Cu1.4Mn1.6O4 as a bifunctional transducer for potentiometric Cu2+ solid-contact ion-selective electrode.

Current potentiometric Cu2+ sensors mostly rely on polymer-membrane-based solid-contact ion-selective electrodes (SC-ISEs) that constitute ion-selective membranes (ISM) and solid contact (SC) for respective ion recognition and ion-to-electron transduction. Herein, we report an ISM-free Cu2+-SC-ISE based on Cu-Mn oxide (Cu1.4Mn1.6O4) as a bifunctional SC layer. The starting point is simplifying complex multi-interfaces for Cu2+-SC-ISEs. Specifically, ion recognition and signal transduction have been achieved synchronously by an ion-coupled-electron transfer of crystal ion transport and electron transfer of Mn4+/3+ in Cu1.4Mn1.6O4. The proposed Cu1.4Mn1.6O4 electrode discloses comparable sensitivity, response time, high selectivity and stability compared with present ISM-based potentiometric Cu2+ sensors. In addition, the Cu1.4Mn1.6O4 electrode also exhibits near Nernstian responses toward Cu2+ in natural water background. This work emphasizes an ISM-free concept and presents a scheme for the development of potentiometric Cu2+ sensors.

Effects of allicin on growth performance, antioxidant profile, and microbiota compared to monensin of growing goats.

Allicin is a sulfur-containing compound extracted from raw garlic (Allium sativum L.). We compared the effect of allicin addition on growth performance, serum biochemical parameters, and rumen microbiota of goats compared to monensin. Twenty-four Anhui white goats were assigned randomly to one of three dietary treatments: 1) a basal diet (CON); 2) the basal diet with allicin addition at 750 mg per head per day (AC); 3) the basal diet with monensin addition at 30 mg per kg of diet (MS). Animals were fed for 8 weeks. Results showed the average daily gain, and feed efficiency was increased with allicin and monensin addition. Serum levels of IgG, total superoxide dismutase, and glutathione peroxidase were higher in the AC group than those in the CON and MS groups. The microbiota analysis revealed that monensin addition mainly affected genera related to carbohydrate and protein metabolism, and allicin mainly affected genera related to energy metabolism and intestinal health. In conclusion, allicin could improve growth performance and have advantages over monensin in improving the antioxidant capacity and immune function of goats. Allicin may be a potential alternative to monensin.

Carbon fiber-based multichannel solid-contact potentiometric ion sensors for real-time sweat electrolyte monitoring.

Solid-contact ion-selective electrodes (SC-ISEs) feature miniaturization and integration that have gained extensive attention in non-invasive wearable sweat electrolyte sensors. The state-of-the-art wearable SC-ISEs mainly use polyethylene terephthalate, gold and carbon nanotube fibers as flexible substrates but suffer from uncomfortableness, high cost and biotoxicity. Herein, we report carbon fiber-based SC-ISEs to construct a four-channel wearable potentiometric sensor for sweat electrolytes monitoring (Na+/K+/pH/Cl-). The carbon fibers were extracted from commercial cloth, of which the starting point is addressing the cost and reproducibility issues for flexible SC-ISEs. The bare carbon fiber electrodes exhibited reversible voltammetric and stable impedance performances. Further fabricated SC-ISEs based on corresponding ion-selective membranes disclosed Nernstian sensitivity and anti-interface ability toward both ions and organic species in sweat. Significantly, these carbon fiber-based SC-ISEs revealed high reproducibility of standard potentials between normal and bending states. Finally, a textile-based sensor was integrated with a solid-contact reference electrode, which realized on-body sweat electrolytes analysis. The results displayed high accuracy compared with ex-situ tests by ion chromatography. This work highlights carbon fiber-based multichannel wearable potentiometric ion sensors with low cost, biocompatibility and reproducibility.

Copper infused fabric attenuates inflammation in macrophages.

