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1.
J Am Chem Soc ; 146(31): 21568-21582, 2024 Aug 07.
Artigo em Inglês | MEDLINE | ID: mdl-39051165

RESUMO

The heterogeneity of hepatocellular carcinoma (HCC) can prevent effective treatment, emphasizing the need for more effective therapies. Herein, we employed arsenene nanosheets coated with manganese dioxide and polyethylene glycol (AMPNs) for the degradation of Pin1, which is universally overexpressed in HCC. By employing an "AND gate", AMPNs exhibited responsiveness toward excessive glutathione and hydrogen peroxide within the tumor microenvironment, thereby selectively releasing AsxOy to mitigate potential side effects of As2O3. Notably, AMPNs induced the suppressing Pin1 expression while simultaneously upregulation PD-L1, thereby eliciting a robust antitumor immune response and enhancing the efficacy of anti-PD-1/anti-PD-L1 therapy. The combination of AMPNs and anti-PD-1 synergistically enhanced tumor suppression and effectively induced long-lasting immune memory. This approach did not reveal As2O3-associated toxicity, indicating that arsenene-based nanotherapeutic could be employed to amplify the response rate of anti-PD-1/anti-PD-L1 therapy to improve the clinical outcomes of HCC patients and potentially other solid tumors (e.g., breast cancer) that are refractory to anti-PD-1/anti-PD-L1 therapy.


Assuntos
Carcinoma Hepatocelular , Neoplasias Hepáticas , Compostos de Manganês , Peptidilprolil Isomerase de Interação com NIMA , Óxidos , Carcinoma Hepatocelular/tratamento farmacológico , Carcinoma Hepatocelular/patologia , Neoplasias Hepáticas/tratamento farmacológico , Neoplasias Hepáticas/patologia , Óxidos/química , Óxidos/farmacologia , Humanos , Peptidilprolil Isomerase de Interação com NIMA/antagonistas & inibidores , Peptidilprolil Isomerase de Interação com NIMA/metabolismo , Compostos de Manganês/química , Compostos de Manganês/farmacologia , Nanoestruturas/química , Antineoplásicos/química , Antineoplásicos/farmacologia , Arsenicais/química , Arsenicais/farmacologia , Arsenicais/uso terapêutico , Camundongos , Animais , Inibidores Enzimáticos/química , Inibidores Enzimáticos/farmacologia , Linhagem Celular Tumoral , Polietilenoglicóis/química
2.
Opt Express ; 32(10): 16867-16878, 2024 May 06.
Artigo em Inglês | MEDLINE | ID: mdl-38858883

RESUMO

In this paper, a highly integrated terahertz (THz) biosensor is proposed and implemented, which pioneered the preparation of low-temperature gallium arsenide (LT-GaAs) thin film photoconductive antenna (PCA) on the sensor for direct generation and detection of THz waves, simplifying complex terahertz time-domain spectroscopy (THz-TDS) systems. A latch type metasurface is deposited in the detection region to produce a resonance absorption peak at 0.6 THz that is independent of polarisation. Microfluidics is utilised and automatic injection is incorporated to mitigate the experimental effects of hydrogen bond absorption of THz waves in aqueous-based environment. Additionally, cell damage is minimised by regulating the cell flow rate. The biosensor was utilised to detect the concentration of three distinct sizes of bacteria with successful results. The assay was executed as a proof of concept to detect two distinct types of breast cancer cells. Based on the experimental findings, it has been observed that the amplitude and blueshift of the resonance absorption peaks have the ability to identify and differentiate various cancer cell types. The findings of this study introduce a novel approach for developing microfluidic THz metasurface biosensors that possess exceptional levels of integration, sensitivity, and rapid label-free detection capabilities.


