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2.
Anal Chem ; 96(26): 10662-10668, 2024 Jul 02.
Artigo em Inglês | MEDLINE | ID: mdl-38875183

RESUMO

The uptake of plastic particles by plants and their transport through the food chain make great risks to biota and human health. Therefore, it is important to trace plastic particles in the plant. Traditional fluorescence imaging in plants usually suffers significant autofluorescence background. Here, we report a persistent luminescence nanoplatform for autofluorescence-free imaging and quantitation of submicrometer plastic particles in plant. The nanoplatform was fabricated by doping persistent luminescence nanoparticles (PLNPs) onto polystyrene (PS) nanoparticles. Cr3+-doped zinc gallate PLNP was employed as the dopant for autofluorescence-free imaging due to its persistent luminescence nature. In addition, the Ga element in PLNP was used as a proxy to quantify the PS in the plant by inductively coupled plasma mass spectrometry (ICP-MS). Thus, the developed nanoplatform allows not only dual-mode autofluorescence-free imaging (persistent luminescence and laser-ablation ICP-MS) but also ICP-MS quantitation for tracking PS in plant. Application of this nanoplatform in a typical plant model Arabidopsis thaliana revealed that PS mainly distributed in the root (>99.45%) and translocated very limited (<0.55%) to the shoot. The developed nanoplatform has great potential for quantitative tracing of submicrometer plastic particles to investigate the environmental process and impact of plastic particles.


Assuntos
Arabidopsis , Nanopartículas , Arabidopsis/química , Nanopartículas/química , Luminescência , Plásticos/química , Tamanho da Partícula , Poliestirenos/química , Imagem Óptica
3.
Biomater Sci ; 12(12): 3229-3237, 2024 Jun 11.
Artigo em Inglês | MEDLINE | ID: mdl-38764365

RESUMO

Precise imaging-guided therapy of a pulmonary metastasis tumor is of great significance for tumor management and prognosis. Persistent luminescence nanoparticles (PLNPs) are promising probes due to their in situ excitation-free and low-background imaging characteristics. However, most of the PLNP-based probes cannot intelligently distinguish between normal and tumor tissues or balance the needs of targeted accumulation and rapid metabolism, resulting in false positive signals and potential side effects. Besides, the luminescence intensity of single-emissive PLNPs is affected by external factors. Herein, we report a self-evolving double-emissive PLNP-based nanoprobe ZGMC@ZGC-TAT for pulmonary metastatic tumor imaging and therapy. Acid-degradable green-emitting PLNPs (ZGMC) with good afterglow performance and therapeutic potential are synthesized by systematic optimization of dopants. Ultra-small red-emitting PLNPs (ZGC) are then prepared as imaging and reference probes. The two PLNPs are finally covalently coupled and further modified with a cell-penetrating peptide (TAT) to obtain ZGMC@ZGC-TAT. Dual emission ensures a stable luminescence ratio (I700/I537) independent of probe concentration, test voltage and time gate. ZGMC degrades and phosphorescence disappears in a tumor microenvironment (TME), resulting in an increase in I700/I537, thus enabling tumor-specific ratiometric imaging. Cu2+ and Mn2+ released by ZGMC degradation achieve GSH depletion and enhance CDT, effectively inhibiting tumor cell proliferation. Meanwhile, the size of ZGMC@ZGC-TAT decreases sharply, and the resulting ZGC-TAT further causes nuclear pyknosis and quickly clear metabolism. The developed ZGMC@ZGC-TAT turns non-targeted lung aggregation of nanomaterials into a unique advantage, and integrates TME-triggered phosphorescence and size self-evolution, and on-demand therapeutic functions, showing outstanding prospects in precise imaging and efficient treatment of pulmonary metastatic tumors.


