Metal-organic framework-based aptasensor utilizing a novel electrochemiluminescence system for detecting acetamiprid residues in vegetables.

The work was based on N-(4-Aminobutyl)-N-ethylisoluminol (ABEI)-functionalized Fe-MIL-101 and gold nanoparticles (AuNPs) as sensing materials, and an electrochemiluminescence (ECL) aptasensor was constructed for detecting acetamiprid. As a metal-organic framework (MOF) material, Fe-MIL-101, was renowned for its unique three-dimensional network structure and efficient catalytic capability. ABEI, a common ECL reagent, was widely applied. ABEI was introduced into the Fe-MIL-101 structure as a luminescence functionalization reagent to form Fe-MIL-101@ABEI. This approach avoided limitations on the loading capacity of luminescent reagents imposed by modification and encapsulation methods. With character of excellent catalytic activity and ease of bioconjugation, AuNPs offered significant advantages in biosensing. Leveraging the reductive properties of ABEI, AuNPs were reduced around Fe-MIL-101@ABEI, resulting in the modified luminescent functionalized material denoted as Fe-MIL-101@ABEI@AuNPs. An aptamer was employed as a recognition element and was modified accordingly. The aptamer was immobilized on Fe-MIL-101@ABEI@AuNPs through gold-sulfur (Au-S) bonds. After capturing acetamiprid, the aptamer induced a decrease in the ECL signal intensity within the ABEI-hydrogen peroxide (H2O2) system, enabling the quantitative detection of acetamiprid. The aptasensor displayed remarkable stability and repeatability, featured a detection range of 1×10-3-1×102 nM, and had a limit of detection (LOD) of 0.3 pM (S/N=3), which underscored its substantial practical application potential.

Synthesis, Structure, Properties, and Applications of Fluorinated Polyurethane.

Fluorinated polyurethane (FPU) is a new kind of polyurethane (PU) material with great applicational potential, which is attributed to its high bond energy C-F bonds. Its unique low surface energy, excellent thermal stability, and chemical stability have attracted considerable research attention. FPU with targeted performance can be precisely synthesized through designing fluorochemicals as hard segments, soft segments, or additives and changes to the production process to satisfy the needs of coatings, clothing textiles, and the aerospace and biomedical industries for materials that are hydrophobic and that are resistant to weathering, heat, and flames and that have good biocompatibility. Here, the synthesis, structure, properties, and applications of FPU are comprehensively reviewed. The aims of this research are to shed light on the design scheme, synthesis method, structure, and properties of FPU synthesized from different kinds of fluorochemicals and their applications in different fields and the prospects for the future development of FPU.

Electrochemiluminescence detection of diazinon in vegetables based on the synergistic interaction of WO3-x dots with Au@SiO2 nanocapsules.

In this work, a simple synthesis of low-toxicity transition metal material of WO3-x dots was used as a co-reactant with Au@SiO2 as a core-shell material and a signal amplification factor to collaboratively promote Ru(bpy)32+ electrochemiluminescence (ECL) for the construction of a highly sensitive aptasensor for the detection of diazinon (DZN) in vegetables. Electrodes modified with multi-walled carbon nanotubes-chitosan composite membranes (MWCNTs-CS) were used to load and immobilize more Ru(bpy)32+.can load more Ru(bpy)32+. WO3-x dots synthesized by a simple method showed excellent ECL efficiency as a novel co-reactant for Ru(bpy)32+. Under optimized conditions, this aptasensor for DZN has a wide detection range (10 pg mL-1 - 1 µg mL-1.) and a low detection limit (0.0197 ng L-1). The aptasensor has shown good results in the analysis of real samples in the experiment. This work provides a new approach to the construction of a novel electrochemiluminescence sensor for the detection of pesticides.

Novel electrochemiluminescence aptasensor based on AuNPs-ABEI encapsulated TiO2 nanorod for the detection of acetamiprid residues in vegetables.

