Guest-Stimulated Nonplanar Porphyrins in Flexible Metal-Organic Frameworks.

Nonplanar porphyrins with out-of-plane distortions play crucial roles in many biological functions and chemical applications. The artificial construction of nonplanar porphyrins usually involves organic synthesis and modification, which is a highly comprehensive approach. However, incorporating porphyrins into guest-stimulated flexible systems allows to manipulate the porphyrin distortion through simple ad/desorption of guest molecules. Here, a series of porphyrinic zirconium metal-organic frameworks (MOFs) is reported that exhibit guest-stimulated breathing behavior. X-Ray diffraction analysis and skeleton deviation plots confirm that the material suffers from porphyrin distortion to form a ruffled geometry under the desorption of guest molecules. Further investigation reveals that not only the degree of nonplanarity can be precisely manipulated but also the partial distortion of porphyrin in a single crystal grain can be readily achieved. As Lewis acidic catalyst, the MOF with nonplanar Co-porphyrin exhibits active properties in catalyzing CO2 /propylene oxide coupling reactions. This porphyrin distortion system provides a powerful tool for manipulating nonplanar porphyrins in MOFs with individual distortion profiles for various advanced applications.

Parameter Determination of the 2S2P1D Model and Havriliak-Negami Model Based on the Genetic Algorithm and Levenberg-Marquardt Optimization Algorithm.

This study utilizes the genetic algorithm (GA) and Levenberg-Marquardt (L-M) algorithm to optimize the parameter acquisition process for two commonly used viscoelastic models: 2S2P1D and Havriliak-Negami (H-N). The effects of the various combinations of the optimization algorithms on the accuracy of the parameter acquisition in these two constitutive equations are investigated. Furthermore, the applicability of the GA among different viscoelastic constitutive models is analyzed and summarized. The results indicate that the GA can ensure a correlation coefficient of 0.99 between the fitting result and the experimental data of the 2S2P1D model parameters, and it is further proved that the fitting accuracy can be achieved through the secondary optimization via the L-M algorithm. Since the H-N model involves fractional power functions, high-precision fitting by directly fitting the parameters to experimental data is challenging. This study proposes an improved semi-analytical method that first fits the Cole-Cole curve of the H-N model, followed by optimizing the parameters of the H-N model using the GA. The correlation coefficient of the fitting result can be improved to over 0.98. This study also reveals a close relationship between the optimization of the H-N model and the discreteness and overlap of experimental data, which may be attributed to the inclusion of fractional power functions in the H-N model.

Porous Fe-N-C Aerogels Derived from Metal-Organic Aerogels as Electrocatalysts for the Oxygen Reduction Reaction.

Synthesis of Fe-N-C electrocatalysts by pyrolysis of porous materials has been shown to be a promising pathway for the oxygen reduction reaction (ORR). Metal-organic aerogels (MOAs) with unique micropores and mesopores should provide an excellent precursor for Fe-N-C electrocatalysts. This work reports a Fe-N-C aerogel synthesized by pyrolysis of MOA. The Fe-N-C aerogel shows excellent ORR performance in alkaline condition with an onset potential of 0.96 V (vs. RHE) and a limiting current density of 5.02 mA cm-2 . The markedly enhanced ORR performance for Fe-N-C aerogel can be assigned to the synergistic catalytic effect between Fe-N catalytic sites and graphitized carbon and excellent mass transport due to the unique hierarchically porous architecture. In addition, satisfactory durability and methanol tolerance were obtained, demonstrating a promising material for ORR.

Integration of Multiple Redox Centers into Porous Coordination Networks for Ratiometric Sensing of Dissolved Oxygen.