Assuntos
Arsenicais , Técnicas Biossensoriais , Gálio , Espectroscopia Terahertz , Gálio/química , Arsenicais/química , Técnicas Biossensoriais/instrumentação , Espectroscopia Terahertz/instrumentação , Humanos , Desenho de Equipamento , Microfluídica/instrumentação
3.
Anal Bioanal Chem ; 416(11): 2809-2818, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38189919

RESUMO

In this study, arsenic (As) speciation was investigated in the freshwater alga Chlamydomonas reinhardtii treated with 20 µg/L arsenate using fractionation as well as ICP-MS/ESI-MS analyses and was compared with the known As metabolite profile of wild-grown Saccharina latissima. While the total As accumulation in C. reinhardtii was about 85% lower than in S. latissima, the relative percentage of arsenolipids was significantly higher in C. reinhardtii (57.0% vs. 5.01%). As-containing hydrocarbons and phospholipids dominated the hydrophobic As profile in S. latissima, but no As-containing hydrocarbons were detectable in C. reinhardtii. Instead for the first time, an arsenoriboside-containing phytol (AsSugPhytol) was found to dominate the hydrophobic arsenicals of C. reinhardtii. Interestingly, this compound and its relatives had so far been only found in green marine microalgae, open sea plankton (mixed assemblage), and sediments but not in brown or red macroalgae. This compound family might therefore relate to differences in the arsenic metabolism between the algae phyla.


Assuntos
Arsênio , Arsenicais , Chlamydomonas reinhardtii , Algas Comestíveis , Laminaria , Arsenicais/química , Arsênio/metabolismo , Chlamydomonas reinhardtii/metabolismo , Hidrocarbonetos
4.
Molecules ; 29(13)2024 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-38999006

RESUMO

Arsenic (As) speciation analysis is scientifically relevant due to the pivotal role the As chemical form plays in toxicity, which, in turn, directly influences the effect it has on the environment. The objective of this study was to develop and optimize a method tailored for studying As compounds in plant samples. Different extraction procedures and HPLC methods were explored to assess their efficiency, determine mass balance, and improve the resolution of compounds in the chromatograms. Conventionally applied anion-exchange chromatography facilitated the separation of well-documented As compounds in the extracts corresponding to 19 to 82% of As present in extracts. To gain insight into compounds which remain undetectable by anion chromatography (18 to 81% of As in the extracts), but still possibly metabolically relevant, we explored an alternative chromatographic approach. The procedure of sample purification and preconcentration through solid-phase extraction, facilitating the detection of those minor As compounds, was developed. The system was further refined to achieve an online 2D-RP-HPLC system, which was employed to analyze the extracts more comprehensively with ICP and ESI MS. Using this newly developed method, As(III)-phytochelatins, along with other arseno-thio-compounds, were detected and identified in extracts derived from the tree roots of seedlings grown in the presence of As(III) and As(V), and a group of arseno lipids was detected in the roots of plants exposed to As(V).


Assuntos
Arsênio , Espectrometria de Massas por Ionização por Electrospray , Cromatografia Líquida de Alta Pressão/métodos , Espectrometria de Massas por Ionização por Electrospray/métodos , Arsênio/análise , Arsênio/isolamento & purificação , Extração em Fase Sólida/métodos , Arsenicais/análise , Arsenicais/química , Arsenicais/isolamento & purificação , Extratos Vegetais/química , Raízes de Plantas/química , Plantas/química , Fitoquelatinas/química , Fitoquelatinas/metabolismo
5.
Molecules ; 29(12)2024 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-38930915

RESUMO

Organic arsenic compounds such as p-aminophenylarsine oxide (p-APAO) are easier for structural optimization to improve drug-like properties such as pharmacokinetic properties, therapeutic efficacy, and target selectivity. In order to strengthen the selectivity of 4-(1,3,2-dithiarsinan-2-yl) aniline 7 to tumor cell, a thiourea moiety was used to strengthen the anticancer activity. To avoid forming a mixture of α/ß anomers, the strategy of 2-acetyl's neighboring group participation was used to lock the configuration of 2,3,4,6-tetra-O-acetyl-ß-d-glucopyranosyl isothiocyanate from 2,3,4,6-tetra-O-acetyl-α-d-glucopyranosyl bromide. 1-(4-(1,3,2-dithiarsinan-2-yl) aniline)-2-N-(2,3,4,6-tetra-O-acetyl-ß-d-glucopyranos-1-yl)-thiourea 2 can increase the selectivity of human colon cancer cells HCT-116 (0.82 ± 0.06 µM vs. 1.82 ± 0.07 µM) to human embryonic kidney 293T cells (1.38 ± 0.01 µM vs. 1.22 ± 0.06 µM) from 0.67 to 1.68, suggesting a feasible approach to improve the therapeutic index of arsenic-containing compounds as chemotherapeutic agents.