Gold nanoparticles (AuNPs)@N-(4-aminobutyl)-N-ethylisoluminol (ABEI)@Titanium dioxide nanorods (TiO2NRs) were used as sensing materials to produce a unique encapsulated nanostructure aptasensor for the detection of acetamiprid residues in this work. ABEI, an analog of luminol, was extensively used as an electrochemiluminescence (ECL) reagent. The ECL mechanism of ABEI- hydrogen peroxide (H2O2) system had connections to a number of oxygen-centered free radicals. TiO2NRs improved ECL response with high electron transfer and a specific surface area. AuNPs were easy to biolabel and could catalyze H2O2 to enhance ECL signal. AuNPs were wrapped around TiO2NRs by utilizing the reduction property of ABEI to form wrapped modified nanomaterials. The sulfhydryl-modified aptamer bound to the nanomaterial by forming gold-sulfur (Au-S) bonds. The aptamer selectively bound to its target with the addition of acetamiprid, which caused a considerable decrease in ECL intensity and enabled quantitative detection of acetamiprid. The aptasensor showed good stability, repeatability and specificity with a broad detection range (1×10-2-1×103 nM) and a lower limit of detection (3 pM) for acetamiprid residues in vegetables. Overall, this aptasensor presents a simple and highly sensitive method for ECL detecting acetamiprid, with potential applications in vegetable safety monitoring.

The association between working memory precision and the nonlinear dynamics of frontal and parieto-occipital EEG activity.

Electrophysiological working memory (WM) research shows brain areas communicate via macroscopic oscillations across frequency bands, generating nonlinear amplitude modulation (AM) in the signal. Traditionally, AM is expressed as the coupling strength between the signal and a prespecified modulator at a lower frequency. Therefore, the idea of AM and coupling cannot be studied separately. In this study, 33 participants completed a color recall task while their brain activity was recorded through EEG. The AM of the EEG data was extracted using the Holo-Hilbert spectral analysis (HHSA), an adaptive method based on the Hilbert-Huang transforms. The results showed that WM load modulated parieto-occipital alpha/beta power suppression. Furthermore, individuals with higher frontal theta power and lower parieto-occipital alpha/beta power exhibited superior WM precision. In addition, the AM of parieto-occipital alpha/beta power predicted WM precision after presenting a target-defining probe array. The phase-amplitude coupling (PAC) between the frontal theta phase and parieto-occipital alpha/beta AM increased with WM load while processing incoming stimuli, but the PAC itself did not predict the subsequent recall performance. These results suggest frontal and parieto-occipital regions communicate through theta-alpha/beta PAC. However, the overall recall precision depends on the alpha/beta AM following the onset of the retro cue.

Characterization of oxidative stress-induced cgahp, a gene coding for alkyl hydroperoxide reductase, from industrial importance Corynebacterium glutamicum.

Alkyl hydroperoxide reductase (Ahp), comprised of four different subunits AhpC, AhpD, AhpE, and AhpF, is a thiol-based antioxidative enzyme with the ability to protect bacteria against oxidative stress. Functionally, AhpC and AhpE considered as peroxidases directly detoxify peroxides, while AhpD and AhpF as oxidoreductases restore oxidized peroxidases to their reduced form. Corynebacterium glutamicum ncgl0877 encodes a putative Ahp with a unique Cys-Pro-Phe-Cys (C-P-G-C) active-site motif, similar with those of the thiol-disulfide oxidoreductases such as thioredoxin (Trx), mycoredoxin-1 (Mrx1) and AhpD. However, its physiological and biochemical functions remain unknown in C. glutamicum. Here, we report that NCgl0877, designated CgAhp, is involved in the protection against organic peroxide (OP) stress. The cgahp-deleted strain is notably more sensitive to OP stress. The cgahp expression is controlled by a MarR-type transcriptional repressor OasR (organic peroxide- and antibiotic-sensing regulator). The physiological role of CgAhp in resistance to OP stresses is corroborated by its induced expression under stresses. Although CgAhp has a weak peroxidase activity toward OP, it mainly supports the OP-scavenging activity of the thiol-dependent peroxidase preferentially linked to the dihydrolipoamide dehydrogenase (Lpd)/dihydrolipoamide succinyltransferase (SucB)/NADH system. The C-P-G-C motif of CgAhp is essential to maintain the reductase activity. In conclusion, our study identifies CgAhp, behaving like AhpD, as a key disulfide oxidoreductase involved in the oxidative stress tolerance and the functional electron donor for peroxidase.

