materials with antibodies, resulting in a more stable construction of the immunosensor. Furthermore, In2O3 serves as a coreaction promoter, enabling the amplification strategy for ECL intensity of CdSSe, thus contributing to the enhanced sensitivity and performance of the immunosensor. The constructed immunosensor exhibited a wide linear range (100 µU mL-1 to 100 U mL-1) and a low detection limit of 80 µU mL-1, demonstrating its high potential and practical value for sensitive detection of CA19-9.


Asunto(s)
Técnicas Biosensibles , Nanopartículas del Metal , Antígeno CA-19-9 , Inmunoensayo/métodos , Técnicas Biosensibles/métodos , Pruebas Inmunológicas , Semiconductores , Mediciones Luminiscentes/métodos , Técnicas Electroquímicas/métodos , Límite de Detección , Oro
5.
Anal Chem ; 96(10): 4067-4075, 2024 Mar 12.
Artículo en Inglés | MEDLINE | ID: mdl-38419337

RESUMEN

In this work, an electrochemiluminescence (ECL) quenching system using multimetal-organic frameworks (MMOFs) was proposed for the sensitive and specific detection of heart-type fatty acid-binding protein (H-FABP), a marker of acute myocardial infarction (AMI). Bimetallic MOFs containing Ru and Mn as metal centers were synthesized via a one-step hydrothermal method, yielding RuMn MOFs as the ECL emitter. The RuMn MOFs not only possessed the strong ECL performance of Ru(bpy)32+ but also maintained high porosity and original metal active sites characteristic of MOFs. Moreover, under the synergistic effect of MOFs and Ru(bpy)32+, RuMn MOFs have more efficient and stable ECL emission. The trimetal-based MOF (FePtRh MOF) was used as the ECL quencher because of the electron transfer between FePtRh MOFs and RuMn MOFs. In addition, active intramolecular electron transfer from Pt to Fe or Rh atoms also occurred in FePtRh MOFs, which could promote intermolecular electron transfer and improve electron transfer efficiency to enhance the quenching efficiency. The proposed ECL immunosensor demonstrated a wide dynamic range and a low detection limit of 0.01-100 ng mL-1 and 6.8 pg mL-1, respectively, under optimal conditions. The ECL quenching system also presented good specificity, stability, and reproducibility. Therefore, an alternative method for H-FABP detection in clinical diagnosis was provided by this study, highlighting the potential of MMOFs in advancing ECL technology.


Asunto(s)
Técnicas Biosensibles , Nanopartículas del Metal , Estructuras Metalorgánicas , Estructuras Metalorgánicas/química , Inmunoensayo/métodos , Técnicas Biosensibles/métodos , Reproducibilidad de los Resultados , Proteína 3 de Unión a Ácidos Grasos , Mediciones Luminiscentes/métodos , Metales , Técnicas Electroquímicas/métodos , Límite de Detección , Nanopartículas del Metal/química
6.
Cardiovasc Diabetol ; 23(1): 274, 2024 Jul 24.
Artículo en Inglés | MEDLINE | ID: mdl-39049097

RESUMEN

Diabetes mellitus (DM) is a metabolic disease that heightens the risks of many vascular complications, including peripheral arterial disease (PAD). Various types of cells, including but not limited to endothelial cells (ECs), vascular smooth muscle cells (VSMCs), and macrophages (MΦs), play crucial roles in the pathogenesis of DM-PAD. Long non-coding RNAs (lncRNAs) are epigenetic regulators that play important roles in cellular function, and their dysregulation in DM can contribute to PAD. This review focuses on the developing field of lncRNAs and their emerging roles in linking DM and PAD. We review the studies investigating the role of lncRNAs in crucial cellular processes contributing to DM-PAD, including those in ECs, VSMCs, and MΦ. By examining the intricate molecular landscape governed by lncRNAs in these relevant cell types, we hope to shed light on the roles of lncRNAs in EC dysfunction, inflammatory responses, and vascular remodeling contributing to DM-PAD. Additionally, we provide an overview of the research approach and methodologies, from identifying disease-relevant lncRNAs to characterizing their molecular and cellular functions in the context of DM-PAD. We also discuss the potential of leveraging lncRNAs in the diagnosis and therapeutics for DM-PAD. Collectively, this review provides a summary of lncRNA-regulated cell functions contributing to DM-PAD and highlights the translational potential of leveraging lncRNA biology to tackle this increasingly prevalent and complex disease.