The application of porphyrin metal-organic frameworks (MOFs) as a ratiometric electrochemical sensing platform is still unexplored. In this paper, we report a ratiometric electrochemical sensor by the integration of multiple redox centers into porphyrin MOFs for the detection of dissolved oxygen (DO). Specifically, the ferrocene (Fc) group was integrated into the nanosized PCN-222(Fe) (PCN = porous coordination networks) via acid-base reaction to synthesize the Fc@PCN-222(Fe) composite with two redox centers of the Fc group and Fe-porphyrin. The Fc group that is insensitive to DO serves as an internal reference, and the Fe-porphyrin in PCN-222(Fe) is a DO indicator. The ratios of the cathodic currents for the two redox centers exhibit a linear relationship with DO concentrations from 2.8 to 28.9 mg mL-1 and a limit of detection of 0.3 mg mL-1. In addition, the ratiometric electrochemical sensor has high selectivity and stability for DO sensing results from the Fc@PCN-222(Fe) composite. Because there are numerous redox centers, such as methylene blue and thionine, which can be integrated into MOFs, many MOF-based ratiometric electrochemical sensors can be simply developed for high-performance biosensing.

Coupling Two Sequential Biocatalysts with Close Proximity into Metal-Organic Frameworks for Enhanced Cascade Catalysis.

The encapsulation of multiple enzyme/nanoenzyme systems within mental-organic frameworks (MOFs) shows great promise for a myriad of practical applications. Herein, two sequential biocatalysts, oxidase and hemin, were coupled together with close proximity using a bifunctional polymer, poly(1-vinylimidazole) (PVI), and encapsulated into MOFs. As a demonstration of the power of such a protocol, glucose oxidase&PVI-hemin encapsulated in ZIF-8 showed significant enhancement of bioactivity for a cascade reaction compared to its counterpart without PVI. For the colorimetric assay of glucose, it showed a low limit of detection of 0.4 µM (S/N = 3), high selectivity, and excellent stability. Because there are numerous biocatalysts that can readily be coupled and encapsulated into MOFs, a myriad of interesting properties can be simply realized by encapsulating different sequential biocatalysts.

A buckypaper decorated with CoP/Co for nonenzymatic amperometric sensing of glucose.

A freestanding and flexible buckypaper modfied with CoP/Co (CoP/Co-BP) is described. It has a sponge-like nanostructure and is shown to enable improved nonenzymatic sensing of glucose. The CoP/Co-BP was prepared by first depositing a uniform layer of ZIF- 67 crystals on BP, followed by two steps of pyrolysis treatment and phosphidation under an argon atmosphere. The morphology and structure of the material were characterized by scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The electrochemical properties were investigated by cyclic voltammetry and amperometric response. The amperometric sensor, best operated at 0.45 V (vs. SCE) at pH 13 has a linear range that extends from 0.5 µM to 1.8 mM of glucose, a 0.2 µM detection limit (at S/N = 3), and a sensitivity of 6427 µA mM-1 cm-2 in alkaline solution. This is mainly attributed to the synergistic effect between the highly active CoP nanostructure and BP which results in excellent conductivity. The uniformly distributed CoP nanoparticles in the network of BP prevent the formation of close-packed structure and facilitate electron transfer. The sensor has good selectivity and excellent long-term stability. It was applied to the determination of glucose in spiked human serum, and satisfactory results were obtained. Graphical abstractSchematic presentation of a freestanding and flexible buckypaper modfied with CoP/Co. It has a sponge-like nanostructure and exhibits improved catalytic activity toward glucose oxidation. This material was used for high-performance electrochemical glucose sensing.

A sensitive acetylcholinesterase biosensor based on gold nanorods modified electrode for detection of organophosphate pesticide.

A sensitive amperometric acetylcholinesterase (AChE) biosensor, based on gold nanorods (AuNRs), was developed for the detection of organophosphate pesticide. Compared with Au@Ag heterogeneous NRs, AuNRs exhibited excellent electrocatalytic properties, which can electrocatalytically oxidize thiocholine, the hydrolysate of acetylthiocholine chloride (ATCl) by AChE at +0.55V (vs. SCE). The AChE/AuNRs/GCE biosensor was fabricated on basis of the inhibition of AChE activity by organophosphate pesticide. The biosensor could detect paraoxon in the linear range from 1nM to 5µM and dimethoate in the linear range from 5nM to 1µM, respectively. The detection limits of paraoxon and dimethoate were 0.7nM and 3.9nM, which were lower than the reported AChE biosensor. The proposed biosensor could restore to over 95% of its original current, which demonstrated the good reactivation. Moreover, the biosensor can be applicable to real water sample measurement. Thus, the biosensor exhibited low applied potential, high sensitivity and good stability, providing a promising tool for analysis of pesticides.

