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1.
Mol Pharm ; 21(4): 1719-1728, 2024 Apr 01.
Artículo en Inglés | MEDLINE | ID: mdl-38411904

RESUMEN

Therapeutic proteins with a high concentration and low viscosity are highly desirable for subcutaneous and certain local injections. The shape of a protein is known to influence solution viscosity; however, the precise quantification of protein shape and its relative impact compared to other factors like charge-charge interactions remains unclear. In this study, we utilized seven model proteins of varying shapes and experimentally determined their shape factors (v) based on Einstein's viscosity theory, which correlate strongly with the ratios of the proteins' surface area to the 2/3 power of their respective volumes, based on protein crystal structures resolved experimentally or predicted by AlphaFold. This finding confirms the feasibility of computationally estimating protein shape factors from amino acid sequences alone. Furthermore, our results demonstrated that, in high-concentration electrolyte solutions, a more spherical protein shape increases the protein's critical concentration (C*), the transition concentration beyond which protein viscosity increases exponentially relative to concentration increases. In summary, our work elucidates protein shape as a key determinant of solution viscosity through quantitative analysis and comparison with other contributing factors. This provides insights into molecular engineering strategies to optimize the molecular design of therapeutic proteins, thus optimizing their viscosity.


Asunto(s)
Anticuerpos Monoclonales , Electrólitos , Anticuerpos Monoclonales/química , Viscosidad , Soluciones/química
2.
Analyst ; 149(6): 1746-1752, 2024 Mar 11.
Artículo en Inglés | MEDLINE | ID: mdl-38349197

RESUMEN

In this work, the supersensitive and selective determination of lincomycin (Lin) was achieved using a novel electroluminescent (ECL) aptasensor based on the synergistic integration of gold functionalized upconversion nanoparticles (UCNPs) and thiolated 3,4,9,10-perylene tetracarboxylic acid (PTCA). The integration of two luminophores of UCNPs and PTCA combined the merits of the cathodoluminescence stability of UCNPs and the high quantum yield of PTCA, which significantly promoted the ECL signal and analytical performance of the proposed sensor. The introduction of gold nanoparticles in UCNPs can not only improve the conductivity and ECL performance of UCNPs but also cause them to easily integrate with thiolated PTCA (t-PTCA) via an Au-S bond. The ECL signal of UCNPs@Au/t-PTCA/GCE was almost twice as strong as that of t-PTCA/GCE and tenfold higher than that of UCNPs@Au/GCE. Because of the non-conductive protein of the Lin aptamer, the ECL intensity of apt/UCNPs@Au/t-PTCA/GCE noticeably decreased. In the presence of Lin, the aptamer was pulled down from the sensing interface, resulting in the recovery of the ECL intensity of the sensor. Under optimal conditions, our proposed sensor can quantify the concentration of Lin in the range from 1.0 × 10-15 to 1.0 × 10-7 M with a low detection limit of 2.4 × 10-16 M (S/N = 3), exhibiting high sensitivity and specificity for the determination of Lin.


Asunto(s)
Aptámeros de Nucleótidos , Técnicas Biosensibles , Nanopartículas del Metal , Perileno/análogos & derivados , Nanopartículas del Metal/química , Oro/química , Aptámeros de Nucleótidos/química , Lincomicina , Técnicas Biosensibles/métodos , Límite de Detección , Mediciones Luminiscentes , Técnicas Electroquímicas/métodos
3.
Analyst ; 149(8): 2291-2298, 2024 Apr 15.
Artículo en Inglés | MEDLINE | ID: mdl-38511612

RESUMEN

Building a high-performance sensing platform is the key to developing sensitive sensors. Herein, a highly sensitive self-powered electrochemical sensor (SPES) was constructed using a WO3·H2O film as the cathode prepared by a hydrothermal method and Zn as the anode, and it could be applied to sensitive detection of microcystin (MC-RR). The WO3·H2O film with a larger specific surface area could boost the oxygen reduction reaction (ORR), which could achieve signal amplification and significantly increase the sensitivity of the sensors. Under the optimal conditions, there was a good linear relationship between the increased electrical power density and the logarithm of MC-RR concentration with a detection limit of 1.31 × 10-15 M (S/N = 3). This method had good anti-interference ability and stability when applied to the determination of MC-RR content in actual samples, which could boost the potential application of electrochemical sensors in the field of environmental monitoring.