While inflammation is an important immune response for protection from infections, excessive or prolonged inflammation can lead to a variety of debilitating diseases including skin disease, diabetes, heart disease, stroke, autoimmune diseases and cancer. Inflammation is a graded response that is typically initiated when resident macrophages sense the presence of pathogens or damage in the tissue and produce inflammatory cytokines and chemokines to kill the pathogen, clear debris and dead tissue, and initiate tissue repair. Here we show that copper-infused fabrics can prevent inflammation by blocking the production of inflammatory cytokines from macrophages after being exposed to LPS, a component of bacterial cell wall. Mechanistically, we show that copper-infused fabrics can significantly reduce the NF-κB and IRF3 activation in LPS-stimulated macrophages. Given the importance of excessive inflammation in diabetes, we show that copper can reduce insulin resistance mediated by inflammatory cytokines in muscle cells. Our data show that copper infused fabrics may be useful to reduce excessive inflammation in macrophages and improve insulin sensitivity in skeletal muscles.

Directly Using Ti3C2Tx MXene for a Solid-Contact Potentiometric pH Sensor toward Wearable Sweat pH Monitoring.

The level of hydrogen ions in sweat is one of the most important physiological indexes for the health state of the human body. As a type of two-dimensional (2D) material, MXene has the advantages of superior electrical conductivity, a large surface area, and rich functional groups on the surface. Herein, we report a type of Ti3C2Tx-based potentiometric pH sensor for wearable sweat pH analysis. The Ti3C2Tx was prepared by two etching methods, including a mild LiF/HCl mixture and HF solution, which was directly used as the pH-sensitive materials. Both etched Ti3C2Tx showed a typical lamellar structure and exhibited enhanced potentiometric pH responses compared with a pristine precursor of Ti3AlC2. The HF-Ti3C2Tx disclosed the sensitivities of -43.51 ± 0.53 mV pH-1 (pH 1-11) and -42.73 ± 0.61 mV pH-1 (pH 11-1). A series of electrochemical tests demonstrated that HF-Ti3C2Tx exhibited better analytical performances, including sensitivity, selectivity, and reversibility, owing to deep etching. The HF-Ti3C2Tx was thus further fabricated as a flexible potentiometric pH sensor by virtue of its 2D characteristic. Upon integrating with a solid-contact Ag/AgCl reference electrode, the flexible sensor realized real-time monitoring of pH level in human sweat. The result disclosed a relatively stable pH value of ~6.5 after perspiration, which was consistent with the ex situ sweat pH test. This work offers a type of MXene-based potentiometric pH sensor for wearable sweat pH monitoring.

Carbon-Based Transducers for Solid-Contact Calcium Ion-Selective Electrodes: Mesopore and Nitrogen-Doping Effects.

Solid-contact ion-selective electrodes (SC-ISEs) exhibit great potential in the detection of routine and portable ions which rely on solid-contact (SC) materials for the transduction of ions to electron signals. Carbon-based materials are state-of-the-art SC transducers due to their high electrical double-layer (EDL) capacitance and hydrophobicity. However, researchers have long searched for ways to enhance the interfacial capacitance in order to improve the potential stability. Herein, three representative carbon-based SC materials including nitrogen-doped mesoporous carbon (NMC), reduced graphene oxide (RGO), and carbon nanotubes (CNT) were compared. The results disclose that the NMC has the highest EDL capacitance owing to its mesopore structure and N-doping while maintaining high hydrophobicity so that no obvious water-layer effect was observed. The Ca2+-SC-ISEs based on the SC of NMC exhibited high potential stability compared with RGO and CNT. This work offers a guideline for the development of carbon-material-based SC-ISEs through mesoporous and N-doping engineering to improve the interfacial capacitance. The developed NMC-based solid-contact Ca2+-SC-ISE exhibited a Nernstian slope of 26.3 ± 3.1 mV dec-1 ranging from 10 µM to 0.1 M with a detection limit of 3.2 µM. Finally, a practical application using NMC-based SC-ISEs was demonstrated through Ca2+ ion analysis in mineral water and soil leaching solutions.

