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1.
J Am Chem Soc ; 146(6): 4144-4152, 2024 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-38315569

RESUMO

Circularly polarized light-emitting diodes (CP-LEDs) are critical for next-generation optical technologies, ranging from holography to quantum information processing. Currently deployed chiral luminescent materials, with their intricate synthesis and processing and limited efficiency, are the main bottleneck for CP-LEDs. Chiral metal nanoclusters (MNCs) are potential CP-LED materials, given their ease of synthesis and processability as well as diverse structures and excited states. However, their films are usually plagued by inferior electronic quality and aggregation-caused photoluminescence quenching, necessitating their incorporation into host materials; without such a scheme, MNC-based LEDs exhibit external quantum efficiencies (EQEs) < 10%. Herein, we achieve an efficiency leap for both CP-LEDs and cluster-based LEDs by using novel chiral MNCs with aggregation-induced emission enhancement. CP-LEDs using enantiopure MNC films attain EQEs of up to 23.5%. Furthermore, by incorporating host materials, the devices yield record EQEs of up to 36.5% for both CP-LEDs and cluster-based LEDs, along with electroluminescence dissymmetry factors (|gEL|) of around 1.0 × 10-3. These findings open a new avenue for advancing chiral light sources for next-generation optoelectronics.

2.
J Am Chem Soc ; 146(23): 16295-16305, 2024 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-38816788

RESUMO

Atomically precise metal nanoclusters (NCs) have become an important class of catalysts due to their catalytic activity, high surface area, and tailored active sites. However, the design and development of bond-forming reaction catalysts based on copper NCs are still in their early stages. Herein, we report the synthesis of an atomically precise copper nanocluster with a planar core and unique shell, [Cu45(TBBT)29(TPP)4(C4H11N)2H14]2+ (Cu45) (TBBT: 4-tert-butylbenzenethiol; TPP: triphenylphosphine), in high yield via a one-pot reduction method. The resulting structurally well-defined Cu45 is a highly efficient catalyst for the hydroboration reaction of alkynes and alkenes. Mechanistic studies show that a single-electron oxidation of the in situ-formed ate complex enables the hydroboration via the formation of boryl-centered radicals under mild conditions. This work demonstrates the promise of tailored copper nanoclusters as catalysts for C-B heteroatom bond-forming reactions. The catalysts are compatible with a wide range of alkynes and alkenes and functional groups for producing hydroborated products.

3.
J Am Chem Soc ; 145(25): 13816-13827, 2023 Jun 28.
Artigo em Inglês | MEDLINE | ID: mdl-37335564

RESUMO

Zero-dimensional (0D) scintillation materials have drawn tremendous attention due to their inherent advantages in the fabrication of flexible high-energy radiation scintillation screens by solution processes. Although considerable progress has been made in the development of 0D scintillators, such as the current leading lead-halide perovskite nanocrystals and quantum dots, challenges still persist, including potential issues with self-absorption, air stability, and eco-friendliness. Here, we present a strategy to overcome those limitations by synthesis and self-assembly of a new class of scintillators based on metal nanoclusters. We demonstrate the gram-scale synthesis of an atomically precise nanocluster with a Cu-Au alloy core exhibiting high phosphorescence quantum yield, aggregation-induced emission enhancement (AIEE) behavior, and intense radioluminescence. By controlling solvent interactions, the AIEE-active nanoclusters were self-assembled into submicron spherical superparticles in solution, which we exploited as a novel building block for flexible particle-deposited scintillation films with high-resolution X-ray imaging performance. This work reveals metal nanoclusters and their self-assembled superstructures as a promising class of scintillators for practical applications in high-energy radiation detection and imaging.