Assuntos
Antineoplásicos , Desenho de Fármacos , Tioureia , Humanos , Tioureia/química , Tioureia/farmacologia , Antineoplásicos/farmacologia , Antineoplásicos/síntese química , Antineoplásicos/química , Glucose/química , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Células HCT116 , Estrutura Molecular , Arsenicais/química , Arsenicais/farmacologia , Arsenicais/síntese química , Relação Estrutura-Atividade
6.
J Sci Food Agric ; 104(11): 6957-6965, 2024 Aug 30.
Artigo em Inglês | MEDLINE | ID: mdl-38597303

RESUMO

BACKGROUND: Including seaweed in cattle feed has gained increased interest, but it is important to take into account that the concentration of toxic metals, especially arsenic, is high in seaweed. This study investigated the arsenic species in milk from seaweed-fed cows. RESULTS: Total arsenic in milk of control diets (9.3 ± 1.0 µg As kg-1, n = 4, dry mass) was significantly higher than seaweed-based diet (high-seaweed diet: 7.8 ± 0.4 µg As kg-1, P < 0.05, n = 4, dry mass; low-seaweed diet: 6.2 ± 1.0 µg As kg-1, P < 0.01, n = 4, dry mass). Arsenic speciation showed that the main species present were arsenobetaine (AB) and arsenate (As(V)) (37% and 24% of the total arsenic, respectively). Trace amounts of dimethylarsinic acid (DMA) and arsenocholine (AC) have also been detected in milk. Apart from arsenate being significantly lower (P < 0.001) in milk from seaweed-fed cows than in milk from the control group, other arsenic species showed no significant differences between groups. CONCLUSION: The lower total arsenic and arsenate in seaweed diet groups indicates a possible competition of uptake between arsenate and phosphate, and the presence of AC indicates that a reduction of AB occurred in the digestive tract. Feeding a seaweed blend (91% Ascophyllum nodosum and 9% Laminaria digitata) does not raise As-related safety concerns for milk. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.


Assuntos
Ração Animal , Arsênio , Leite , Alga Marinha , Animais , Alga Marinha/química , Alga Marinha/metabolismo , Bovinos/metabolismo , Leite/química , Leite/metabolismo , Arsênio/análise , Arsênio/metabolismo , Ração Animal/análise , Feminino , Dieta/veterinária , Arsenicais/análise , Arsenicais/metabolismo , Arsenicais/química , Arseniatos/análise , Arseniatos/metabolismo , Arseniatos/química , Contaminação de Alimentos/análise
7.
Zhongguo Zhong Yao Za Zhi ; 49(9): 2532-2543, 2024 May.
Artigo em Zh | MEDLINE | ID: mdl-38812149

RESUMO

This study employed knowledge graph technology to analyze the research status and hot spots of Realgar and provide guidance for clinical application and further research of this drug. The research articles both in English and Chinese involving Realgar were retrieved from five databases including CNKI, Wanfang, VIP, SinoMed, and Web of Science. And NoteExpress, a literature management software was used to screen literature. CiteSpace was utilized for visualized analysis and presentations of the authors, institutions, and keywords. 2 879 articles in Chinese and 194 articles in English were included. China Journal of Chinese Materia Medica and Journal of Ethnopharmacology were the top Chinese and English journals in terms of publication volume. Realgar is widely used in the treatment of skin diseases, blood diseases, and cancer. JIANG Hong was the author who have published more articles in Chinese and English working with teams. School of Public Health of China Medical University and China Academy of Chinese Medical Sciences published the most articles in Chinese and English. The research on Realgar mainly focuses on clinical application, mechanism of action, reduction of toxicity, and enhancement of efficacy. The authors and institutions of Realgar research are mainly concentrated in China. The study on the mechanism of treating hematological diseases and cancer with Realgar, as well as the research on its effects of reducing toxicity and enhancing efficacy, are the current research hotspots. The mechanism of "same treatment for different diseases" in Realgar needs to be further explored. It is urgent to carry out interdisciplinary research on Realgar. This study can provide a refe-rence for the clinical application of Realgar and provide ideas for further research on Realgar.


