Variety Of Nanostructures Research Articles

Galvanic Replacement Reaction: Enabling the Creation of Active Catalytic Structures.

The galvanic replacement reaction (GRR) is recognized as a redox process where one metal undergoes oxidation by the ions of another metal possessing a higher reduction potential. This reaction takes place at the interface between a substrate and a solution containing metal ions. Utilizing metal or metal oxide as sacrificial templates enables the synthesis of metallic nanoparticles, oxide-metal composites, and mixed oxides through GRR. Growing evidence showed that GRR has a direct impact on surface structures and properties. This has generated significant interest in catalysis and opened up new horizons for the application of GRR in energy and chemical transformations. This review provides a comprehensive overview of the synthetic strategies utilizing GRR for the creation of catalytically active structures. It discusses the formation of alloys, intermetallic compounds, single atom alloys, metal-oxide composites, and mixed metal oxides with diverse nanostructures. Additionally, GRR serves as a postsynthesis method to modulate metal-oxide interfaces through the replacement of oxide domains. The review also outlines potential future directions in this field.

Large-scale assembly of geometrically diverse metal nanoparticles-based 3D plasmonic DNA nanostructures for SERS detection of PNK in cancer cells

The organization of geometrically diverse metal nanoparticles into a core/satellite structure at a large scale is a promising strategy for improve SERS performance due to hot spots localized enrichment and signal increase. However, due to the lack of extensional frames and strong electrostatic repulsion between plasma NPs, the fabrication of such 3D architectures with a high-density periodic hotspot in the focus volume has proven exceedingly difficult. Herein, we demonstrate a facile large-scale assembly of geometrically diverse metal nanoparticles strategy for constructing spatially extended 3D plasmonic nanostructures resembling “signal towers” based on RCA-mediated periodic organization of gold nanospheres (GNS) surrounding gold nanorods (GNRs). Using cancer cell T4 PNK as a model, a padlock probe with 5′- hydroxyl (P-circle) was designed as the T4 PNK substrate. The center Au nanorod was coated with P1 and served as a “pedestal” to allow substantial loading of P-circle after target phosphorylation to initiate the rolling ring amplification reaction (RCA). The resultant DNA nanowire serves as an “antenna” to successively lock numerous Raman reporter P2 (Cy3-P2-SH) through base pairing at regular intervals. Finally, the 3D plasma DNA nanostructures that resemble “signal towers” could be obtained by placing a large number of GNS with a strong affinity for Au–S. The proposed 3D SERS sensor exhibited a sensitivity of LOD as low as 0.274 mU/mL, which was attributed to a substantial electromagnetic field enhancement at the inter-nanoparticle gaps between the adjacent pedestal and antenna. Moreover, by exploiting the synergistic effect of the periodically extended DNA scaffold generated by RCA amplification and the co-assembly of thiol ligand, the loaded GNS can be extended to three-dimensional space, forming a high-density periodic hotspot in the focal volume, thereby ensuring high enhancement and high reproducibility of Raman signals. In addition, this method can be used to quantify T4 PNK in HeLa cells, demonstrating its applicability in diagnosing and estimating PNK-related diseases in complex fluids.

Synthesis of RNA-Amphiphiles via Atom Transfer Radical Polymerization in the Organic Phase.

The combination of hydrophobic polymers with nucleic acids is a fascinating way to engineer the self-assembly behavior of nucleic acids into diverse nanostructures such as micelles, vesicles, nanosheets, and worms. Here we developed a robust route to synthesize a RNA macroinitiator with protecting groups on the 2'-hydroxyl groups in the solid phase using an oligonucleotide synthesizer. The protecting groups successfully solubilized the RNA macroinitiator, enabling atom transfer radical polymerization (ATRP) of hydrophobic monomers. As a result, the RNA-polymer hybrids obtained by ATRP exhibited enhanced chemical stability by suppressing cleavage. In addition, we demonstrated evidence of controlled polymerization behavior as well as control over the molecular weight of the hydrophobic polymers grown from RNA. We envision that this methodology will expand the field of RNA-polymer conjugates while vastly enhancing the possibility to alter and engineer the properties of RNA-based polymeric materials.