Assuntos
Neoplasias Pulmonares , Nanopartículas , Neoplasias Pulmonares/diagnóstico por imagem , Neoplasias Pulmonares/tratamento farmacológico , Nanopartículas/química , Animais , Humanos , Camundongos , Imagem Óptica , Luminescência , Linhagem Celular Tumoral , Camundongos Endogâmicos BALB C , Antineoplásicos/farmacologia , Antineoplásicos/química , Antineoplásicos/administração & dosagem , Camundongos Nus , Peptídeos Penetradores de Células/química , Peptídeos Penetradores de Células/farmacologia
4.
J Hazard Mater ; 472: 134469, 2024 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-38691995

RESUMO

The scarcity of selective adsorbents for efficient extraction and removal of microcystins (MCs) from complex samples greatly limits the precise detection and effective control of MCs. Three-dimensional covalent organic frameworks (3D COFs), characterized by their large specific surface areas and highly ordered rigid structure, are promising candidates, but suffer from lack of specific recognition. Herein, we design to engineer molecularly imprinted cavities within 3D COFs via molecularly imprinted technology, creating a novel adsorbent with exceptional selectivity, kinetics and capacity for the efficient extraction and removal of MCs. As proof-of-concept, a new CC bond-containing 3D COF, designated JNU-7, is designed and prepared for copolymerization with methacrylic acid, the pseudo template L-arginine and ethylene dimethacrylate to yield the JNU-7 based molecularly imprinted polymer (JNU-7-MIP). The JNU-7-MIP exhibits a great adsorption capacity (156 mg g-1) for L-arginine. Subsequently, the JNU-7-MIP based solid-phase extraction coupled with high performance liquid chromatography-mass spectrometry achieves low detection limit of 0.008 ng mL-1, wide linear range of 0.025-100 ng mL-1, high enrichment factor of 186, rapid extraction of 10 min, and good recoveries of 92.4%-106.5% for MC-LR. Moreover, the JNU-7-MIP can rapidly remove the MC-LR from 1 mg L-1 to levels (0.26-0.35 µg L-1) lower than the WHO recommended limit for drinking water (1 µg L-1). This work reveals the considerable potential of 3D COF based MIPs as promising adsorbents for the extraction and removal of contaminants in complex real samples.


Assuntos
Microcistinas , Impressão Molecular , Extração em Fase Sólida , Poluentes Químicos da Água , Microcistinas/isolamento & purificação , Microcistinas/química , Microcistinas/análise , Adsorção , Extração em Fase Sólida/métodos , Poluentes Químicos da Água/química , Poluentes Químicos da Água/isolamento & purificação , Poluentes Químicos da Água/análise , Estruturas Metalorgânicas/química , Arginina/química , Polímeros Molecularmente Impressos/química , Cromatografia Líquida de Alta Pressão , Limite de Detecção
5.
J Colloid Interface Sci ; 668: 540-550, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-38691963

RESUMO

Photocatalysis is considered as an environmentally friendly and sustainable method as it can produce active species to degrade pollutants. However, its applications are hindered by the turbidity of pollutants and the requirements for continuous or repeated in situ irradiation. To avoid the need for continuous in situ irradiation in the photocatalytic process, herein we report the doping of Cu(II) ions into zinc gallate (ZnGa2O4) as traps to capture photo-generated electrons. In this way, long lifetime charge release and separation were effectively achieved for the persistent degradation of organic dyes in wastewater. The Cu(II) doped ZnGa2O4 (ZGC) nanoparticles with a small size about 7.7 nm synthesized via a hydrothermal method exhibited a persistent photocatalytic activity with continuous production of reactive oxygen species for at least 96 h without in situ irradiation due to its unique electronic structure and carrier transport path, and enabled to degrade 82.2 % of rhodamine B in 1 h. Further investigation revealed that the doped Cu(II) ions occupied the octahedral sites of ZGC and highly increased the persistent production and availability of active species for the persistent degradation of organic dyes under pre-illuminated conditions.