Assuntos
Arsenicais , Sulfetos , Humanos , Arsenicais/química , China , Medicamentos de Ervas Chinesas/química , Medicamentos de Ervas Chinesas/uso terapêutico , Pesquisa Biomédica
8.
Nanotechnology ; 34(14)2023 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-36595322

RESUMO

Self-assembled quantum dots (QDs) based on III-V semiconductors have excellent properties for applications in quantum optics. However, the presence of a 2D wetting layer (WL) which forms during the Stranski-Krastanov growth of QDs can limit their performance. Here, we investigate WL formation during QD growth by the droplet epitaxy technique. We use a combination of photoluminescence excitation spectroscopy, lifetime measurements, and transmission electron microscopy to identify the presence of an InGaAs WL in these droplet epitaxy QDs, even in the absence of distinguishable WL luminescence. We observe that increasing the amount of Ga deposited on a GaAs (100) surface prior to the growth of InGaAs QDs leads to a significant reduction in the emission wavelength of the WL to the point where it can no longer be distinguished from the GaAs acceptor peak emission in photoluminescence measurements. However increasing the amount of Ga deposited does not suppress the formation of a WL under the growth conditions used here.


Assuntos
Arsenicais , Gálio , Pontos Quânticos , Arsenicais/química , Luminescência , Gálio/química
9.
Nanotechnology ; 34(38)2023 Jul 06.
Artigo em Inglês | MEDLINE | ID: mdl-37321202

RESUMO

Control over the distribution of dopants in nanowires is essential for regulating their electronic properties, but perturbations in nanowire microstructure may affect doping. Conversely, dopants may be used to control nanowire microstructure including the generation of twinning superlattices (TSLs)-periodic arrays of twin planes. Here the spatial distribution of Be dopants in a GaAs nanowire with a TSL is investigated using atom probe tomography. Homogeneous dopant distributions in both the radial and axial directions are observed, indicating a decoupling of the dopant distribution from the nanowire microstructure. Although the dopant distribution is microscopically homogenous, radial distribution function analysis discovered that 1% of the Be atoms occur in substitutional-interstitial pairs. The pairing confirms theoretical predictions based on the low defect formation energy. These findings indicate that using dopants to engineer microstructure does not necessarily imply that the dopant distribution is non-uniform.


Assuntos
Arsenicais , Nanofios , Nanofios/química , Nanotecnologia/métodos , Propriedades de Superfície , Arsenicais/química
10.
Anal Bioanal Chem ; 415(28): 6915-6929, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37410126

RESUMO

Arsenic (As) is one of the most concerning elements due to its high exposure risks to organisms and ecosystems. The interaction between arsenicals and proteins plays a pivotal role in inducing their biological effects on living systems, e.g., arsenicosis. In this review article, the recent advances in analytical techniques and methods of As-binding proteomes were well summarized and discussed, including chromatographic separation and purification, biotin-streptavidin pull-down probes, in situ imaging using novel fluorescent probes, and protein identification. These analytical technologies could provide a growing body of knowledge regarding the composition, level, and distribution of As-binding proteomes in both cells and biological samples, even at the organellar level. The perspectives on analysis of As-binding proteomes are also proposed, e.g., isolation and identification of minor proteins, in vivo targeted protein degradation (TPD) technologies, and spatial As-binding proteomics. The application and development of sensitive, accurate, and high-throughput methodologies of As-binding proteomics would enable us to address the key molecular mechanisms underlying the adverse health effects of arsenicals.