Asunto(s)
Células Endoteliales , Macrófagos , Miocitos del Músculo Liso , Enfermedad Arterial Periférica , ARN Largo no Codificante , Humanos , ARN Largo no Codificante/genética , ARN Largo no Codificante/metabolismo , Enfermedad Arterial Periférica/genética , Enfermedad Arterial Periférica/metabolismo , Enfermedad Arterial Periférica/fisiopatología , Animales , Miocitos del Músculo Liso/metabolismo , Miocitos del Músculo Liso/patología , Células Endoteliales/metabolismo , Células Endoteliales/patología , Macrófagos/metabolismo , Músculo Liso Vascular/metabolismo , Músculo Liso Vascular/patología , Regulación de la Expresión Génica , Angiopatías Diabéticas/genética , Angiopatías Diabéticas/metabolismo , Angiopatías Diabéticas/fisiopatología , Diabetes Mellitus/genética , Diabetes Mellitus/metabolismo , Diabetes Mellitus/diagnóstico , Transducción de Señal , Remodelación Vascular/genética , Epigénesis Genética
7.
Mikrochim Acta ; 191(8): 480, 2024 Jul 24.
Artículo en Inglés | MEDLINE | ID: mdl-39046571

RESUMEN

An original molecular imprinting photoelectrochemical (PEC) sensor for sarcosine detection based on stable lead-free inorganic halide double perovskite Cs2AgBiBr6 is proposed. Cs2AgBiBr6 as a lead-free halide perovskite material possesses several positive optoelectronic properties for PEC analysis, such as long-lived component to the charge-carrier lifetime, and strong absorption of visible light. At the same time, two-dimensional materials also offer excellent electronic and mechanical properties; thus, Bi2O2S was used and combined with Cs2AgBiBr6 to provide a stable and large photocurrent, which also benefits from the  stability of perovskite Cs2AgBiBr6. Based on this novel PEC assay, the detection range for sarcosine was between 0.005 and 5000 ng/mL with a low detection limit of 0.002 ng/mL. This work also improved the adhibition of metal halide perovskite in analytical chemistry field, providing a novel way for other small molecule detection.

8.
Mikrochim Acta ; 191(2): 89, 2024 Jan 11.
Artículo en Inglés | MEDLINE | ID: mdl-38206415

RESUMEN

The interaction between the sensitive interfaces of photoelectrochemical (PEC) semiconductor nanomaterials and microscopic matter creates endless potential for the efficient detection of endocrine disruptor. This work presents the development of a high-efficiency PEC aptasensor for bisphenol A (BPA) monitoring based on Cu3BiS3 sensitized CuV2O6 nanocomposites with exceptional visible-light PEC activity. We implemented the integration of Cu3BiS3 nanosheet photosensitizer to sensitize the CuV2O6 nanowire structure that was synthesized utilizing a facile hydrothermal approach. The band gap alignment between Cu3BiS3 and CuV2O6 facilitated enduring PEC response yielding an efficient interfacial structure. The surface of the CuV2O6/Cu3BiS3 electrode was modified with BPA aptamer, enabling specific binding with BPA and precise quantification of its content. The developed aptamer sensors possess a wide detection range of 5.00 × 10-1 to 5.00 × 104 ng/mL, and a low detection limit of 1.60 × 10-1 ng/mL (at S/N = 3). After undergoing 20 testing cycles and enduring long-term storage, the sensor maintained its stability and showcased excellent repeatability and reproducibility. This study presents a promising methodology for the detection of BPA in environmental settings.