4.
Analyst ; 2024 Sep 12.
Artículo en Inglés | MEDLINE | ID: mdl-39264159

RESUMEN

In this study, a novel electrochemiluminescent (ECL) sensor for highly sensitive detection of trilobatin (Tri) was developed based on silver metal-organic frameworks (AgMOFs) and nitrogen-doped carbon quantum dots (N-CDs). N-CDs exhibited high ECL intensity but poor ECL stability, while AgMOFs had a large specific surface area, high porosity, and good adsorption properties. Compositing both of them not only improved the ECL stability of N-CDs, but also enhanced the ECL strength of materials, so AgMOF@N-CD composites were used as the luminophore of the sensor. Under the optimized conditions, the ECL sensor showed a linear range of 1.0 × 10-7 M to 1.0 × 10-3 M for the detection of Tri, and the detection limit was as low as 5.99 × 10-8 M (S/N = 3). In addition, the sensor had excellent reproducibility, stability, and anti-interference ability. It could be utilized for the detection of Tri in real samples with recoveries of 95.78-102.26%, indicating that the constructed ECL sensor for detecting Tri possessed better application prospects.

5.
J Chem Inf Model ; 64(12): 4739-4758, 2024 Jun 24.
Artículo en Inglés | MEDLINE | ID: mdl-38863138

RESUMEN

Despite recent success in the computational approaches of cyclic peptide design, current studies face challenges in modeling noncanonical amino acids and nonstandard cyclizations due to limited data. To address this challenge, we developed an integrated framework for the tailored design of stapled peptides (SPs) targeting the bromodomain of CREBBP (CREBBP-BrD). We introduce a powerful combination of anchored stapling and hierarchical molecular dynamics to design and optimize SPs by employing the MultiScale integrative conformational dynamics assessment (MSICDA) strategy, which involves an initial virtual screening of over 1.5 million SPs, followed by comprehensive simulations amounting to 154.54 µs across 5418 of instances. The MSICDA method provides a detailed and holistic stability view of peptide-protein interactions, systematically isolated optimized peptides and identified two leading candidates, DA#430 and DA#99409, characterized by their enhanced stability, optimized binding, and high affinity toward the CREBBP-BrD. In cell-free assays, DA#430 and DA#99409 exhibited 2- to 12-fold greater potency than inhibitor SGC-CBP30. Cell studies revealed higher peptide selectivity for cancerous versus normal cells over small molecules. DA#430 combined with (+)-JQ-1 showed promising synergistic effects. Our approach enables the identification of peptides with optimized binding, high affinity, and enhanced stability, leading to more precise and effective cyclic peptide design, thereby establishing MSICDA as a generalizable and transformative tool for uncovering novel targeted drug development in various therapeutic areas.


Asunto(s)
Proteína de Unión a CREB , Simulación de Dinámica Molecular , Proteína de Unión a CREB/química , Proteína de Unión a CREB/metabolismo , Proteína de Unión a CREB/antagonistas & inhibidores , Humanos , Péptidos Cíclicos/química , Péptidos Cíclicos/farmacología , Péptidos Cíclicos/metabolismo , Dominios Proteicos , Conformación Proteica , Péptidos/química , Péptidos/metabolismo , Péptidos/farmacología , Línea Celular Tumoral , Unión Proteica
6.
Phys Chem Chem Phys ; 26(9): 7618-7626, 2024 Feb 28.
Artículo en Inglés | MEDLINE | ID: mdl-38363116

RESUMEN

Poor conductivity of the metal-organic frameworks (MOFs) limits their applications in overall water splitting. Surface sulfur (S) doping transition metal hydroxides would effectively improve the conductivity and adjust the electronic structure to generate additional electroactive sites. Herein, we fabricated a Ni-S/Co-MOF/NF catalyst by electroplating a Ni-S film on the 3D flower-like Co-MOF. Because the 3D flower-like structures are covered in Ni foam, the high exposure of active sites and good conductivity are obtained. Moreover, the synergistic effect between Ni-S and Co-MOF contributes to the redistribution of electrons in the catalyst, which can then optimize the catalytic performance of the material. The obtained 3D flower-like Ni-S/Co-MOF/NF demonstrates excellent activity toward both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) in 1 M KOH, which only requires a low overpotential of 248 mV@10 mA cm-2 for the OER and 127 mV@10 mA cm-2 for the HER, respectively. At a current density of 10 mA cm-2, the Ni-S/Co-MOF/NF‖Ni-S/Co-MOF/NF requires a low cell voltage of 1.59 V to split overall water splitting.

