Bimodal DNA self-origami material with nucleic acid function enhancement.

BACKGROUND: The design of DNA materials with specific nanostructures for biomedical tissue engineering applications remains a challenge. High-dimensional DNA nanomaterials are difficult to prepare and are unstable; moreover, their synthesis relies on heavy metal ions. Herein, we developed a bimodal DNA self-origami material with good biocompatibility and differing functions using a simple synthesis method. We simulated and characterized this material using a combination of oxDNA, freeze-fracture electron microscopy, and atomic force microscopy. Subsequently, we optimized the synthesis procedure to fix the morphology of this material. RESULTS: Using molecular dynamics simulation, we found that the bimodal DNA self-origami material exhibited properties of spontaneous stretching and curling and could be fixed in a single morphology via synthesis control. The application of different functional nucleic acids enabled the achievement of various biological functions, and the performance of functional nucleic acids was significantly enhanced in the material. Consequently, leveraging the various functional nucleic acids enhanced by this material will facilitate the attainment of diverse biological functions. CONCLUSION: The developed design can comprehensively reveal the morphology and dynamics of DNA materials. We thus report a novel strategy for the construction of high-dimensional DNA materials and the application of functional nucleic acid-enhancing materials.

Dual-sensitized heterojunction PDA/ZnO@MoS2 QDs combined with multilocus domino-like DNA cascade reaction for ultrasensitive photoelectrochemical biosensor.

In this work, by integrating with a highly efficient multilocus domino-like cascade reaction on DNA nanonet, an ultrasensitive PEC biosensor based on dual-sensitized PDA/ZnO@MoS2 QDs photoactive material as signal probe was proposed for detection of miRNA-182-5p. The dual-sensitized PDA/ZnO@MoS2 QD composed by both of p-n and S-scheme heterojunctions on electrode generated an extremely high initial PEC signal, which however quenched by CdTe QDs decorated on DNA nanonet owing to the significant p-n quenching effect. Thereafter, the output DNA (RS) from DSN enzyme-assisted target recycling amplification triggered an ingenious multilocus domino-like DNA cascade reaction on DNA nanonet for releasing numerous CdTe QDs. Thanks to the multilocus domino-like mode that owned abundant binding sites for increasing trigger efficiency and drove cascade reaction automatically advance along four stated pathways, the target conversion rate could be improved effectively compared with that of traditional approaches, significantly enhancing the detection sensitivity. Consequently, the developed PEC biosensor exhibited a low detection limit to 0.17 fM, providing a new avenue for sensitive, fast and reliable sensing of various DNA/RNA.

Lead-Free Copper-Based Perovskite Nanonets for Deep Ultraviolet Photodetectors with High Stability and Better Performance.

Considering practical application and commercialization, the research of non-toxic and stable halide perovskite and its application in the field of photoelectric detection have received great attention. However, there are relatively few studies on deep ultraviolet photodetectors, and the perovskite films prepared by traditional spin-coating method have disadvantages such as uneven grain size and irregular agglomeration, which limit their device performance. Herein, uniform and ordered Cs3Cu2I5 nanonet arrays are fabricated based on monolayer colloidal crystal (MCC) templates prepared with 1 µm polystyrene (PS) spheres, which enhance light-harvesting ability. Furthermore, the performance of the lateral photodetector (PD) is significantly enhanced when using Cs3Cu2I5 nanonet compared to the pure Cs3Cu2I5 film. Under deep ultraviolet light, the Cs3Cu2I5 nanonet PD exhibits a high light responsivity of 1.66 AW-1 and a high detection up to 2.48 × 1012 Jones. Meanwhile, the unencapsulated PD has almost no response to light above 330 nm and shows remarkable stability. The above results prove that Cs3Cu2I5 nanonet can be a great potential light-absorbing layer for solar-blind deep ultraviolet PD, which can be used as light absorption layer of UV solar cell.

Biodegradable, biomimetic, and nanonet-engineered membranes enable high-flux and highly-efficient oil/water separation.

