2D/3D hierarchical porous structure of mNPC/SMOH@C to construct an electrochemical sensor for the simultaneous determination of p-acetylaminophenol and p-aminophenol.

BACKGROUND: As persistent organic pollutants (POPs), the accumulation of p-acetylaminophenol (PAT) and p-aminophenol (PAP) in water can seriously damage the health of plants and animals, ultimately leading to threats to human health and safety. Electrochemical sensors have the advantages of being fast, inexpensive, and accurate compared to the complex, expensive, and cumbersome conventional analytical methods. In this study, we designed and synthesized composites with two-dimensional/three-dimensional (2D/3D) porous structures to construct an efficient electrochemical platform for the simultaneous detection of PAT and PAP. RESULTS: In this work, a novel 3D foamy birnessite Na0.55Mn2O4·1.5H2O@C (SMOH@C) was synthesized, which was composited with 2D ordered mesoporous nanosheets (mNPC) to construct electrochemical sensors detecting PAT and PAP simultaneously. The prepared 2D/3D porous structure of mNPC/SMOH@C increased the exposure of active sites due to its large specific surface area. The introduction of a 3D carbon skeleton altered the charge transfer rate of SMOH@C, and the rich pore structure and oxygen-rich vacancies created favorable conditions for the diffusion and adsorption of PAP and PAT, which enabled the sensitive detection of PAT and PAP. The constructed mNPC/SMOH@C electrochemical sensor could simultaneously detect PAT (1 × 10-7 - 1 × 10-4 M) and PAP (5 × 10-8 - 1 × 10-4 M) with detection limits of 20.4 nM and 30.1 nM, respectively. The sensor has good repeatability (RSD <4 %) and reproducibility (RSD <4 %), and satisfactory recoveries (96.7-102.8 %) were obtained in the analysis of natural water samples. SIGNIFICANCE: In this paper, for the first time, we present the synthesis of 3D foam birnessite and its composite with mNPC for the electrochemical simultaneous detection of PAT and PAP. Our proposed strategy for fabricating 2D/3D porous composites lays the foundation for the design and synthesis of other porous materials. In addition, this study provides new ideas for developing efficient and practical electrochemical sensors for detecting pollutants in aquatic environments.

Detection of gallic acid in food using an ultra-sensitive electrochemical sensor based on glass carbon electrode modified by bimetal doped carbon nanopolyhedras.

Gallic acid is widely used as an antioxidant in food because of its good antioxidant function, but excessive intake induces side effects in humans, so it is essential to devise a highly responsive technique for detecting gallic acid. In this work, we synthesized ZIF-67@FePc by the one-pot method. The synthesized material is more stable at high temperatures compared to ZIF-67 and maintains its original morphology during pyrolysis, when iron was introduced as a second metal active site during the synthesis process. Subsequently, Co/FeOX@NC-800 was employed to fabricate a GA sensor on a GCE. The developed sensor exhibited remarkable sensitivity towards GA, featuring a low LOD of 1.30 nM and a linear range spanning from 5 to 4500 nM. The electrochemical sensors we have prepared also showed good selectivity, stability, and reproducibility. It has been successfully employed for detecting GA in actual samples such as apples, grapes, tomatoes, and red wine.

An ultrasensitive dietary caffeic acid electrochemical sensor based on Pd-Ru bimetal catalyst doped nano sponge-like carbon.

Caffeic acid (CA) is widely present in the human daily diet, and a reliable CA detection method is beneficial to food safety. Herein, we constructed a CA electrochemical sensor employing a glassy carbon electrode (GCE) which was modified by the bimetallic Pd-Ru nanoparticles decorated N-doped spongy porous carbon obtained by pyrolysis of the energetic metal-organic framework (MET). The high-energy bond N-NN in MET explodes to form N-doped sponge-like carbon materials (N-SCs) with porous structures, boosting the adsorptive capacity for CA. The addition of Pd-Ru bimetal improves the electrochemical sensitivity. The linear range of the PdRu/N-SCs/GCE sensor is 1 nM-100 nM and 100 nM-15 µM, with a low detection limit (LOD) of 0.19 nM. It has a high sensitivity (55 µA/µM) and repeatability. The PdRu/N-SCs/GCE sensor has been used to detect CA in actual samples of red wine, strawberries, and blueberries, providing a novel approach for CA detection in food analysis.