7.
Phys Chem Chem Phys ; 26(27): 18953-18961, 2024 Jul 10.
Artículo en Inglés | MEDLINE | ID: mdl-38952230

RESUMEN

Rational coupling of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) catalysts is extremely important for practical overall water splitting; however, it is still challenging to construct such bifunctional heterostructures. Herein, a CeO2/W@Co-MOF/NF bifunctional electrocatalyst was prepared via a two-step in situ growth method involving an electrodeposition process. The incorporation of the W element enhanced the electronic interaction and enlarged the electrochemical surface area. After the electrodeposition of CeO2, the obtained CeO2/W@Co-MOF/NF possessed abundant heterointerfaces with a modulated local distribution, which promoted water dissociation and rapid electrocatalytic kinetics. In particular, it required very low overpotentials of 239 mV and 87 mV to reach a current density of 10 mA cm-2 in OER and HER, respectively. A corresponding alkaline electrolysis cell afforded a cell voltage of 1.54 V at 10 mA cm-2 to boost overall water splitting. This work provides a feasible strategy to fabricate MOF-based complexes and explores their possible use as bifunctional catalysts toward overall water splitting.

8.
Phys Chem Chem Phys ; 26(12): 9096-9111, 2024 Mar 20.
Artículo en Inglés | MEDLINE | ID: mdl-38456310

RESUMEN

As one of the most promising energy storage devices, supercapacitors exhibit a higher power density than batteries. However, its low energy density usually requires high-performance electrode materials. Although the RuO2 material shows desirable properties, its high cost and toxicity significantly limit its application in supercapacitors. Recent developments demonstrated that Co-based materials have emerged as a promising alternative to RuO2 for supercapacitors due to their low cost, favorable redox reversibility and environmental friendliness. In this paper, the morphological control and performance engineering of Co-based materials are systematically reviewed. Firstly, the principle of supercapacitors is briefly introduced, and the characteristics and advantages of pseudocapacitors are emphasized. The special forms of cobalt-based materials are introduced, including 1D, 2D and 3D nanomaterials. After that, the ways to enhance the properties of cobalt-based materials are discussed, including adding conductive materials, constructing heterostructures and doping heteroatoms. Particularly, the influence of morphological control and modification methods on the electrochemical performances of materials is highlighted. Finally, the application prospect and development direction of Co-based materials are proposed.

9.
Angew Chem Int Ed Engl ; : e202411579, 2024 Jul 31.
Artículo en Inglés | MEDLINE | ID: mdl-39086196

RESUMEN

Prussian blue analogues (PBAs) have been widely studied in aqueous zinc-ion batteries (AZIBs) due to the characteristics of large specific surface area, open aperture, and straightforward synthesis. In this work, vanadium-based PBA nanocubes were firstly prepared using a mild in-situ conversion strategy at room temperature without the protection of noble gas. Benefiting from the multiple-redox active sites of V3+/V4+, V4+/V5+ and Fe2+/Fe3+, the cathode exhibited an excellent discharge specific capacity of 200 mA h g-1 in AZIBs, which is much higher than those of other metal-based PBAs nanocubes. To further improve the long-term cycling stability of the V-PBA cathode, a high concentration water-in-salt electrolyte (4.5 M ZnSO4 + 3 M Zn(OTf)2), and a water-based eutectic electrolyte (5.55 M glucose + 3 M Zn(OTf)2) were designed to successfully inhibit the dissolution of vanadium and improve the deposition of Zn2+ onto the zinc anode. More importantly, the assembled AZIBs maintained 55% of their highest discharge specific capacity even after 10000 cycles at 10 A g-1 with superior rate capability. This study provides a new strategy for the preparation of pure PBA nanostructures and a new direction for enhancing the long-term cycling stability of PBA-based AZIBs at high current densities for industrialization prospects.