Assuntos
Arsênio , Arsenicais , Proteoma , Ecossistema , Arsenicais/química , Biotina/química
11.
Biotechnol Appl Biochem ; 70(2): 811-823, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36070882

RESUMO

During the past few years, advances in drag delivery have provided many opportunities in the treatment of various diseases and cancer. Arsenic trioxide (ATO) and Erlotinib (Erlo) are two drugs, approved by the United States Food and Drug Administration to treat cancer, but their use is limited in terms of the toxicity of ATO and the low solubility of Erlo. This study aimed to prepare arginine-glycine-aspartic acid (RGD)-decorated nanoliposomes (NLPs) containing Erlo and ATO (NLPs-ATO-Erlo-RGD) to increase the solubility and reduce the toxicity of Erlo and ATO for cancer treatment. The results of transmission electron microscopy and dynamic light scattering showed that NLPs were synthesized uniformly, with spherical shape morphology and particle sizes between 140 and 160 nm. High-performance liquid chromatography and ICP-MS results showed that about 90% of the drug was loaded in the NLPs. In comparison with NLPs-ATO-Erlo, NLPs-ATO-Erlo-RGD demonstrated considerable toxicity against the αvß3 overexpressing PC3 cell line in the MTT experiment. It had no effect on the PANC-1 cell line. In addition, apoptosis assays using Annexin V/PI demonstrated that NLPs-ATO-Erlo-RGD generated the highest apoptotic rates in PC3 cells when compared with NLPs-ATO-Erlo and the combination of free ATO and Erlo. Furthermore, treatment with NLPs-ATO-Erlo-RGD in (p < 0.05) PC3 cell line significantly reduced EGFR level. It is concluded NLPs-ATO-Erlo-RGD as a novel drug delivery system may be a promising platform for the treatment of cancer.


Assuntos
Antineoplásicos , Arsenicais , Humanos , Trióxido de Arsênio/farmacologia , Cloridrato de Erlotinib/farmacologia , Células PC-3 , Óxidos/farmacologia , Arsenicais/farmacologia , Arsenicais/química , Arsenicais/uso terapêutico , Linhagem Celular Tumoral , Apoptose , Oligopeptídeos/farmacologia , Oligopeptídeos/química , Antineoplásicos/farmacologia , Antineoplásicos/química
12.
Environ Sci Technol ; 56(6): 3575-3586, 2022 03 15.
Artigo em Inglês | MEDLINE | ID: mdl-35174706

RESUMO

Arsenic (As) accumulation in rice is of global concern for human health and international trade. Rice is typically reported to contain inorganic As (iAs) and dimethylated arsenate (DMA), with current food guidelines limiting toxic iAs but not less-toxic DMA. Here, we show that the highly toxic dimethylated monothioarsenate (DMMTA) is also found in rice worldwide and has been unknowingly determined as less-toxic DMA by previous routine analytical methods. Using enzymatic extraction followed by high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) analysis with a C18 column, DMMTA was detected in rice grains (n = 103) from a field survey from China and in polished rice grains (n = 140) from a global market-basket survey. Concentration ranged from <0.20 to 34.8 µg/kg (median 10.3 µg/kg), accounting for 0 to 21% of total As. A strong linear correlation was observed in all rice samples between DMA and DMMTA (being 30 ± 8% of DMA) concentrations. This robust relationship allows an estimation of DMMTA in rice grains from the DMA data reported in previous market-basket surveys, showing a general global geographical pattern with DMMTA concentration increasing from the equator toward high-latitude regions. Based on the global occurrence and potential high toxicity, DMMTA in rice should be considered in health risk assessments and for setting food regulations.


Assuntos
Arsênio , Arsenicais , Oryza , Arsenicais/química , Ácido Cacodílico , Cromatografia Líquida de Alta Pressão , Comércio , Humanos , Internacionalidade
13.
Ecotoxicol Environ Saf ; 239: 113662, 2022 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-35617903

RESUMO

Understanding the interplay between the gut microbiome and arsenolipids can help us manage the potential health risk of consuming seafood, but little is known about the bioconversion fate of arsenolipids in the gastrointestinal tract. We use an in vitro mucosal simulator of the human intestinal microbial ecosystem (M-SHIME) to mimic the digestive tract of four healthy donors during exposure to two arsenolipids (an arsenic fatty acid AsFA 362 or an arsenic hydrocarbon AsHC 332). The metabolites were analyzed by HPLC-mass spectrometry. The human gut bacteria accumulated arsenolipids in a donor-dependent way, with higher retention of AsHC 332. Colonic microbiota partly transformed both arsenolipids to their thioxo analogs, while AsFA 362 was additionally transformed into arsenic-containing fatty esters, arsenic-containing fatty alcohols, and arsenic-containing sterols. There was no significant difference in water-soluble arsenicals between arsenolipid treatments. The study shows that arsenolipids can be quickly biotransformed into several lipid-soluble arsenicals of unknown toxicity, which cannot be excluded when considering potential implications on human health.