Ultrasensitive Determination of Natural Flavonoid Rutin Using an Electrochemical Sensor Based on Metal-Organic Framework CAU-1/Acidified Carbon Nanotubes Composites.

Rutin, a natural flavonol glycoside, is widely present in plants and foods, such as black tea and wheat tea. The antioxidant and anti-inflammatory effects of flavonoids are well known. In this study, a new electrochemical rutin sensor was developed using multiwalled carbon nanotubes/aluminum-based metal-organic frameworks (MWCNT/CAU-1) (CAU-1, a type of Al-MOF) as the electrode modification material. The suspension of multiwalled carbon tubes was dropped on the surface of the GCE electrode to make MWCNT/GCEs, and CAU-1 was then attached to the electrode surface by electrodeposition. MWCNTs and CAU-1 were characterized using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Due to the synergistic effect of CAU-1 and MWCNT-COOH, the prepared sensor showed an ultrasensitive electrochemical response to rutin. Under optimized conditions, the sensor showed a linear relationship between 1.0 × 10-9~3.0 × 10-6 M with a detection limit of 6.7 × 10-10 M (S/N = 3). The sensor also showed satisfactory stability and accuracy in the detection of real samples.

Ultrasensitive catechin electrochemical sensor based on uniform ordered mesoporous carbon hollow spheres (MCHSs) advanced carbon-based conductive materials.

Catechin is one of the flavonoids with antioxidant activity and has attracted great interest. A rapid and accurate detection of catechin is of great significance. Herein, an ultrasensitive catechin electrochemical sensor based on uniform ordered mesoporous carbon hollow spheres (MCHSs) advanced carbon-based conductive material modified glass carbon electrode was constructed. The MCHSs were synthesized by pyrolysis using nitrogen protection and template removal methods, and they exhibited excellent electrochemical detection for catechin owing to their high conductivity and uniform and small spheres with a large specific surface area and hollow structure. Under optimal conditions for the detection of catechin, the MCHSs/GCE showed a wider linear range (10 -1400 nM) and lower detection limit (LOD, 2.82 nM, (S/N = 3)). Furthermore, the electrochemical reaction sites and redox mechanisms of catechin were revealed by electrochemical behavior and density flooding theory. Moreover, the sensor we constructed exhibited good accuracy and stability for the detection of catechin in actual sample detections.

Ultrasensitive Luteolin Electrochemical Sensor Based on Novel Lamellar CuZn@ Nitrogen-Containing Carbon Nanosheets.

The Cu/Zn-zeolitic imidazolate framework (Cu/Zn-ZIF) was synthesized using the traditional hydrothermal method, and its surface morphology was controlled by adding polyvinylpyrrolidone (PVP) during its synthesis. It was then calcined at 800 °C to form the nitrogen-containing carbon material CuZn@NC, which improved the electron transfer rate. Scanning electron microscopy (SEM), X-ray crystal diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to investigate the surface morphology and structure. Finally, the electrochemical sensing platform for luteolin was effectively constructed by changing the metal-ion ratio during synthesis to achieve the most suitable electrode material. The sensor platform detects luteolin well, with an operating curve equation of Ip (A) = 0.0571C (nM) - 1.2913 and a minimum detection limit of 15 nM, and the platform has been successfully employed for luteolin detection in real samples.

Synthesis of Functionalized Vinylsilanes via Metal-Free Dehydrogenative Silylation of Enamides.

A novel method of metal-free dehydrogenative silylation of enamides has been developed. The desired functionalized vinylsilane products were obtained in moderate to good yield and with high stereoselectivities. This protocol displays good tolerance of various functionalities. Furthermore, the high chemoselectivity of this reaction enables us to introduce different unsaturated C-C moieties to the products. The ease of further derivatization of the products to other useful compounds also demonstrates the highly synthetic utility of the current methodology.

Copper-catalyzed silylation reactions of propargyl epoxides: easy access to 2,3-allenols and stereodefined alkenes.

