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1.
J Am Chem Soc ; 2024 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-38593469

RESUMO

Hydrolytically stable materials exhibiting a wide range of programmable water sorption behaviors are crucial for on-demand water sorption systems. While notable advancements in employing metal-organic frameworks (MOFs) as promising water adsorbents have been made, developing a robust yet easily tailorable MOF scaffold for specific operational conditions remains a challenge. To address this demand, we employed a topology-guided linker installation strategy using NU-600, which is a zirconium-based MOF (Zr-MOF) that contains three vacant crystallographically defined coordination sites. Through a judicious selection of three N-heterocyclic auxiliary linkers of specific lengths, we installed them into designated sites, giving rise to six new MOFs bearing different combinations of linkers in predetermined positions. The resulting MOFs, denoted as NU-606 to NU-611, demonstrate enhanced structural stability against capillary force-driven channel collapse during water desorption due to the increased connectivity of the Zr6 clusters in the resulting MOFs. Furthermore, incorporating these auxiliary linkers with various hydrophilic N sites enables the systematic modulation of the pore-filling pressure from about 55% relative humidity (RH) for the parent NU-600 down to below 40% RH. This topology-driven linker installation strategy offers precise control of water sorption properties for MOFs, highlighting a facile route to design MOF adsorbents for use in water sorption applications.

2.
J Am Chem Soc ; 145(5): 3055-3063, 2023 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-36696577

RESUMO

Reticular chemistry allows for the rational assembly of metal-organic frameworks (MOFs) with designed structures and desirable functionalities for advanced applications. However, it remains challenging to construct multi-component MOFs with unprecedented complexity and control through insertion of secondary or ternary linkers. Herein, we demonstrate that a Zr-based MOF, NU-600 with a (4,6)-connected she topology, has been judiciously selected to employ a linker installation strategy to precisely insert two linear linkers with different lengths into two crystallographically distinct pockets in a one-pot, de novo reaction. We reveal that the hydrolytic stability of these linker-inserted MOFs can be remarkably reinforced by increasing the Zr6 node connectivity, while maintaining comparable water uptake capacity and pore-filling pressure as the pristine NU-600. Furthermore, introducing hydrophilic -OH groups into the linear linker backbones to construct multivariate MOFs can effectively shift the pore-filling step to lower partial pressures. This methodology demonstrates a powerful strategy to reinforce the structural stability of other MOF frameworks by increasing the connectivity of metal nodes, capable of encouraging developments in fundamental sciences and practical applications.

3.
Front Neuroendocrinol ; 66: 100992, 2022 07.
Artigo em Inglês | MEDLINE | ID: mdl-35278579

RESUMO

Type 2 diabetes mellitus (T2DM) is associated with abnormal communication among large-scale brain networks, revealed by resting-state functional connectivity (rsFC), with inconsistent results between studies. We performed a meta-analysis of seed-based rsFC studies to identify consistent network connectivity alterations. Thirty-three datasets from 30 studies (1014 T2DM patients and 902 healthy controls [HC]) were included. Seed coordinates and between-group effects were extracted, and the seeds were divided into networks based on their location. Compared to HC, T2DM patients showed hyperconnectivity and hypoconnectivity within the DMN, DMN hypoconnectivity with the affective network (AN), ventral attention network (VAN) and frontal parietal network, and DMN hyperconnectivity with the VAN and visual network. T2DM patients also showed AN hypoconnectivity with the somatomotor network and hyperconnectivity with the VAN. T2DM illness durations negatively correlated with within-DMN rsFC. These DMN-centered impairments in large-scale brain networks in T2DM patients may help to explain the cognitive deficits associated with T2DM.


