Shao-Yi Jia

Hemin@metal–organic framework with peroxidase-like activity and its application to glucose detection

A composite material has been successfully prepared for the first time using an amino-containing metal–organic framework (MOF) as a new type of host matrix material to anchor hemin and simulate the peptidic microenvironment of the native peroxidase. The material was characterized by XRD, SEM, EDS, FT-IR techniques and an N2 adsorption method. It exhibited peroxidase-like activity through catalytic oxidation of the peroxidase substrate 3,3,5,5-tetramethylbenzidine (TMB) in the presence of H2O2, producing a blue-colored solution. Under optimal conditions, the absorbance at 652 nm is linearly correlated with the concentration of H2O2 from 5.0 × 10−6 mol L−1 to 2.0 × 10−4 mol L−1 (R2 = 0.994). More importantly, a sensitive and selective method for glucose detection was developed using the as-prepared mimetic peroxidase as a catalyst with the help of glucose oxidase (GOx). The analytical platform for glucose detection was observed to have a linear range from 1.0 × 10−5 mol L−1 to 3.0 × 10−4 mol L−1 (R2 = 0.993). This work informs researchers of the advantages of MOFs for preparing biomimetic catalysts and extends the functionality of MOFs to biosensor applications.

Response surface optimization of ultrasound-assisted enzymatic extraction polysaccharides from Lycium barbarum

In this study, an efficient ultrasound-assisted enzymatic extraction procedure for the water-soluble polysaccharides from the fruit of Lycium barbarum was investigated and optimized. Response surface methodology (RSM) based on a three-level four-factor Box Behnken Design (BBD) was employed to optimize the extraction conditions inlcluding extraction time, ultrasonic output power, cellulose concentration and extraction temperature. The experimental data were adequately fitted into a second-order polynomial model. The optimized conditions were as follows: extraction time 20.29 min, ultrasonic output power 78.6 W, cellulose concentration 2.15%, extraction temperature 55.79°C. Under these conditions, the experimental yield of polysaccharides was 6.31±0.03%, which matched with the predictive yield of 6.32% well.

Adsorptive removal of bisphenol A from aqueous solution using metal-organic frameworks

AbstractAdsorptive removal of bisphenol A (BPA) from aqueous solution has been studied over two highly porous metal-organic frameworks (MIL-101(Cr) and MIL-100(Fe)) in view of the adsorption kinetics, adsorption isotherm, effect of initial pH and effect of ionic strength. The adsorption kinetics fit pseudo-second-order kinetic model well and the adsorption isotherms follow the Langmuir model. The adsorption kinetics and capacity of BPA over MIL-101(Cr) generally depend on the average pore size and specific surface area (or pore volume), respectively. The adsorption mechanism may be explained with π–π interaction and hydrogen bonding between BPA and MIL-101(Cr). Finally, it can be suggested that metal-organic frameworks possessing high porosity and large pore size can be used as potential adsorbents to remove harmful endocrine disrupting chemicals in contaminated water.

Response surface optimization of enzyme-assisted extraction polysaccharides from Dictyophora indusiata.

An enzyme-assisted procedure for the extraction of the water-soluble polysaccharides from the stipe of Dictyophora indusiata was investigated using response surface methodology. The orthogonal array design was employed to optimize the concentration of three kinds of enzyme (cellulase, papain and pectolyase) and the optimal cellulose, papain and pectolyase concentration were 2.0% (wt.% of D. indusiata powder), 2.0% and 1.5%, respectively. And then the effect such as temperature, time and pH was studied based on a three-level three-factor Box-Behnken design. The optimized conditions were as follows: extraction temperature 52.5 °C, extraction time 105 min and pH 5.25. Under these conditions, the experimental yield of polysaccharides was 9.77±0.18%, which was well matched with the predictive yield of 9.87%. As it turned out, enzyme-assisted procedure was an effective method.

Adsorptive removal of dibenzothiophene from model fuels over one-pot synthesized PTA@MIL-101(Cr) hybrid material.