4.
Opt Express ; 31(12): 18931-18938, 2023 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-37381322

RESUMO

Current near-field antenna measurement methods are commonly based on metal probes, with the accuracy limited and hard to be optimized due to the drawbacks they suffered, such as large volume, severe metal reflection/interference and complex circuit signal processing in parameter extracting. In this work, a novel method is proposed based on Rydberg atom in the near-field antenna measurement, which can offer a higher accuracy due to its intrinsic character of traceability to electric field. Replacing the metal probe in near-field measurement system by Rydberg atoms contained in a vapor cell (probe), amplitude- and phase- measurements on a 2.389 GHz signal launched out from a standard gain horn antenna are conducted on a near-field plane. They are transformed to far-field pattern and agree well with simulated results and measured results by using a traditional metal probe method. A high precision in longitudinal phase testing with an error below 1.7% can be achieved.

5.
Opt Express ; 31(22): 36255-36262, 2023 Oct 23.
Artigo em Inglês | MEDLINE | ID: mdl-38017780

RESUMO

Researchers are interested in the sensor based on Rydberg atoms because of its broad testing frequency range and outstanding sensitivity. However, the discrete frequency detection limits its further employment. We expand the frequency range of microwaves using Rydberg atoms under the Zeeman effect. In such a scheme, the magnetic field is employed as a tool to split and modify adjacent Rydberg level intervals to realize tunable frequency measurement over 100 MHz under 0-31.5 Gauss magnetic field. In this frequency range, the microwave has a linear dynamic variation range of 63 dB, and has achieved a sensitivity of 11.72 µV cm-1Hz-1/2 with the minimum detectable field strength of 17.2 µV/cm.. Compared to the no magnetic field scenario, the sensitivity would not decrease. By theoretical analysis, in a strong magnetic field, the tunable frequency range can be much larger than 100 MHz. The proposed method for achieving tunable frequency measurement provides a crucial tool in radars and communication.

6.
Analyst ; 148(20): 5124-5132, 2023 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-37681669

RESUMO

Targeted imaging is playing an increasingly important role in the early detection and precise diagnosis of cancer. This need has motivated research into sensory nanomaterials that can be constructed into imaging agents to serve as biosensors. Graphene quantum dots (GQDs) as a valuable nanoprobe show great potential for use in two-photon biological imaging. However, most as-prepared GQDs exhibit a low two-photon absorption cross-section, narrow spectral coverage, and "one-to-one" signal conversion mode, which greatly hamper their wide application in sensitive early-stage cancer detection. Herein, a versatile strategy has been employed to fabricate an aptamer Sgc8c-functionalized hybrid as a proof-of-concept of the signal amplification strategy for targeted cancer imaging. In this study, GQDs with two-photon imaging performance, and silica nanoparticles (SiO2 NPs) as nanocarriers to provide amplified recognition events by high loading of GQD signal tags, were adopted to construct a two-photon hybrid-based signal amplification strategy. Thus, the obtained hybrid (denoted SiO2@GQDs) enabled extremely strong fluorescence with a quantum yield up to 0.49, excellent photostability and biocompatibility, and enhanced bright two-photon fluorescence up to 2.7 times that of bare GQDs (excitation at 760 nm; emission at 512 nm). Moreover, further modification with aptamer Sgc8c showed little disruption to the structure of the SiO2@GQDs-hybrid and the corresponding two-photon emission. Hence, SiO2@GQDs-Sgc8c showed specific responses to target cells. Moreover, it could be used as a signal-amplifying two-photon nanoprobe for targeted cancer imaging with high specificity and great efficiency, which exhibits a distinct green fluorescence compared to that of GQDs-Sgc8c or SiO2@GQDs. This signal amplification strategy holds great potential for the accurate early diagnosis of tumors and offers new tools for the detection a wide variety of analytes in clinical application.