Assuntos
Disfunção Cognitiva , Diabetes Mellitus Tipo 2 , Encéfalo/diagnóstico por imagem , Humanos , Imageamento por Ressonância Magnética/métodos , Vias Neurais
4.
Inorg Chem ; 62(14): 5479-5486, 2023 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-36961751

RESUMO

Acid modulator has been the most widely employed ingredient for highly crystalline metal-organic framework (MOF) synthesis. However, the mechanistic understanding of thorium (Th)-based MOF crystallization remains a great challenge due to the intrinsic properties of fast olation and oxolation reactions of Th species in solution. Here, we constructed a series of Th-based MOFs by adding different modulators (formic acid, acetic acid, trifluoroacetic acid, and benzoic acid) to a synthetic solution along with tetratopic 1,3,5,7-adamantane tetracarboxylic acid (H4ATC), a three-dimensional (3D) ligand with a rigid aliphatic backbone. This work presents an in-depth study of the structure-modulator relationship between the H4ATC ligand and coordinating modulators in the Th-based MOF crystallization process. Crystal structures of these Th-based MOFs reveal that formic acid and acetic acid modulators can compete with the H4ATC ligand to form NU-52 and NU-54; these MOFs possess Th nodes linked by the corresponding modulator. Alternatively, usage of trifluoroacetic acid and benzoic acid modulators results in NU-53 and NU-55; these MOFs possess Th nodes coordinated by only the H4ATC ligand, regardless of the modulator amount. This work highlights that both the identity and amount of modulator play a crucial role in determining the resulting Th-based MOF structures when H4ATC is selected as the coordinated ligand.

5.
Physiol Mol Biol Plants ; 29(7): 971-983, 2023 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-37649887

RESUMO

Mulberry (Morus alba L.) leaves are known as an ideal vegetable with good antioxidant effect, which can bring delicious taste and multiple health benefits. In the present study, the effects of 4-Chlorophenoxyacetic acid sodium salt (4-CPANa) treatment on growth and content of flavonoid compounds in mulberry leaves were investigated. Moreover, the changes in the expression levels of genes involved in flavonoid biosynthetic pathways, and the accumulation of important secondary metabolites including rutin (Rut), chlorogenic acid (ChA), isoquercitrin (IQ) and astragalin (Ast), were investigated in mulberry leaves. The results showed that 4-CPANa treatment could significantly promote the differentiation and growth of mulberry, increased shoot number, bud number, leaf fresh weight and leaf area of mulberry compared with control. Besides, the contents of ChA, Rut, IQ and Ast were significantly increased after 4-CPANa (5 mg/L) treatment. Further analysis revealed that 5 mg/L 4-CPANa strongly induced the expression of flavonoid biosynthesis-related genes including flavonoid 3-O-glucosyltransferase (F3GT) gene, chalcone synthase (CHS) gene, 4-xoumarate-CoA ligase (4CL) and phenylalanine ammonia lyase (PAL) gene. In conclusion, exogenous spraying of 4-CPANa provides a new way to improve the medicinal quality and development of mulberry leaf food with high value. Supplementary Information: The online version contains supplementary material available at 10.1007/s12298-023-01339-z.

6.
Angew Chem Int Ed Engl ; 62(34): e202308068, 2023 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-37400421

RESUMO

Zn metal as one of the promising anodes of aqueous batteries possesses notable advantages, but it faces severe challenges from severe side reactions and notorious dendrite growth. Here, ultrathin nanosheets of α-zirconium phosphate (ZrP) are explored as an electrolyte additive. The nanosheets not only create a dynamic and reversible interphase on Zn but also promote the Zn2+ transportation in the electrolyte, especially in the outer Helmholtz plane near ZrP. Benefited from the enhanced kinetics and dynamic interphase, the pouch cells of Zn||LiMn2 O4 using this electrolyte remarkably improve electrochemical performance under harsh conditions, i.e. Zn powders as the Zn anode, high mass loading, and wide temperatures. The results expand the materials available for this dynamic interphase, provide an insightful understanding of the enhanced charge transfer in the electrolyte, and realize the combination of dynamic interphase and enhanced kinetics for all-climate performance.

