Hybrid nanomaterials have recently emerged as a new interface of nanobiocatalysis, serving as a host platform for enzyme immobilization. Enzyme immobilization in inorganic crystal nanoflowers and metal-organic frameworks (MOFs) has sparked the bulk of scientific interest due to their superior performances. Many breakthroughs have been achieved recently in the preparation of various types of enzyme@MOF and enzyme-hybrid nanoflower composites. However, it is unfortunate that there are few reviews in the literature related to enzyme@MOF and enzyme-hybrid nanoflower composites and their improved synthesis strategies and their applications in biotechnology. In this review, innovative synthetic strategies for enzyme@MOF composites and enzyme-hybrid nanoflower composites are discussed. Enzyme@MOF composites and enzyme-hybrid nanoflower composites are reviewed in terms of biotechnological applications and potential research directions. We are convinced that a fundamental study and application of enzyme@MOF composites and enzyme-hybrid nanoflower composites will be understood by the reader as a result of this work. The summary of different synthetic strategies for enzyme@MOF composites and enzyme-hybrid nanoflower composites and the improvement of their synthetic strategies will also benefit the readers and provide ideas and thoughts in the future research process.

The biomass of filamentous fungi is an important cost-effective biomass for heavy metal biosorption. However, use of free fungal cells can cause difficulties in the separation of biomass from the effluent. In this study, we immobilized the living conidia of the heavy metal-resistant Penicillium janthinillum strain GXCR by polyvinyl alcohol (PVA)-sodium alginate (SA) beads to remove heavy metals from an aqueous solution containing a low concentration (70 mg/L) of Cu, Pb, and Cd. The PVA-SA-conidia beads showed perfect characters of appropriate mechanical strength suitable for metal removal from the dynamic wastewater environment, an ideal settleability, easy separation from the solution, and a high metal biosorption and removal rate even after four cycles of successive sorption-desorption of the beads, overcoming disadvantages when fungal biomasses alone are used for heavy metal removal from wastewater. We also discuss the major biosorption-affecting factors, biosorption models, and biosorption mechanisms.

It is critical to identify and evaluate efficient phosphate-solubilizing bacteria (PSB) that enable P uptake from unavailable forms, and therefore improve the phosphorus (P) uptake efficiency of crops. The Enterobacter cloacae strain NG-33, belonging to PSB, was isolated and identified from calcareous rhizosphere soils in Nonggang National Reserve, Guangxi, China. The stain NG-33 could reduce the pH of the medium to below 5.6, and had the ability to release soluble phosphorus (P; 180.7 μg ml⁻¹) during the culture in the National Botanical Research Institute’s Phosphate medium (NBRIP), and produced such organic acids as gluconic acid (4,881 mg L⁻¹), acetic acid (346 mg L⁻¹), and indole-3-acetic acid (20.4 μg ml⁻¹). It could also convert inorganic P in AlPO₄ (Al-P) and FePO₄ (Fe-P) into soluble P, with conversion efficiencies of 19.2 μg ml⁻¹ and 16.3 μg ml⁻¹, respectively. Under pot experiments and when compared controls without inoculating NG-33, the shoot and root biomass of maize seedlings showed increases by 140% for shoot biomass and by 97% for root biomass in loamy soil (P sufficient) inoculated with NG-33. In sandy soil (P deficit) supplemented with tricalcium phosphate and inoculated with NG-33, the soluble P content was significantly higher, 58.6% in soil and 33.6% in roots, meanwhile, the biomass of shoots and roots increased by 14.9 and 24.9%, respectively. The growth-promoting effects coupled to the significant increase in leaf net photosynthetic rate and stomatal conductance of plants grown in NG-33-inoculated soil. Inoculating NG-33 could significantly improve the diversity and richness of bacterial population and altered the dominant bacterial population in soil.

Drinking water safety cannot be overemphasized. Filamentous fungi have many excellent features for metal removal. Both graphene oxide (GO) and activated carbon (AC) are conventional metal adsorbents, but they are not suitable for large-scale use due to high cost. In this study, a low dosage of conidia (2.0 × 10⁴ conidia/mL) of metal-resistant/adapted filamentous fungus Penicillium janthinillum strain GXCR were co-immobilized with a low dosage of 0.5 mg/L GO or 0.5 mg/L AC by embedding in 2% polyvinyl alcohol (PVA)-3% sodium alginate (SA), generating six types of microbead adsorbents (MBAs) to remove metals from a low concentration of either single metal (100 mg/L) or mixed metals (100 mg/L each) of Pb (II), Fe (III) and Cu (II) in drinking water. Fungus GXCR-containing MBAs had higher specific surface areas (SSAs), better mesoporous structures, and a higher removal rate (85-98.99%) of single or mixed metals. Singl-metal adsorptions of MBAs were almost unaffected by temperature changes. MBAs showed a stable removal rate of 87-94% during four cycles of adsorption-desorption of single metal. Single-metal adsorptions were well described by multiple models of Freundlich isotherm with constant values of 0.21-0.432, Langmuir isotherm with constant values of 0.037-0.17, Pseudo-fist-order, Pseudo-second-order, and intra-particle diffusion (IPD). In conclusion, co-immobilization between GXCR, GO and AC can make metal removal more efficient. Adsorption capacity is increased with SSAs but not in the same proportion. Single-metal adsorptions involve multiple mechanisms of monolayer and multilayer adsorptions, external mass transfer, and IPD. IPD is important but not the only one rate-controlling step for single-metal adsorptions.