Assuntos
Arsênio , Arsenicais , Microbioma Gastrointestinal , Arsênio/análise , Arsenicais/química , Cromatografia Líquida de Alta Pressão/métodos , Ecossistema , Humanos
14.
Chem Soc Rev ; 50(4): 2260-2279, 2021 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-33367452

RESUMO

Pnictogens (the non-metal phosphorus, metalloids arsenic and antimony, and metal bismuth) possess diverse chemical characteristics that support the formation of extended molecular structures. As witnessed by the centuries-old (and ongoing) clinical utilities, pnictogen-based compounds have secured their places in history as "magic bullet" therapeutic drugs in medicinal contexts. Moreover, with the development of recent metalloproteomics and bio-coordination chemistry, the pnictogen-based drugs functionally binding to proteins/enzymes in biological systems have been underlaid for "drug repurposing" with promising opportunities. Furthermore, advances in the modern materials science and nonotechnology have stimulated a revolution in other newly discovered forms of pnictogens-phosphorene, arsenene, antimonene, and bismuthine (layered pnictogens). Based on their favorable optoelectronic properties, layered pnictogens have shown dramatic superiority as emerging photonic nanomedicines for the treatment of various diseases. This tutorial review outlines the history and mechanism of action of ancient pnictogen-based drugs (e.g., arsenical compounds in traditional Chinese medicine) and their repurposing into modern therapeutics. Then, the revolutionary use of emerging layered pnictogens as photonic nanomedicines, alongside assessments of their in vivo biosafety, is discussed. Finally, the challenges to further development of pnictogens are set forth and insights for further exploration of their appealing properties are offered. This tutorial review may also provide some deep insights into the fields of integrated traditional Chinese and Western medicines from the perspective of materials science and nanotechnology.


Assuntos
Antimônio/química , Arsenicais/química , Bismuto/química , Nanoestruturas/química , Preparações Farmacêuticas/química , Compostos de Fósforo/química , Animais , Antimônio/farmacologia , Arsenicais/farmacologia , Materiais Biocompatíveis/química , Bismuto/farmacologia , Humanos , Imunoterapia , Estrutura Molecular , Nanomedicina , Dispositivos Ópticos , Compostos de Fósforo/farmacologia , Fototerapia , Ligação Proteica , Radioterapia
15.
Int J Mol Sci ; 23(9)2022 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-35563560

RESUMO

In this work, a finite periodic superlattice is studied, analyzing the probability of electronic transmission for two types of semiconductor heterostructures, GaAs/AlGaAs and InSe/InP. The changes in the maxima of the quasistationary states for both materials are discussed, making variations in the number of periods of the superlattice and its shape by means of geometric parameters. The effect of a non-resonant intense laser field has been included in the system to analyze the changes in the electronic transport properties by means of the Landauer formalism. It is found that the highest tunneling current is given for the GaAs-based compared to the InSe-based system and that the intense laser field improves the current-voltage characteristics generating higher current peaks, maintaining a negative differential resistance (NDR) effect, both with and without laser field for both materials and this fact allows to tune the magnitude of the current peak with the external field and therefore extend the range of operation for multiple applications. Finally, the power of the system is discussed for different bias voltages as a function of the chemical potential.


Assuntos
Arsenicais , Gálio , Arsenicais/química , Eletrônica , Gálio/química , Lasers
16.
Anal Chem ; 93(45): 15115-15123, 2021 11 16.
Artigo em Inglês | MEDLINE | ID: mdl-34714618