7.
Anal Chem ; 94(8): 3485-3493, 2022 03 01.
Artigo em Inglês | MEDLINE | ID: mdl-35170953

RESUMO

Distinguished by the coupled catalysis-facilitated high turnover and admirable specificity, enzyme cascades have sparked tremendous attention in bioanalysis. However, three-enzyme cascade-based versatile platforms have rarely been explored without resorting to tedious immobilization procedures. Herein, we have demonstrated that formamide-converted transition metal-nitrogen-carbon (f-MNC, M = Fe, Cu, Mn, Co, Zn) with a high loading of atomically dispersed active sites possesses intrinsic peroxidase-mimetic activity following the activity order of f-FeNC > f-CuNC > f-MnNC > f-CoNC > f-ZnNC. Ulteriorly, benefitting from the greatest catalytic performance and explicit catalytic mechanism of f-FeNC, versatile enzyme cascade-based colorimetric bioassays for ultrasensitive detection of diabetes-related glucose and α-glucosidase (α-Glu) have been unprecedentedly devised using f-FeNC-triggered chromogenic reaction of 3,3',5,5'-tetramethylbenzidine as an amplifier. Notably, several types of α-Glu substrates can be effectively utilized in this three-enzyme cascade-based α-Glu assay, and it can be further employed for screening α-Glu inhibitors that are used as antidiabetic and antiviral drugs. These versatile assays can also be extended to detect other H2O2-generating or -consuming biomolecules and other bioenzymes that are capable of catalyzing glucose generation procedures. These nanozyme-involved multienzyme cascades without intricate enzyme-engineering techniques may provide a concept to facilitate the deployment of nanozymes in celestial versatile bioassay fabrication, disease diagnosis, and biomedicine.


Assuntos
Carbono , Nitrogênio , Bioensaio , Carbono/química , Catálise , Colorimetria/métodos , Peróxido de Hidrogênio , Nitrogênio/química
8.
Crit Rev Food Sci Nutr ; 62(30): 8497-8517, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-34058921

RESUMO

Food additives refer to all kinds of trace substances used in food or food processing to preserve flavor or enhance food taste, appearance, or other qualities. At present, artificial synthetic food additives have gradually replaced the natural food additives and many problems related to food additives, involving the abuse of food additives, excessive additives or even toxic additives. Obviously, food additives can bring people great sensory enjoyment and commercial convenience, but they may also cause potential risks to human health. So, it is of high significance to conduct quantitative analysis on the content of food additives. According to their functions and the regulatory requirements of food additives, this review starts from the classification and structures of various food additives involving colorants, preservatives, antioxidants, sweeteners, emulsifiers, stabilizers, thickeners, gelling agents. It then summarizes and discusses analytical methods for quantification of food additives including modern immunoassays and other biotechnological methods. The proposed review aspires to fill in the knowledge gap of food additives between academia and industry by covering all kinds of analytical methods for quantifying food additives.


Assuntos
Aditivos Alimentares , Edulcorantes , Humanos , Aditivos Alimentares/efeitos adversos , Antioxidantes , Emulsificantes , Paladar
9.
Analyst ; 147(2): 238-246, 2022 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-34913935

RESUMO

A convenient and sensitive antioxidant assay with high performance is essential for assessing food quality and monitoring the oxidative stress level of biological matrices. Although coordination polymer nanoparticles (CPNs)-based nanozymes have emerged as candidates in the analytical field, strategies to improve the catalytic activity of CPNs have been scarcely revealed and studied. Herein, we demonstrate a manganese (Mn) doping strategy to enhance the peroxidase-mimetic activity of Fe-based CPNs. By tuning the Mn doping amounts and selecting 2,5-dihydroxyterephthalic acid (H4DHTP) as ligands, the produced nanozymes in amorphous state followed the catalytic activity order of Fe5Mn-DHTP > Fe8Mn-DHTP > Fe2Mn-DHTP > Fe-DHTP > Mn-DHTP. Ulteriorly, benefitting from the best catalytic performance and definite catalytic mechanism of Fe5Mn-DHTP, versatile colorimetric assays for ultrasensitive detection of one exogenous antioxidant (ascorbic acid, AA) and two endogenous antioxidants (glutathione, GSH; cysteine, Cys) have been deftly devised based on the inhibition of the 3,3',5,5'-tetramethylbenzidine chromogenic reaction in presence of H2O2. It was found that mercaptan (GSH and Cys) and AA exhibited different inhibition mechanisms. Practically, such a colorimetric assay was viable to determine the total antioxidant capacity of drugs and foods with desirable results. This work proposes a feasible strategy for embellishing CPN nanozymes used for designing sensitive and convenient assays for various antioxidants based on an explicit detection mechanism.