Synthesis and Properties of the Novel High-Performance Hydroxyl-Terminated Liquid Fluoroelastomer.

Functional liquid fluoroelastomers are in high demand in new energy fields. And these materials have potential applications in high-performance sealing materials and as electrode materials. In this study, a novel high-performance hydroxyl-terminated liquid fluoroelastomer (t-HTLF) with a high fluorine content, temperature resistance, and curing efficiency was synthesised from a terpolymer of vinylidene fluoride (VDF), tetrafluoroethylene (TFE), and hexafluoropylene (HFP). A carboxyl-terminated liquid fluoroelastomer (t-CTLF) with controllable molar mass and end-group content was first prepared from a poly(VDF-ter-TFE-ter-HFP) terpolymer using a unique oxidative degradation method. Subsequently, an efficient "one-step" reduction of the carboxyl groups (COOH) in t-CTLF into hydroxyl groups (OH) was achieved via the functional-group conversion method using lithium aluminium hydride (LiAlH4) as the reductant. Thus, t-HTLF with a controllable molar mass and end-group content and highly active end groups was synthesised. Owing to the efficient curing reaction between OH and isocyanate groups (NCO), the cured t-HTLF exhibits good surface properties, thermal properties, and chemical stability. The thermal decomposition temperature (Td) of the cured t-HTLF reaches 334 °C, and it exhibits hydrophobicity. The oxidative degradation, reduction, and curing reaction mechanisms were also determined. The effects of solvent dosage, reaction temperature, reaction time, and ratio of the reductant to the COOH content on the carboxyl conversion were also systematically investigated. An efficient reduction system comprising LiAlH4 can not only achieve an efficient conversion of the COOH groups in t-CTLF to OH groups but also the in situ hydrogenation and addition reactions of residual double bonds (C=C) groups in the chain, such that the thermal stability and terminal activity of the product are improved while maintaining a high fluorine content.

Perfluorooctanoic Acid (PFOA) Incorporated into Iron Particles Promoted the Formation of Disinfection Byproducts under Drinking Water Conditions.

Perfluorooctanoic acid (PFOA) is an emerging persistent organic pollutant that is frequently detected throughout the drinking water supply system. Here, we first found that PFOA could significantly increase the formation of disinfection byproducts (DBPs) in unlined iron pipes (UIPs) during the distribution process. The increased DBPs were not due to the reaction of PFOA itself with free chlorine, but the in situ formed Fe-PFOA complex played a key role. Notably, PFOA could enhance iron release from UIPs and was greatly incorporated into the iron particles to form Fe-PFOA complex. The •OH generated by the Fe-PFOA heterogeneous reaction could break large dissolved organic matter into small molecules that had higher reactivity with chlorine. In addition, DBP precursors with more aromatic structures were favorable for forming strong Fe-π interactions with Fe-PFOA complex, resulting in more •OH for the formation of aromatic DBPs. The cytotoxicity test showed that the viability of cells exposed to DBPs from UIPs with 100 ng/L PFOA was 46.9%, while that without PFOA was 67.91%. Overall, this study provided a new perspective on the risk of PFOA, with a focus not on PFOA itself but on its potential to promote DBP-associated toxicity in iron-based drinking water distribution pipes.

Selective Elimination of NRF2-Activated Cells by Competition With Neighboring Cells in the Esophageal Epithelium.