Beyond Nonactin: Potentiometric Ammonium Ion Sensing Based on Ion-selective Membrane-free Prussian Blue Analogue Transducers.

The determination of ammonium ions (NH4+) is of significance to environmental, agriculture, and human health. Potentiometric NH4+ sensors based on solid-contact ion selective electrodes (SC-ISEs) feature point-of-care testing and miniaturization. However, the state-of-the-art SC-ISEs of NH4+ during the past 20 years strongly rely on the organic ammonium ionophore-based ion selective membrane (ISM), typically by nonactin for the NH4+ recognition. Herein, we report a Prussian blue analogue of copper(II)-hexacyanoferrate (CuHCF) for an ISM-free potentiometric NH4+ sensor without using the ionophores. CuHCF works as a bifunctional transducer that could realize the ion-to-electron transduction and NH4+ recognition. CuHCF exhibits competitive analytical performances regarding traditional nonactin-based SC-ISEs of NH4+, particularly for the selectivity toward K+. The cost and preparation process have been remarkably reduced. The theoretical calculation combined with electrochemical tests further demonstrate that relatively easier intercalation of NH4+ into the lattices of CuHCF determines its selectivity. This work provides a concept of the ISM-free potentiometric NH4+ sensor beyond the nonactin ionophore through a CuHCF bifunctional transducer.

Recent Advances in Wearable Potentiometric pH Sensors.

Wearable sensors reflect the real-time physiological information and health status of individuals by continuously monitoring biochemical markers in biological fluids, including sweat, tears and saliva, and are a key technology to realize portable personalized medicine. Flexible electrochemical pH sensors can play a significant role in health since the pH level affects most biochemical reactions in the human body. pH indicators can be used for the diagnosis and treatment of diseases as well as the monitoring of biological processes. The performances and applications of wearable pH sensors depend significantly on the properties of the pH-sensitive materials used. At present, existing pH-sensitive materials are mainly based on polyaniline (PANI), hydrogen ionophores (HIs) and metal oxides (MOx). In this review, we will discuss the recent progress in wearable pH sensors based on these sensitive materials. Finally, a viewpoint for state-of-the-art wearable pH sensors and a discussion of their existing challenges are presented.

A Solid-Contact Reference Electrode Based on Silver/Silver Organic Insoluble Salt for Potentiometric Ion Sensing.

Solid-contact ion-selective electrodes are a type of ion measurement devices that have been focused in wearable biotechnology based on the features of miniaturization and integration. However, the solid-contact reference electrodes (SC-REs) remain relatively less focused compared with numerous working (or indicator) electrodes. Most SC-REs in wearable sensors rely on Ag/AgCl reference electrodes with solid electrolytes, for example, the hydrophilic electrolyte salts in polymer matrix, but face the risk of electrolyte leakage. Herein, we report a type of SC-REs based on the silver/silver tetraphenylborate (Ag/AgTPB) organic insoluble electrode. The SC-RE consists of a Ag substrate, a solid contact (AgTPB), and a plasticized poly(vinyl chloride) (PVC) membrane containing the hydrophobic organic salt of tetrabutylammonium tetraphenylborate (TBATPB). The potentiometric measurements demonstrated that the SC-RE of Ag/AgTPB/PVC-TBATPB showed a reproducible standard potential in various electrolytes and disclosed high long-term stability. This SC-RE was further fabricated on a flexible substrate and integrated into all-solid-state wearable potentiometric ion sensor for sweat Cl- monitoring.

Solid-Contact Potentiometric Anion Sensing Based on Classic Silver/Silver Insoluble Salts Electrodes without Ion-Selective Membrane.