Assuntos
Colorimetria , Nanopartículas , Antioxidantes , Peróxido de Hidrogênio , Ferro , Manganês , Peroxidase , Peroxidases , Polímeros
10.
Inorg Chem ; 61(7): 3281-3287, 2022 Feb 21.
Artigo em Inglês | MEDLINE | ID: mdl-35138838

RESUMO

Chemotherapy is still an important and effective clinical treatment for cancer. However, individual drugs hardly achieve precise controlled release and targeted therapy, thus resulting in unavoidable side effects. Fortunately, the emergence of drug carriers is expected to solve the above problems. In this work, the MOF-on-MOF strategy was adopted to encapsulate DOX into double-layer NH2-MIL-88B to fabricate a core-shell-structured DOX@NH2-MIL-88B-On-NH2-MIL-88B (DMM) and then realize the pH and GSH dual-responsive controlled DOX release. Because of the core-shell structure, the drug-loading capacity of DMM reached 14.4 wt %, which was nearly twice that of DOX@NH2-MIL-88B (DM), and the controlled release performance of DMM was also improved at the same time, greatly improving the kinetics equilibrium time of DOX from 2 h (DM) to 16 h (DMM) at pH 5.0. Moreover, we found that DMM also possessed peroxidase-like catalytic activity under acidic conditions, which could catalyze H2O2 to produce •OH, exhibiting the potential chemodynamical treatment of cancer. Cell experiments showed that DMM had a significant inhibitory effect against 4T1 cancer cells, and the survival rate of 4T1 cells was less than 20% at 100 ppm.


Assuntos
Peróxido de Hidrogênio
11.
J Sep Sci ; 45(7): 1326-1335, 2022 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-35172035

RESUMO

Many plants have a high polyphenol content, which causes the matrix effect and makes the analysis of trace pesticide residues highly challenging. A common approach to improving matrix effects is to purify pesticides through the use of sorbents, but this requires a combination of multiple sorbents and extensive use. Zeolitic imidazolate framework-8 is widely used for pesticide analysis due to its high porosity, large specific surface area, and versatility. Here, we established and validated a modified quick, easy, cheap, effective, rugged, and safe method based on a zeolitic imidazolate framework-8 that was used to test the removal ability for polyphenols. To this end, 145 pesticide residues in peppermint, perilla, fennel, and mulberry leaves were analyzed by the modified method coupled with liquid chromatography with tandem mass spectrometry. The mean recoveries of all pesticide residues were in the range of 74.3-103.7%, with mean relative standard deviations ≤9.1% at spiked concentrations of 1, 10, 50, and 100 µg/kg for mulberry leaves. The limits of quantitation of the method ranged from 1 to 50 µg/kg. This study offers a reliable approach for the accurate quantitative analysis of various trace substances in the polyphenol-rich plants.


Assuntos
Resíduos de Praguicidas , Zeolitas , Resíduos de Praguicidas/análise , Polifenóis/análise , Extração em Fase Sólida/métodos , Espectrometria de Massas em Tandem/métodos
12.
Ecotoxicol Environ Saf ; 239: 113675, 2022 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-35617907

RESUMO

A variety of pesticides are often used in agricultural management to control target pests but may trigger disruptions in the metabolism of nontarget organisms, ultimately affecting crop quality. Acetamiprid (ACE) and cyromazine (CYR) are two frequently used insecticides on cowpea, so it is critical to understand whether these two insecticides cause metabolic disorders in cowpea quality changes and the mechanism by which they do so. Here, we used metabolomic and transcriptomic methods to explore the mechanisms of the effects of ACE, CYR, and their mixture (MIX) on cowpea. In this study, ACE, CYR and MIX had no significant effects on plant biomass or growth status but decreased the contents of starch, soluble protein, and total flavonoids. All treatments reduced the total flavonoid content, but MIX showed the largest reduction of 10.02%. Metabolomic and transcriptomic analyses revealed that ACE markedly affected amino acid metabolism, and CYR and MIX affected sugar metabolism and flavonoid synthesis pathways. ACE and CYR reduced the levels of alanine, glutamic acid, isoleucine and phenylalanine and the expression of amino acid-related genes in cowpea, while MIX significantly increased the levels of most amino acids. All pesticide treatments reduced saccharide levels and related genes, with the most pronounced reduction in the MIX treatment. Exposure to ACE decreased the content of naringenin chalcone and quercetin and increased the content of anthocyanins in cowpeas, while MIX caused a significant decrease in the contents of quercetin and anthocyanins. According to the current study, single and mixed pesticides had different effects on the active ingredients of cowpea, with MIX causing the most significant decrease in the metabolite content of cowpea. These results provide important insights from a molecular perspective on how neonicotinoids and triazine insecticides affect cowpea metabolism.