BACKGROUND & AIMS: NF-E2-related factor 2 (NRF2) is a transcription factor that regulates cytoprotective gene expression in response to oxidative and electrophilic stresses. NRF2 activity is mainly controlled by Kelch-like ECH-associated protein 1 (KEAP1). Constitutive NRF2 activation by NRF2 mutations or KEAP1 dysfunction results in a poor prognosis for esophageal squamous cell carcinoma (ESCC) through the activation of cytoprotective functions. However, the detailed contributions of NRF2 to ESCC initiation or promotion have not been clarified. Here, we investigated the fate of NRF2-activated cells in the esophageal epithelium. METHODS: We generated tamoxifen-inducible, squamous epithelium-specific Keap1 conditional knockout (Keap1-cKO) mice in which NRF2 was inducibly activated in a subset of cells at the adult stage. Histologic, quantitative reverse-transcription polymerase chain reaction, single-cell RNA-sequencing, and carcinogen experiments were conducted to analyze the Keap1-cKO esophagus. RESULTS: KEAP1-deleted/NRF2-activated cells and cells with normal NRF2 expression (KEAP1-normal cells) coexisted in the Keap1-cKO esophageal epithelium in approximately equal numbers, and NRF2-activated cells formed dysplastic lesions. NRF2-activated cells exhibited weaker attachment to the basement membrane and gradually disappeared from the epithelium. In contrast, neighboring KEAP1-normal cells exhibited accelerated proliferation and started dominating the epithelium but accumulated DNA damage that triggered carcinogenesis upon carcinogen exposure. CONCLUSIONS: Constitutive NRF2 activation promotes the selective elimination of epithelial cells via cell competition, but this competition induces DNA damage in neighboring KEAP1-normal cells, which predisposes them to chemical-induced ESCC.

Impact of initial chlorine concentration on water quality change in old unlined iron pipes.

Unlined iron pipe (UIP) is still widely in use in drinking water distribution systems (DWDS), discoloration easily happens after a long-time retention due to iron release, but the influence of initial chlorine on water quality under this condition is not clear. Here, we studied the water quality changes in UIP section reactors under different initial chlorine dosages. Results showed that chlorine could disappeared rapidly within 0.5 h in the UIP. The water with higher initial chlorine (5 mg/L) had higher turbidity in a short time (within 1.5 h), but for a longer retention time (2∼12 h), the highest turbidity was in the iron pipe without initial chlorine. Interestingly, a clear increase in adenosine triphosphate in the UIPs was observed with the increase of initial chlorine, which was in accordance with the results of heterotrophic plate count. Polysaccharide and protein increased with the increase of initial chlorine, which would benefit the formation of a protective layer to inhibit corrosion. This study reflects that during the overnight retention in UIP, raising chlorine would be effective to control discoloration, but chemical and microbiological risks may increase.

Structure, preparation and properties of liquid fluoroelastomers with different end groups.

In order to design and prepare liquid fluoroelastomers with different end groups, and reveal the relationship between the molecular chain structure and properties, we studied on the oxidation degradation method and functional group conversion method to prepare carboxyl-terminated and hydroxyl-terminated liquid fluoroelastomers, respectively. The reaction mechanisms were also deduced. Furthermore, the curing system was created for liquid fluoroelastomers, and systematically analyzed their properties. The sequence type and content of the -C[double bond, length as m-dash]C- and oxygen-containing groups in the samples were measured and characterized by attenuated total reflectance/Fourier transform infrared (ATR-FTIR) spectroscopy, 1H nuclear magnetic resonance (1H-NMR), 19F-NMR spectroscopy and chemical titration, the molecular weights of liquid fluoroelastomers were measured by gel permeation chromatography (GPC). Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to examine the thermal properties, while a viscometer was used to measure the dynamic viscosity of the liquid fluoroelastomers. Then the mechanical and surface properties of the cured samples were examined by universal testing machine and contact angle measurement instrument, respectively. The results show that carboxyl-terminated liquid fluoroelastomer with 2.71 wt% carboxyl terminal groups can be prepared by oxidation degradation method. When lithium aluminium hydride (LiAlH4) was used as the reducing agent, it can efficiently convert carboxyl group to hydroxyl group with a conversion rate of more than 95%. In addition, it can be seen that the dynamic viscosity of the liquid fluoroelastomers were all decreased with the increase of temperature, and it is similar to about 10 Pa s at 70 °C. Compared with carboxyl-terminated liquid fluoroelastomers, hydroxyl-terminated liquid fluoroelastomers has higher curing reactivity, higher glass transition temperature (T g) and thermal decomposition temperature (T d), and better mechanical properties of cured samples. The two types of liquid fluoroelastomers with distinct end groups presented distinct hydrophilicity.