9.
J Integr Plant Biol ; 66(6): 1052-1067, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38501444

RESUMEN

ACYL-CoA-BINDING PROTEINs (ACBPs) play crucial regulatory roles during plant response to hypoxia, but their molecular mechanisms remain poorly understood. Our study reveals that ACBP4 serves as a positive regulator of the plant hypoxia response by interacting with WRKY70, influencing its nucleocytoplasmic shuttling in Arabidopsis thaliana. Furthermore, we demonstrate the direct binding of WRKY70 to the ACBP4 promoter, resulting in its upregulation and suggesting a positive feedback loop. Additionally, we pinpointed a phosphorylation site at Ser638 of ACBP4, which enhances submergence tolerance, potentially by facilitating WRKY70's nuclear shuttling. Surprisingly, a natural variation in this phosphorylation site of ACBP4 allowed A. thaliana to adapt to humid conditions during its historical demographic expansion. We further observed that both phosphorylated ACBP4 and oleoyl-CoA can impede the interaction between ACBP4 and WRKY70, thus promoting WRKY70's nuclear translocation. Finally, we found that the overexpression of orthologous BnaC5.ACBP4 and BnaA7.WRKY70 in Brassica napus increases submergence tolerance, indicating their functional similarity across genera. In summary, our research not only sheds light on the functional significance of the ACBP4 gene in hypoxia response, but also underscores its potential utility in breeding flooding-tolerant oilseed rape varieties.


Asunto(s)
Proteínas de Arabidopsis , Arabidopsis , Regulación de la Expresión Génica de las Plantas , Factores de Transcripción , Arabidopsis/genética , Arabidopsis/metabolismo , Proteínas de Arabidopsis/metabolismo , Proteínas de Arabidopsis/genética , Proteínas de Unión al ADN , Fosforilación , Regiones Promotoras Genéticas/genética , Factores de Transcripción/metabolismo , Factores de Transcripción/genética
10.
Anal Chem ; 95(38): 14317-14323, 2023 09 26.
Artículo en Inglés | MEDLINE | ID: mdl-37695886

RESUMEN

Inspired by the signal accumulation of circular DNA strand displacement reactions (CD-SDRs) and the in situ generation of silver nanoclusters (AgNCs) from signature template sequences, a dual-signal integrated aptasensor was designed for microcystin-LR (MC-LR) detection. The aptamer was programmed to be included in an enzyme-free CD-SDR, which utilized MC-LR as the primer and outputted the H1/H2 dsDNA in a continuous manner according to the ideal state. Ingeniously, H1/H2 dsDNA was enriched with signature template sequences, allowing in situ generation of AgNCs signal probes. To enhance the signal amplification performance, co-reaction acceleration strategies and CRISPR-Cas12a nucleases were invoked. The H1/H2 dsDNA could trigger the incidental cleavage performance of CRISPR-Cas12a nucleases: cis-cleavage reduced signature template sequences for the synthetic AgNCs, while trans-cleavage enabled fluorescence (FL) analysis. Meanwhile, AuPtAg was selected as the substrate material to facilitate the S2O82- reduction reaction for enhancing the electrochemiluminescence (ECL) basal signals. ECL and FL detection do not interfere with each other and have improved accuracy and sensitivity, with limits of detection of 0.011 and 0.023 pmol/L, respectively. This widens the path for designing dual-mode sensing strategies for signal amplification.