6.
Food Chem ; 451: 139427, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-38692237

RESUMO

Here, we report a monomer planarity modulation strategy for room-temperature constructing molecularly imprinted-covalent organic frameworks (MI-COFs) for selective extraction of ochratoxin A (OTA). 2,4,6-triformylphloroglucinol (Tp) was used as basic building block, while three amino monomers with different planarity were employed as modulators to explore the effect of planarity on the selectivity of MI-COFs. The MI-TpTapa constructed from Tp and the lowest planarity of monomer Tapa gave the highest selectivity for OTA, and was further used as the adsorbent for dispersed-solid phase extraction (DSPE) of OTA in alcohol samples. Coupling MI-TpTapa based DSPE with high-performance liquid chromatography allowed the matrix-effect free determination of OTA in alcohol samples with the limit of detection of 0.023 µg kg-1 and the recoveries of 91.4-97.6%. The relative standard deviation (RSD, n = 6) of intra and inter day was <3.2%. This work provides a new way to construct MI-COFs for selective extraction of hazardous targets.


Assuntos
Contaminação de Alimentos , Impressão Molecular , Ocratoxinas , Extração em Fase Sólida , Ocratoxinas/análise , Ocratoxinas/isolamento & purificação , Ocratoxinas/química , Extração em Fase Sólida/métodos , Extração em Fase Sólida/instrumentação , Cromatografia Líquida de Alta Pressão , Contaminação de Alimentos/análise , Adsorção , Álcoois/química , Álcoois/isolamento & purificação , Estruturas Metalorgânicas/química
7.
Chemistry ; 30(36): e202400950, 2024 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-38655749

RESUMO

It is usually believed that doping with photosensitizers capable of generating singlet oxygen (1O2) plays a pivotal role in enhancing the afterglow performance of semiconducting polymer nanoparticles (SPNs). However, the effect of doping photosensitizer bearing electron-withdrawing groups has not been reported. Here we report the effect of doping with six photosensitizers possessing different electron-withdrawing groups on the afterglow performance of SPNs using poly[(9,9-di(2-ethylhexyl)-9H-fluo-rene-2,7-vinylene)-co-(1-methoxy-4-(2-ethylhexyloxy)-2,5-phenylenevinylene)] (PF-MEHPPV) as substrate. It was found that the afterglow performance of SPNs was significantly influenced by doping with photosensitizers bearing electron-withdrawing groups. For the doped photosensitizers with strong electron-withdrawing groups, the stronger the electron-withdrawing ability of the group, the worse of the afterglow performance of the SPN regardless of the 1O2 generation ability of the photosensitizer. When the doped photosensitizer exhibited weak or none electron-withdrawing effect, the 1O2 generation ability of the photosensitizer played a dominant role on the afterglow performance of the SPNs. This work deepens the understanding of the design and synthesis of SPNs with different afterglow properties.

8.
Sci Total Environ ; 927: 172268, 2024 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-38583629

RESUMO

Due to the inappropriate disposal of waste materials containing lead (Pb) and irrigation with sewage containing Pb, the migration of Pb2+ within the soil profile has been extensively investigated. The conventional Pb2+ block method is challenging to implement due to its complex operational procedures and high construction costs. To address this issue, this study introduces the microbial-induced carbonate precipitation (MICP) technique as a novel approach to impede the migration of Pb2+ in the soil profile. Soil acclimatization with urea resulted in an increased proportion of urease-producing microorganisms, including Bacillus, Paenibacillus, and Planococcaceae, along with heightened expression of urea-hydrolyzing genes (UreA, UreB, UreC, and UreG). This indicates that urea-acclimatized soil (Soil-MICP) possesses the potential to induce carbonate precipitation. Batch Pb2+ fixation experiments confirmed that the fixation efficiency of Soil-MICP on Pb2+ exceeded that of soil without MICP, attributed to the MICP process within the Soil-MICP group. Dynamic migration experiments revealed that the MICP reaction transformed exchangeable lead into carbonate-bound Pb, effectively impeding Pb2+ migration in the soil profile. Additionally, the migration rate of Pb2+ in Soil-MICP was influenced by varying urea amounts, pH levels, and pore flow rates, leading to a slowdown in migration. The Two-site sorption model aptly described the Pb2+ migration process in the Soil-MICP column. This study aims to elucidate the MICP biomineralization process, uncover the in-situ blocking mechanism of MICP on lead in soil, investigate the impact of Pb on key genes involved in urease metabolism, enhance the comprehension of the chemical morphology of lead mineralization products, and provide a theoretical foundation for MICP technology in preventing the migration of Pb2+ in soil profiles.