10.
Anal Chem ; 95(33): 12358-12364, 2023 08 22.
Artículo en Inglés | MEDLINE | ID: mdl-37605797

RESUMEN

This study focused on the electrochemical properties of tetrazolium salts to develop a simple method for evaluating viable bacterial counts, which are indicators of hygiene control at food and pharmaceutical manufacturing sites. Given that the oxidized form of 3-(4,5-di-methylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT), which has excellent cell membrane permeability, changes to the insoluble reduced form of formazan inside the cell, the number of viable cells was estimated by focusing on the reduction current of MTT remaining in the suspension. Dissolved oxygen is an important substance for bacterial activity; however, it interferes with the electrochemical response of MTT. We investigated the electrochemical properties of MTT to obtain a potential-selective current response that was not affected by dissolved oxygen. Real-time observation of viable bacteria in suspension revealed that uptake of MTT into bacteria was completed within 10 min, including the lag period. In addition, we observed that the current response depends on viable cell density regardless of the bacterial species present. Our method enables a rapid estimation of the number of viable bacteria, making it possible to confirm the safety of food products before they are shipped from the factory and thereby prevent food poisoning.


Asunto(s)
Bacterias , Bromuros , Sales de Tetrazolio , Transporte Biológico , Oxígeno
11.
Anal Chem ; 95(34): 12595-12599, 2023 Aug 29.
Artículo en Inglés | MEDLINE | ID: mdl-37522904

RESUMEN

Self-powered electrochemical sensors, which can function without external electricity, are incredibly valuable in the realm of sensing. However, most of the present testing methods are normally confined to high environmental requirements, restricted lighting conditions, and temperature differences. Herein, an innovative self-powered electrochemical sensor was successfully developed based on hydrovoltaic effect coupling with capacitor amplification. Due to the combined merits from the two-dimensional transition metal carbides and nitrides (MXene)-polyaniline (PANI) with high surface potential and good hydrophilicity, and the capacitor amplification strategy, the device could harvest electric energy from water evaporation and displayed a high short circuit current value. Under optimal conditions, the proposed self-powered electrochemical sensor presented excellent sensitivity and high specificity for enrofloxacin (ENR) detection in the concentration range from 1 fM to 1 nM with a detection limit of 0.585 fM. Such a proposed sensor also has the advantages of environmental friendliness and ease of use, which is an ideal choice for accurately and precisely detecting ENR in real samples. The mode of such electrochemical detection outlined in this technical note implements a breakthrough in designing self-powered electrochemical sensors, providing a rational basis for development of a diversified sensing platform.

12.
Langmuir ; 2023 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-36626237

RESUMEN

Nanodisc (ND)-forming membrane scaffold proteins or peptides developed from apolipoprotein A-I (apoA-I) have led to considerable promise in structural biology and therapeutic applications. However, the rationale and regularity characteristics in peptide sequence design remain inconclusive. Here, we proposed a consensus-based normalization approach through the reversed engineering of apoA-IΔ1-45 to design reconfigurable apoA-I peptide analogs (APAs) for tunable ND assembly. We present extensive morphological validations and computational simulation analyses on divergent APA-NDs that are generated by our method. Fifteen divergent APAs were generated accordingly to study the assembly machinery of NDs. We show that APA designs exhibit multifactorial influence in terms of varying APA tandem repeats, sequence composition, and lipid-to-APA ratio to form tunable diameters of NDs. There is a strong positive correlation between DMPC-to-APA ratios and ND diameters. Longer APA with more tandem repeats tends to yield higher particle size homogeneity. Our results also suggest proline is a dispensable residue for the APA-ND formation. Interestingly, proline-rich substitution not only provides an inward-bending effect in forming smaller NDs but also induces the cumulative chain flexibility that enables larger ND formation at higher lipid ratios. Additionally, proline-tryptophan residues in APAs play a dominant role in forming larger NDs. Molecular simulation shows that enriched basic and acidic residues in APAs evoke abundant hydrogen-bond and salt bridge networks to reinforce the structural stability of APA-NDs. Together, our findings provide a rational basis for understanding APA design. The proposed model could be extended to other apolipoproteins for desired ND engineering.