Rational design of xylose dehydrogenase for improved thermostability and its application in development of efficient enzymatic biofuel cell.

In this paper, the construction of 3D model structure of xylose dehydrogenase (XDH) by using homology modeling to guide the rational design of the enzyme for improving thermostability was reported. Three XDH mutants of NA-1 (+249L), NA-2 (G149P) and NA-3 (+249L/G149P) were designed and displayed on the surface of bacteria. Among them, bacteria displaying NA-1 (NA-1-bacteria) exhibited superior thermostability without compromising its activity and substrate specificity in comparison with its wild-type counterpart. NA-1-bacteria retained its original activity after incubation at room temperature for one-month with the half-life of 9.8 days at 40°C. Finally, the NA-1-bacteria were applied to construct xylose/O2 based biofuel cell with good performance including enhanced operational stability. Thus, the approach described here could be explored for engineering of other enzymes for improving certain characters without three-dimensional structure identified by experimental methods.

Microbial surface displayed enzymes based biofuel cell utilizing degradation products of lignocellulosic biomass for direct electrical energy.

In this work, a bacterial surface displaying enzyme based two-compartment biofuel cell for the direct electrical energy conversion from degradation products of lignocellulosic biomass is reported. Considering that the main degradation products of the lignocellulose are glucose and xylose, xylose dehydrogenase (XDH) displayed bacteria (XDH-bacteria) and glucose dehydrogenase (GDH) displayed bacteria (GDH-bacteria) were used as anode catalysts in anode chamber with methylene blue as electron transfer mediator. While the cathode chamber was constructed with laccase/multi-walled-carbon nanotube/glassy-carbon-electrode. XDH-bacteria exhibited 1.75 times higher catalytic efficiency than GDH-bacteria. This assembled enzymatic fuel cell exhibited a high open-circuit potential of 0.80 V, acceptable stability and energy conversion efficiency. Moreover, the maximum power density of the cell could reach 53 µW cm(-2) when fueled with degradation products of corn stalk. Thus, this finding holds great potential to directly convert degradation products of biomass into electrical energy.

Biofuel cell based self-powered sensing platform for L-cysteine detection.

L-cysteine (L-Cys) detection is of great importance because of its crucial roles in physiological and clinical diagnoses. In this study, a glucose/O2 biofuel cell (BFC) was assembled by using flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH)-based bioanode and laccase-based biocathode. Interestingly, the open circuit potential (OCP) of the BFC could be inhibited by Cu(2+) and subsequently activated by L-Cys, by which a BFC-based self-powered sensing platform for the detection of L-Cys was proposed. The FAD-GDH activity can be inhibited by Cu(2+) and, in turn, subsequent reversible activation by L-Cys because of the binding preference of L-Cys toward Cu(2+) by forming the Cu-S bond. The preferential interaction between L-Cys and Cu(2+) facilitated Cu(2+) to remove from the surface of the bioanode, and thus, the OCP of the system could be turned on. Under optimized conditions, the OCP of the BFC was systematically increased upon the addition of the L-Cys. The OCP increment (ΔOCP) was linear with the concentration of L-Cys within 20 nM to 3 µM. The proposed sensor exhibited lower detection limit of 10 nM L-Cys (S/N = 3), which is significantly lower than those values for other methods reported so far. Other amino acids and glutathione did not affect L-Cys detection. Therefore, this developed approach is sensitive, facile, cost-effective, and environmental-friendly, and could be very promising for the reliable clinically detecting of L-Cys. This work would trigger the interest of developing BFCs based self-powered sensors for practical applications.

Enhanced performance of a glucose/O(2) biofuel cell assembled with laccase-covalently immobilized three-dimensional macroporous gold film-based biocathode and bacterial surface displayed glucose dehydrogenase-based bioanode.