Assuntos
Inseticidas , Vigna , Aminoácidos/metabolismo , Antocianinas/metabolismo , Inseticidas/metabolismo , Inseticidas/toxicidade , Neonicotinoides/metabolismo , Neonicotinoides/toxicidade , Quercetina , Transcriptoma , Triazinas/metabolismo , Triazinas/toxicidade , Vigna/genética , Vigna/metabolismo
13.
Mikrochim Acta ; 189(9): 347, 2022 08 24.
Artigo em Inglês | MEDLINE | ID: mdl-36001192

RESUMO

Considering the limitations associated with existing methods for the detection of trace amounts of trichlorfon, this paper proposes a novel molecularly imprinted electrochemiluminescence (ECL) sensor for the detection of trichlorfon by utilizing the double enhancement effect of trichlorfon and Ag nanoparticles supported by multi-walled carbon nanotubes (MWCNTs/Ag NPs) in a luminol-H2O2 ECL system. Here, trichlorfon was electropolymerized on the surface of the MWCNT/Ag NP-modified gold nanoelectrode with o-phenylenediamine to prepare the molecularly imprinted polymer-based sensor. After eluting the trichlorfon, imprinted holes for the identification of trichlorfon were retained on the sensor, which were used as signal switches to obtain different ECL intensities through the adsorption of different concentrations of trichlorfon. The ECL signal of the sensitized luminol-H2O2 was doubly enhanced by the MWCNTs/Ag and trichlorfon, improving the sensitivity of the sensor. The trichlorfon concentration was positively correlated with the enhanced ECL intensity of the sensor in the range 5.0 × 10-8-5.0 × 10-11 mol L-1, and the detection limit of trichlorfon was 3.9 × 10-12 mol L-1. Moreover, the proposed sensor was successfully applied to the detection of trichlorfon residues in real samples, and the recovery ranged between 91.8 and 109%. A molecularly imprinted electrochemiluminescence sensor for trichlorfon detection by utilizing the double enhancement effect of trichlorfon and Ag nanoparticles supported by multi-walled carbon nanotubes in a luminol-H2O2 ECL system. The dual enhancement of the ECL signal improved the sensitivity of the sensor.


Assuntos
Nanopartículas Metálicas , Nanotubos de Carbono , Peróxido de Hidrogênio , Medições Luminescentes/métodos , Luminol/química , Nanopartículas Metálicas/química , Nanotubos de Carbono/química , Prata , Triclorfon
14.
Molecules ; 27(21)2022 Nov 07.
Artigo em Inglês | MEDLINE | ID: mdl-36364466

RESUMO

A rapid, efficient, simple, and high-throughput method for the simultaneous determination of 108 pesticide residues in three traditional Chinese medicines (TCMs) was established, comprising an improved QuEChERS method in combination with HPLC-MS/MS based on mixed samples. A quantity of 10 mL of acetonitrile was used as extraction solvent, and 10 mg of amino-modified multi-walled carbon nanotubes (MWCNTs-NH2) and 150 mg of anhydrous magnesium sulfate (MgSO4) were selected as sorbents for dispersive solid phase extraction. The performance of the method was verified according to the analytical quality control standards of SANTE/11813/2017 guidelines. With good linearity (R2 > 0.9984) in the range of 2−200 µg/L for all pesticides in the selected matrices, and good accuracy, precision, and high sensitivity, the recoveries were in the range of 70−120% for more than 95% of the pesticides, with a relative standard deviation (RSD) of less than 16.82% for all. The limit of detection (LOD) and limit of quantification (LOQ) of the method were 0.01−3.87 µg/kg and 0.07−12.90 µg/kg, respectively, for Fritillaria thunbergii Miq (F. thunbergii), Chrysanthemum Morifolium Ramat (C. morifolium), and Dendrobium officinale Kimura et Migo (D. officinale). The method was successfully applied to 60 batches of actual samples from different regions.