Assuntos
Carbonatos , Chumbo , Microbiologia do Solo , Poluentes do Solo , Solo , Solo/química , Urease/metabolismo , Precipitação Química
9.
Nat Commun ; 15(1): 1995, 2024 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-38443404

RESUMO

Cardiac macrophage contributes to the development of cardiac fibrosis, but factors that regulate cardiac macrophages transition and activation during this process remains elusive. Here we show, by single-cell transcriptomics, lineage tracing and parabiosis, that cardiac macrophages from circulating monocytes preferentially commit to macrophage-to-myofibroblast transition (MMT) under angiotensin II (Ang II)-induced hypertension, with accompanying increased expression of the RNA N6-methyladenosine demethylases, ALKBH5. Meanwhile, macrophage-specific knockout of ALKBH5 inhibits Ang II-induced MMT, and subsequently ameliorates cardiac fibrosis and dysfunction. Mechanistically, RNA immunoprecipitation sequencing identifies interlukin-11 (IL-11) mRNA as a target for ALKBH5-mediated m6A demethylation, leading to increased IL-11 mRNA stability and protein levels. By contrast, overexpression of IL11 in circulating macrophages reverses the phenotype in ALKBH5-deficient mice and macrophage. Lastly, targeted delivery of ALKBH5 or IL-11 receptor α (IL11RA1) siRNA to monocytes/macrophages attenuates MMT and cardiac fibrosis under hypertensive stress. Our results thus suggest that the ALKBH5/IL-11/IL11RA1/MMT axis alters cardiac macrophage and contributes to hypertensive cardiac fibrosis and dysfunction in mice, and thereby identify potential targets for cardiac fibrosis therapy in patients.


Assuntos
Adenina , Hipertensão , Interleucina-11 , Animais , Humanos , Camundongos , Adenina/análogos & derivados , Homólogo AlkB 5 da RNA Desmetilase , Angiotensina II , Cardiotônicos , Macrófagos , Miofibroblastos , RNA
10.
Anal Chem ; 96(14): 5608-5614, 2024 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-38534147

RESUMO

Understanding the individual fluorescence response mechanism of covalent organic frameworks (COFs) at a single-crystal level is of great significance for the rational design of COF-based microsensors but unreachable because all previous COF-based sensors are performed with average fluorescence response behavior of various sized polycrystalline COFs. Herein, we design to explore the fluorescence response of a monodisperse single-crystal COF and further reveal the individual heterogeneity of the response mechanism. Three-dimensional single-crystal COF-301 (SCOF-301) with an intramolecular H-bond-induced excited-state intramolecular proton-transfer effect is selected as a proof-of-concept SCOF. With ethanol, benzene, and ammonia as model analytes, three different deformation and competition H-bond site-induced fluorescence response mechanisms related to crystal size are revealed. Small single particles of SCOF-301 (SSCOF-301) exhibit a more flexible structure, leading to the dominant role of deformation in the fluorescence response of small-sized SSCOF-301. The decreasing flexibility of SSCOF-301 with the increase of crystal size results in involvement of competition of the H-bond site to the fluorescence response besides deformation. Further increase of the crystal size makes the large-sized SSCOF-301 difficult to deform; thus, the competition of the H-bond site dominates the fluorescence response. This work provides a deep understanding of the individual fluorescence response mechanism of COFs to guide the design of a functional COF sensor with suitable size and mechanism for different structural analytes.