Assuntos
Grafite , Nanopartículas , Neoplasias , Pontos Quânticos , Humanos , Pontos Quânticos/química , Grafite/química , Dióxido de Silício/química , Nanopartículas/química , Oligonucleotídeos , Neoplasias/diagnóstico por imagem
7.
BMC Public Health ; 23(1): 1894, 2023 10 02.
Artigo em Inglês | MEDLINE | ID: mdl-37784046

RESUMO

BACKGROUND: Pelvic inflammatory disease (PID) is a widespread female public problem worldwide. And it could lead to infertility, preterm labor, chronic pelvic pain, and ectopic pregnancy (EP) among reproductive-aged women. This study aimed to assess the global burden and trends as well as the chaning correlation between PID and EP in reproductive-aged women from 1990 to 2019. METHODS: The data of PID and EP among reproductive-aged women (15 to 49 years old) were extracted from the Global Burden of Disease study 2019. The disease burden was assessed by calculating the case numbers and age-standardized rates (ASR). The changing trends and correlation were evaluated by calculating the estimated annual percentage changes (EAPC) and Pearson's correlation coefficient. RESULTS: In 2019, the ASR of PID prevalence was 53.19 per 100,000 population with a decreasing trend from 1990 (EAPC: - 0.50), while the ASR of EP incidence was 342.44 per 100,000 population with a decreasing trend from 1990 (EAPC: - 1.15). Globally, PID and EP burdens changed with a strong positive correlation (Cor = 0.89) globally from 1990 to 2019. In 2019, Western Sub-Saharan Africa, Australasia, and Central Sub-Saharan Africa had the highest ASR of PID prevalence, and Oceania, Eastern Europe, and Southern Latin America had the highest ASR of EP incidence. Only Western Europe saw significant increasing PID trends, while Eastern Europe and Western Europe saw increasing EP trends. The highest correlations between PID and EP burden were observed in Burkina Faso, Laos, and Bhutan. General negative correlations between the socio-demographic index and the ASR of PID prevalence and the ASR of EP incidence were observed at the national levels. CONCLUSION: PID and EP continue to be public health burdens with a strong correlation despite slightly decreasing trends detected in ASRs globally. Effective interventions and strategies should be established according to the local situation by policymakers.


Assuntos
Doença Inflamatória Pélvica , Gravidez Ectópica , Gravidez , Recém-Nascido , Feminino , Humanos , Adulto , Adolescente , Adulto Jovem , Pessoa de Meia-Idade , Doença Inflamatória Pélvica/epidemiologia , Doença Inflamatória Pélvica/complicações , Gravidez Ectópica/epidemiologia , Gravidez Ectópica/etiologia , Reprodução , Incidência , Australásia/epidemiologia , Carga Global da Doença , Saúde Global
8.
Sensors (Basel) ; 23(12)2023 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-37420688

RESUMO

The potential of the Internet of Body (IoB) to support healthcare systems in the future lies in its ability to enable proactive wellness screening through the early detection and prevention of diseases. One promising technology for facilitating IoB applications is near-field inter-body coupling communication (NF-IBCC), which features lower power consumption and higher data security when compared to conventional radio frequency (RF) communication. However, designing efficient transceivers requires a profound understanding of the channel characteristics of NF-IBCC, which remain unclear due to significant differences in the magnitude and passband characteristics of existing research. In response to this problem, this paper clarifies the physical mechanisms of the differences in the magnitude and passband characteristics of NF-IBCC channel characteristics in existing research work through the core parameters that determine the gain of the NF-IBCC system. The core parameters of NF-IBCC are extracted through the combination of transfer functions, finite element simulations, and physical experiments. The core parameters include the inter-body coupling capacitance (CH), the load impedance (ZL), and the capacitance (Cair), coupled by two floating transceiver grounds. The results illustrate that CH, and particularly Cair, primarily determine the gain magnitude. Moreover, ZL mainly determines the passband characteristics of the NF-IBCC system gain. Based on these findings, we propose a simplified equivalent circuit model containing only core parameters, which can accurately capture the gain characteristics of the NF-IBCC system and help to concisely describe the channel characteristics of the system. This work lays a theoretical foundation for developing efficient and reliable NF-IBCC systems that can support IoB for early disease detection and prevention in healthcare applications. The potential benefits of IoB and NF-IBCC technology can, thus, be fully realized by developing optimized transceiver designs based on a comprehensive understanding of the channel characteristics.