Porous membranes with fascinating super-wettable surface and tunable porous architecture for oil-water separation have been developed rapidly, however, the serious secondary marine pollution caused by the non-degradable defectiveness of membranes themselves is still a thorny problem. Herein, we create an eco-friendly membrane with biomimetic cobweb-like nanostructure via assembling two-dimensional bacterial cellulose nanonets on the starch nanofibrous membrane on a large scale. The obtained novel composite membranes exhibit integrated properties of sub-micron pore size, ultrahigh porosity, superhydrophilicity, and underwater superoleophobicity, stemming from the synergistic effect of the hydrated nanonet-skin-layer and porous starch matrix. By virtue of the narrow-distributed sub-micron pores, ultrahigh porosity, and ultrathin thickness, the resulting membrane shows outstanding performance of excellent separation efficiency (up to 99.996%), high percolation flux (maximum of 15968 L m-2 h-1), well surpassing the conventional microfiltration membranes. More significantly, with the advantage of biodegradability and anti-oil-fouling property, the membrane could serve as the robust platform for long-term wastewater remediation.

Effect of Process Control Parameters on the Filtration Performance of PAN-CTAB Nanofiber/Nanonet Web Combined with Meltblown Nonwoven.

Nanofibers have potential applications as filters for particles with diameters <10 µm owing to their large specific surface area, macropores, and controllable geometry or diameter. The filtration efficiency can be increased by creating nanonets (<50 nm) whose diameter is smaller than that of nanofibers. This study investigates the effect of process conditions on the generation of nanonet structures from a polyacrylonitrile (PAN) solution containing cation surfactants; in addition, the filtration performance is analyzed. The applied electrospinning voltage and the electrostatic treatment of meltblown polypropylene (used as a substrate) are the most influential process parameters of nanonet formation. Electrospun polyacrylonitrile-cetylmethylammonium bromide (PAN-CTAB) showed a nanofiber/nanonet structure and improved thermal and mechanical properties compared with those of the electrospun PAN. The pore size distribution and filter efficiency of the PAN nanofiber web and PAN-CTAB nanofiber/nanonet web with meltblown were measured. The resulting PAN-CTAB nanofiber/nanonet air filter showed a high filtration efficiency of 99% and a low pressure drop of 7.7 mmH2O at an air flow rate of 80 L/min. The process control methods for the nanonet structures studied herein provide a new approach for developing functional materials for air-filtration applications.

Fabrication and Characterization of Nanonet-Channel LTPS TFTs Using a Nanosphere-Assisted Patterning Technique.

We present the fabrication and electrical characteristics of nanonet-channel (NET) low-temperature polysilicon channel (LTPS) thin-film transistors (TFTs) using a nanosphere-assisted patterning (NAP) technique. The NAP technique is introduced to form a nanonet-channel instead of the electron beam lithography (EBL) or conventional photolithography method. The size and space of the holes in the nanonet structure are well controlled by oxygen plasma treatment and a metal lift-off process. The nanonet-channel TFTs show improved electrical characteristics in terms of the ION/IOFF, threshold voltage, and subthreshold swing compared with conventional planar devices. The nanonet-channel devices also show a high immunity to hot-carrier injection and a lower variation of electrical characteristics. The standard deviation of VTH (σVTH) is reduced by 33% for a nanonet-channel device with a gate length of 3 µm, which is mainly attributed to the reduction of the grain boundary traps and enhanced gate controllability. These results suggest that the cost-effective NAP technique is promising for manufacturing high-performance nanonet-channel LTPS TFTs with lower electrical variations.

Micro/nano-textured hierarchical titanium topography promotes exosome biogenesis and secretion to improve osseointegration.

BACKGROUND: Micro/nano-textured hierarchical titanium topography is more bioactive and biomimetic than smooth, micro-textured or nano-textured titanium topographies. Bone marrow mesenchymal stem cells (BMSCs) and exosomes derived from BMSCs play important roles in the osseointegration of titanium implants, but the effects and mechanisms of titanium topography on BMSCs-derived exosome secretion are still unclear. This study determined whether the secretion behavior of exosomes derived from BMSCs is differently affected by different titanium topographies both in vitro and in vivo. RESULTS: We found that both micro/nanonet-textured hierarchical titanium topography and micro/nanotube-textured hierarchical titanium topography showed favorable roughness and hydrophilicity. These two micro/nano-textured hierarchical titanium topographies enhanced the spreading areas of BMSCs on the titanium surface with stronger promotion of BMSCs proliferation in vitro. Compared to micro-textured titanium topography, micro/nano-textured hierarchical titanium topography significantly enhanced osseointegration in vivo and promoted BMSCs to synthesize and transport exosomes and then release these exosomes into the extracellular environment both in vitro and in vivo. Moreover, micro/nanonet-textured hierarchical titanium topography promoted exosome secretion by upregulating RAB27B and SMPD3 gene expression and micro/nanotube-textured hierarchical titanium topography promoted exosome secretion due to the strongest enhancement in cell proliferation. CONCLUSIONS: These findings provide evidence that micro/nano-textured hierarchical titanium topography promotes exosome biogenesis and extracellular secretion for enhanced osseointegration. Our findings also highlight that the optimized titanium topography can increase exosome secretion from BMSCs, which may promote osseointegration of titanium implants.

