Peptide-Based Nanoarchitectonics for the Treatment of Liver Fibrosis

Liver fibrosis is a process of excessive accumulation of extracellular matrix caused by liver injury. Liver fibrosis can progress to cirrhosis or even liver cancer without proper intervention. Until now, no effective therapeutic drugs have been clinically approved for treating liver fibrosis. Hence, the development of safe and effective antifibrotic drugs is particularly important. As a representative biomaterial, peptides have been investigated as key components for constructing antifibrotic nanomaterials given their advantages of biological origination, synthetic availability, and good biocompatibility. Peptides serve as multifunctional motifs in antifibrotic nanomaterials, such as liver-targeting molecules, antifibrotic molecules, and self-assembling building blocks for the formation of the nanomaterials. In this review, we focus on peptide-based nanoarchitectonics for treating liver fibrosis, including nanomaterials modified with liver-targeting peptides, nanomaterials for the efficient delivery of antifibrotic peptides, and self-assembled peptide nanomaterials for the delivery of antifibrotic drugs. The design rules of these peptide-based nanomaterials are described. The antifibrotic mechanisms and effects of these peptide-based nanomaterials in treating liver fibrosis and related diseases are highlighted. The challenges and future perspectives of using peptide-based nanoarchitectonics for the treatment of liver fibrosis are discussed. These results are expected to accelerate the rational design and clinical translation of antifibrotic nanomaterials.     

自组装肽基纳米材料运载药物和基因的研究进展

肽基分子自组装以其丰富的自组装驱动力、新颖的自组装体纳米结构、自组装体的特殊功能及良好的生物相容性等,在纳米生物材料、护肤和化妆产品、药物传输释放、组织工程支架材料等方面有着广泛的应用前景。由天然氨基酸组成的自组装短肽具有良好的低细胞毒性,可控的降解性能,高的运载效率及细胞摄取率,同时还具有降低药物的毒副作用等优点。因此,它在作为药物和基因的纳米载药材料方面有着巨大的发展前景。使用自组装肽基材料形成的纳米载体对疏水性抗癌药物、蛋白质药物及基因等进行传递释放已成为生物医药学领域的研究重点,因此,对近年来自组装肽基纳米材料作为药物和基因载体在生物医药学上的研究进展做了综述。     

Programmable peptide-directed two dimensional arrays of various nanoparticles on graphene sheets

In this research, we report an innovative, chemical strategy for the in situ synthesis and direct two-dimensional (2D) arraying of various nanoparticles (NPs) on graphenes using both programmed-peptides as directing agents and graphenes as pre-formed 2D templates. The peptides were designed for manipulating the enthalpic (coupled interactions) constraint of the global system. Along with the functionalization of graphene for the stable dispersion, peptides directed the growth and array of NPs in a controllable manner. In particular, the sequences of peptides were encoded by the combination of glutamic acid (E), glycine (G), and phenylalanine (F) amino acids as follows: (E-G-F)(3)-G, with E for the interaction with NPs and F and G for the interaction with graphenes. For the entropic (restricted geometry) constraint, graphene was used as a 2D scaffold to tune the size, density, and position of NPs, while maintaining the intrinsic properties for electrochemical applications. The excellent quality of the resultant hybrids was demonstrated by their high electrocatalytic activity in the electrooxidation of methanol. This synergistic combination of peptides and graphenes allowed for a uniform 2D array and spontaneous organization of various NPs (i.e., Pt, Au, Pd, and Ru), which would greatly expand the utility and versatility of this approach for the synthesis and array of the advanced nanomaterials.     

A comparative study of superhydrophobicity of 0D/1D/2D thermally functionalized carbon nanomaterials