Phosphates Induced H-Type or J-Type Aggregation of Cationic Porphyrins with Varied Side Chains.

Non-covalent interactions have been extensively used to fabricate nanoscale architectures in supramolecular chemistry. However, the biomimetic self-assembly of diverse nanostructures in aqueous solution with reversibility induced by different important biomolecules remains a challenge. Here, we report the synthesis and aqueous self-assembly of two chiral cationic porphyrins substituted with different types of side chains (branched or linear). Helical H-aggregates are induced by pyrophosphate (PPi) as indicated by circular dichroism (CD) measurement, while J-aggregates are formed with adenosine triphosphate (ATP) for the two porphyrins. By modifying the peripheral side chains from linear to a branched structure, more pronounced H- or J-type aggregation was promoted through the interactions between cationic porphyrins and the biological phosphate ions. Moreover, the phosphate-induced self-assembly of the cationic porphyrins is reversible in the presence of the enzyme alkaline phosphatase (ALP) and repeated addition of phosphates.

Development of Two-Dimensional Functional Nanomaterials for Biosensor Applications: Opportunities, Challenges, and Future Prospects.

New possibilities for the development of biosensors that are ready to be implemented in the field have emerged thanks to the recent progress of functional nanomaterials and the careful engineering of nanostructures. Two-dimensional (2D) nanomaterials have exceptional physical, chemical, highly anisotropic, chemically active, and mechanical capabilities due to their ultra-thin structures. The diversity of the high surface area, layered topologies, and porosity found in 2D nanomaterials makes them amenable to being engineered with surface characteristics that make it possible for targeted identification. By integrating the distinctive features of several varieties of nanostructures and employing them as scaffolds for bimolecular assemblies, biosensing platforms with improved reliability, selectivity, and sensitivity for the identification of a plethora of analytes can be developed. In this review, we compile a number of approaches to using 2D nanomaterials for biomolecule detection. Subsequently, we summarize the advantages and disadvantages of using 2D nanomaterials in biosensing. Finally, both the opportunities and the challenges that exist within this potentially fruitful subject are discussed. This review will assist readers in understanding the synthesis of 2D nanomaterials, their alteration by enzymes and composite materials, and the implementation of 2D material-based biosensors for efficient bioanalysis and disease diagnosis.

Remote-Triggered Domino-like Cyclodehydrogenation in Second-Layer Topological Graphene Nanoribbons

Cyclodehydrogenation reactions in the on-surface synthesis of graphene nanoribbons (GNRs) usually involve a series of Csp2-Csp2 and/or Csp2-Csp3 couplings and just happen on uncovered metal or metal oxide surfaces. It is still a big challenge to extend the growth of second-layer GNRs in the absence of necessary catalytic sites. Here, we demonstrate the direct growth of topologically nontrivial GNRs via multistep Csp2-Csp2 and Csp2-Csp3 couplings in the second layer by annealing designed bowtie-shaped precursor molecules over one monolayer on the Au(111) surface. After annealing at 700 K, most of the polymerized chains that appear in the second layer covalently link to the first-layer GNRs that have partially undergone graphitization. Following annealing at 780 K, the second-layer GNRs are formed and linked to the first-layer GNRs. Benefiting from the minimized local steric hindrance of the precursors, we suggest that the second-layer GNRs undergo domino-like cyclodehydrogenation reactions that are remotely triggered at the link. We confirm the quasi-freestanding behaviors in the second-layer GNRs by measuring the quasiparticle energy gap of topological bands and the tunable Kondo resonance from topological end spins using scanning tunneling microscopy/spectroscopy combined with first-principles calculations. Our findings pave the avenue to diverse multilayer graphene nanostructures with designer quantum spins and topological states for quantum information science.

