Design of Cyclodextrin-Based Functional Systems for Biomedical Applications.

Cyclodextrins (CDs) are a family of α-1,4-linked cyclic oligosaccharides that possess a hydrophobic cavity and a hydrophilic outer surface with abundant hydroxyl groups. This unique structural characteristic allows CDs to form inclusion complexes with various guest molecules and to functionalize with different substituents for the construction of novel sophisticated systems, ranging from derivatives to polymers, metal-organic frameworks, hydrogels, and other supramolecular assemblies. The excellent biocompatibility, selective recognition ability, and unique bioactive properties also make these CD-based functional systems especially attractive for biomedical applications. In this review, we highlight the characteristics and advantages of CDs as a starting point to design different functional materials and summarize the recent advances in the use of these materials for bioseparation, enzymatic catalysis, biochemical sensing, biomedical diagnosis and therapy.

Supramolecular Polymer Nanocomposites for Biomedical Applications.

Polymer nanocomposites, a class of innovative materials formed by polymer matrixes and nanoscaled fillers (e.g., carbon-based nanomaterials, inorganic/semiconductor nanoparticles, metal/metal-oxide nanoparticles, polymeric nanostructures, etc.), display enhanced mechanical, optoelectrical, magnetic, catalytic, and bio-related characteristics, thereby finding a wide range of applications in the biomedical field. In particular, the concept of supramolecular chemistry has been introduced into polymer nanocomposites, which creates myriad "smart" biomedical materials with unique physicochemical properties and dynamic tunable structures in response to diverse external stimuli. This review aims to provide an overview of the chemical composition, morphological structures, biological functionalities, and reinforced performances of supramolecular polymer nanocomposites. Additionally, recent advances in biomedical applications such as therapeutic delivery, bioimaging, and tissue engineering are also discussed, especially their excellent properties leveraged in the development of multifunctional intelligent biomedical materials.

Graphene oxide-based colorimetric detection of organophosphorus pesticides via a multi-enzyme cascade reaction.

Size-tunable graphene oxides (GO) were synthesized as a horseradish peroxidase (HRP) mimic for colorimetric detection of organophosphorus pesticides (OPs) at nanomolar levels via a cascade reaction. A GO-based colorimetric method showed high sensitivity and stability toward OPs, which hold great potential in public health applications.

Computational Design and Study of Artificial Selenoenzyme with Controllable Activity Based on an Allosteric Protein Scaffold.

The establishment of new enzymatic function in an existing scaffold is a great challenge for protein engineers. In previous work, a highly efficient artificial selenoenzyme with controllable activity was constructed, based on a Ca2+ -responsive recoverin (Rn) protein. In this study, a design strategy combining docking, molecular dynamics, and MM-PBSA is presented, to predict the catalytically active site of glutathione peroxidase (GPx) on the allosteric domain of Rn. The energy contributions of the binding hot spot residues are evaluated further by energy decomposition analysis to determine the detailed substrate recognition mechanism of Rn, which provides clear guidance for artificial enzyme design for improved substrate binding (Michaelis-Menten constant, Km ).

A quencher-free DNAzyme beacon for fluorescently sensing uranyl ions via embedding 2-aminopurine.

DNAzyme-based fluorescent probes have provided valuable protocols for detecting uranium, one of the most common radioactive contaminants in the environment, with ultra-high selectivity and sensitivity. Designing novel DNAzyme beacons to update the mode of fluorescence reporting and/or quenching will continuously enhance "turn-on" sensing performance as well as promote actual application of the biological probes. In this work, we developed a novel quencher-free DNAzyme beacon by embedding fluorescent 2-aminopurine for rapid detection of uranyl ion. 2-aminopurine is able to substitute adenine and keep strong fluorescence in single-stranded DNA whereas being quenched in the hybridized double-stranded DNA by the base-stacking interaction. The combination of such trait of 2-aminopurine and cleavage reaction of DNAzyme in the presence of target co-factors possesses two main advantages for ion sensing: simplicity for avoidance of extra quencher groups and high performance because of superiority of DNAzyme essence. The experimental conditions including embedding site, pH and salt concentration of buffer solutions, and the amount ratio of enzyme strand to substrate strand used to form DNAzymes were systematically optimized to inspire the highest performance of the biological beacon. Thus, a detection limit of 9.6 nM, a wide linear range from 5 nM to 400 nM (R2 = 0.997), and selectivity of more than 400 000-fold over other metal ions were achieved by the novel DNAzyme probes. The highly sensitive, selective and quencher-free DNAzyme probes accommodated a simple and cost-efficient alternative to current fluorescent counterparts, holding a great potential for further application in practical ion assay.