Hybrid nanomaterials comprising phosphotungstic acid (PTA) and MIL-101(Cr) were prepared through one-pot synthesis and post-modification methods and then were used as adsorbents of dibenzothiophene (DBT) from simulated diesel fuels. Samples obtained by different ways (encapsulation and impregnation) were characterized by nitrogen adsorption, transmission electron microscope (TEM), X-ray diffraction (XRD), Fourier transform infrared spectrum (FT-IR) and series of adsorption experiments. The equilibrium adsorption capacities of PTA@MIL-101(Cr) illustrated that the direct introduction of PTA into MIL-101(Cr) during synthesis resulted in a 10.7% increase compared with MIL-101(Cr). However, porous hybrid adsorbent PTA/MIL-101(Cr) prepared via post-modification method exhibited lower adsorption capacity than virgin MIL-101(Cr). The theoretical maximum adsorption capacity (Q0) of PTA@MIL-101(Cr) is 136.5mg S/g adsorbent, 4.2 times of MIL-101(Cr). Even in competitive adsorption between aromatic compounds, which possess strong affinity with MOFs, and DBT, PTA@MIL-101(Cr) and MIL-101(Cr) remained their effectiveness in removal of DBT in the system. Based on these results, it can be presumed that MIL-101(Cr), modified properly, can be used as a promising adsorbent for eliminating aromatics and S-compounds in commercial fuels simultaneously.

Drying effects on the antioxidant properties of polysaccharides obtained from Agaricus blazei Murrill.

Three polysaccharides (ABMP-F, ABMP-V, ABMP-A) were obtained from Agaricus blazei Murrill via methods such as freeze drying, vacuum drying and air drying, respectively. Their chemical compositions were examined, and antioxidant activities were investigated on the basis of assay for hydroxyl radical, DPPH radical, ABTS free radical scavenging ability and assay for Fe(2+)-chelating ability. Results showed that the three ABMPs have different physicochemical and antioxidant properties. Compared with air drying and vacuum drying methods, freeze drying method resulted to ABMP with higher neutral sugar, polysaccharide yield, uronic acid content, and stronger antioxidant abilities of hydroxyl radical, DPPH radical, ABTS radical scavenging and Fe(2+)-chelating. As a result, Agaricus blazei Murrill polysaccharides are natural antioxidant and freeze drying method serves as a good choice for the preparation of such polysaccharides and should be used to produce antioxidants for food industry.

Effects of extraction methods on the antioxidant activities of polysaccharides from Agaricus blazei Murrill.

Five polysaccharides were obtained from Agaricus blazei Murrill (ABM) through different extraction methods including hot water extraction, single enzyme extraction (pectinase, cellulase or papain) and compound enzymes extraction (cellulase:pectinase:papain). Their characteristics such as the polysaccharide yield, polysaccharide content, protein content, infrared spectra were determined, and antioxidant activities were investigated on the basis of hydroxyl radical, DPPH free radical, ABTS free radical and reducing power. The results showed that five extracts exhibited antioxidant activities in a concentration-dependent manner. Compared with other methods, the compound enzymes extraction method was found to present the highest polysaccharides yield (17.44%). Moreover, compound enzymes extracts exhibited the strongest reducing power and highest scavenging rates on hydroxyl radicals, DPPH radicals and ABTS radicals. On the contrary, hot water extraction method had the lowest polysaccharides yield of 11.95%, whose extracts also exhibited the lowest antioxidant activities. Overall, the available data obtained in vitro models suggested that ABM extracts were natural antioxidants and compound enzymes extraction was an appropriate, mild and effective extracting method for obtaining the polysaccharide extracts from Agaricus blazei Murrill (ABM).