11.
J Hazard Mater ; 467: 133755, 2024 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-38359765

RESUMO

Covalent organic frameworks (COFs) are promising adsorbents for extraction, but their selectivity for molecular recognition remains a challenging issue due to the very limited structural design with rigid structure. Herein, we report an elegant strategy for the design and synthesis of molecularly imprinted flexible COFs (MI-FCOFs) via one-pot reaction between the flexible building block of 2,4,6-tris(4-formylphenoxy)- 1,3,5-triazine and linear 4-phenylenediamine for selective extraction of aflatoxins. The flexible chain structure enabled the developed MI-FCOF to adjust the shape and conformation of frameworks to suit the template molecule, giving high selectivity for aflatoxins recognition. Moreover, MI-FCOF with abundant imprinted sites and function groups exhibited an exceptional adsorption capacity of 258.4 mg g-1 for dummy template which is 3 times that of no-imprinted FCOF (NI-FCOF). Coupling MI-FCOF based solid-phase extraction with high-performance liquid chromatography gave low detection limits of 0.003-0.09 ng mL-1 and good precision with relative standard deviations ≤ 6.7% for the determination of aflatoxins. Recoveries for the spiked rice, corn, wheat and peanut samples were in the range of 85.4%- 105.4%. The high selectivity of the developed MI-FCOF allows matrix-free determination of AFTs in food samples. This work offers a new way to the design of MI-FCOF for selective molecular recognition.


Assuntos
Aflatoxinas , Estruturas Metalorgânicas , Impressão Molecular , Adsorção , Arachis
12.
Anal Chem ; 96(8): 3561-3568, 2024 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-38372135

RESUMO

Covalent organic frameworks (COFs) are attractive adsorbents for sample pretreatment due to their unique structure and properties. However, the selectivity of COFs for the extraction of hazardous compounds is still limited due to the lack of specific interactions between COFs and targets. Herein, we report a pore size adjustment strategy for room-temperature synthesis of molecularly imprinted COF (MICOF) for selective extraction of zearalenone (ZEN) in complex food samples. The three-dimensional building block tetra(4-aminophenyl) methane was used as a functional monomer, while dialdehyde monomers with different numbers of benzene ring were used to adjust the pore size of MICOF to match with the size of ZEN molecules. The prepared MICOF gave the largest adsorption capacity of 177.2 mg g-1 and the highest imprinting factor of 10.1 for ZEN so far. MICOF was used as the adsorbent for dispersed solid-phase extraction in combination with high-performance liquid chromatography for the determination of trace ZEN in cereals. The high selectivity of the developed method allows simple aqueous standard calibration for the matrix effect-free determination of ZEN in food samples. The limit of detection and the recoveries of the developed method were 0.21 µg kg-1 and 93.7-101.4%, respectively. The precision for the determination of ZEN was less than 3.8% (RSD, n = 6). The developed method is promising for the selective determination of ZEN in complex matrices.


Assuntos
Estruturas Metalorgânicas , Nanosferas , Zearalenona , Estruturas Metalorgânicas/química , Zearalenona/análise , Grão Comestível/química , Temperatura , Cromatografia Líquida de Alta Pressão/métodos , Extração em Fase Sólida/métodos , Adsorção
13.
J Colloid Interface Sci ; 662: 11-18, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38335735

RESUMO

Near-infrared (NIR)-emitting persistent luminescence nanoparticles (PLNPs) are ideal optical imaging contrast reagents characterized by autofluorescence-free optical imaging for their frontier applications in long-term bioimaging. Preparation of uniform small-sized PLNPs with excellent luminescence performance is crucial for biomedical applications, but challenging. Here, we report a facile magnesium doping strategy to achieve size-independent boost of NIR persistent luminescence in typical and most concerned ZnGa2O4:Cr3+ PLNPs. This strategy relies on the doping of Mg2+ ions that with similar size of Zn2+ ions in the host lattice matrix, and concomitant to the electron traps tailoring tuned by varying the feed ratio of Mg2+. The optimum Mg2+-doped PLNPs give a long afterglow time (signal-to-noise ratio (SNR) = 31.6 at 30 d) without changing the desirable uniform sub-10 nm size of the original nanocrystals. The appropriate increase of the depth and concentration of electron trap contribute jointly to the enhancement of lifetime (488 % longer, 20.57 s) and afterglow time for 700 nm persistent luminescence. Meanwhile, these PLNPs keep the original excellent rechargeability and promote over 60 times increase of SNR in renewable in vivo imaging. This simple strategy provides a basis for new opportunities to address the critical challenge of effective optical performance boost in small-sized PLNPs.