Asunto(s)
Aptámeros de Nucleótidos , Técnicas Biosensibles , Nanopartículas del Metal , ADN Circular , Plata , ADN/genética , Aptámeros de Nucleótidos/genética , Límite de Detección
11.
Anal Chem ; 95(13): 5695-5701, 2023 04 04.
Artículo en Inglés | MEDLINE | ID: mdl-36952259

RESUMEN

The controlled release strategy can make the constructed sensor have the function of self-on/off, which has an obvious effect on improving the sensitivity in immunoassays. Metal organic gels (MOGs) are the most noteworthy. They are materials with ultrahigh surface area, highly dispersed atomical metal sites, and well-defined porosity and can be used as an efficient luminophore to cause the developed sensor to have good hydrophilicity and adjustability, thus further improving the detection sensitivity. In this work, a novel on/off electrochemiluminescence (ECL) gel aptasensor was constructed using the Cys-[Ru(dcbpy)3]2+ gel as a luminophore, ZnS quantum dots (QDs) as quenchers, and aminated mesoporous silica nanocontainers (SiO2-NH2) as carriers of controlled release for prostate specific antigen (PSA) detection. Specifically, the ssDNA and PSA aptamer made up clamp-like molecules to block holes of the SiO2-NH2 after encapsulating the quencher ZnS QDs. Because of the specific binding between the PSA antigen and aptamer, the clamp-like molecules of ssDNA and the PSA aptamer were disassembled. Finally, the release of ZnS QDs was triggered, thereby realizing a self-off mode of the ECL signals under a co-reactant-free environment by ECL resonance energy transfer (ECL-RET) between the Cys-[Ru(dcbpy)3]2+ and ZnS QDs. In addition, the quenching mechanism was confirmed by molecular orbitals from the theoretical calculation level. The detection limit of the gel aptasensor for PSA was as low as 1.01 fg/mL, showing excellent sensitivity and accuracy. These strategies provided a feasible idea for PSA and even other tumor marker immunoassays.


Asunto(s)
Técnicas Biosensibles , Nanopartículas del Metal , Puntos Cuánticos , Humanos , Masculino , Antígeno Prostático Específico , Dióxido de Silicio/química , Preparaciones de Acción Retardada , Mediciones Luminiscentes , Puntos Cuánticos/química , Oligonucleótidos , Técnicas Electroquímicas , Nanopartículas del Metal/química
12.
Anal Chem ; 95(45): 16761-16770, 2023 Nov 14.
Artículo en Inglés | MEDLINE | ID: mdl-37905934

RESUMEN

Copper nanoclusters (Cu NCs) are highly promising nanomaterials in the field of electrochemiluminescence (ECL). Nevertheless, their limited stability and efficiency have impeded their practical applications. Here, we introduced a novel supramolecular anchoring strategy resulting in the creation of exceptionally stable Cu NCs (CET-Cu NCs) with remarkable ECL properties. Specifically, CET-Cu NCs exhibited a relative ECL efficiency (ΦECL) of 62% based on the annihilation ECL efficiency of [Ru(bpy)3]2+ (100%), with tripropylamine employed as a coreactant. Moreover, CET-Cu NCs can generate ECL emission through multiple different paths, which enables them to serve as signal probes in a wider range of testing scenarios, thereby enhancing the reliability and robustness of sensing and analytical systems. To demonstrate the practical utility, CET-Cu NCs were selected as an ECL signal probe for a sensing platform that facilitated ultrasensitive detection of progesterone via oriented immobilization technology and antibody/aptamer sandwich assays. This study surmounted the barriers to the practical application of Cu NCs through the implementation of a supramolecular anchoring strategy, thereby providing enhanced utility of Cu NCs in ECL sensing and analysis.

