Using nanomaterials to achieve functional enzyme mimics (nanozymes) is attractive for both applied and fundamental research. Laccases are multicopper oxidases highly important for biotechnology and environmental remediation. In this work, we report an exceptionally simple yet functional laccase mimic based on guanosine monophosphate (GMP) coordinated copper. It forms an amorphous metal-organic framework (MOF) material. The ratio of copper and GMP is 3:4 as determined by isothermal titration calorimetry. It has excellent laccase-like activity and converts a diverse range of phenol containing substrates such as hydroquinone, naphthol, catechol and epinephrine. Comparative work shows that the activity is originated from guanosine coordination instead of phosphate binding in GMP. Cu is required and cannot be substituted by other metal ions. At the same mass concentration, the Cu/GMP nanozyme has a higher V and similar K compared to the protein laccase. To achieve the same catalytic efficiency, the cost of the Gu/GMP is ∼2400-fold lower than that of laccase. The Cu/GMP is much more stable at extreme pH, high salt, high temperature and for long-term storage. This is one of the first laccase-mimicking nanozymes, which will find important applications in analytical chemistry, environmental protection, and biotechnology.
From social media has emerged continuous needs for automatic travel recommendations. Collaborative filtering (CF) is the most well-known approach. However, existing approaches generally suffer from various weaknesses. For example, sparsity can significantly degrade the performance of traditional CF. If a user only visits very few locations, accurate similar user identification becomes very challenging due to lack of sufficient information for effective inference. Moreover, existing recommendation approaches often ignore rich user information like textual descriptions of photos which can reflect users' travel preferences. The topic model (TM) method is an effective way to solve the "sparsity problem," but is still far from satisfactory. In this paper, an author topic model-based collaborative filtering (ATCF) method is proposed to facilitate comprehensive points of interest (POIs) recommendations for social users. In our approach, user preference topics, such as cultural, cityscape, or landmark, are extracted from the geo-tag constrained textual description of photos via the author topic model instead of only from the geo-tags (GPS locations). Advantages and superior performance of our approach are demonstrated by extensive experiments on a large collection of data.
Preserving enzyme activity and promoting synergistic activity via co-localization of multiple enzymes are key topics in bionanotechnology, materials science, and analytical chemistry.This study reports a facile method for co-immobilizing multiple enzymes in metal coordinated hydrogel nanofibers. Specifically, four types of protein enzymes, including glucose oxidase, Candida rugosa lipase, α-amylase, and horseradish peroxidase were respectively encapsulated in a gel nanofiber made of Zn 2+ and adenosine monophosphate (AMP) with a simple mixing step. Most enzymes achieved quantitatively loading and retained full activity. At the same time, the entrapped enzymes were more stable against temperature variation (by 7.5 C), protease attack, extreme pH (by 2-fold), and organic solvents. After storage for 15 days, the entrapped enzyme still retained 70% activity while the free enzyme nearly completely lost activity. Compared to nanoparticles formed with AMP and lanthanide ions, the nanofiber gels allowed much higher enzyme activity. Finally, a highly sensitive and selective biosensor for glucose was prepared using the gel nanofiber to co-immobilize glucose oxidase and horseradish peroxidase for an enzyme cascade system. A detection limit of 0.3 µM glucose with excellent selectivity was achieved. This work indicates that metal coordinated materials using nucleotides are highly useful for interfacing with biomolecules.3
Specificity of nucleobase pairing provides essential foundation for genetic information storage, replication, transcription and translation in all living organisms. However, the wobble base pairs, where U in RNA (or T in DNA) pairs with G instead of A, might compromise the high specificity of the base pairing. The U/G wobble pairing is ubiquitous in RNA, especially in non-coding RNA. In order to increase U/A pairing specificity, we have hypothesized to discriminate against U/G wobble pair by tailoring the steric and electronic effects at the 2-exo position of uridine and replacing the 2-exo oxygen with a selenium atom. We report here the first synthesis of the 2-Se-U-RNAs as well as the 2-Se-uridine (SeU) phosphoramidite. Our biophysical and structural studies of the SeU-RNAs indicate that this single atom replacement can indeed create a novel U/A base pair with higher specificity than the natural one. We reveal that the SeU/A pair maintains a structure virtually identical to the native U/A base pair, while discriminating against U/G wobble pair. This oxygen replacement with selenium offers a unique chemical strategy to enhance the base pairing specificity at the atomic level.
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