14.
Clin Exp Immunol ; 216(2): 200-210, 2024 Apr 23.
Artigo em Inglês | MEDLINE | ID: mdl-38290436

RESUMO

Mucosal bile acid (BA) profile is still unestablished in diarrhea-predominant irritable bowel syndrome (IBS-D). The aim of this study was to explore colonic mucosal BAs and their associations with mucosal mast cell (MMC)-derived nerve growth factor (NGF) and bowel symptoms in IBS-D. Colonic mucosal biopsies from 36 IBS-D patients and 35 healthy controls (HCs) were obtained for targeted BA profiling. MMC count and the expression of NGF and tight junction proteins (TJPs) were examined. We found that colonic mucosal BA profile was altered in the IBS-D cohort. The proportion of primary BAs was significantly higher and that of secondary BAs was lower in IBS-D patients. According to the 90th percentile of total mucosal BA content of HCs, IBS-D patients were divided into BA-H (n = 7, 19.4%) and BA-L (n = 29, 80.6%) subgroups. BA-H patients showed significantly higher total mucosal BA content compared to BA-L subgroup and HCs. The mucosal content of 11 BA metabolites significantly increased in BA-H subgroup, e.g. cholic acid (CA) and taurocholic acid (TCA). Moreover, BA-H patients displayed significantly elevated MMC count and NGF expression, with decreased expression of TJPs (claudin-1, junctional adhesion molecule-A and zonula occludens-1). Correlation analyses revealed that mucosal TCA content positively correlated with MMC count, MMC-derived NGF levels, and abdominal pain while negatively correlated with TJP expression. In conclusion, IBS-D patients showed an altered BA profile in the colonic mucosa. Approximately 20% of them exhibit elevated mucosal BA content, which may be associated with MMC-derived NGF signaling and bowel symptoms.

15.
Clin Transl Gastroenterol ; 15(2): e00658, 2024 02 01.
Artigo em Inglês | MEDLINE | ID: mdl-37937852

RESUMO

INTRODUCTION: The mucosa-associated microbiota (MAM) is not as frequently studied in diarrhea-predominant irritable bowel syndrome (IBS-D) compared with the fecal microbiota. In this study, we examined the MAM in the terminal ileum and its correlation with bowel symptoms in IBS-D. METHODS: Mucosal biopsies of the terminal ileum from 25 patients with IBS-D and 25 healthy controls were collected for 16S ribosomal RNA gene sequencing. Correlation analysis was performed. RESULTS: Compared with healthy controls, the MAM in the terminal ileum showed a decreased alpha diversity in the IBS-D cohort (Chao1 and Shannon indexes, P < 0.05). And the overall MAM profile clustered separately into 2 groups (ADONIS [PERMANOVA, permutational multivariate analysis of variance], P < 0.05). At the phylum level, the relative abundance of Proteobacteria was significantly higher in the ileal MAM of patients with IBS-D while that of Firmicutes was significantly lower. At the genus level, the relative abundance of Pseudomonas was significantly higher in the IBS-D cohort, with lower Bacteroides and Ruminococcus . Moreover, 40.0% of patients with IBS-D had multiple small nodules (nodular lymphoid hyperplasia) on the mucosal surface of the terminal ileum, which indicated a low-grade inflammation. In patients with IBS-D with nodular lymphoid hyperplasia, the changes of Pseudomonas and Bacteroides were more overt. Correlation analysis revealed that the relative abundance of Pseudomonas positively correlated with abdominal pain and the severity of IBS. DISCUSSION: Patients with IBS-D showed a dysbiosis of MAM in the terminal ileum, which may be associated with bowel symptoms. Moreover, 40.0% of them displayed mucosal low-grade inflammation, with a more severe mucosal microbial disturbance.