A remote optically controlled hydrolase model based on supramolecular assembly and disassembly of its enzyme-like active site.

A photoresponsive hydrolase model was constructed through the spatial organization of histidine/arginine-containing peptide supra-amphiphiles that are held together by cucurbit[8]uril (CB[8]) methylviologen (MV) azobenzene (Azo) ternary complexation and subsequently self-assemble into highly uniform giant vesicles. The reversible morphological transition of the vesicular structures to non-assembled peptide fragments was triggered by azobenzene photoisomerization. This enables the assembly/disassembly of its enzyme-like active site to cause a dramatic change in hydrolytic activity. The dynamic process can be directly monitored to determine the supramolecular structure-related enzymatic parameters, which may help to understand how the regulation of enzyme activity is coupled to the aggregation behaviors of natural enzymes.

Designing a new type of neutron detector for neutron and gamma-ray discrimination via GEANT4.

Design of a new type of neutron detector, consisting of a fast neutron converter, plastic scintillator, and Cherenkov detector, to discriminate 14-MeV fast neutrons and gamma rays in a pulsed n-γ mixed field and monitor their neutron fluxes is reported in this study. Both neutrons and gamma rays can produce fluorescence in the scintillator when they are incident on the detector. However, only the secondary charged particles of the gamma rays can produce Cherenkov light in the Cherenkov detector. The neutron and gamma-ray fluxes can be calculated by measuring the fluorescence and Cherenkov light. The GEANT4 Monte Carlo simulation toolkit is used to simulate the whole process occurring in the detector, whose optimum parameters are known. Analysis of the simulation results leads to a calculation method of neutron flux. This method is verified by calculating the neutron fluxes using pulsed n-γ mixed fields with different n/γ ratios, and the results show that the relative errors of all calculations are <5%.

Monte Carlo simulation of moderator and reflector in coal analyzer based on a D-T neutron generator.

Coal is one of the most popular fuels in the world. The use of coal not only produces carbon dioxide, but also contributes to the environmental pollution by heavy metals. In prompt gamma-ray neutron activation analysis (PGNAA)-based coal analyzer, the characteristic gamma rays of C and O are mainly induced by fast neutrons, whereas thermal neutrons can be used to induce the characteristic gamma rays of H, Si, and heavy metals. Therefore, appropriate thermal and fast neutrons are beneficial in improving the measurement accuracy of heavy metals, and ensure that the measurement accuracy of main elements meets the requirements of the industry. Once the required yield of the deuterium-tritium (d-T) neutron generator is determined, appropriate thermal and fast neutrons can be obtained by optimizing the neutron source term. In this article, the Monte Carlo N-Particle (MCNP) Transport Code and Evaluated Nuclear Data File (ENDF) database are used to optimize the neutron source term in PGNAA-based coal analyzer, including the material and shape of the moderator and neutron reflector. The optimized targets include two points: (1) the ratio of the thermal to fast neutron is 1:1 and (2) the total neutron flux from the optimized neutron source in the sample increases at least 100% when compared with the initial one. The simulation results show that, the total neutron flux in the sample increases 102%, 102%, 85%, 72%, and 62% with Pb, Bi, Nb, W, and Be reflectors, respectively. Maximum optimization of the targets is achieved when the moderator is a 3-cm-thick lead layer coupled with a 3-cm-thick high-density polyethylene (HDPE) layer, and the neutron reflector is a 27-cm-thick hemispherical lead layer.