13.
Eur J Clin Microbiol Infect Dis ; 42(11): 1389-1394, 2023 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-37792119

RESUMEN

This study aimed to determine the clinical characteristics and the prognostic risk factors in non-neutropenic patients with candidemia. Data were retrospectively collected through the medical record information system. Non-neutropenic patients with candidemia were relatively aged, with a more than one-third rate of in-hospitalization mortality. In multivariate analysis, APACHE II score (adjusted odds ratio [aOR], 1.138; 95% confidence interval [CI], 1.067-1.213), septic shock (aOR, 5.704; 95% CI, 2.639-12.326) and RRT (aOR, 16.152; 95% CI, 2.628-99.275) (all P < 0.01) were independent related with non-survivors. In conclusion, non-neutropenic patients with candidemia have a high in-hospitalization mortality, and APACHE II, septic shock, and RRT are independently factors.


Asunto(s)
Candidemia , Choque Séptico , Humanos , Anciano , Candidemia/diagnóstico , Candidemia/epidemiología , Estudios Retrospectivos , Pronóstico , Choque Séptico/diagnóstico , Choque Séptico/epidemiología , Choque Séptico/microbiología , Factores de Riesgo
14.
Analyst ; 148(18): 4470-4478, 2023 Sep 11.
Artículo en Inglés | MEDLINE | ID: mdl-37574902

RESUMEN

In this work, a super-sensitive electrochemiluminescence (ECL) aptamer sensor was constructed using a multiple signal amplification strategy to realize ultra-sensitive detection of di-(2-ethylhexyl) phthalate (DEHP). The incorporation of a highly efficient electrocatalytic metal-organic framework (NH2-Zr-MOF) and graphdiyne (GDY) composite has significantly enhanced the overall electrochemically active surface area, facilitating electron transfer during the entire electrochemical reaction process, and the large number of pores in graphdiyne and NH2-Zr-MOF limited a series of redox reactions within a certain range. This resulted in the generation of a greater number of SO4˙- radicals, thereby boosting the ECL intensity of the GDY in the K2S2O8 system. To increase the performance of the sensor even further, sodium ascorbate (NaAsc) as an accelerator was added to the co-reactant system. Additionally, nitrogen micro-nano bubbles with higher stability and stronger mass transfer have been introduced into the ECL system for the first time. Based on these, the aptamer as the recognition element realized the ultra-sensitive detection of DEHP in the linear range of 1.0 × 10-12 to 1.0 × 10-4 mg mL-1 with the limit of detection (LOD) of 2.43 × 10-13 mg mL-1. In summary, we have utilized the electrocatalytic activity of the porous MOF and the reducing capability of sodium ascorbate to enhance the ECL emission of GDY, which has been successfully applied to the detection of DEHP in water samples.

15.
Analyst ; 148(10): 2335-2342, 2023 May 16.
Artículo en Inglés | MEDLINE | ID: mdl-37186001

RESUMEN

Trilobatin is a flavonoid that has wide application prospects due to its various pharmacological effects, such as anti-inflammation and anti-oxidation. In this work, a novel electrochemical sensor based on gold nanobipyramids (AuNBs) and L-cysteine (L-cys) was constructed for the sensitive and selective determination of trilobatin. The AuNBs, which were prepared by a seed-mediated growth method, had large specific surface areas and excellent electrical conductivity. A layer of L-cys film, which provided more active sites through the amino and hydroxyl groups, was modified on the surface of the AuNBs by electropolymerization. Significantly, the Au-S bond between the L-cys film and AuNBs could improve the stability of the sensor and it exhibited satisfactory electrocatalytic oxidation activity for trilobatin. Under optimized conditions, the sensor based on poly-L-cys/AuNBs/GCE was used to determine trilobatin by differential pulse voltammetry (DPV). Two wide linear ranges between the current peak and the concentration of trilobatin were obtained in the range from 5 to 100 µM and 100 to 1000 µM, and the low detection limit (LOD) was up to 2.55 µM (S/N = 3). The sensor demonstrated desirable reproducibility, stability, and selectivity and was applied to detect real trilobatin samples extracted from Lithocarpus polystachyus Rehd.'s leaves, showing recoveries of 98.36%-104.96%, with satisfactory results.