Assuntos
Nanotubos de Carbono , Resíduos de Praguicidas , Praguicidas , Resíduos de Praguicidas/análise , Cromatografia Líquida de Alta Pressão , Espectrometria de Massas em Tandem/métodos , Nanotubos de Carbono/química , Extração em Fase Sólida/métodos , China
15.
Nonlinear Dyn ; 107(4): 3557-3572, 2022.
Artigo em Inglês | MEDLINE | ID: mdl-35125653

RESUMO

This paper investigates the guaranteed cost positive consensus for linear multi-agent systems (MASs) with multiple time-varying delays and switching topologies. First, necessary and sufficient conditions for the positivity of the focused system are given. The positive consensus criterion and switching signals are derived by combining multiple Lyapunov-Krasovskii functionals with mode-dependent average dwell time approaches. Then, the guaranteed cost positive consensus is studied via the state errors among neighbouring agents and control inputs. It realizes a trade-off between the consensus regulation performance and the control energy consumption of MASs. Particularly, the determined upper bound of the cost function depends merely on the initial conditions of the agents and is independent of the switching movements. Finally, simulation results are given to validate the proposed control scheme.

16.
Angew Chem Int Ed Engl ; 61(7): e202116048, 2022 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-34889508

RESUMO

The practical application of lithium-sulfur batteries is still limited by the lithium polysulfides (LiPSs) shuttling effect on the S cathode and uncontrollable Li-dendrite growth on the Li anode. Herein, elaborately designed WSe2 flakelets immobilized on N-doped graphene (WSe2 /NG) with abundant active sites are employed to be a dual-functional host for satisfying both the S cathode and Li anode synchronously. On the S cathode, the WSe2 /NG with a strong interaction towards LiPSs can act as a redox accelerator to promote the bidirectional conversion of LiPSs. On the Li anode, the WSe2 /NG with excellent lithiophilic features can regulate the uniform Li plating/stripping to mitigate the growth of Li dendrite. Taking advantage of these merits, the assembled Li-S full batteries exhibit remarkable rate performance and stable cycling stability even at a higher sulfur loading of 10.5 mg cm-2 with a negative to positive electrode capacity (N/P) ratio of 1.4 : 1.

17.
Analyst ; 146(5): 1650-1655, 2021 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-33522553

RESUMO

In this work, a novel convenient colorimetric method for sensitive detection of thiocyanate (SCN-) has been developed based on its suppression of the oxidase-like activity of palladium square nanoplates on reduced graphene oxide (Pd SP@rGO). SCN- can be adsorbed onto the surface of Pd SP@rGO via binding with Pd atoms and blocks the active sites that mimic oxidase, thus inhibiting the corresponding chromogenic reaction of 3,3',5,5'-tetramethylbenzidine, which has been comprehensively revealed by the UV-vis spectra and X-ray photoelectron spectra. The color fading exhibits SCN- concentration-dependent behavior and can be easily recorded by either UV-vis spectroscopy or naked-eye observation. Therefore, both quantitative detection via measurement of the decrease in absorbance and visual detection of SCN- can be achieved. Owing to the intrinsic amplification of signals by the oxidase-like activity of Pd SP@rGO without resorting to unstable and destructive H2O2, this assay is straightforward, robust and sensitive enough for the detection of SCN- in real samples. Furthermore, an "INH" logic gate is rationally constructed based on the proposed colorimetric SCN- sensor.


Assuntos
Paládio , Tiocianatos , Domínio Catalítico , Colorimetria , Peróxido de Hidrogênio , Oxirredutases
18.
Mikrochim Acta ; 188(4): 114, 2021 03 07.
Artigo em Inglês | MEDLINE | ID: mdl-33677782

RESUMO

Enzyme-mimetic properties of nanomaterials can be efficiently tuned by controlling their size, composition, and structure. Here, ultrathin PdCu alloy nanosheet-assembled three-dimensional (3D) nanoflowers (Pd1Cux NAFs) with tunable surface composition are obtained via a generalized strategy. In presence of H2O2, the as-synthesized Pd1Cux NAFs can catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to the oxidized form of TMB (oxTMB) with a characteristic absorption peak at 652 nm. Interestingly, Pd1Cux NAFs show obviously composition-dependent peroxidase-like catalytic activities because of the synergistic interaction of nanoalloy. Additionally, different from 2D Pd nanosheets, the distinctive 3D superstructures are featured with rich approachable sites and proper layer spacing, which are in favor of fast mass transport and electron transfers during the catalytic process. Among the studied Pd1Cux NAFs, the Pd1Cu1.7 NAFs show the highest enzyme-like activities and can be successfully applied for the colorimetric detection of glucose with a low detection limit of 2.93 ± 0.53 µM. This work provides an efficient avenue to fabricate PdCu NAF nanozymes in biosensing toward glucose detection. Two-dimensional (2D) PdCu ultrathin nanosheet-assembled 3D nanoflowers (Pd1Cux NAFs) with tunable surface composition exhibit substantially enhanced intrinsic peroxidase-like catalytic activities. The Pd1Cu1.7 NAFs are successfully used as peroxidase mimic catalyst for the colorimetric detection of glucose with low detection limit of 2.93 µM.


