Trametes versicolor Laccase-Based Magnetic Inorganic-Protein Hybrid Nanobiocatalyst for Efficient Decolorization of Dyes in the Presence of Inhibitors.

In the present investigation, an ecofriendly magnetic inorganic-protein hybrid system-based enzyme immobilization was developed using partially purified laccase from Trametes versicolor (TvLac), Fe3O4 nanoparticles, and manganese (Mn), and was successfully applied for synthetic dye decolorization in the presence of enzyme inhibitors. After the partial purification of crude TvLac, the specific enzyme activity reached 212 U∙mg total protein-1. The synthesized Fe3O4/Mn3(PO4)2-laccase (Fe3O4/Mn-TvLac) and Mn3(PO4)2-laccase (Mn-TvLac) nanoflowers (NFs) exhibited encapsulation yields of 85.5% and 90.3%, respectively, with relative activities of 245% and 260%, respectively, compared with those of free TvLac. One-pot synthesized Fe3O4/Mn-TvLac exhibited significant improvements in catalytic properties and stability compared to those of the free enzyme. Fe3O4/Mn-TvLac retained a significantly higher residual activity of 96.8% over that of Mn-TvLac (47.1%) after 10 reuse cycles. The NFs showed potential for the efficient decolorization of synthetic dyes in the presence of enzyme inhibitors. For up to five reuse cycles, Fe3O4/Mn-TvLac retained a decolorization potential of 81.1% and 86.3% for Coomassie Brilliant Blue R-250 and xylene cyanol, respectively. The synthesized Fe3O4/Mn-TvLac showed a lower acute toxicity towards Vibrio fischeri than pure Fe3O4 nanoparticles did. This is the first report of the one-pot synthesis of biofriendly magnetic protein-inorganic hybrids using partially purified TvLac and Mn.

Sequential Co-Immobilization of Enzymes on Magnetic Nanoparticles for Efficient l-Xylulose Production.

Multi-enzymatic strategies have shown improvement in bioconversion during cofactor regeneration. In this study, purified l-arabinitol 4-dehydrogenase (LAD) and nicotinamide adenine dinucleotide oxidase (Nox) were immobilized via individual, mixed, and sequential co-immobilization approaches on magnetic nanoparticles, and were evaluated to enhance the conversion of l-arabinitol to l-xylulose. Initially, the immobilization of LAD or Nox on the nanoparticles resulted in a maximum immobilization yield and relative activity of 91.4% and 98.8%, respectively. The immobilized enzymes showed better pH and temperature profiles than the corresponding free enzymes. Furthermore, co-immobilization of these enzymes via mixed and sequential methods resulted in high loadings of 114 and 122 mg/g of support, respectively. Sequential co-immobilization of these enzymes proved more beneficial for higher conversion than mixed co-immobilization because of better retaining Nox residual activity. Sequentially co-immobilized enzymes showed a high relative conversion yield with broader pH, temperature, and storage stability profiles than the controls, along with high reusability. To the best of our knowledge, this is the first report on the mixed or sequential co-immobilization of LAD and Nox on magnetic nanoparticles for l-xylulose production. This finding suggests that selecting a sequential co-immobilization strategy is more beneficial than using individual or mixed co-immobilized enzymes on magnetic nanoparticles for enhancing conversion applications.

Boosting the performance of NO2 gas sensors based on n-n type mesoporous ZnO@In2O3 heterojunction nanowires: in situ conducting probe atomic force microscopic elucidation of room temperature local electron transport.