Block Copolymer Enabled Synthesis and Assembly of Chiral Metal Oxide Nanoparticle

Chiral metal oxide nanostructures have received tremendous attention in nanotechnological applications owing to their intriguing chiroptical and magnetic properties. Current synthetic methods mostly rely on the use of amino acids or peptides as chiral inducers. Here, we report a general approach to fabricate chiral metal oxide nanostructures with tunable magneto-chiral effects, using block copolymer (BCP) inverse micelle and R/S-mandelic acid (MA). Diverse chiral metal oxide nanostructures are prepared by the selective incorporation of precursors within micellar cores followed by the oxidation process, exhibiting intense chiroptical properties with a g-factor up to 7.0 × 10-3 in the visible-NIR range for the Cr2O3 nanoparticle multilayer. The BCP inverse micelle is found to inhibit the racemization of MA, allowing MA to act as a chiral dopant that imparts chirality to nanostructures via hierarchical chirality transfer. Notably, for paramagnetic nanostructures, magneto-chiroptical modulation is realized by regulating the direction of the external magnetic field. This BCP-driven approach can be extended to the mass production of chiral nanostructures with tunable architectures and optical activities, which may provide insights into the development of chiroptical functional materials.

Center backbone-rigidified DNA polygonal nanostructures and bottom face-templated polyhedral pyramids with structural stability in a complex biological medium.

Due to the sequence programmability, good biocompatibility, versatile functionalities and vast sequence space, DNA oligonucleotides are considered to be ideal building blocks for the assembly of diverse nanostructures in one, two and three dimensions that are capable of engineering of multiple functional nucleic acids into a useful tool to implement intended tasks in biological and medical field. However, the construction of wireframe nanostructures consisting of only a few DNA strands remains quite challenging mainly because of the molecular flexibility-based uncontrollability of size and shape. In this contribution, utilizing gel electrophoretic analysis and atomic force microscopy, we demonstrate the modeling assembly technique for the construction of wireframe DNA nanostructures that can be divided into two categories: rigid center backbone-guided modeling (RBM) and bottom face-templated assembly (BTA) that are responsible for the construction of DNA polygons and polyhedral pyramids, respectively. The highest assembly efficiency (AE) is about 100%, while the lowest AE is not less than 50%. Moreover, when adding one edge for polygons or one side face for pyramids, we only need to add one oligonucleotide strand. Especially, the advanced polygons (e.g., pentagon and hexagon) of definite shape are for the first time constructed. Along this line, introduction of cross-linking strands enables the hierarchical assembly of polymer polygons and polymer pyramids. These wireframe DNA nanostructures exhibit the substantially enhanced resistance to nuclease degradation and maintain their structural integrity in fetal bovine serum for several hours even if the vulnerable nicks are not sealed. The proposed modeling assembly technique represents important progress toward the development of DNA nanotechnology and is expected to promote the application of DNA nanostructures in biological and biomedical fields. STATEMENT OF SIGNIFICANCE: DNA oligonucleotides are considered to be ideal building blocks for the assembly of diverse nanostructures. However, the construction of wireframe nanostructures consisting of only a few DNA strands remains quite challenging. In this contribution, we demonstrate the modeling technique for the construction of different wireframe DNA nanostructures: rigid center backbone-guided modeling (RBM) and bottom face-templated assembly (BTA) that are responsible for the assembly of DNA polygons and polyhedral pyramids, respectively. Moreover, cross-linking strands enables the hierarchical assembly of polymer polygons and polymer pyramids. These wireframe DNA nanostructures exhibit the substantially enhanced resistance to nuclease degradation and maintain their structural integrity in fetal bovine serum for several hours, promoting the application of DNA nanostructures in biological and biomedical fields.

Construction of Multiform Hollow‐Structured Covalent Organic Frameworks via a Facile and Universal Strategy for Enhanced Sonodynamic Cancer Therapy

AbstractThe special structural morphology of hollow covalent organic frameworks (HCOFs) has an important influence on their applications. However, the rapid and precise control of morphology for HCOFs still remains largely challenging. Herein, we present a facile and universal two‐step strategy based on solvent evaporation and oxidation of imine bond for the controllable synthesis of HCOFs. The strategy enables to prepare HCOFs in a greatly shortened reaction time and seven kinds of HCOFs are fabricated by the oxidation of imine bond via hydroxyl radicals (⋅OH) generated from Fenton reaction. Importantly, a fascinating library of HCOFs with diverse nanostructures, including bowl‐like, yolk‐shell, capsule‐like and flower‐like morphologies, has been ingeniously constructed. Owing to the large cavities, the obtained HCOFs are ideal candidates for drug delivery, which are employed to load five small molecule drugs, achieving the enhanced sonodynamic cancer therapy in vivo.