Assuntos
Ligas/química , Glicemia/análise , Nanoestruturas/química , Benzidinas/química , Técnicas Biossensoriais/métodos , Glicemia/química , Catálise , Compostos Cromogênicos/química , Colorimetria/métodos , Cobre/química , Humanos , Peróxido de Hidrogênio/análise , Peróxido de Hidrogênio/química , Cinética , Limite de Detecção , Oxirredução , Paládio/química
19.
Mikrochim Acta ; 188(5): 162, 2021 04 10.
Artigo em Inglês | MEDLINE | ID: mdl-33839958

RESUMO

A convenient and sensitive colorimetric assay for acetylcholinesterase (AChE) and its inhibitor has been designed based on the oxidase-like activity of {100}-faceted Pd square nanoplates which are grown in situ on reduced graphene oxide (PdSP@rGO). PdSP@rGO can effectively catalyze the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) without the assistance of H2O2 to generate blue oxidized TMB (oxTMB) with a characteristic absorption peak at 652 nm. In the presence of AChE, acetylthiocholine (ATCh), a typical AChE substrate, is hydrolyzed to thiocholine (TCh). The generated TCh can effectively inhibit the PdSP@rGO-triggered chromogenic reaction of TMB via cheating with Pd, resulting in color fading and decrease in absorbance. Thus, a sensitive probe for AChE activity is constructed with a working range of 0.25-5 mU mL-1 and  a limit of detection (LOD) of 0.0625 mU mL-1. Furthermore, because of the inhibition effect of tacrine on AChE, tacrine is also detected through the colorimetric AChE assay system within the concentrations range 0.025-0.4 µM with a LOD of 0.00229 µM. Hence, a rapid and facile colorimetric procedure to sensitively detect AChE and its inhibitor can be anticipated through modulating the oxidase-like activity of PdSP@rGO. Colorimetric method for detection of AChE and its inhibitor is established by modulating the oxidase mimetic activity of {100}-faceted Pd square nanoplates on reduced graphene oxide (PdSP@rGO).


Assuntos
Acetilcolinesterase/sangue , Colorimetria/métodos , Grafite/química , Nanopartículas Metálicas/química , Acetilcolinesterase/química , Acetiltiocolina/química , Benzidinas/química , Catálise , Inibidores da Colinesterase/análise , Compostos Cromogênicos/química , Humanos , Limite de Detecção , Oxirredução , Paládio/química , Tacrina/análise
20.
Molecules ; 26(20)2021 Oct 14.
Artigo em Inglês | MEDLINE | ID: mdl-34684791

RESUMO

A supramolecular network [H4bdcbpy(NO3)2·H2O] (H4bdcbpy = 1,1'-Bis(3,5-dicarboxybenzyl)-4,4'-bipyridinium) (1) was prepared by a zwitterionic viologen carboxylate ligand in hydrothermal synthesis conditions. The as-synthesized (1) has been well characterized by means of single-crystal/powder X-ray diffraction, elemental analysis, thermogravimetric analysis and infrared and UV-vis spectroscopy. This compound possesses a three-dimensional supramolecular structure, formed by the hydrogen bond and π-π interaction between the organic ligands. This compound shows photochromic properties under UV light, as well as vapochromic behavior upon exposure to volatile amines and ammonia, in which the electron transfer from electron-rich parts to the electron-deficient viologen unit gives rise to colored radicals. Moreover, the intensive intermolecular H-bonding networks in 1 endows it with a proton conductivity of 1.06 × 10-3 S cm-1 in water at 90 °C.

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