13.
Biochem Biophys Res Commun ; 639: 134-141, 2023 01 08.
Artículo en Inglés | MEDLINE | ID: mdl-36493556

RESUMEN

In cyanobacteria and algae (but not plants), flavodoxin (Fld) replaces ferredoxin (Fd) under stress conditions to transfer electrons from photosystem I (PSI) to ferredoxin-NADP+ reductase (FNR) during photosynthesis. Fld constitutes a small electron carrier noncovalently bound to flavin mononucleotide (FMN), and also an ideal model for revealing the protein/flavin-binding mechanism because of its relative simplicity compared to other flavoproteins. Here, we report two crystal structures of apo-Fld from Synechococcus sp. PCC 7942, one dimeric structure of 2.09 Å and one monomeric structure of 1.84 Å resolution. Analytical ultracentrifugation showed that in solution, apo-Fld exists both as monomers and dimers. Our dimer structure contains two ligand-binding pockets separated by a distance of 45 Å, much longer than the previous structures of FMN-bound dimers. These results suggested a potential dimer-monomer transition mechanism of cyanobacterial apo-Fld. We further propose that the dimer represents the "standby" state to stabilize itself, while the monomer constitutes the "ready" state to bind FMN. Furthermore, we generated a new docking model of cyanobacterial Fld-FNR complex based on the recently reported cryo-EM structures, and mapped the special interactions between Fld and FNR in detail.


Asunto(s)
Anabaena , Cianobacterias , Flavodoxina/química , Flavodoxina/metabolismo , Ferredoxinas/metabolismo , Anabaena/metabolismo , Flavoproteínas , Ferredoxina-NADP Reductasa/química , Cianobacterias/metabolismo , Oxidación-Reducción
14.
Breast Cancer Res Treat ; 199(3): 435-444, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-37071267

RESUMEN

PURPOSE: This study aimed to correlate clinicopathological parameters with survival outcomes in a cohort of patients diagnosed with malignant phyllodes tumors (MPTs). We also analyzed the malignancy grade of MPTs and investigated the prognostic significance of the malignancy grading system. METHODS: Clinicopathological parameters, malignancy grades, and clinical follow-up data of 188 women diagnosed with MPTs in a single-institution were analyzed. MPTs of the breast were grouped according to stromal atypia, stromal overgrowth, mitotic count, tumor differentiation, and necrosis. A Fleiss' kappa statistic was calculated to test the agreement between the pathologists for the grading of MPTs. Disease-free survival (DFS), distant metastasis-free survival (DMFS) and overall survival (OS) were estimated using the Kaplan-Meier method and compared between groups using the log-rank test. Cox regression was carried out to identify factors predictive of locoregional recurrence (LRR), distant metastasis (DM) and death. RESULTS: A total of 188 MPTs were classified according to the malignancy grading system: 88 (46.8%) as low grade, 77 (41%) as an intermediate grade, and 23 (12.2%) as high grade. Excellent agreement between pathologists for the grading of MPTs (Fleiss' kappa 0.807). In our study population, the occurrence of DM and death were associated with the malignancy grade of MPTs (P < 0.001). Based on the DFS curves, the presence of heterologous elements (P = 0.025) and younger age (P = 0.014) were independent prognostic indicators. Additionally, the malignancy grade retained independent prognostic significance for predicting DMFS and OS (P < 0.001 and P = 0.009). CONCLUSIONS: Higher malignancy grade, presence of heterologous elements, younger age, larger tumor size, and recent rapid tumor growth are poor prognostic factors for MPTs of the breast. The malignancy grading system may be generalized in the future.


Asunto(s)
Neoplasias de la Mama , Tumor Filoide , Humanos , Femenino , Tumor Filoide/patología , Recurrencia Local de Neoplasia , Pronóstico , Mama/patología , Clasificación del Tumor , Estudios Retrospectivos
15.
Breast Cancer Res Treat ; 199(1): 25-33, 2023 May.
Artículo en Inglés | MEDLINE | ID: mdl-36930346