Assuntos
Síndrome do Intestino Irritável , Microbiota , Humanos , Síndrome do Intestino Irritável/diagnóstico , Diarreia/microbiologia , Disbiose/microbiologia , Hiperplasia , Fezes/microbiologia , Íleo , Mucosa , Inflamação , Bacteroides
16.
ACS Sens ; 8(12): 4747-4755, 2023 Dec 22.
Artigo em Inglês | MEDLINE | ID: mdl-38054443

RESUMO

Chiral flavor substances play an important role in the human perception of different tastes. Here, we report a pure covalent-organic framework (COF) membrane nanochannel in combination with a chiral gold nanoparticles (AuNPs) selector for sensing chiral flavor substances. The pure COF membrane with a proper pore size is selected as the nanochannel, while l-cysteine-modified AuNPs (l-Cys-AuNPs) are used as the chiral selector. l-Cys-AuNPs show stronger binding to the S-enantiomer than the R-enantiomer, causing current reduction to different degrees for the R- and S-enantiomer to achieve chiral sensing due to the synergistic effect of the size exclusion of the COF nanochannel and the chiral selectivity of l-Cys-AuNPs. The developed COF membrane nanochannel sensing platform not only allows an easy balance of the permeability and selectivity, which is difficult to achieve in traditional polymer membrane nanochannel sensors, but also exhibits better chiral performance than commercial artificial anodic aluminum oxide (AAO) nanochannel sensors. The developed nanochannel sensor is successfully applied for sensing flavor enantiomers such as limonene, propanediol, methylbutyric acid, and butanol with the enantiomer excess values of 55.2% (propanediol) and 72.4% (limonene) and the low detection limits of 36 (limonene) and 71 (propanediol) ng L-1. This study provides a new idea for the construction of nanochannel platforms based on the COF for sensitive and selective chiral sensing.


Assuntos
Nanopartículas Metálicas , Estruturas Metalorgânicas , Humanos , Ouro/química , Nanopartículas Metálicas/química , Biomimética , Limoneno , Cisteína , Propilenoglicóis
17.
ACS Appl Mater Interfaces ; 15(47): 54977-54985, 2023 Nov 29.
Artigo em Inglês | MEDLINE | ID: mdl-37963803

RESUMO

Covalent organic frameworks (COFs) are promising as stationary phases for gas chromatography (GC). The successful anchoring of COFs to the inner walls of the capillary with good uniformity is an important prerequisite to ensure the excellent separation performance of columns. However, current methods for the fabrication of COF-based capillary columns cannot always meet this requirement when faced with different COFs, which hampers the further development of COF-based GC stationary phases. Here, we show a general two-step method for the fabrication of COF-bound capillary column. The first step enables the formation of uniform amorphous polymer layer on the inner walls of capillary, while the second step allows the facile transformation of the amorphous polymer layer into a highly crystalline COF layer. COF-bound capillary columns with different framework structures were fabricated successfully by the developed two-step method. Impressively, the COF layers bound on the inner walls of these capillary columns showed good uniformity and high crystallinity. More importantly, as an example, the fabricated Tab-DHTA-bound capillary column showed good resolution (R > 1.5) and high column efficiency (700-39,663 plates m-1) for the tested isomers of ethylbenzene, xylene, dichlorobenzene, chlorotoluene, pinene, 1,3-dichloropropene, and propylbenzene with good precision (RSD, run-to-run, n = 5) (retention time, 0.2-0.6%; peak area, 0.5-1.1%; and peak height, 0.5-1.4%). In general, the fabricated Tab-DHTA-bound capillary column exhibited better performance for the separation isomers than commercial columns DB-5 and HP-FFAP. These results indicate that the two-step method is an efficient way to fabricate the COF-bound capillary column with excellent separation performance.

18.
J Mater Chem B ; 11(46): 11094-11102, 2023 11 29.
Artigo em Inglês | MEDLINE | ID: mdl-37987617

RESUMO

Covalent organic frameworks (COFs) have promising applications in enhanced phototherapy. However, COFs that can sustainably play a role in phototherapy without continuous irradiation are extremely scarce. Herein, we report the fabrication of porphyrin-anthracene multifunctional COFs (Por-DPA) for sustainable photosterilization and bacterial-infected wound healing. A porphyrin photosensitizer, as one of the monomers, was used to provide photothermal and photodynamic activities under irradiation. An anthracene derivative, a good chemical source of singlet oxygen (1O2), was selected as another monomer to capture 1O2 and release it continuously via cycloreversion in the dark. The prepared Por-DPA COF prevents the self-aggregation quenching of the photosensitizer and thermal damage caused by continuous exposure to external light sources. Besides, Por-DPA exhibits good photothermal conversion performance and efficient 1O2 production capacity through dual pathways of photosensitization and cycloreversion. The developed sustainable photosterilization platform not only has good bactericidal effects on Escherichia coli and Staphylococcus aureus, but also promotes wound healing without obvious side effects, and is expected to be a novel efficient bactericide.