Growing vertical aligned mesoporous silica thin film on nanoporous substrate for enhanced degradation, drug delivery and bioactivity.

Mesoporous silica thin film has been widely used in various fields, particularly the medical implant coating for drug delivery. However, some drawbacks remain with the films produced by traditional method (evaporation-induced self-assembly, EISA), such as the poor permeability caused by their horizontal aligned mesochannels. In this study, the vertical aligned mesoporous silica thin film (VMSTF) is uniformly grown alongside the walls of titania nanotubes array via a biphase stratification growth method, resulting in a hierarchical two-layered nanotubular structure. Due to the exposure of opened mesopores, VMSTF exhibits more appealing performances, including rapid degradation, efficient small-molecular drug (dexamethasone) loading and release, enhanced early adhesion and osteogenic differentiation of MC3T3-E1 cells. This is the first time successfully depositing VMSTF on nanoporous substrate and our findings suggest that the VMSTF may be a promising candidate for bone implant surface coating to obtain bioactive performances.

Optimization of GOPS-Based Functionalization Process and Impact of Aptamer Grafting on the Si Nanonet FET Electrical Properties as First Steps towards Thrombin Electrical Detection.

Field effect transistors (FETs) based on networks of randomly oriented Si nanowires (Si nanonets or Si NNs) were biomodified using Thrombin Binding Aptamer (TBA-15) probe with the final objective to sense thrombin by electrical detection. In this work, the impact of the biomodification on the electrical properties of the Si NN-FETs was studied. First, the results that were obtained for the optimization of the (3-Glycidyloxypropyl)trimethoxysilane (GOPS)-based biofunctionalization process by using UV radiation are reported. The biofunctionalized devices were analyzed by atomic force microscopy (AFM) and scanning transmission electron microscopy (STEM), proving that TBA-15 probes were properly grafted on the surface of the devices, and by means of epifluorescence microscopy it was possible to demonstrate that the UV-assisted GOPS-based functionalization notably improves the homogeneity of the surface DNA distribution. Later, the electrical characteristics of 80 devices were analyzed before and after the biofunctionalization process, indicating that the results are highly dependent on the experimental protocol. We found that the TBA-15 hybridization capacity with its complementary strand is time dependent and that the transfer characteristics of the Si NN-FETs obtained after the TBA-15 probe grafting are also time dependent. These results help to elucidate and define the experimental precautions that must be taken into account to fabricate reproducible devices.

3D DNA nanonet structure coupled with target-catalyzed hairpin assembly for dual-signal synergistically amplified electrochemical sensing of circulating microRNA.

DNA nanomaterials are reliable and powerful tools in the development of a variety of biosensors owing to their notable self-assembly ability and precise recognition capability. Here, we propose a DNA nanomaterial-based system for the dual-amplified electrochemical sensing of circulating microRNAs by a coupled cascade of catalyzed hairpin assembly (CHA) and three-dimensional (3D) DNA nanonet structure. In the target-assisted CHA process, the stable hairpin structures H1 and H2 act as probes for the recognition and recycling of circulating microRNAs, leading to the formation of abundant H1-H2 duplexes with tails. Subsequently, a 3D DNA nanonet structure was introduced, which was assembled using three DNA strands constructed X-DNA monomers as the building blocks, and hybridized to the tails of H1-H2 duplexes. The successful integration of target-assisted CHA and 3D DNA nanonet structure induced the second signal amplification. The designed biosensor performed under optimized experimental conditions, and exposed admirable analytical performance for the detection of circulating miR-21, with a wide linear range from 10 fM to 1 nM, high sensitivity of limit of detection (LOD) of 3.6083 fM, good specificity in the face of single nucleotides and other microRNAs, satisfactory stability and reproducibility for practical analysis. Furthermore, the clinical applicability for circulating miR-21 detection was verified in human serum samples without additional treatment. We hope that this elaborated biosensor will provide new opportunities for bioassays based on DNA nanomaterials.