RESUMEN

PURPOSE: Multifocal or multicentric (MFMC) breast cancer is mainly focused on breast cancer patients with unknown BRCA status, the incidence and clinical relevance of MFMC disease in BRCA1/2 carriers is less explored to date. Our study was to investigate the incidence of MFMC disease in BRCA1/2 carriers and whether MFMC disease influences local recurrence and clinical outcomes. METHODS: In this retrospective study, 479 breast cancer patients with BRCA1/2 variants and 1437 age-matched noncarriers were enrolled and patients received either breast-conserving therapy (BCT) or mastectomy with or without radiotherapy. RESULTS: The rates of MFMC disease in BRCA1 and BRCA2 carriers, and noncarriers were 33.0% (61 of 185), 37.4% (110 of 294), and 31.2% (449 of 1437), respectively. MFMC disease in BRCA2 carriers was significantly higher than that in noncarriers (P = 0.039). After a median follow-up of 8.1 years, among patients treated with BCT, BRCA2 carriers with MFMC disease experienced a significantly higher rate of ipsilateral breast tumor recurrence (IBTR) than those with unifocal disease (16.7% vs 4.1%, P = 0.044). Moreover, BRCA2 carriers with MFMC disease had a significantly worse RFS (unadjusted hazard ratio [HR], 3.65 [95% CI 1.40-9.52]; P = 0.008), DRFS (unadjusted HR, 3.07 [95% CI 1.07-8.80]; P = 0.037), and OS (unadjusted HR, 4.96 [95% CI 1.18-20.02]; P = 0.029) than those with unifocal disease when treated with BCT. CONCLUSION: MFMC breast cancer is more common in BRCA2 carriers, and BRCA2 carriers with MFMC disease treated with BCT exhibit a higher rate of IBTR and may have a poor survival.


Asunto(s)
Neoplasias de la Mama , Neoplasias Mamarias Animales , Humanos , Animales , Femenino , Neoplasias de la Mama/epidemiología , Neoplasias de la Mama/genética , Neoplasias de la Mama/tratamiento farmacológico , Proteína BRCA1/genética , Mastectomía , Estudios Retrospectivos , Proteína BRCA2/genética , Recurrencia Local de Neoplasia/epidemiología , Recurrencia Local de Neoplasia/genética , Recurrencia Local de Neoplasia/cirugía , Neoplasias Mamarias Animales/cirugía , Mutación
16.
Opt Express ; 31(10): 17017-17026, 2023 May 08.
Artículo en Inglés | MEDLINE | ID: mdl-37157767

RESUMEN

The determination of electron spin polarization by controlling the atomic population distributions of ground states has been proposed. The polarization could be deduced by generating different population symmetries by polarized lights. The polarization of the atomic ensembles was decoded from optical depth in different transmissions of linearly and elliptic polarized lights. The feasibility of the method has been validated theoretically and experimentally. Moreover, the influences of relaxation and magnetic fields are analyzed. The transparency induced by high pump rates are investigated experimentally, and the influences of ellipticity of lights are also discussed. The in-situ polarization measurement was achieved without changing optical path of atomic magnetometer, which provides a new way to interrogate the performance of atomic magnetometer and in-situ monitoring the hyperpolarization of nuclear spins for atomic co-magnetometer.

17.
Chemphyschem ; 24(20): e202300536, 2023 Oct 17.
Artículo en Inglés | MEDLINE | ID: mdl-37525230

RESUMEN

The electrocatalytic nitrate reduction reaction (NO3 - RR) enables the reduction of nitrate to ammonium ions under ambient conditions. It was considered as an alternative reaction for the production of ammonia (NH3 ) in recent years. In this paper, we report that the Fe doping CoS2 nanoarrays can effectively catalyze the formation of NH3 from nitrate (NO3 - ) under ambient conditions. This is mainly due to the increase of the NO3 - reaction active site by Fe doping and the porous nanostructure of the catalyst, which greatly improves the catalytic activity. Specifically, at -0.9 V vs. RHE, the NH3 yield rate (RNH3 ) of Fe-CoS2 /CC is 17.8×10-2  mmol h-1 cm-2 with Faraday Efficiency (FE) of 88.93 %. Besides, such catalyst shows good durability and catalytic stability, which provides the possibility for the future application of electrocatalytic NH3 production.