Asunto(s)
Cisteína , Oro , Oro/química , Reproducibilidad de los Resultados , Oxidación-Reducción , Técnicas Electroquímicas , Electrodos
16.
Analyst ; 148(23): 6087-6096, 2023 Nov 20.
Artículo en Inglés | MEDLINE | ID: mdl-37916516

RESUMEN

Nowadays, bacterial resistance caused by the abuse of antibiotics has become a worldwide problem. In this work, a quinolone antibiotic, enrofloxacin (ENR), was rapidly monitored by combining a selective molecular imprinting polymer (MIP) with the electrochemiluminescence (ECL) method. Zn-PTC, a novel zinc-based metal-organic framework (MOF) that has a large specific surface area and ultra-high luminous efficiency, was used as the ECL luminophore. Chitosan (CHIT) was used to contact the specific surface area of molecularly imprinted polymer films and further improved the detection sensitivity. Subsequently, the molecularly imprinted polypyrrole was electropolymerized on the surface of the Zn-PTC and CHIT modified glassy carbon electrode (GCE). The specific sites that could target recombining ENR were shaped on the surface of MIP after extracting the ENR templates. The specific concentrations of ENR could be detected according to the difference in ECL intensity (ΔECL) between the eluting and rebinding of ENR. After optimization, a good linear response of ΔECL and a logarithm of specific ENR concentrations could be obtained in the range of 1.0 × 10-12-1.0 × 10-4 mol L-1, with a detection limit of 9.3 × 10-13 mol L-1 (S/N = 3). Notably, this study provided a rapid, convenient, and cheap method for the detection of ENR in actual samples.


Asunto(s)
Quitosano , Estructuras Metalorgánicas , Polímeros , Enrofloxacina , Pirroles , Zinc , Antibacterianos
17.
Inorg Chem ; 62(31): 12590-12599, 2023 Aug 07.
Artículo en Inglés | MEDLINE | ID: mdl-37480341

RESUMEN

In this paper, Pr0.7Sr0.3Co1-xRuxO3 perovskite oxides were synthesized by the sol-gel method as bifunctional catalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The overpotentials of PSCR0.05 against HER and OER at 10 mA cm-2 were 319 and 321 mV in alkaline medium, respectively. The Tafel slopes of HER and OER were 87.32 and 118.1 mV/dec, respectively. PSCR0.05 showed the largest electrochemical active area, the smallest charge transfer resistance, and excellent long-term durability. Meanwhile, the PSCR0.05 electrocatalyst was applied for overall water splitting and its cell voltage was maintained at 1.77 V at 10 mA cm-2. The super-exchange interaction between adjacent RuO6-CoO6 octahedra in perovskite made of PSCR0.05 contains sufficient active sites (such as Co2+/Co3+, Ru3+/Ru4+, and O22-/O-). The increase of surface oxygen vacancy and active site is the main reason for the improvement of difunctional catalyst performance. In this work, the electrocatalytic performance of perovskite-type oxides was further optimized by the method of A- and B-site cationic doping regulation, which provides a new idea for perovskite-type bifunctional electrocatalysts.