Current solid potentiometric ion sensors mostly rely on polymeric-membrane-based, solid-contact, ion-selective electrodes (SC-ISEs). However, anion sensing has been a challenge with respect to cations due to the rareness of anion ionophores. Classic metal/metal insoluble salt electrodes (such as Ag/AgCl) without an ion-selective membrane (ISM) offer an alternative. In this work, we first compared the two types of SC-ISEs of Cl- with/without the ISM. It is found that the ISM-free Ag/AgCl electrode discloses a comparable selectivity regarding organic chloride ionophores. Additionally, the electrode exhibits better comprehensive performances (stability, reproducibility, and anti-interference ability) than the ISM-based SC-ISE. In addition to Cl-, other Ag/AgX electrodes also work toward single and multi-valent anions sensing. Finally, a flexible Cl- sensor was fabricated for on-body monitoring the concentration of sweat Cl- to illustrate a proof-of-concept application in wearable anion sensors. This work re-emphasizes the ISM-free SC-ISEs for solid anion sensing.

Synthesis of Enantioenriched α,α-Difluoro-ß-arylbutanoic Esters by Pd-Catalyzed Asymmetric Hydrogenation.

Synthesis of optically active gem-difluorinated organic molecules attracts a great deal of interest due to their unique properties in pharmaceutical and agrochemical areas. Herein, a series of enantioenriched α,α-difluoro-ß-arylbutanoic esters were prepared in high yields (83-99%) with moderate to excellent enantioselectivities (≤97:3 er) by palladium-catalyzed asymmetric hydrogenation.

Nickel-catalyzed regio- and diastereoselective hydroarylative and hydroalkenylative cyclization of 1,6-dienes.

An unprecedented nickel-catalyzed hydroarylative and hydroalkenylative cyclization of unsymmetrically substituted 1,6-dienes with organoboronic acid was developed by using MeOH as the hydrogen source and employing commercially available Ni(η2-1,5-cyclooctadiene)2 as the catalyst. A series of biologically interesting cyclic products were afforded in moderate to excellent yields with high regio- and diastereoselectivities.

Lutidine-Based Chiral Pincer Manganese Catalysts for Enantioselective Hydrogenation of Ketones.

A series of MnI complexes containing lutidine-based chiral pincer ligands with modular and tunable structures has been developed. The complex shows unprecedentedly high activities (up to 9800 TON; TON=turnover number), broad substrate scope (81 examples), good functional-group tolerance, and excellent enantioselectivities (85-98 % ee) in the hydrogenation of various ketones. These aspects are rare in earth-abundant metal catalyzed hydrogenations. The utility of the protocol have been demonstrated in the asymmetric synthesis of a variety of key intermediates for chiral drugs. Preliminary mechanistic investigations indicate that an outer-sphere mode of substrate-catalyst interactions probably dominates the catalysis.

Gelator-polysaccharide hybrid hydrogel for selective and controllable dye release.

In this paper, 1,4-bi(phenylalanine-diglycol)-benzene (PDB) based Low-Molecular-Weight-Gelator (LMWG) hydrogels are modified using hydrophilic polysaccharide (sodium alginate). A set of techniques including Fourier transform infrared (FT-IR) spectroscopy, (1)H Nuclear Magnetic Resonance ((1)H NMR), X-ray powder diffraction (XRD), Ultraviolet-Visible (UV-Vis), and circular dichroism (CD) had confirmed a ß-turn arrangement of PDB gelators and a semi-interpenetrating network (semi-IPN), which was formed through hydrogen bonds between LMWG fibers and polysaccharide chains. The evaluation of physicochemical properties of hydrogels indicates that gelator-polysaccharide hybrid hydrogels possess better mechanical and water retention properties than LMWG hydrogels. The release study of dyes (model drug) from both LMWG and hybrid hydrogels was carried out. Compared with PDB based hydrogels, hybrid hydrogels show a selective and controllable release property for certain dyes. The results suggest LMWG-polysaccharide hybrid gels may find potential applications as promising drug delivery vehicles for drug molecules.