Tunable Non-Enzymatic Glucose Electrochemical Sensing Based on the Ni/Co Bimetallic MOFs.

Constructing high-performance glucose sensors is of great significance for the prevention and diagnosis of diabetes, and the key is to develop new sensitive materials. In this paper, a series of Ni2Co1-L MOFs (L = H2BPDC: 4,4'-biphenyldicarboxylic acid; H2NDC: 2,6-naphthalenedicarboxylic acid; H2BDC: 1,4-benzenedicarboxylic acid) were synthesized by a room temperature stirring method. The effects of metal centers and ligands on the structure, compositions, electrochemical properties of the obtained Ni2Co1-L MOFs were characterized, indicating the successful preparation of layered MOFs with different sizes, stacking degrees, electrochemical active areas, numbers of exposed active sites, and glucose catalytic activity. Among them, Ni2Co1-BDC exhibits a relatively thin and homogeneous plate-like morphology, and the Ni2Co1-BDC modified glassy carbon electrode (Ni2Co1-BDC/GCE) has the highest electrochemical performance. Furthermore, the mechanism of the enhanced glucose oxidation signal was investigated. It was shown that glucose has a higher electron transfer capacity and a larger apparent catalytic rate constant on the Ni2Co1-BDC/GCE surface. Therefore, tunable non-enzymatic glucose electrochemical sensing was carried out by regulating the metal centers and ligands. As a result, a high-sensitivity enzyme-free glucose sensing platform was successfully constructed based on the Ni2Co1-BDC/GCE, which has a wide linear range of 0.5-2899.5 µM, a low detection limit of 0.29 µM (S/N = 3), and a high sensitivity of 3925.3 µA mM-1 cm-2. Much more importantly, it was also successfully applied to the determination of glucose in human serum with satisfactory results, demonstrating its potential for glucose detection in real samples.

Novel Functionalized Boron Nitride Nanosheets Achieved by Radiation-Induced Oxygen Radicals and Their Enhancement for Polymer Nanocomposites.

Boron nitride nanosheets (BNNSs) exfoliated from hexagonal boron nitride (h-BN) show great potential in polymer-based composites due to their excellent mechanical properties, highly thermal conductivity, and insulation properties. Moreover, the structural optimization, especially the surface hydroxylation, of BNNSs is of importance to promote their reinforcements and optimize the compatibility of its polymer matrix. In this work, BNNSs were successfully attracted by oxygen radicals decomposed from di-tert-butylperoxide (TBP) induced by electron beam irradiation and then treated with piranha solution. The structural changes of BNNSs in the modification process were deeply studied, and the results demonstrate that the as-prepared covalently functionalized BNNSs possess abundant surface hydroxyl groups as well as reliable structural integrity. Of particular importance is that the yield rate of the hydroxyl groups is impressive, whereas the usage of organic peroxide and reaction time is greatly reduced due to the positive effect of the electron beam irradiation. The comparisons of PVA/BNNSs nanocomposites further indicate that the hydroxyl-functionalized BNNSs effectively promote mechanical properties and breakdown strength due to the enhanced compatibility and strong two-phase interactions between nanofillers and the polymer matrix, which further verify the application prospects of the novel route proposed in this work.

Ultrasensitive and Simple Dopamine Electrochemical Sensor Based on the Synergistic Effect of Cu-TCPP Frameworks and Graphene Nanosheets.

Dopamine (DA) is an important neurotransmitter. Abnormal concentration of DA can result in many neurological diseases. Developing reliable determination methods for DA is of great significance for the diagnosis and monitoring of neurological diseases. Here, a novel and simple electrochemical sensing platform for quantitative analysis of DA was constructed based on the Cu-TCPP/graphene composite (TCPP: Tetrakis(4-carboxyphenyl)porphyrin). Cu-TCPP frameworks were selected in consideration of their good electrochemical sensing potential. The graphene nanosheets with excellent conductivity were then added to further improve the sensing efficiency and stability of Cu-TCPP frameworks. The electrochemical properties of the Cu-TCPP/graphene composite were characterized, showing its large electrode active area, fast electron transfer, and good sensing performance toward DA. The signal enhancement mechanism of DA was explored. Strong accumulation ability and high electrocatalytic rate were observed on the surface of Cu-TCPP/graphene-modified glassy carbon electrode (Cu-TCPP/graphene/GCE). Based on the synergistic sensitization effect, an ultrasensitive and simple DA electrochemical sensor was developed. The linear range is 0.02-100 and 100-1000 µM, and the detection limit is 3.6 nM for the first linear range. It was also successfully used in detecting DA in serum samples, and a satisfactory recovery was obtained.

Construction of a High Nuclear Gadolinium Cluster with Enhanced Magnetocaloric Effect through Structural Transition.