The power output and stability of enzyme-based biofuel cells (BFCs) is greatly dependent on the properties of both the biocathode and bioanode, which may be adapted for portable power production. In this paper, a novel highly uniform three-dimensional (3D) macroporous gold (MP-Au) film was prepared by heating the gold "supraspheres", which were synthesized by a bottom-up protein templating approach, and followed by modification of laccase on the MP-Au film by covalent immobilization. The as-prepared laccase/MP-Au biocathode exihibited an onset potential of 0.62 V versus saturated calomel electrode (SCE, or 0.86 V vs NHE, normal hydrogen electrode) toward O2 reduction and a high catalytic current of 0.61 mAcm(-2). On the other hand, mutated glucose dehydrogenase (GDH) surface displayed bacteria (GDH-bacteria) were used to improve the stability of the glucose oxidation at the bioanode. The as-assembled membraneless glucose/O2 fuel cell showed a high power output of 55.8 ± 2.0 µW cm(-2) and open circuit potential of 0.80 V, contributing to the improved electrocatalysis toward O2 reduction at the laccase/MP-Au biocathode. Moreover, the BFC retained 84% of its maximal power density even after continuous operation for 55 h because of the high stability of the bacterial surface displayed GDH mutant toward glucose oxidation. Our findings may be promising for the development of more efficient glucose BFC for portable battery or self-powered device applications.

Preparation, structural diversity and characterization of a family of Cd(II)-organic frameworks.

Two Cd(II)-organic frameworks based on 5-iodoisophthalate (IIP(2-)), {[Cd(IIP)(bte)(H2O)]·H2O}n (1) and [Cd(IIP)(bpp)(H2O)]n (2), were obtained either at an ambient temperature or under solvothermal conditions at 120 °C in the presence of 1,4-bis(1,2,4-triazol-1-yl)ethane (bte) and 1,3-bis(4-pyridyl)propane (bpp) as auxiliary ligands, respectively. 1 is a novel discrete single-walled Cd(II)-organic tube (SWCOT) which further extends into a 3D supramolecular interdigitated microporous columnar architecture supported by C-I···I halogen bonds and hydrogen bonds, while 2 exhibits an interesting two-fold interpenetrated 3D diamond network architecture. When the auxiliary ligands bte or bpp were replaced by a longer spacer ligand with more flexibility, 1,4-bis(triazol-1-ylmethyl)benzene (bbtz), the unique discrete single-walled Cd(II)-organic nanotube (SWCONT), {[Cd(IIP)(bbtz)(H2O)]·H2O}n (3), which further extends into a 3D supramolecular microporous framework supported by face-to-face π···π stacking interactions and hydrogen bonds, was generated at room temperature. Under solvothermal conditions at 120 °C, an interesting two-fold 2D "embracing" (4,4) topological network, [Cd(IIP)(bbtz)(H2O)] (4), which further extends into a two-fold 3D "embracing" supramolecular framework through O-H···O hydrogen bonds, is obtained. 4 loses crystallinity in air, leading to the formation of [Cd(IIP)(bbtz)]·0.5H2O (4A) evidenced by elemental analysis, thermogravimetric analysis (TGA) and powder X-ray diffraction (PXRD). Remarkably, in situ rapid and reversible dehydration-rehydration in static air occurs in 1-3, indicating their potential applications as water absorbent and sensing materials. Dehydrated 1 and 3 show selective gas adsorption of CO2 over N2 and dehydrated 3 can adsorb methanol and ethanol vapors strongly. These compounds exhibit blue fluorescence in the solid state.

(110)-oriented ZIF-8 thin films on ITO with controllable thickness.

(110)-oriented zeolitic imidazolate framework (ZIF)-8 thin films with controllable thickness are successfully deposited on indium tin oxide (ITO) electrodes at room temperature. The method applied uses 3-aminopropyltriethoxysilane (APTES) in the form of self-assembled monolayers (SAMs), followed by a subsequent adoption of the layer-by-layer (LBL) method. The crystallographic preferential orientation (CPO) index shows that the ZIF-8 thin films are (110)-oriented. A possible mechanism for the growth of the (110)-oriented ZIF-8 thin films on 3-aminopropyltriethoxysilane modified ITO is proposed. The observed cross-sectional scanning electron microscopy (SEM) images and photoluminescent (PL) spectra of the ZIF-8 thin films indicate that the thickness of the ZIF-8 layers is proportional to the number of growth cycles. The extension of such a SAM method for the fabrication of ZIF-8 thin films as described herein should be applicable in other ZIF materials, and the as-prepared ZIF-8 thin films on ITO may be explored for photoelectrochemical applications.