Assuntos
Comunicação , Internet , Capacitância Elétrica , Impedância Elétrica
9.
J Asian Nat Prod Res ; 25(4): 387-402, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-35672874

RESUMO

The aim of this study is to explore the effect and mechanism of 3,6'-disinapoylsucrose (DISS) on an Alzheimer's disease (AD) mice model induced by APPswe695 lentivirus (LV) and intraperitoneal injection of lipopolysaccharide (LPS). The results show that DISS improves cognitive ability, decreases the levels of IL-2, IL-6, IL-1ß, and TNF-α, reduces the expression of NF-κB p65, and alleviates Aß deposition and nerve cell damage. DISS can regulate tyrosine kinase B (TrkB)/brain-derived neurotrophic factor (BDNF) signaling in the hippocampus. In summary, DISS can significantly alleviate neuroinflammation, spatial learning and memory disorders in AD model mice.


Assuntos
Doença de Alzheimer , Disfunção Cognitiva , Camundongos , Animais , Proteínas Tirosina Quinases/metabolismo , Proteínas Tirosina Quinases/farmacologia , Precursor de Proteína beta-Amiloide/metabolismo , Precursor de Proteína beta-Amiloide/farmacologia , Fator Neurotrófico Derivado do Encéfalo/metabolismo , Fator Neurotrófico Derivado do Encéfalo/farmacologia , Lipopolissacarídeos/farmacologia , Regulação para Cima , Disfunção Cognitiva/metabolismo , Doença de Alzheimer/metabolismo , Hipocampo/metabolismo , Peptídeos beta-Amiloides/metabolismo
10.
Angew Chem Int Ed Engl ; 62(37): e202307140, 2023 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-37471684

RESUMO

Elucidating single-atom effects on the fundamental properties of nanoparticles is challenging because single-atom modifications are typically accompanied by appreciable changes to the overall particle's structure. Herein, we report the synthesis of a [Cu58 H20 PET36 (PPh3 )4 ]2+ (Cu58 ; PET: phenylethanethiolate; PPh3 : triphenylphosphine) nanocluster-an atomically precise nanoparticle-that can be transformed into the surface-defective analog [Cu57 H20 PET36 (PPh3 )4 ]+ (Cu57 ). Both nanoclusters are virtually identical, with five concentric metal shells, save for one missing surface copper atom in Cu57 . Remarkably, the loss of this single surface atom drastically alters the reactivity of the nanocluster. In contrast to Cu58 , Cu57 shows promising activity for click chemistry, particularly photoinduced [3+2] azide-alkyne cycloaddition (AAC), which is attributed to the active catalytic site in Cu57 after the removal of one surface copper atom. Our study not only presents a unique system for uncovering the effect of a single-surface atom modification on nanoparticle properties but also showcases single-atom surface modification as a powerful means for designing nanoparticle catalysts.

11.
Sensors (Basel) ; 22(19)2022 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-36236641

RESUMO

The method of using millimeter-wave radar sensors to detect human vital signs, namely respiration and heart rate, has received widespread attention in non-contact monitoring. These sensors are compact, lightweight, and able to sense and detect various scenarios. However, it still faces serious problems of noisy interference in hardware, which leads to a low signal-to-noise ratio (SNR). We used a frequency-modulated continuous wave (FMCW) radar sensor operating at 77 GHz in an office environment to extract the respiration and heart rate of a person accustomed to sitting in a chair. Indeed, the proposed signal processing includes novel impulse denoising operations and the spectral estimation decision method, which are unique in terms of noise reduction and accuracy improvement. In addition, the proposed method provides high-quality, repeatable respiration and heart rates with relative errors of 1.33% and 1.96% on average compared with the reference values measured by a reliable smart bracelet.