Construction of Multiform Hollow-Structured Covalent Organic Frameworks via a Facile and Universal Strategy for Enhanced Sonodynamic Cancer Therapy.

The special structural morphology of hollow covalent organic frameworks (HCOFs) has an important influence on their applications. However, the rapid and precise control of morphology for HCOFs still remains largely challenging. Herein, we present a facile and universal two-step strategy based on solvent evaporation and oxidation of imine bond for the controllable synthesis of HCOFs. The strategy enables to prepare HCOFs in a greatly shortened reaction time and seven kinds of HCOFs are fabricated by the oxidation of imine bond via hydroxyl radicals (⋅OH) generated from Fenton reaction. Importantly, a fascinating library of HCOFs with diverse nanostructures, including bowl-like, yolk-shell, capsule-like and flower-like morphologies, has been ingeniously constructed. Owing to the large cavities, the obtained HCOFs are ideal candidates for drug delivery, which are employed to load five small molecule drugs, achieving the enhanced sonodynamic cancer therapy in vivo.

Flexible inorganic piezoelectric functional films and their applications

Piezoelectric materials play an increasingly important role in energy harvesters, sensors, and actuators. Flexible and thin piezoelectric films have been demonstrated to provide advanced functionalities and improved performances. However, the research on flexible inorganic piezoelectric thin films has rarely been systematically summarized. Here, we summarize the recent advances in the flexible inorganic piezoelectric thin films, focusing on their structural designs, fabrication techniques, and applications in various practical scenarios. Specifically, different fabrication techniques suitable for diverse inorganic piezoelectric nanostructures are reviewed, including sol–gel, hydrothermal, electrospinning, and other techniques, and the integration process with flexible substrates is further discussed. Biomedical and industrial applications of the flexible piezoelectric thin films are emphasized. Finally, some existing challenges and future perspectives are discussed.

Self-assembling peptides as immunomodulatory biomaterials.

Self-assembling peptides are a type of biomaterial rapidly emerging in the fields of biomedicine and material sciences due to their promise in biocompatibility and effectiveness at controlled release. These self-assembling peptides can form diverse nanostructures in response to molecular interactions, making them versatile materials. Once assembled, the peptides can mimic biological functions and provide a combinatorial delivery of therapeutics such as cytokines and drugs. These self-assembling peptides are showing success in biomedical settings yet face unique challenges that must be addressed to be widely applied in the clinic. Herein, we describe self-assembling peptides' characteristics and current applications in immunomodulatory therapeutics.

Confinement of Assemblies of Peptides by Chemical Reactions in Living Cells.

The self-assembly of peptides plays an important role in optics, catalysis, medicine, and disease treatment. In recent years, peptide-based materials have exhibited great potential for cancer therapy and disease imaging due to their excellent biocompatibility, structural tenability, and ease of functionality. Peptides could self-assemble into diverse nanostructures in vivo triggered by endogenous stimuli, which initiated chemical reactions and self-assembled to achieve desired biological functions in the tumor microenvironment. This concept introduces the utilization of endogenous triggers to construct functional nanostructures in vivo and their corresponding biological applications. After briefly discussing the representative example of chemical reactions induced self-assembly of peptides in the living system, we describe the several stimuli triggered self-assembly for constructing therapeutic assemblies and serving as an imaging probe. Finally, we give a brief outlook to discuss the future direction of this exciting new field.

A Diphenylalanine Based Pentapeptide with Fibrillating Self-Assembling Properties.

Peptides and their related compounds can self-assemble into diverse nanostructures of different shapes and sizes in response to various stimuli such as pH, temperature or ionic strength. Here we report the synthesis and characterization of a lysozyme derived pentapeptide and its ability to build well-defined fibrillar structures. Lysozyme FESNF peptide fragment was synthesized by solid phase peptide synthesis using the Fmoc/t-Bu strategy, purified by analytical high-performance liquid chromatography (HPLC) and its molecular weight was confirmed by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Spectroscopic features of this pentapeptide were investigated by UV-visible spectroscopy and fluorimetry showing the pattern of marginal phenylalanine residues within the peptide sequence. Self-assembling properties were determined using atomic force microscopy (AFM), aggregation index and thioflavin T assay (ThT). FESNF generating fibrillar structures observed by AFM and aggregation propensity were primarily influenced by pH conditions. Moreover, the experimental data were confirmed by molecular dynamics simulation studies. The obtained fibrils will be used next to explore their potential to act as support material for medical and cosmetic application.