Efficient silylation reactions of propargyl epoxides catalyzed by copper catalysts have been developed. Under mild reaction conditions, tri- and tetra-substituted functionalized allenols and alkenes could be selectively obtained in moderate to high yields via tuning the bases and solvents used in the reactions. This work provides straightforward and efficient approaches to the synthesis of multifunctionalized 2,3-allenols and stereodefined alkenes from the same starting material of propargyl epoxides.

[Synthesis and Properties of 1,11,15,25-Tetrahydroxy-4,8,18,22-Di (Bridged Dipropionate Carboxyl) Phthalocyanine Copper].

In this dissertation, we study the synthesis and character of new substituted Phthalocyanine. Due to the widely application of Pcs in the fields, such as the communication, medical treatment, chemical industry and so on, therefore, they have been a hot topic over several decades by scientists. Nowadays, scientists have prepared thousands of Pcs and their derivatives. However, along with the human society development and the progress in science and technology, the new phthalocyanine with novle characteristics are still the goal of the scientists. In this dissertion, the synthetic methods of the phthlocyanine is improved. The synthesis and characterization of 1,11,15,25-tetrahydroxy-4,8,18,22-di(bridged dipropionate carboxyl) phthalocyanines are reported in this paper. The mixtures of malonic acid and 3,6-dihydroxy-phthalonitrile was added to water under stiriing. Then, a catalyst amount of sulfuric acid was added. The first synthetic precursor, i. e., malonic acid 3,3'-bis(6-hydroxy phthalonitrile) butter, its molecular formula is C19H8N4O6. phthalocyanines was prepared by malonic acid 3,3'-bis(6-hydroxy phthalonitrile) butter and dihydrate zinc acetate, copper acetate monohydrate in n-amyl alcohol, using DBU as a catalyst under the 135 °C, molecular formula of phthalocyanine complexes is C38H16N8O12M. The product was characterized by Ultraviolet-visible (UV/Vis) Spectrum absorption and fluorescence, The results are agreement with the proposed structures. And electrochemical properties were studied.

Role of transient receptor potential vanilloid subetype 1 in the increase of thermal pain threshold by moxibustion.

UNLABELLED: OBTECTIVE: To explore the role of transient receptor potential vanilloid subetype 1 (TRPV1) in the increase of the thermal pain threshold by moxibustion. METHODS: Forty Kunming mice (20 ± 2) g were randomized into control group, capsaicin group, capsazepine group, moxibustion group and moxibustion + capsazepine (MC) group with 8 mice in each, and 16 C57BL/6 wild-type mice (18 ± 2) g were randomized into wild-type (WT) control group and WT moxibustion group with 8 mice in each, and 14 TRPV1 knockout mice (18 ± 2) g were randomized into knockout (KO) control group and KO moxibustion-group with 7 in each. Each mouse in the capsaicin group was subcutaneously injected with the amount of 0.1 mL/10 g into L5 and L6 spinal cords; each mouse in the capsazepine group was intraperitoneally injected with the amount of 0.1 mL/10 g. Similarly, each mouse in the moxibustion group was given a suspended moxibustion with specially-made moxa-stick for 20 min on L5 and L6 spinal cords. Each mouse in MC group was intraperitoneally injected with the amount of 0.1 mL/1 0 g first, then after 15 min was given a suspended moxibustion for 20 min on L5 and L6 spinal cords. Each mouse in WT moxibustion group and KO moxibustion group was given a suspended moxibustion with specially-made moxa-stick for 20 min on L5 and L6 spinal cords. The control group, WT control group and KO control group were of no treatment in any way. After all treatments were completed, the digital-display measurement instrument for thermal pain was used to measure the threshold of thermal pain in each group respectively. RESULTS: Compared with the control group, the thresholds of thermal pain in the moxibustion group and MC group were significantly increased (P <0.01); no significant changes in the thresholds in the capsaicin group and the capsazepine group (P > 0.05); compared with moxibustion group, he threshold of thermal in MC group was obviously decreased (P < 0.01). Compared with WT control group, the threshold of thermal pain in WT moxibustion group was significantly increased (P < 0.01); compared with KO control group, no changes in the threshold in KO moxibustion group (P > 0.05). CONCLUSION: TRPV1 participated in the process of increasing the threshold of thermal pain by stimulating L5 and L6 of mice spinal cord with burning mosa-stick.