Assuntos
Radar , Sinais Vitais , Algoritmos , Frequência Cardíaca/fisiologia , Humanos , Monitorização Fisiológica/métodos , Respiração , Processamento de Sinais Assistido por Computador
12.
J Am Chem Soc ; 143(29): 11026-11035, 2021 Jul 28.
Artigo em Inglês | MEDLINE | ID: mdl-34255513

RESUMO

Precise identification and in-depth understanding of defects in nanomaterials can aid in rationally modulating defect-induced functionalities. However, few studies have explored vacancy defects in ligand-stabilized metal nanoclusters with well-defined structures, owing to the substantial challenge of synthesizing and isolating such defective metal nanoclusters. Herein, a novel defective copper hydride nanocluster, [Cu36H10(PET)24(PPh3)6Cl2] (Cu36; PET: phenylethanethiolate; PPh3: triphenylphosphine), is successfully synthesized at the gram scale via a simple one-pot reduction method. Structural analysis reveals that Cu36 is a distorted half cubic nanocluster, evolved from the perfect Nichol's half cube. The two surface copper vacancies in Cu36 are found to be the principal imperfections, which result in some structural adjustments, including copper atom reconstruction near the vacancies as well as ligand modifications (e.g., substitution, migration, and exfoliation). Density functional theory calculations imply that the above-mentioned defects have a considerable influence on the electronic structure and properties. The modeling suggests that the formation of defective Cu36 rather than the perfect half cube is driven by the enlargement of the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital of the nanocluster. The structural evolution induced by the surface copper atom vacancies provides atomically precise insights into the defect-induced readjustment of the local structure and introduces new avenues for understanding the chemistry of defects in nanomaterials.

13.
Small ; 17(27): e2006839, 2021 07.
Artigo em Inglês | MEDLINE | ID: mdl-33739606

RESUMO

Due to their atomically precise structure, photoluminescent copper nanoclusters (Cu NCs) have emerged as promising materials in both fundamental studies and technological applications, such as bio-imaging, cell labeling, phototherapy, and photo-activated catalysis. In this work, a facile strategy is reported for the synthesis of a novel Cu NCs coprotected by thiolate and phosphine ligands, formulated as [Cu15 (PPh3 )6 (PET)13 ]2+ , which exhibits bright emission in the near-infrared (NIR) region (≈720 nm) and crystallization-induced emission enhancement (CIEE) phenomenon. Single crystal X-ray crystallography shows that the NC possesses an extraordinary distorted trigonal antiprismatic Cu6 core and a, unique among metal clusters, "tri-blade fan"-like structure. An in-depth structural investigation of the ligand shell combined with density functional theory calculations reveal that the extended CH···π and π-π intermolecular ligand interactions significantly restrict the intramolecular rotations and vibrations and, thus, are a major reason for the CIEE phenomena. This study provides a strategy for the controllable synthesis of structurally defined Cu NCs with NIR luminescence, which enables essential insights into the origins of their optical properties.


Assuntos
Cobre , Luminescência , Cristalização , Ligantes , Tomografia por Emissão de Pósitrons
14.
BMC Cancer ; 21(1): 609, 2021 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-34034697

RESUMO

BACKGROUND: Increasing evidence indicates that site-distant metastases are associated with survival outcomes in patients with epithelial ovarian cancer. This study aimed to investigate the prognostic values of site-distant metastases and clinical factors and develop a prognostic nomogram score individually predicting overall survival (OS, equivalent to all-cause mortality) and cancer specific survival (CSS, equivalent to cancer-specific mortality) in patients with epithelial ovarian cancer. METHODS: We retrospectively collected data on patients with epithelial ovarian cancer from the Surveillance, Epidemiology, and End Results (SEER) database between 1975 and 2016. Multivariate Cox regression was performed to identify survival trajectories. A nomogram score was used to predict long-term survival probability. A comparison between the nomogram and the International Federation of Gynecology and Obstetrics (FIGO 2018) staging system was conducted using time-dependent receiver operating characteristic (tROC) curve. RESULTS: A total of 131,050 patients were included, 18.2, 7.8 and 66.1% had localized, regional and distant metastases, respectively. Multivariate analysis identified several prognostic factors for OS including race, grade, histology, FIGO staging, surgery, bone metastasis, liver metastasis, lung metastasis, and lymphatic metastasis. Prognostic factors for CSS included grade, site, FIGO staging, surgery, bone metastasis, brain metastasis, lung metastasis, lymphatic metastasis, and insurance. Following bootstrap correction, the C-index of OS and CSS was 0.791 and 0.752, respectively. These nomograms showed superior performance compared with the FIGO 2018 staging criteria (P < 0.05). CONCLUSIONS: A novel prognostic nomogram score provides better prognostic performance than the FIGO 2018 staging system. These nomograms contribute to directing clinical treatment and prognosis assessment in patients harboring site-distant metastases.