RESUMO

Designing new catalysts with high activity and stability is crucial for the effective analysis of environmental pollutants under mild conditions. Here, we developed a superior catalyst of Pt single atoms anchored on MoS2 (Pt1/MoS2) to catalyze the determination of As(III). A detection sensitivity of 3.31 µA ppb-1 was obtained in acetate buffer solution at pH 6.0, which is the highest compared with those obtained by other Pt-based nanomaterials currently reported. Pt1/MoS2 exhibited excellent electrochemical stability during the detection process of As(III), even in the coexistence of Cu(II), Pb(II), and Hg(II). X-ray absorption fine structure spectroscopy and theoretical calculations revealed that Pt single atoms were stably fixed by four S atoms and activated the adjacent S atoms. Then, Pt and S atoms synergistically interacted with O and As atoms, respectively, and transferred some electrons to H3AsO3, which change the rate-determining step of H3AsO3 reduction and reduce reaction energy barriers, thereby promoting rapid and efficient accumulation for As(0). Compared with Pt nanoparticles, the weaker interaction between arsenic species and Pt1/MoS2 enabled the effortless regeneration and cyclic utilization of active centers, which is more favorable for the oxidation of As(0). This work provides inspiration for developing highly efficient sensing platforms from the perspective of atomic-level catalysis and affords references to explore the detection mechanism of such contaminants.


Assuntos
Arsenicais , Nanoestruturas , Arsenicais/química , Catálise , Molibdênio , Oxirredução , Platina
17.
Bioconjug Chem ; 32(3): 497-501, 2021 03 17.
Artigo em Inglês | MEDLINE | ID: mdl-33576604

RESUMO

A new fluorescent biarsenical peptide labeling probe was synthesized and labeled with the radioactive isotopes 11C and 18F. The utility of this probe was demonstrated by installing each of these isotopes into a melanocortin 1 receptor (MC1R) binding peptide, which targets melanoma tumors. Its applicability was further showcased by subsequent in vitro imaging in cells as well as in vivo imaging in melanoma xenograft mice by fluorescence and positron emission tomography.


Assuntos
Arsenicais/química , Corantes Fluorescentes/química , Melanoma Experimental/diagnóstico por imagem , Tomografia por Emissão de Pósitrons , Animais , Linhagem Celular Tumoral , Xenoenxertos , Melanoma Experimental/metabolismo , Camundongos , Peptídeos/metabolismo , Receptor Tipo 1 de Melanocortina/metabolismo
18.
Electrophoresis ; 42(4): 465-472, 2021 02.
Artigo em Inglês | MEDLINE | ID: mdl-33049065

RESUMO

Ti (IV)-modified vinyl phosphate magnetic nanoparticles (Fe3 O4 @SiO2 @KH570-PO4 -Ti (IV)) was prepared for simultaneous extraction of multiple arsenic species, followed by high performance liquid chromatography (HPLC)- inductively coupled plasma mass spectrometry (ICP-MS) analysis. Inorganic arsenic (iAs), dimethyl arsenic acid (DMA), monomethyl arsenic acid (MMA), p-amino phenyl arsenic acid (p-ASA), 4-hdroxyphenylarsenic acid (4-OH), phenyl arsenic acid (PAA), and 3-nitro-4-hydroxyphenylarsenic acid (ROX) were investigated as interest analytes. It was found that they were quantitatively adsorbed on Fe3 O4 @SiO2 @KH570-PO4 -Ti (IV) at pH 5, and desorbed completely with 0.1 mol/L sodium hydroxide solution. Enrichment factor of 100-fold was obtained by consuming 100 mL sample solution. Under the optimal conditions, the method combining MSPE with HPLC-ICP-MS presented a linear range of 1-5000 ng/L for seven arsenic species. The limits of detection were 0.39, 0.60, 0.23, 1.85, 0.54, 0.48, and 0.84 ng/L for DMA, MMA, p-ASA, iAs, 4-OH, PAA, ROX, with the relative standard deviations (c = 10 ng/L, n = 7) of 3.6, 3.9, 5.5, 12.4, 6.1, 5.8, 5.0, respectively. The accuracy of the method was validated by analyzing BCR 627 Tuna fish. The application potential of the method was further evaluated by chicken muscle and liver samples. No target arsenic species were detected in these samples, and good recoveries (80.6-123%) were obtained for the spiked samples at low, medium, and high concentration levels.