18.
J Org Chem ; 88(7): 4442-4451, 2023 Apr 07.
Artículo en Inglés | MEDLINE | ID: mdl-36896970

RESUMEN

A robust palladium-catalyzed decarbonylative alkynylation of aryl anhydrides is reported. The catalytic system of Pd(OAc)2/XantPhos and DMAP as a nucleophilic additive has been identified as effective promoters for decarbonylative Sonogashira alkynylation. Recently, activated esters, amides, and carboxylic acids were applied as electrophiles in transition-metal-catalyzed decarbonylative alkynylation. The present process expands this reactivity to readily available aryl anhydrides as electrophilic reagents for decarbonylative alkynylation. It is worth noting that the reactivity of aryl anhydrides is higher than that of esters, amides, and carboxylic acids in decarbonylative alkynylation. Broad substrate scope and excellent functional group tolerance are presented, demonstrating that aryl anhydrides may serve as a general and practical class of electrophiles to achieve the synthesis of internal alkynes.

19.
Molecules ; 28(6)2023 Mar 13.
Artículo en Inglés | MEDLINE | ID: mdl-36985559

RESUMEN

Rapid RAFT polymerization can significantly improve production efficiency of PAM with designed molecular structure. This study shows that ideal Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization of acrylamide is achieved in dimethyl sulfoxide (DMSO) solution at 70 °C. The key to success is the appropriate choice of both a suitable RAFT chain transfer agent (CTA) and initiating species. It is illustrated that dodecyl trithiodimethyl propionic acid (DMPA) is a suitable trithiocarbonate RAFT CTA and is synthesized more easily than other CTAs. Compared to other RAFT processes of polymers, the reaction system shortens reaction time, enhances conversion, and bears all the characteristics of a controlled radical polymerization. The calculation result shows that high concentrations can reduce high conversions, accelerate the reaction rate, and widen molecular weight distributions slightly. This work proposes an excellent approach for rapid synthesis of PAMs with a restricted molecular weight distribution.

20.
Analyst ; 147(21): 4768-4776, 2022 Oct 24.
Artículo en Inglés | MEDLINE | ID: mdl-36149312

RESUMEN

Cardiac troponin I (cTnI) is one of the structural subunits of cardiac troponin complexes and a significant biomarker of acute myocardial infarction (AMI). Therefore, a sensitive detection of cTnI in the early stages is of great significance. Here, a sensitive sandwiched electrochemiluminescence (ECL) immunosensor was built for the detection of cTnI, where molybdenum disulfide@cuprous oxide-silver nanoparticles (MoS2@Cu2O-Ag) immobilized cTnI the capture antibody (Ab1), and cerium-doped zinc oxide@nitrogen-doped graphene quantum dots (Ce:ZnO@NGQDs) loaded the signal antibody (Ab2). The MoS2@Cu2O-Ag nanoparticles not only indicated excellent electroconductivity and biocompatibility but also provided a large specific surface. Ce:ZnO as a co-reaction accelerator can convert the Ce4+ ↔ Ce3+ reaction and might increase the rate of electron exchange to accomplish signal enhancement. Under optimum conditions, the sensor possessed a wide linear range from 10 pg mL-1 to 100 ng mL-1, and the LOD was 2.90 fg mL-1 (S/N = 3). In addition, the sensor plays a good role in serum detection, indicating that it has potential for application in the detection of biomolecules.


Asunto(s)
Técnicas Biosensibles , Cerio , Grafito , Nanopartículas del Metal , Óxido de Zinc , Técnicas Electroquímicas , Electrodos , Grafito/química , Inmunoensayo , Límite de Detección , Mediciones Luminiscentes , Nanopartículas del Metal/química , Molibdeno , Nitrógeno/química , Plata/química , Troponina I , Óxido de Zinc/química , Puntos Cuánticos
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