Assuntos
Neoplasias Ósseas/epidemiologia , Carcinoma Epitelial do Ovário/epidemiologia , Neoplasias Hepáticas/epidemiologia , Neoplasias Pulmonares/epidemiologia , Nomogramas , Neoplasias Ovarianas/mortalidade , Adulto , Idoso , Idoso de 80 Anos ou mais , Neoplasias Ósseas/diagnóstico , Neoplasias Ósseas/secundário , Neoplasias Ósseas/terapia , Carcinoma Epitelial do Ovário/diagnóstico , Carcinoma Epitelial do Ovário/secundário , Carcinoma Epitelial do Ovário/terapia , Quimioterapia Adjuvante/estatística & dados numéricos , Feminino , Seguimentos , Humanos , Incidência , Neoplasias Hepáticas/diagnóstico , Neoplasias Hepáticas/secundário , Neoplasias Hepáticas/terapia , Neoplasias Pulmonares/diagnóstico , Neoplasias Pulmonares/secundário , Neoplasias Pulmonares/terapia , Metástase Linfática , Pessoa de Meia-Idade , Estadiamento de Neoplasias , Neoplasias Ovarianas/diagnóstico , Neoplasias Ovarianas/patologia , Neoplasias Ovarianas/terapia , Ovariectomia/estatística & dados numéricos , Curva ROC , Estudos Retrospectivos , Medição de Risco/métodos , Medição de Risco/estatística & dados numéricos , Fatores de Risco , Programa de SEER/estatística & dados numéricos , Resultado do Tratamento
15.
Neural Plast ; 2021: 9938566, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34367273

RESUMO

Background: Parkinson's disease (PD) is a common neurological degenerative disease that cannot be completely cured, although drugs can improve or alleviate its symptoms. Optogenetic technology, which stimulates or inhibits neurons with excellent spatial and temporal resolution, provides a new idea and approach for the precise treatment of Parkinson's disease. However, the neural mechanism of photogenetic regulation remains unclear. Objective: In this paper, we want to study the nonlinear features of EEG signals in the striatum and globus pallidus through optogenetic stimulation of the substantia nigra compact part. Methods: Rotenone was injected stereotactically into the substantia nigra compact area and ventral tegmental area of SD rats to construct rotenone-treated rats. Then, for the optogenetic manipulation, we injected adeno-associated virus expressing channelrhodopsin to stimulate the globus pallidus and the striatum with a 1 mW blue light and collected LFP signals before, during, and after light stimulation. Finally, the collected LFP signals were analyzed by using nonlinear dynamic algorithms. Results: After observing the behavior and brain morphology, 16 models were finally determined to be successful. LFP results showed that approximate entropy and fractal dimension of rats in the control group were significantly greater than those in the experimental group after light treatment (p < 0.05). The LFP nonlinear features in the globus pallidus and striatum of rotenone-treated rats showed significant statistical differences before and after light stimulation (p < 0.05). Conclusion: Optogenetic technology can regulate the characteristic value of LFP signals in rotenone-treated rats to a certain extent. Approximate entropy and fractal dimension algorithm can be used as an effective index to study LFP changes in rotenone-treated rats.