Herein, n-n type one dimensional ZnO@In2O3 heterojunction nanowires have been developed and their local electron transport properties during trace-level NO2 gas sensing process have been probed at room-temperature using conducting probe atomic microscopy. Solvothermally synthesized 1D ZnO@In2O3 heterojunction nanowires have been characterized by various spectroscopic and microscopic techniques, which revealed the mesoporous structure indicating their enhanced sensing properties. The dangling bonds and fraction of metal ions to oxygen ions existing on the exposed crystal facets of the heterojunction nanowires have been visualized by employing crystallographic simulations with TEM analysis, which aided in forecasting the nature of surface adsorption of NO2 gas species. In situ electrical characteristics and Scanning Spreading Resistance Microscopic (SSRM) imaging of single ZnO@In2O3 heterojunction nanowires revealed the local charge transport properties in n-n type ZnO@In2O3 heterojunction nanowires. Moreover, the ZnO@In2O3 heterojunction nanowires based sensor exhibited excellent sensitivity (S = 274%), a fast response (4-6 s) and high selectivity towards trace-level concentration (500 ppb) of NO2 gas under ambient conditions with low power consumption. Spatially resolved surface potential (SP) variations in ZnO@In2O3 heterojunction nanowires have been visualized using in situ Scanning Kelvin Probe Force Microscopy (SKPM) under NO2 gas environment at room temperature, which was further correlated with its energy band structure. The work functions of the material evaluated by SKPM reveal considerable changes in the energy band structure owing to the local electron transport between ZnO and In2O3 at the heterojunctions upon exposure to NO2 gas indicating the charge carrier recombination. A plausible mechanism has been proposed based on the experimental evidences. The results suggest that new insights into complex sensing mechanisms deduced from the present investigation on n-n type MOS based heterojunction nanowires under ambient conditions can pave the way for the novel design and development of affordable and superior real-time gas sensors.

Highly Sensitive, Temperature-Independent Oxygen Gas Sensor Based on Anatase TiO2 Nanoparticle Grafted, 2D Mixed Valent VO x Nanoflakelets.

Herein, we report a facile approach for the synthesis of TiO2 nanoparticles tethered on 2D mixed valent vanadium oxide (VO x/TiO2) nanoflakelets using a thermal decomposition assisted hydrothermal method and investigation of its temperature-independent performance enhancement in oxygen-sensing properties. The material was structurally characterized using XRD, TEM, Raman, DSC, and XPS analysis. The presence of mixed valent states, such as V2O5 and VO2 in VO x, and the metastable properties of VO2 have been found to play crucial roles in the temperature-independent electrical conductivity of VO x/TiO2 nanoflakelets. Though pristine VO x exhibited characteristic semiconductor-to-metal transition of monoclinic VO2, pure VO x nanoflakelets exhibited poor sensitivity toward sensing oxygen. VO x/TiO2 nanoflakelets showed a very low temperature coefficient of resistance above 150 °C with improved sensitivity (35 times higher than VO x for 100 ppm) toward oxygen gas. VO x/TiO2 nanoflakelets exhibited much higher response, faster adsorption and desorption toward oxygen as compared to pristine VO x beyond 100 °C, which endowed the sensor with excellent temperature-independent sensor properties within 150-500 °C. The faster adsorption and desorption after 100 °C led to shorter response time (3-5 s) and recovery time (7-9 s). The results suggest that 2D VO x/TiO2 can be a promising candidate for temperature-independent oxygen sensor applications.

Analysis on surface nanostructures present in hindwing of dragon fly (Sympetrum vulgatum) using atomic force microscopy.

The present study involves the analysis of surface nanostructures and its variation present in the hind wing of dragon fly (Sympetrum vulgatum) using atomic force microscopy (AFM). The hindwing was dissected into 4 parts (D1-D4) and each dissected section was analyzed using AFM in tapping mode at different locations. The AFM analysis revealed the presence of irregular shaped nanostructures on the surface of the wing membrane with size varying between 83.25±1.79 nm to 195.08±10.25 nm. The size and shape of the nanostructure varied from tip (pterostigma) to the costa part. The membrane surface of the wing showed stacked arrangement leading to increase in size of the nanostructure. Such arrangement of the nanostructures has lead to the formation of nanometer sized valleys of different depth and length on the membrane surface giving them ripple wave morphology. The average roughness of the surface nanostructures varied from 18.58±3.12 nm to 24.25±8.33 nm. Surfaces of the wings had positive skewness in D1, D2 and D4 regions and negative skewness in D3 region. These surface nanostructures may contribute asymmetric resistance under mechanical loading during the flight by increasing the bending and torsional resistance of the wing.