Functional Insights From the Evolutionary Diversification of Big Defensins.

Big defensins are antimicrobial polypeptides believed to be the ancestors of ß-defensins, the most evolutionary conserved family of host defense peptides (HDPs) in vertebrates. Nevertheless, big defensins underwent several independent gene loss events during animal evolution, being only retained in a limited number of phylogenetically distant invertebrates. Here, we explore the evolutionary history of this fascinating HDP family and investigate its patchy distribution in extant metazoans. We highlight the presence of big defensins in various classes of lophotrochozoans, as well as in a few arthropods and basal chordates (amphioxus), mostly adapted to life in marine environments. Bivalve mollusks often display an expanded repertoire of big defensin sequences, which appear to be the product of independent lineage-specific gene tandem duplications, followed by a rapid molecular diversification of newly acquired gene copies. This ongoing evolutionary process could underpin the simultaneous presence of canonical big defensins and non-canonical (ß-defensin-like) sequences in some species. The big defensin genes of mussels and oysters, two species target of in-depth studies, are subjected to gene presence/absence variation (PAV), i.e., they can be present or absent in the genomes of different individuals. Moreover, big defensins follow different patterns of gene expression within a given species and respond differently to microbial challenges, suggesting functional divergence. Consistently, current structural data show that big defensin sequence diversity affects the 3D structure and biophysical properties of these polypeptides. We discuss here the role of the N-terminal hydrophobic domain, lost during evolution toward ß-defensins, in the big defensin stability to high salt concentrations and its mechanism of action. Finally, we discuss the potential of big defensins as markers for animal health and for the nature-based design of novel therapeutics active at high salt concentrations.

Inositol polyphosphate multikinase is a metformin target that regulates cell migration.

Metformin has been shown to alter cell adhesion protein expression, which is thought to play a role in its observed antitumor properties. We found that metformin treatment down-regulated integrin ß1 concomitant with the loss of inositol polyphosphate multikinase (IPMK) in murine myocytes, adipocytes, and hepatocytes. To determine if IPMK was upstream of integrin ß1 expression, we examined IPMK-/- mouse embryonic fibroblast cells and found that integrins ß1 and ß3 gene expression was reduced by half, relative to wild-type cells, whereas focal adhesion kinase (FAK) activity and Rho/Rac/Cdc42 protein levels were increased, resulting in migration defects. Using nanonet force microscopy, we determined that cell:extracellular matrix adhesion and cell contractility forces were decreased, confirming the functional relevance of integrin and Rho protein dysregulation. Pharmacological studies showed that inhibition of both FAK1 and proline-rich tyrosine kinase 2 partially restored integrin ß1 expression, suggesting negative regulation of integrin ß1 by FAK. Together our data indicate that IPMK participates in the regulation of cell migration and provides a potential link between metformin and wound healing impairment.-Tu-Sekine, B., Padhi, A., Jin, S., Kalyan, S., Singh, K., Apperson, M., Kapania, R., Hur, S. C., Nain, A., Kim, S. F. Inositol polyphosphate multikinase is a metformin target that regulates cell migration.

Linear-Polyethyleneimine-Templated Synthesis of N-Doped Carbon Nanonet Flakes for High-performance Supercapacitor Electrodes.

Novel N-doped carbon nanonet flakes (NCNFs), consisting of three-dimensional interconnected carbon nanotube and penetrable mesopore channels were synthesized in the assistance of a hybrid catalytic template of silica-coated-linear polyethyleneimine (PEI). Resorcinol-formaldehyde resin and melamine were used as precursors for carbon and nitrogen, respectively, which were spontaneously formed on the silica-coated-PEI template and then annealed at 700 °C in a N2 atmosphere to be transformed into the hierarchical 3D N-doped carbon nanonetworks. The obtained NCNFs possess high surface area (946 m2 g-1), uniform pore size (2-5 nm), and excellent electron and ion conductivity, which were quite beneficial for electrochemical double-layered supercapacitors (EDLSs). The supercapacitor synthesized from NCNFs electrodes exhibited both extremely high capacitance (up to 613 F g-1 at 1 A g-1) and excellent long-term capacitance retention performance (96% capacitive retention after 20,000 cycles), which established the current processing among the most competitive strategies for the synthesis of high performance supercapacitors.