Assuntos
Gânglios da Base/efeitos dos fármacos , Potenciais da Membrana/efeitos dos fármacos , Neurônios/efeitos dos fármacos , Optogenética/métodos , Rotenona/farmacologia , Animais , Masculino , Ratos , Ratos Sprague-Dawley , Desacopladores/farmacologia
16.
J Am Chem Soc ; 142(19): 8696-8705, 2020 May 13.
Artigo em Inglês | MEDLINE | ID: mdl-32315164

RESUMO

Copper-based nanomaterials have attracted tremendous interest due to their unique properties in the fields of photoluminescence and catalysis. As a result, studies on the correlation between their molecular structure and their properties are of great importance. Copper nanoclusters are a new class of nanomaterials that can provide an atomic-level view of the crystal structure of copper nanoparticles. Herein, a high-nuclearity copper nanocluster with 81 copper atoms, formulated as [Cu81(PhS)46(tBuNH2)10(H)32]3+ (Cu81), was successfully synthesized and fully studied by X-ray crystallography, X-ray photoelectron spectroscopy, hydrogen evolution experiments, electrospray ionization mass spectrometry, nuclear magnetic resonance spectroscopy, and density functional theory calculations. Cu81 exhibits extraordinary structural characteristics, including (i) three types of novel epitaxial surface-protecting motifs; (ii) an unusual planar Cu17 core; (iii) a hemispherical shell, comprised of a curved surface layer and a planar surface layer; and (iv) two distinct, self-organized arrangements of protective ligands on the curved and planar surfaces. The present study sheds light on structurally unexplored copper nanomaterials and paves the way for the synthesis of high-nuclearity copper nanoclusters.

17.
Cell Mol Biol (Noisy-le-grand) ; 66(2): 71-73, 2020 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-32415930

RESUMO

Mesenchymal stromal cells (MSCs) are important components of the tumor microenvironment and are believed to facilitate cancer growth affecting cancer cells. We investigated this issue in breast cancer patients. In this cross-sectional study biopsy or mastectomy specimens from breast cancer patients who underwent surgery were evaluated based on the presence of MSCs. Flow cytometric analysis was used to evaluate the expression of CD73, CD90, CD105, and absence of CD11b or CD14, CD79, CD45, and HLA-DR expression as the criteria of MSC presence. Patients were divided into MSC (+) or (-). SPSS software was used to evaluate the association of age, tumor type, tumor size, disease grade, stage, and metastasis with the presence of MSC cells in adipose tissue of specimens. 82 patients with a mean age of 44.43±9.2 years were included in the study. MSC (+) happened in 13 (15.83) patient's samples. A regression model was conducted to evaluate the association of patient characteristics and the MSC positivity. The patient's age was associated with MSC positivity (B=-0.194, p=0.006); and the disease stage was associated with MSC positivity (B=-0.734, p=0.019). Significantly lower age of patients was seen in MSC (+) patients vs. MSC (-) patients (p=0.002). While no difference in the case of tumor type, tumor size, disease grade, stage, and metastasis was seen between two groups (P>0.05). Our result indicated that Mesenchymal stromal cells are seen more in the tumor microenvironment of younger breast cancer patients. Also, patients having mesenchymal stromal cells may have milder disease and lower disease stage.


Assuntos
Tecido Adiposo/citologia , Neoplasias da Mama/patologia , Células-Tronco Mesenquimais/citologia , Adulto , Fatores Etários , Neoplasias da Mama/metabolismo , Estudos Transversais , Feminino , Citometria de Fluxo , Humanos , Células-Tronco Mesenquimais/metabolismo , Pessoa de Meia-Idade , Metástase Neoplásica , Estadiamento de Neoplasias , Microambiente Tumoral
18.
J Am Chem Soc ; 141(24): 9585-9592, 2019 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-31135146

RESUMO

Here, we demonstrate an approach to synthesizing and structurally characterizing three atomically precise anion-templated silver thiolate nanoclusters, two of which form one- and two-dimensional structural frameworks composed of bipyridine-linked nanocluster nodes (referred to as nanocluster-based frameworks, NCFs). We describe the critical role of the chloride (Cl-) template in controlling the nanocluster's nuclearity with atomic precision and the effect of a single Ag atom difference in the nanocluster's size in controlling the NCF dimensionality, modulating the optical properties, and improving the thermal stability. With atomically precise assembly and size control, nanoclusters could be widely adopted as building blocks for the construction of tunable cluster-based framework materials.