Bio-Based Eucommia ulmoides Gum Composites with High Electromagnetic Interference Shielding Performance.

Herein, high-performance electromagnetic interference (EMI) shielding bio-based composites were prepared by using EUG (Eucommia ulmoides gum) with a crystalline structure as the matrix and carbon nanotube (CNT)/graphene nanoplatelet (GNP) hybrids as the conductive fillers. The morphology of the CNT/GNP hybrids in the CNT/GNP/EUG composites showed the uniform distribution of CNTs and GNPs in EUG, forming a denser filler network, which afforded improved conductivity and EMI shielding effect compared with pure EUG. Accordingly, EMI shielding effectiveness values of the CNT/GNP/EUG composites reached 42 dB in the X-band frequency range, meeting the EMI shielding requirements for commercial products. Electromagnetic waves were mainly absorbed via conduction losses, multiple reflections from interfaces and interfacial dipole relaxation losses. Moreover, the CNT/GNP/EUG composites exhibited attractive mechanical properties and high thermal stability. The combination of excellent EMI shielding performance and attractive mechanical properties render the as-prepared CNT/GNP/EUG composites attractive candidates for various applications.

Synthesis and characterization of biobased thermoplastic polyester elastomers containing Poly(butylene 2,5-furandicarboxylate).

A series of sustainable and reprocessible thermoplastic polyester elastomers P(BF-PBSS)s were synthesized using dimethyl-2,5-furandicarboxylate, 1,4-butanediol, and synthetic low-molecular-weight biobased polyester (PBSS). The P(BF-PBSS)s contain poly(butylene 2,5-furandicarboxylate) (PBF) as their hard segment and PBSS as their soft segment. The microstructures of the P(BF-PBSS)s were confirmed by nuclear magnetic resonance, demonstrating that a higher content of the soft segment was incorporated into P(BF-PBSS)s with higher PBSS content. Interestingly, dynamic mechanical analysis indicated that P(BF-PBSS)s comprised two domains: crystalline PBF and a mixture of amorphous PBF and PBSS. Consequently, the microphase separations of P(BF-PBSS)s were mainly induced by the crystallization of their PBF segments. More importantly, the thermal, crystallization, and mechanical properties could be tailored by tuning the PBSS content. Our results indicate that the as-prepared P(BF-PBSS)s are renewable, thermally stable, and nontoxic, and have good tensile properties, indicating that they could be potentially applied in biomedical materials.

Hot nitric acid diffusion in fluoroelastomer composite and its degradation.

Fluoroelastomers (FKM) are vital sealing materials in acidic environment and their failure can cause severe safety problems. Therefore, investigation of the degradation behavior and mechanism of FKM materials is of great significant. Herein, we investigate a diffusion model of an acidic solution into an FKM composite and its degradation behavior upon immersion in hot nitric acid solution. The results indicate that the diffusion process of the HNO3 solution into the FKM composite conforms to the Fick diffusion model at a low concentration of nitric acid solution. Besides, the concentration of HNO3 solution affects the diffusion process of solvent molecules and the dissolution process of the filler particles to some extent. SEM showed that the surface topography of the FKM was significantly altered after it was immersed in HNO3 solution. The structural and chemical changes of the FKM were studied using ATR-FTIR, SEM-EDS and MAS NMR, which demonstrated the occurrence of decrosslinking via hydrolysis of the crosslinks and backbone cleavage by dehydrofluorination. This was also manifested by the decrease in crosslinking degree and mechanical properties. The present study is helpful for revealing the chemical changes in FKM in hot HNO3 solution.