Starting from a dinuclear complex {Gd2(L)2(NO3)4(H2O)2}·2(CH3CN) (1) based on 2,6-dimethoxyphenol (HL), a nonanuclear cluster {Gd9(L)4(µ4-OH)2(µ3-OH)8(µ2-OCH3)4(NO3)8 (H2O)8}(OH)·2H2O (2) was obtained via modulating the amount of the ligand and base. Both of them have been structurally and magnetically characterized. Complex 1 decorates the Gd2 core bridged by double µ2-phenoxyl oxygen atoms and coordinated neutral CH3CN molecules, while 2 features the Gd9 core with a sandglass-like topology. Magnetic investigations reveal that the weaker antiferromagnetic interactions between adjacent metal ions exist in complex 2 than in 1, which is in agreement with the theoretical results. Meanwhile, the magnetocaloric effect with a maximum -ΔS m value changes from 27.32 to 40.60 J kg-1 K-1 at 2 K and 7 T.

Cu-TCPP Nanosheets-Sensitized Electrode for Simultaneous Determination of Hydroquinone and Catechol.

It is quite important to develop sensitive, simple, and convenient methods for the simultaneous determination of Hydroquinone (HQ) and Catechol (CC) due to their wide existence, the difficulty of degradation, and the high toxicity. Herein, Cu-TCPP nanosheets were prepared in N,N-dimethylformamide (DMF) through the solvent exfoliation method. The morphology and electrochemical performance of Cu-TCPP were characterized, revealing its stacked sheet structure with abundant pores, a fast electron transfer ability, and a large electrode active area. Using Cu-TCPP nanosheets as the sensitive material to modify the glassy carbon electrodes (Cu-TCPP/GCEs), it was found that they had an obvious enhancement effect on the electrochemical oxidation currents of HQ and CC. The signal enhancement mechanism was explored. The Cu-TCPP nanosheets not only enhanced the accumulation abilities of HQ and CC, but also improved their apparent catalytic rate, displaying high sensitivity for HQ and CC. The values of the detection limit were calculated to be 3.4 and 2.3 nM for HQ and CC. A satisfactory recovery was obtained when this method was used in measuring HQ and CC in the water samples.

Facile and Controllable Preparation of Poly(St-co-MMA)/FA Microspheres Used as Ultra-Lightweight Proppants.

Hydraulic fracturing is an important technology for the exploitation of unconventional oil or gas reservoirs. In order to increase the production of oil or gas, ultra-lightweight proppants with a high compressive strength are highly desirable in hydraulic fracture systems. In this work, a new type of ultra-lightweight proppant, poly(styrene-co-methyl methacrylate)/fly ash (poly(St-co-MMA)/FA) composites with a high compressive strength were prepared via in situ suspension polymerization. The Fourier transform infrared (IR) and X-ray powder diffraction (XRD) analyses confirmed that the poly(St-co-MMA)/FA composites were successfully prepared. The morphology analysis indicated that the composite microspheres show good sphericity, and FA powder was evenly dispersed in the matrix. The apparent density of the microspheres was between 1 and 1.3 g/cm3, which is suitable for hydraulic fracturing. Furthermore, the compressive strength and thermostability were dramatically improved with the incorporation of FA, which could withstand high pressures and temperatures underground. The obtained poly(St-co-MMA)/FA composite microspheres are promising for application as an ultra-lightweight (ULW) proppant in oil or gas exploitation, which provides a new approach for the design of high performance proppants.

Cathodic electrodeposited Cu-BTC MOFs assembled from Cu(II) and trimesic acid for electrochemical determination of bisphenol A.

The authors describe a novel electrochemical determination method for bisphenol A (BPA) based on the electrosynthesised Cu-BTC (H3BTC: trimesic acid) films. Using H3BTC as the ligand, Cu(NO3)2 as the precursor of copper ions, and triethylamine hydrochloride (Et3NHCl) as the probase source, Cu-BTC films were directly deposited on glassy carbon electrode (GCE) surface via cathodic electrochemical reduction under -1.30 V. Considering the electrocatalytic activity of metal center Cu2+, Cu-BTC films were applied to construct the electrochemical determination platform for BPA. Chronocoulometry and electrochemical impedance spectroscopy were used to study the signal enhancement mechanism. The determination conditions were optimized. As a result, a sensitive electrochemical method was constructed for BPA. The peak currents, best measured at voltage of 0.496 V vs. SCE (KCl saturated calomel reference electrode), increase linearly in the range from 5.0 to 2000 nM. The value of determination limit is 0.72 nM. The proposed method was successfully applied to determine BPA in spiked urine, spiked waste water samples and plastic products. The results were in good agreement with those obtained for the same samples by high-performance liquid chromatography (HPLC). Graphical abstract Schematics for the construction of electrochemical determination for bisphenol A.