Metal-organic framework templated synthesis of Co3O4 nanoparticles for direct glucose and H2O2 detection.

Co(3)O(4) nanoparticles (NPs) with an average diameter of about 20 nm were synthesized by using MOFs as a template. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to characterize the as-prepared Co(3)O(4) NPs. Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) were used to confirm the structure of the Co(3)O(4) NPs. Then the Co(3)O(4) NPs were modified on a glassy carbon electrode (GCE) to obtain a non-enzymatic glucose and H(2)O(2) sensor. The NPs show electrocatalytic activity toward oxidation of glucose and H(2)O(2) in alkaline medium. For glucose detection, the developed sensor shows a short response time (less than 6 s), a high sensitivity of 520.7 µA mM(-1) cm(-2), a detection limit of 0.13 µM (S/N = 3), and good selectivity. The high concentration of NaCl does not poison the electrode. Its application for the detection of glucose in a human blood serum sample shows good agreement with the results obtained from the hospital. Furthermore, the proposed sensor was used for the detection of H(2)O(2). The results indicate that the detection limit and sensitivity for H(2)O(2) are 0.81 µM and 107.4 µA mM(-1) cm(-2), respectively. Determination of H(2)O(2) concentration in a disinfectant sample by the proposed biosensor also showed satisfactory result. The high sensitivity and low detection limit can be attributed to the excellent electrocatalytic performance of the as-prepared Co(3)O(4) NPs. These results demonstrate that the as-prepared Co(3)O(4) NPs have great potential applications in the development of sensors for enzyme-free detection of glucose and H(2)O(2).

Simultaneous determination of ultratrace lead and cadmium by square wave stripping voltammetry with in situ depositing bismuth at Nafion-medical stone doped disposable electrode.

An ultrasensitive electrochemical method for simultaneous determination of lead and cadmium was first developed using the novel bismuth-Nafion-medical stone doped disposable electrode (an improved wax-impregnated graphite electrode). Through the synergistic sensitization effect of the resulting composite material, the disposable electrode showed remarkable electrochemical responses to lead and cadmium. The oxidation of the two metals produced two well-defined and separated square wave peaks at about -0.62 V for Pb(2+) and -0.85 V for Cd(2+), respectively. The effects of the amount of medical stone, concentration of Nafion, thickness of bismuth, pH of buffer solution, deposition potential, accumulation time, voltammetric measurement and possible interferences were investigated in detail. Under the optimal conditions, the fabricated electrode exhibited linear ranges from 2.0 to 12.0 µg L(-1) with detection limit of 0.07 µg L(-1) for lead and 2.0-12.0 µg L(-1) with detection limit of 0.47 µg L(-1) for cadmium. The assay results of heavy metals in wastewater with the proposed method were in acceptable agreement with the atomic absorption spectroscopy method.

A sub-nanomole level electrochemical method for determination of prochloraz and its metabolites based on medical stone doped disposable electrode.

A ultrasensitive, simple and convenient electrochemical method was firstly developed for the determination of prochloraz and its metabolites as 2,4,6-trichlorophenol (2,4,6-TCP) using nano-aperture medical stone. Compared with the undoped disposable electrode (UDE), nano-aperture medical stone doped disposable electrode (MSDDE) not only significantly enhances the oxidation peak current of 2,4,6-TCP but also lowers the oxidation overpotential, suggesting that the nano-aperture MSDDE can remarkably improve the sensitivity of 2,4,6-TCP. The experimental conditions such as pH values of buffer solution, the content of nano-aperture medical stone, accumulation potential and time were optimized for the determination of 2,4,6-TCP. At optimal conditions, the oxidation peak current is proportional to the concentration of 2,4,6-TCP over the range from 6.0 × 10(-9) to 8.0 × 10(-5)mol L(-1). Finally, this novel method was successfully employed to detect prochloraz and its metabolites in orange rind with the detection limit of 8.4 × 10(-10)mol L(-1) (0.3 ng g(-1)) and the method was validated by gas chromatography.