Evolution of Protein Assemblies Driven by the Switching of Interplay Mode.

A protein assembly with the ability to switch interplay modes of multiple driving forces has been achieved. Although biomolecular systems driven by multiple driving forces have been exploited, work on such a protein assembly capable of switching the interplay modes at nanoscale has been rarely reported so far as a result of their great fabrication challenge. In this work, two sets of driving forces such as ligand-ligand interaction and protein-protein interaction were leveraged to antagonistically underpin the multilayered stackings and trigger the hollow evolution to afford the well-defined hollow rectangular frame of proteins. While these protein frames further collapsed into aggregates, the ligand-ligand interactions were weakened, and the interplay of two sets of driving forces thereby tended to switch into synergistic mode, converting the protein packing mode from porously loose packing to axially dense packing and thus giving rise to a morphological evolution toward a nanosized protein tube. This strategy not only provides a nanoscale understanding on the mechanism underlying the switch of interplay modes in the context of biomacromolecules but also may provide access for diverse sophisticated biomacromolecular nanostructures that are historically inaccessible for conventional self-assembly strategies.

Elucidating the role of multivalency, shape, size and functional group density on antibacterial activity of diversified supramolecular nanostructures enabled by templated assembly.

With the increased prevalence of antibiotic-resistant infections, there is an urgent need to develop novel antibacterial materials. In addition, gaining a complete understanding of the structural features that impart activity toward target microorganisms is essential to enable materials optimisation. Here we have reported a rational design to fabricate antibacterial supramolecular nanoparticles with variable shape, size and cationic group density, by exploiting noncovalent interactions between a shape determining template amphiphile and a cationic amphiphile to introduce charge on the nanoparticle surface. We have shown that the monomeric cationic amphiphile alone showed poor antibacterial activity, whereas nanostructures formed by co-assembling the complementary units showed significantly enhanced antibacterial efficiency. Further, the systematic variation of several structural parameters such as shape, spacing between the cationic groups and size of these nanostructures allowed us to elicit the role of each parameter on the overall antibacterial properties. Finally, we investigated the origin of the differing antibacterial activity of these nanoparticles having different shape and size but with the same molecular composition, by comparing the thermodynamic parameters of their binding interactions with a bacterial membrane mimic.

Influence of the different nanostructures of acrylonitrile butadiene styrene/carbon nanotubes nanocomposites on laser cutting properties: Machining and chemical aspects

Reported on in depth for the first time herein is the influence of the diverse nanostructures of acrylonitrile butadiene styrene (ABS)/multi-walled carbon nanotubes (MWCNTs) on its chemical, physical and electrical properties after laser cutting. Injection moulding was used to fabricate the nanocomposite samples in various structures with a thickness of 3 mm by adjusting temperature and pressure. The samples’ nanostructures were evaluated prior to cutting with a CO2 laser. Design of experiments (DoE) by a full-factorial method used three levels laser power 45, 55 and 65 W) and the cutting velocity at three levels (4, 8 and 12 mm/s) as independent variables. The findings from this work are significant and support new theories. It was revealed different surface damage modes such as shrink holes, cracks, decomposed smithereens and sink marks. These were affected by the laser energy density criterion which means that the ratio of power to cutting velocity was the governing factor, whilst the effect of primary nanostructures was negligible. Unlike surface damage, the width of heat affected zone (HAZ) was found to depend on the thermal conductivity, which directly relates to the samples’ nanostructure. Minimum HAZ was obtained at 0.45 mm for the sample with maximum thermal conductivity equal to 0.23 W/mK. Analysis of the post-laser cut surface and HAZ indicated that the MWCNTs were well dispersed with higher orientation and degrees of distribution. This, naturally, allows the inference that application of low laser energy density accounted for and governed oxidation of these regions. The results show that the nanotexture of the post-laser cut surface is completely changed in comparison with the as-moulded surface, leading to the lowest reduction in surface electrical resistivity to 3.2 kΩ for the sample produced at a temperature of 220 °C and a holding pressure of 70 bar.