Morphology-dependent electrochemical sensing performance of metal (Ni, Co, Zn)-organic frameworks.

To clarify the morphology effect of metal-organic frameworks (MOFs) on their electrochemistry as well as to explore their electrochemical applications, three MOFs with metal centers of nickel, cobalt, and zinc are synthesized. The used organic ligand is only 1,3,5-benzenetricarboxylic acid. Characterizations using Fourier Transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and electrochemical techniques reveal that these MOFs possess similar bonding properties, crystalline structures and phase purity, but various morphology and electrochemical activities, including their own redox behavior, electrochemical response toward redox probes and analytes in solutions. As a case study of analytes, voltammetry of Ponceau 4R is investigated on three MOFs. Its sensitive and selective monitoring is further achieved on nickel MOFs with a linear range from 0.5 to 150 nM and a detection limit of 80 pM. Therefore, the morphology of MOFs determines electrochemistry of MOFs and their electrochemical sensing applications.

Simultaneous determination of environmental estrogens: Diethylstilbestrol and estradiol using Cu-BTC frameworks-sensitized electrode.

It is quite important to monitor environmental estrogens in a rapid, sensitive, simple and cost-effective manner due to their wide existence and high toxicity. Using 1,3,5-Benzenetricarboxylic acid (H3BTC) as the ligand and copper ions as the center, Cu-BTC frameworks with surface area of 654.6m(2)/g were prepared, and then used to construct a novel electrochemical sensing platform for diethylstilbestrol (DES) and estradiol (E2). On the surface of Cu-BTC frameworks, two oxidation waves at 0.26V and 0.45V are observed for DES and E2, and the oxidation signals are improved greatly. The prepared Cu-BTC frameworks not only enhance the accumulation efficiency of DES and E2, but also improve their electron transfer ability. The influences of pH value, modification amount of Cu-BTC and accumulation time were examined. As a result, a highly-sensitive, rapid and convenient electrochemical method was developed for the simultaneous determination of DES and E2, with detection limit of 2.7nM and 1.1nM. The practical applications manifest this new sensing system is accurate and feasible.

Synergetic enhancement of gold nanoparticles and 2-mercaptobenzothiazole as highly-sensitive sensing strategy for tetrabromobisphenol A.

Various gold nanoparticles (AuNPs) were in-situ prepared on the electrode surface through electrochemical reduction under different potentials such as -0.60, -0.50, -0.40, -0.30 and -0.20 V. The reduction potentials heavily affect the surface morphology and electrochemical activity of AuNPs such as effective area and catalytic ability, as confirmed using atomic force microscopy and electrochemical impedance spectroscopy. The electrochemical behaviors of tetrabromobisphenol A (TBBPA), a widely-existed pollutant with severe adverse health effects, were studied. The oxidation activity of TBBPA enhances obviously on the surface of AuNPs, and the signal improvements of TBBPA show difference on the prepared AuNPs. Interestingly, the existence of 2-mercaptobenzothiazole (MBT) further improves the oxidation signals of TBBPA on AuNPs. The synergetic enhancement effects of AuNPs and MBT were studied using cyclic voltammetry and chronocoulometry. The numerous nano-scaled gold particles together with the strong hydrophobic interaction between TBBPA and the assembled MBT on AuNPs jointly provide highly-effective accumulation for TBBPA. As a result, a sensitive and simple electrochemical method was developed for the direct determination of TBBPA, with detection limit of 0.12 µg L(-1) (0.22 nM). The practical applications in water samples manifest that this new sensing system is accurate and feasible.

Morphology-dependent Electrochemical Enhancements of Porous Carbon as Sensitive Determination Platform for Ascorbic Acid, Dopamine and Uric Acid.

Using starch as the carbon precursor and different-sized ZnO naoparticles as the hard template, a series of porous carbon materials for electrochemical sensing were prepared. Experiments of scanning electron microscopy, transmission electron microscopy and Nitrogen adsorption-desorption isotherms reveal that the particle size of ZnO has big impacts on the porous morphology and surface area of the resulting carbon materials. Through ultrasonic dispersion of porous carbon and subsequent solvent evaporation, different sensing interfaces were constructed on the surface of glassy carbon electrode (GCE). The electrochemical behaviors of ascorbic acid (AA), dopamine (DA) and uric acid (UA) were studied. On the surface of porous carbon materials, the accumulation efficiency and electron transfer ability of AA, DA and UA are improved, and consequently their oxidation signals enhance greatly. Moreover, the interface enhancement effects of porous carbon are also controlled by the particle size of hard template. The constructed porous carbon interface displays strong signal amplification ability and holds great promise in constructing a sensitive platform for the simultaneous determination of AA, DA and UA.