Assuntos
Estruturas Metalorgânicas , Porfirinas , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/química , Estruturas Metalorgânicas/farmacologia , Estruturas Metalorgânicas/química , Porfirinas/farmacologia , Porfirinas/química , Fototerapia , Oxigênio Singlete/metabolismo
19.
BMJ Open ; 13(10): e071521, 2023 10 31.
Artigo em Inglês | MEDLINE | ID: mdl-37907291

RESUMO

OBJECTIVES: To estimate the level of anhedonia among adolescents and explore the association between anhedonia and childhood trauma (CT). DESIGN: A stratified random cluster sample of adolescents participated in a survey, which included three questionnaires: Snaith-Pamilton Pleasure Scale, Childhood Trauma Questionnaire and Patient Health Questionnaire-9. SETTING: The study was conducted in 60 classes in 10 primary, middle and high schools in five economically developed cities along the Southeast Coast of China from April to October 2022. PARTICIPANTS: One thousand seven hundred and forty-five adolescents with ages ranging from 9 to 18 years participated in the study. PRIMARY AND SECONDARY OUTCOMES: The primary outcome was the level of anhedonia, CT and depression among adolescents. The association between anhedonia and CT was determined. RESULTS: The mean scores of anhedonia, CT and depression were 24.88 (6.18), 36.75 (8.87) and 4.46 (5.36), respectively. Anhedonia scores of boys (24.24±6.12) and girls (25.62±6.16) were different (t=-4.69, p<0.01). After controlling for sex, age, the presence of siblings and depression, CT was associated with adolescent anhedonia. Emotional abuse (ß=0.14), emotional neglect (ß=0.15) and physical neglect (ß=0.10) positively predicted adolescent anhedonia (p<0.01), whereas physical abuse negatively predicted adolescent anhedonia (ß=-0.07, p<0.01). Sex had a moderating effect on the relationship between adolescent anhedonia and emotional neglect during childhood, and the negative effect of emotional neglect on adolescent anhedonia in girls was greater than in boys. CONCLUSIONS: CT, including emotional abuse, physical abuse, emotional neglect, and physical neglect, was an independent predictor of adolescents' ability to experience pleasure in daily life. Therefore, awareness of CT should be promoted. Emotional neglect had a more severe effect on anhedonia among girls than among boys, suggesting that emotional neglect should be paid much attention among girls.


Assuntos
Experiências Adversas da Infância , Anedonia , Maus-Tratos Infantis , População do Leste Asiático , Adolescente , Criança , Feminino , Humanos , Masculino , Estudos Transversais , Inquéritos e Questionários , China
20.
Sci Total Environ ; 901: 165973, 2023 Nov 25.
Artigo em Inglês | MEDLINE | ID: mdl-37532034

RESUMO

Carbon dots (CDs)-enabled agriculture has been developing rapidly, but small-scale synthesis and high costs hinder the agricultural application of CDs. Herein, biomass-derived carbon dots (B-CDs) were prepared on a gram-level with low cost, and these B-CDs significantly improved crop photosynthesis. The B-CDs, exhibiting small size and blue fluorescence, were absorbed by crops and enhanced photosynthesis via light-harvesting. Foliar application of B-CDs (10 mg·kg-1) could promote chlorophyll synthesis (30-100 %), Ferredoxin (Fd, 40-80 %), Rubisco enzyme (20-110 %) and upregulated gene expression (20-70 %), resulting in higher net photosynthetic rates (130-300 %), dry biomass (160-300 %) and fresh biomass (80-150 %). Further, the B-CDs could increase crop photosynthesis under nutrient deficient conditions, which was attributed to the release of nutrients from B-CDs. Therefore, the B-CDs enhanced the photosynthesis via enhancing light conversion and nutrient supply. This study provides a promising material capable of enhancing photosynthesis for sustainable agriculture production.

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