The concentration-, pH- and temperature-responsive self-assembly of undenatured type II collagen: Kinetics, thermodynamics, nanostructure and molecular mechanism

In this work, the undenatured type II collagen (UC-II) with an intact triple helix structure was obtained from chicken breast cartilage by the enzymatic extraction method. The self-assembly kinetics of UC-II at different parameters of concentration, pH and temperature was characterized by ultraviolet–visible spectroscopy (UV–vis). It occurred at pH 4.5–7.0 and was promoted by rising concentration and temperature in a certain range, and conformed to the first-order dynamics equation. The activation enthalpy (ΔH = 55.76 kJ mol−1) and entropy transition (ΔG = 69.30–71.40 kJ mol−1) revealed that the self-assembly of UC-II was a non-spontaneous heat absorption process. It was observed by atomic force microscopy (AFM) that, regulated by concentration, pH and temperature, the UC-II self-assemblies displayed diverse nanostructure, such as protofibrils, proto- and nano-filaments, nanofibrils of varying thickness and dense degree. Based on the results of circular dichroism (CD) and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), the UC-II self-assembly was mainly triggered by hydrophobic effects driven by a partial transition of the left-handed polyproline II (PP II) conformation, and both hydrogen bonding and electrostatic interactions were also involved in the self-assembly process. These results would lay the theoretical foundation for the fabrication and application of controllable UC-II self-assemblies.

GLAD Based Advanced Nanostructures for Diversified Biosensing Applications: Recent Progress.

Glancing angle deposition (GLAD) is a technique for the fabrication of sculpted micro- and nanostructures under the conditions of oblique vapor flux incident and limited adatom diffusion. GLAD-based nanostructures are emerging platforms with broad sensing applications due to their high sensitivity, enhanced optical and catalytic properties, periodicity, and controlled morphology. GLAD-fabricated nanochips and substrates for chemical and biosensing applications are replacing conventionally used nanomaterials due to their broad scope, ease of fabrication, controlled growth parameters, and hence, sensing abilities. This review focuses on recent advances in the diverse nanostructures fabricated via GLAD and their applications in the biomedical field. The effects of morphology and deposition conditions on GLAD structures, their biosensing capability, and the use of these nanostructures for various biosensing applications such as surface plasmon resonance (SPR), fluorescence, surface-enhanced Raman spectroscopy (SERS), and colorimetric- and wettability-based bio-detection will be discussed in detail. GLAD has also found diverse applications in the case of molecular imaging techniques such as fluorescence, super-resolution, and photoacoustic imaging. In addition, some in vivo applications, such as drug delivery, have been discussed. Furthermore, we will also provide an overview of the status of GLAD technology as well as future challenges associated with GLAD-based nanostructures in the mentioned areas.

Development and classification of RNA aptamers for therapeutic purposes: an updated review with emphasis on cancer.

Today, RNA aptamers are being considered promising theranostic tools against a wide variety of disorders. RNA aptamers can fold into complex shapes and bind to diverse nanostructures, macromolecules, cells, and viruses. It is possible to isolate RNA aptamers from a vast pool of nucleic acids via the Systematic Evolution of Ligands by Exponential Enrichment (SELEX) method. As therapeutics, aptamers have great potential because of their ability to bind to proteins and selectively limit their activities with negligible side effects. Several RNA aptamers with potential implications in cancer diagnosis are known to confer a great affinity for single-stranded DNA molecules, long non-coding RNAs, circulating tumor cells, vascular endothelial growth factors, and tissue and sera-derived exosomes in patients with different malignancies. Furthermore, clinical investigations have revealed the efficacy of RNA aptamer-based agents in imaging modalities. This review seeks to deliver new insights into the development, classification, nanomerization, and modification of RNA aptamers, as well as their applications in cancer theranostics. The aptamers' mechanism of action and their interest to clinical trials as theranostic agents are also discussed.