Cumulative live birth and surplus embryo incidence after frozen-thaw cycles in PCOS: how many oocytes do we need?

PURPOSE: This study aimed to evaluate the cumulative live birth rate (CLBR) and surplus embryo rate of polycystic ovarian syndrome (PCOS) patients during in vitro fertilization and embryo transfer (IVF-ET) treatment. METHODS: In this retrospective cohort study, we analyzed 1142 PCOS patients who underwent first IVF in our institution between January 2011 and December 2014. All patients were categorized into five groups according to the number of oocytes retrieved. Main outcomes include CLBR and surplus embryo rate. RESULTS: A strong correlation was observed between number of oocytes retrieved and CLBR as well as surplus embryo rate in PCOS patients. CLBR was elevated with the increasing number of oocytes and plateaued when oocyte number was up to ten, whereas the surplus embryo rate steadily increased in line with the increase of oocyte number. Patients transferred with frozen embryos showed higher CLBR and LBR during first ET than patients transferred with fresh embryos. CONCLUSIONS: For PCOS patients, retrieving more than ten oocytes leads to no significant benefit to CLBR but generates surplus embryos. Thus, moderate ovarian stimulation should be reconsidered during IVF treatment.

Metabolomic characterization of a low phytic acid and high anti-oxidative cultivar of turmeric.

Turmeric, the rhizome of Curcuma longa, has a long history of use as a spice and also as a traditional medicine in many Asian countries. To reveal unique morphological features of a newly registered Curcuma cultivar, C. longa cv. Okinawa Ougon (Ougon), non-targeted LC-MS and GC-MS analyses were conducted. The analysis revealed its distinctive chemical properties: lower amount of phytic acid and inorganic metals such as Fe, Mn, and Al, as well as higher concentrations of reduced derivatives of curcuminoids, such as dihydrobisdemethoxycurcumin, tetrahydrobisdemethoxycurcumin, dihydrodemethoxycurcumin, and tetrahydrodemethoxycurcumin. In addition, germacrane-type sesquiterpenes were almost absent although α-humulene and ß-caryophyllene, generated by the same biosynthetic route, were present. Presumably the alternation of the metal ion content, serving as a cofactor of sesquiterpene synthase, modulates the resulting variation of the sesquiterpenes. In summary, the cultivar Ougon is considered a promising candidate for functional food additives.

Targeted Integration of RNA-Seq and Metabolite Data to Elucidate Curcuminoid Biosynthesis in Four Curcuma Species.

Curcuminoids, namely curcumin and its analogs, are secondary metabolites that act as the primary active constituents of turmeric (Curcuma longa). The contents of these curcuminoids vary among species in the genus Curcuma. For this reason, we compared two wild strains and two cultivars to understand the differences in the synthesis of curcuminoids. Because the fluxes of metabolic reactions depend on the amounts of their substrate and the activity of the catalysts, we analyzed the metabolite concentrations and gene expression of related enzymes. We developed a method based on RNA sequencing (RNA-Seq) analysis that focuses on a specific set of genes to detect expression differences between species in detail. We developed a 'selection-first' method for RNA-Seq analysis in which short reads are mapped to selected enzymes in the target biosynthetic pathways in order to reduce the effect of mapping errors. Using this method, we found that the difference in the contents of curcuminoids among the species, as measured by gas chromatography-mass spectrometry, could be explained by the changes in the expression of genes encoding diketide-CoA synthase, and curcumin synthase at the branching point of the curcuminoid biosynthesis pathway.