19.
Chemistry ; 25(13): 3376-3381, 2019 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-30633396

RESUMO

Silver chalcogenolate clusters (SCCs) and silver cluster-assembled materials (SCAMs) are an important category of novel luminescent materials, the emission of which can be modulated by variation of the cluster nodes and linker species. Here, the successfully synthesis of two isostructural 2D SCAMs is reported: Ag12 bpa and Ag12 bpe are formed by using two linkers with different conformational freedom (bpa=1,2-bis(4-pyridyl)ethane, bpe=1,2-bis(4-pyridyl)ethylene), with dodenuclear silver chalcogenolate clusters as secondary building units (SBUs). Interestingly, nonluminescent Ag12 bpa at room temperature could quickly transform into 1D Ag10 bpa, with concomitant dissociation of two silver atoms and the remaining ten silver atoms rearranging in the cluster, thus exhibiting an intense yellow phosphorescence after being triggered by acetonitrile (CH3 CN). Similarly, stimulating Ag12 bpe with CH3 CN, by contrast, gave another 2D structure Ag12 bpe-1b with the distorted SBUs and different topology structure, and both of them are merely red-emissive at low temperature. To note, after exchanging ligands, room-temperature nonluminescent 2D Ag12 bpe-1b can be transformed into intensely luminescent 1D Ag10 bpa. This linker-flexibility-dependent structural transformation and cluster-based SBU controlled luminescence remains scarce. Our work provides new insights into structure-luminescence relationship in clustered metal-organic frameworks and intelligent stimulus-responsive luminescent materials.

20.
Mikrochim Acta ; 186(3): 201, 2019 02 22.
Artigo em Inglês | MEDLINE | ID: mdl-30796531

RESUMO

This article describes the development of several nanoconjugates composed of cobalt (III) oxyhydroxide and DEASPI/ßCDP, where DEASPI stands for the dye trans-4-[p-(N,N-diethylamino)styryl]-N-methylpyridinium, and ßCDP stands for ß-cyclodextrin. The material enables sensitive fluorometric detection and 3D imaging of ascorbic acid (AA) in biological samples. A nanomicelle composed of DEASPI and ßCDP was prepared to act as a two-photon absorbance (TPA) nanofluorophore with desirable two-photon-sensitized fluorescence, high penetration depth, and excellent cell-permeability). The CoOOH nanoflakes were placed on the surface of the nanomicelle to act as both a quencher of fluorescence and as the recognition unit for AA. In the presence of AA, the CoOOH nanoflakes are reduced to Co (II), and this triggers the recovery of fluorescence. This new nanoprobe exhibits amplified two-photon fluorescence (excitation at 840 nm; emission at 565 nm), high sensitivity, and good selectivity. In-vitro imaging of endogenous AA was demonstrated in living HeLa cells. It was also employed to 3D imaging of exogenous AA in tissue by two-photon excitation microscopy to a depth of up to 320 µm. In our perception, this nanoprobe represents a valuable tool for elucidating the roles of AA in biochemical and clinical studies. Graphical abstract Schematic presentation of the preparation of a novel Poly ß-Cyclodextrin/TPdye conjugated with cobalt oxyhydroxide nanoplatform and its application for high sensitive and two-photon 3D imaging of ascorbic acid (AA) in living cells and deep tissues.


Assuntos
Ácido Ascórbico/análise , Carbocianinas/química , Cobalto/química , Nanoestruturas/química , Óxidos/química , Propilenoglicóis/química , beta-Ciclodextrinas/química , Técnicas Biossensoriais , Corantes Fluorescentes/química , Células HeLa , Humanos , Microscopia de Fluorescência por Excitação Multifotônica , Nanocompostos/química , Oxirredução , Tamanho da Partícula , Propriedades de Superfície , Distribuição Tecidual
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