18.
Inorg Chem ; 62(44): 18189-18197, 2023 Nov 06.
Artículo en Inglés | MEDLINE | ID: mdl-37883780

RESUMEN

Recently, transition metal phosphides (TMPs) have been widely explored for the hydrogen evolution reaction (HER) due to their advantaged activity. Nevertheless, the OER performance of TMPs in an alkaline medium is still unsatisfactory. Therefore, interfacial engineering of TMPs to enhance the OER performance is highly desirable. Herein, a Co(OH)2 nanosheet coupled with a CoP sphere supported on nickel foam (NF) is developed by a simple two-step electrodeposition. The large surface area derived from stacked nanosheets and the electronic regulation induced by heterostructure can significantly enhance charge/mass transfer and expose more active sites, thus accelerating the kinetics of the reaction. In addition, the strong electronic interaction between CoP and Co(OH)2 is conducive to the generation of a high valence cobalt center; thus, the electrocatalytic performances toward HER and OER are remarkably improved. Impressively, the optimized CoP/Co(OH)2@NF heterostructure obtains an excellent HER and OER performance with low overpotentials of 76 and 266 mV at 10 mA cm-2, respectively, superior to the commercial Pt/C and RuO2. Moreover, the optimized CoP/Co(OH)2@NF can afford the lowest cell voltage of 1.58 V to achieve 10 mA cm-2 for alkaline overall water splitting and shows outstanding long-term stability.

19.
Environ Res ; 225: 115499, 2023 05 15.
Artículo en Inglés | MEDLINE | ID: mdl-36848978

RESUMEN

A novel core-shell composite of PCN-222 and molecularly imprinted poly (ionic liquid) (PCN-222@MIPIL) with high conductivity and selectivity was prepared for electrochemical sensing 4-nonylphenol (4-NP). The electrical conductivities of some MOFs including PCN-222, ZIF-8, NH2-UIO-66, ZIF-67, and HKUST-1 were explored. The results indicated that PCN-222 had the highest conductivity and was then used as a novel imprinted support. PCN-222@MIPIL with core-shell and porous structure was synthesized using PCN-222 as support and 4-NP as template. The average pore volume of PCN-222@MIPIL was 0.085 m3 g-1. In addition, the average pore width of PCN-222@MIPIL was from 1.1 to 2.7 nm. The electrochemical response for PCN-222@MIPIL sensor for 4-NP was 2.54, 2.14, and 4.24 times that of non-molecularly imprinted poly (ionic liquid) (PCN-222@NIPIL), PCN-222, and MIPIL sensors, respectively, which result from superior conductivity and imprinted recognition sites of PCN-222@MIPIL. The current response of PCN-222@MIPIL sensor to 4-NP concentration from 1 × 10-4 to 10 µM presented an excellent linear relationship. The detection limit of 4-NP was 0.03 nM. The synergistic effect between the PCN-222 supporter with high conductivity, specific surface area and shell layer of surface MIPIL results in the outstanding performance of PCN-222@MIPIL. PCN-222@MIPIL sensor was adopted for detecting 4-NP in real samples and presented to be a reliable approach for determining 4-NP.


Asunto(s)
Líquidos Iónicos , Polímeros , Polímeros/química , Líquidos Iónicos/química , Fenoles , Límite de Detección
20.
Mikrochim Acta ; 190(9): 373, 2023 08 30.
Artículo en Inglés | MEDLINE | ID: mdl-37648847

RESUMEN

Ciprofloxacin (CIP), a quinolone antibiotic, was rapidly and sensitively detected by integrating the molecularly imprinted polymer (MIP) with an ultra-sensitive electrochemiluminescence (ECL) method. g-C3N4, a typical polymer semiconductor, exhibited outstanding ECL efficiency and excellent ECL stability after combining with an iron-based metal-organic framework (MIL-101). Subsequently, the molecularly imprinted polypyrrole was electropolymerized on the composites of MIL-101-g-C3N4 modified glassy carbon electrode (GCE). The specific sites that could target rebinding the CIP molecules were formed on the surface of MIP after extracting the CIP templates. The determination of specific concentrations of CIP could be realized according to the difference in ECL intensity (△ECL) between the eluting and rebinding of the CIP. Under optimal conditions, a good linear response of △ECL and the logarithm of CIP concentrations was obtained in the range 1.0 × 10-9 ~ 1.0 × 10-5 mol/L, with a detection limit of 4.5 × 10-10 mol/L (S/N = 3) (the working potential was -1.8 ~ 0 V). The RSD of all points in the calibration plot was less than 5.0% and the real samples recovery was between 98.0 and 104%. This paper displays satisfactory selectivity and sensitivity, providing a rapid, convenient, and cheap method for the determination of CIP in real samples.


Asunto(s)
Estructuras Metalorgánicas , Polímeros , Pirroles , Ciprofloxacina , Polímeros Impresos Molecularmente
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