Anchoring gold nanoparticles on poly(3,4-ethylenedioxythiophene) (PEDOT) nanonet as three-dimensional electrocatalysts toward ethanol and 2-propanol oxidation.

Renewable alcohol oxidation is of vital significance for clean energy conversion and storage. Here, we fabricated a three-dimensional (3D) nanonet-like hybrid catalyst combining Au nanoparticles and poly(3,4-ethylenedioxythiophene) (PEDOT) together, in which PEDOT nanonets act as the framework of the 3D catalyst and the support for the dispersion of Au nanoparticles. The catalyst was designated as Au-PEDOT. By using conductive carbon cloth (CC) as electrode substrates, the as-fabricated Au-PEDOT/CC electrodes were applied to evaluate the electrocatalytic activity towards ethanol and 2-propanol in the alkaline media, respectively. The catalytic activity on Au-PEDOT/CC in terms of the peak current and/or peak current density towards ethanol and 2-propanol oxidation is five times higher than that on comparative Au/CC catalysts, respectively, which is also higher than that on some similar materials reported in the literature. In addition, the Au-PEDOT/CC electrode also possessed great durability and reproducibility. This enhancement in electrocatalytic activity can be attributed to a number of factors: the nano-scale of the Au catalysts, the 3D nanostructure of the catalysts, the conductivity of PEDOT, as well as the effect of alkaline media. These results indicate the as-synthesized Au-PEDOT is a promising electrocatalyst for liquid fuel oxidation.

Evolution of Structural and Electrical Properties of Oxygen-Deficient VO2 under Low Temperature Heating Process.

Structural stability and functional performances of vanadium dioxide (VO2) are strongly influenced by oxygen vacancies. However, the mechanism of metal-insulator transition (MIT) influenced by defects is still under debate. Here, we study the evolution of structure and electrical property of oxygen-deficient VO2 by a low temperature annealing process (LTP) based on a truss-structured VO2 nanonet. The oxygenation process of the oxygen-deficient VO2 is greatly prolonged, which enables us to probe the gradual change of properties of the oxygen-deficient VO2. A continuous lattice reduction is observed during LTP. No recrystallization and structural collapse of the VO2 nanonet can be found after LTP. The valence-band X-ray photoelectron spectroscopy (XPS) measurements indicate that the oxygen deficiency strongly affects the energy level of the valence band edge. Correspondingly, the resistance changes of the VO2 films from 1 to 4.5 orders of magnitude are achieved by LTP. The effect of oxygen vacancy on the electric field driven MIT is investigated. The threshold value of voltage triggering the MIT decreases with increasing the oxygen vacancy concentration. This work demonstrates a novel and effective way to control the content of oxygen vacancies in VO2 and the obvious impact of oxygen vacancy on MIT, facilitating further research on the role of oxygen vacancy in structure and MIT of VO2, which is important for the deep understanding of MIT and exploiting innovative functional application of VO2.

Silicon nanonets for biological sensing applications with enhanced optical detection ability.

Optical sensors based on fluorescence methods are used in numerous areas of society, ranging from healthcare to environmental monitoring. But the race to elaborate portable and highly sensitive detection systems leads to the huge development of nanomaterial-based sensors. Here, we have fabricated a silicon nanonet, or silicon nanowire (SiNW) network, -based biosensor for DNA hybridization detection by fluorescence microscopy. We demonstrate that by leveraging the properties of the SiNWs such as their large specific surface and the high aspect ratio, these nanonet sensors have significantly enhanced sensitivity and better selectivity compared to plane substrates. The fluorescence signal shows an intensity increasing with the SiNW density on the nanonet and for the denser nanonets, the detection limit for DNA hybridization is 1 nM. The elaborated Si nanonet-based DNA sensors present more than 50% change in fluorescence intensity between complementary DNA and 1 base mismatch DNA which shows their high selectivity. Finally, we have integrated the Si nanonet-based sensor into a DNA chip and we have shown that this selective sensor can be reproduced on a large scale area.