Assuntos
Arsênio , Arsenicais , Cromatografia Líquida de Alta Pressão/métodos , Nanopartículas de Magnetita/química , Espectrometria de Massas/métodos , Animais , Arsênio/análise , Arsênio/química , Arsênio/isolamento & purificação , Arsenicais/análise , Arsenicais/química , Arsenicais/isolamento & purificação , Galinhas , Limite de Detecção , Modelos Lineares , Fígado/química , Carne/análise , Músculos/química , Compostos Organofosforados/química , Reprodutibilidade dos Testes , Titânio/química , Atum , Compostos de Vinila/química
19.
Nanotechnology ; 31(31): 315101, 2020 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-32252029

RESUMO

In this paper, amphiphilic conjugated triphenylamine-porphyrins TPA-Por-TPA and TPA-Por were designed and synthesized. The water-soluble nanostructures TPA-Por-TPA NPs and TPA-Por NPs spontaneously assembled after π-π stacking, which can be changed by improving the internal transfer ability of electrons. The intercalation and external binding modes of these free porphyrins and nanoporphyrins interacting with ct-DNA were confirmed by UV-vis and fluorescence spectroscopy. Reactive oxygen species (ROS) production was studied by 2',7'-dichlorofluorescein diacetate, demonstrating that the rate of production of ROS is TPA-Por-TPA NPs > TPA-Por-TPA > TPA-Por NPs > TPA-Por. In addition, the structure of the NP enhanced the acceptor-donor conjugated structure, resulting in fluorescence quenching and promoting non-radiative heat generation. The photothermal conversion efficiencies of the TPA-Por-TPA NPs and TPA-Por NPs were measured and calculated to be 34.89% and 37.99%, respectively. At the same time, the three nanomaterials showed good photocytotoxicity, and the IC50 of the TPA-Por-TPA NPs and TPA-Por NPs was 32.18 and 36.62 µg ml-1, respectively, at 10 min after laser irradiation. The cellular uptake and subcellular localization of these NPs were further evaluated through a confocal laser scanning microscope. The results showed that the conjugated NPs have good biocompatibility properties in the cancer cells. These properties make it possible for triphenylamine porphyrin NPs to become photosensitizers for the photodynamic and photothermal synergistic treatment of tumors, and have potential prospects for applications in cancer diagnosis and treatment.


Assuntos
Arsenicais/química , DNA/metabolismo , Neoplasias/metabolismo , Fármacos Fotossensibilizantes/farmacologia , Porfirinas/farmacologia , Sobrevivência Celular/efeitos dos fármacos , Células HeLa , Humanos , Nanopartículas , Neoplasias/terapia , Fotoquimioterapia , Fármacos Fotossensibilizantes/química , Terapia Fototérmica , Porfirinas/química , Espécies Reativas de Oxigênio/metabolismo
20.
Anal Bioanal Chem ; 412(14): 3447-3456, 2020 May.
Artigo em Inglês | MEDLINE | ID: mdl-32236656

RESUMO

During recent years, mid-infrared (MIR) spectroscopy has matured into a versatile and powerful sensing tool for a wide variety of analytical sensing tasks. Attenuated total reflection (ATR) techniques have gained increased interest due to their potential to perform non-destructive sensing tasks close to real time. In ATR, the essential component is the sampling interface, i.e., the ATR waveguide and its material properties interfacing the sample with the evanescent field ensuring efficient photon-molecule interaction. Gallium arsenide (GaAs) is a versatile alternative material vs. commonly used ATR waveguide materials including but not limited to silicon, zinc selenide, and diamond. GaAs-based internal reflection elements (IREs) are a new generation of semiconductor-based waveguides and are herein used for the first time in direct spectroscopic applications combined with conventional Fourier transform infrared (FT-IR) spectroscopy. Next to the characterization of the ATR waveguide, exemplary surface reactions were monitored, and trace-level analyte detection via signal amplification taking advantage of surface-enhanced infrared absorption (SEIRA) effects was demonstrated. As an example of real-world relevance, the mycotoxin aflatoxin B1 (AFB1) was used as a model analyte in food and feed safety analysis. Graphical abstract.


Assuntos
Arsenicais/química , Gálio/química , Semicondutores , Espectroscopia de Infravermelho com Transformada de Fourier/instrumentação , Aflatoxina B1/análise , Desenho de Equipamento , Análise de Alimentos/instrumentação , Propriedades de Superfície
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