Formation of iron (hydr)oxides during the abiotic oxidation of Fe(II) in the presence of arsenate

Abiotic oxidation of Fe(II) is a common pathway in the formation of Fe (hydr)oxides under natural conditions, however, little is known regarding the presence of arsenate on this process. In hence, the effect of arsenate on the precipitation of Fe (hydr)oxides during the oxidation of Fe(II) is investigated. Formation of arsenic-containing Fe (hydr)oxides is constrained by pH and molar ratios of As:Fe during the oxidation Fe(II). At pH 6.0, arsenate inhibits the formation of lepidocrocite and goethite, while favors the formation of ferric arsenate with the increasing As:Fe ratio. At pH 7.0, arsenate promotes the formation of hollow-structured Fe (hydr)oxides containing arsenate, as the As:Fe ratio reaches 0.07. Arsenate effectively inhibits the formation of magnetite at pH 8.0 even at As:Fe ratio of 0.01, while favors the formation of lepidocrocite and green rust, which can be latterly degenerated and replaced by ferric arsenate with the increasing As:Fe ratio. This study indicates that arsenate and low pH value favor the slow growth of dense-structured Fe (hydr)oxides like spherical ferric arsenate. With the rapid oxidation rate of Fe(II) at high pH, ferric (hydr)oxides prefer to precipitate in the formation of loose-structured Fe (hydr)oxides like lepidocrocite and green rust.

Effects of Mn(II) on the sorption and mobilization of As(V) in the presence of hematite.

In this study, the effects of Mn(II) on the sorption and mobilization of As(V) by synthetic hematite were investigated. Our results showed that As(V) removal by hematite was evidently dependent on pH, and simultaneous addition of Mn(II) and As(V) into hematite suspension resulted in more removal of As(V) via electrostatic attraction at pH 4.0, 7.0 and 8.3. However, in Mn(II) pre-loaded system, the removal percentages of As(V) at pH 8.3 decreased by 17.0%, 20.7% and 26.7% after 24h at the aging time of 2, 12 and 36 h, respectively. The concentrations of the released As(V) after the addition of 1mM Mn(II) were 23.6, 12.9 and 7.0 μM at pH 8.5 in 2, 3 and 4 g L(-1) hematite suspension, respectively. But Ca(2+) did not show such an effect under similar experimental conditions. Abiotic oxidation of Mn(II) on hematite played an important role in As(V) mobilization. The growing thin layer of Mn(III, IV) (hydr)oxides (MnO(x)) formed on hematite would take up the sorption sites pre-occupied by As(V) and resulted in the release of the adsorbed As(V) back into solution. This study enriched our understanding on As(V) fate in the coexistence of iron oxides and Mn(II).

Abiotic oxidation of Mn(II) induced oxidation and mobilization of As(III) in the presence of magnetite and hematite

Manganese (hydr)oxides are powerful oxidants mediating the transformation of As(III) to As(V) under natural conditions, however, the presence of Mn(II) on the oxidation of As(III) in the pH range of 7.0-9.0 has not been reported so far. In this study, abiotic oxidation of Mn(II) to amorphous Mn(III, IV) (hydr)oxides (MnOx) on magnetite and hematite was confirmed, and the impact of newly formed MnOx on the fate of As(III) was investigated. With the addition of Mn(II) into As(III)-preloaded systems, the dissolved and the adsorbed As(III) was oxidized to As(V) at high pH, and Mn(II) mobilized the adsorbed As(III) and As(V) in hematite system. High production of dissolved As(V) and significant mobilization of As(III) were even more significant in hematite suspension (total As was 18.96 mgL(-1) after 60 h at pH 8.62) with simultaneous addition of Mn(II) and As(III), while magnetite showed a higher capacity for the retention of As(III) and As(V). It could therefore be deduced that the newly formed MnOx on iron oxides could oxidize the dissolved and the adsorbed As(III) to As(V). In addition, the MnOx formed at high pH would take up the sorption sites previously occupied by the adsorbed As(III), and then mobilized a fraction of the adsorbed As(III) into solution. The present study reveals that MnOx formed via abiotic oxidation on iron oxides plays an important role in the oxidation and mobilization of both dissolved and adsorbed As(III) in aquatic environment.