Superhydrophobic coatings promise various practical applications. A one-step, ingenious yet economical thermal curing method is devised to render the carbon nanomaterials superhydrophobic. This study aims to compare the degree of superhydrophobicity of the carbon/polydimethylsiloxane (PDMS) synthesized from the 2D graphene nanoplatelets (GNPs), 1D multiwalled carbon nanotubes (MWCNTs), and 0D carbon black (CB) nanomaterials. The superhydrophobic GNPs/PDMS, MWCNTs/PDMS and CB/PDMS are synthesized when thermally functionalized with the siloxane groups. The Fourier transform infrared spectroscopy data signifies the successful functionalization of the carbon nanostructures by siloxane chains and the Raman spectroscopy analyses indicate that GNPs/PDMS manifests the highest degree of structural defects due to functionalization. The degree of superhydrophobicity induced on the carbon/PDMS coatings correlates with the dimensions of the carbon nanomaterials (0D, 1D and 2D), which is intimately associated with the effective surface areas of the nanomaterials susceptible of chemical functionalization. The promising applications of the superhydrophobic coatings are demonstrated. This study proposes a novel wettability tuning method and provides insightful analyses and characterization of the superhydrophobicity of the thermally functionalized carbon nanomaterials with different dimensions of varied nano-geometries.     

Investigation of the effect of the structure of large-area carbon nanotube/fuel composites on energy generation from thermopower waves

Thermopower waves are a recently developed energy conversion concept utilizing dynamic temperature and chemical potential gradients to harvest electrical energy while the combustion wave propagates along the hybrid layers of nanomaterials and chemical fuels. The intrinsic properties of the core nanomaterials and chemical fuels in the hybrid composites can broadly affect the energy generation, as well as the combustion process, of thermopower waves. So far, most research has focused on the application of new core nanomaterials to enhance energy generation. In this study, we demonstrate that the alignment of core nanomaterials can significantly influence a number of aspects of the thermopower waves, while the nanomaterials involved are identical carbon nanotubes (CNTs). Diversely structured, large-area CNT/fuel composites of one-dimensional aligned CNT arrays (1D CNT arrays), randomly oriented CNT films (2D CNT films), and randomly aggregated bulk CNT clusters (3D CNT clusters) were fabricated to evaluate the energy generation, as well as the propagation of the thermal wave, from thermopower waves. The more the core nanostructures were aligned, the less inversion of temperature gradients and the less cross-propagation of multiple thermopower waves occurred. These characteristics of the aligned structures prevented the cancellation of charge carrier movements among the core nanomaterials and produced the relative enhancement of the energy generation and the specific power with a single-polarity voltage signal. Understanding this effect of structure on energy generation from thermopower waves can help in the design of optimized hybrid composites of nanomaterials and fuels, especially designs based on the internal alignment of the materials. More generally, we believe that this work provides clues to the process of chemical to thermal to electrical energy conversion inside/outside hybrid nanostructured materials.     

Recent advances in nanofibrous assemblies based on β‐sheet‐forming peptides for biomedical applications

Amyloid fibrils are supramolecular polymers with β‐sheet‐rich structures formed by polymerization of protein/peptide with intermolecular interaction. Amyloid fibrils have been miscast as toxic villains since they have historically been studied as pathogens associated with serious diseases, including Alzheimer's and Parkinson's disease. However, recent studies on their toxicity and formation mechanism and discovery of their functionality in nature correct the misconception and strongly facilitate the possible use of β‐sheet‐forming peptides in designing novel nanomaterials. Self‐assembly based on β‐sheet‐forming peptides can provide highly ordered nanostructures under certain conditions. Therefore, ingenious design of the building block peptides allows the construction of nano‐assemblies, which contain large quantities of bio‐functional molecules, including drugs and bioactive peptides, and exhibit unique properties, such as assembly or disassembly in response to external stimulus or specific molecules. These properties provide a novel strategy for the creation of innovative nanomaterials, especially for biomedical applications. Here, we describe recent progress in the biomedical application of fibrous assemblies based on β‐sheet‐forming peptides, such as the suppression of aberrant protein aggregation, controlled release, tissue engineering and other applications. This review focuses not only on the function of the nanofibrous assemblies but also on the functions of component molecules, namely amyloidogenic peptides. © 2016 Society of Chemical Industry     

Modification of hydrogenated Bisphenol A epoxy adhesives using nanomaterials

Color-stable hydrogenated Bisphenol A (HBA) epoxy adhesives, containing organic-inorganic hybrid nanomaterials, were prepared and their properties investigated. Poly(propylene glycol)bis(2-aminopropyl ether) (D230) was used as the room temperature curing agent, and functional organic-inorganic hybrid nanomaterials, to tailor the adhesives, were prepared by a sol-gel reaction of 3-glycidoxypropyltrimethoxysilane and tetraethoxysilane. The commercial polyhedral oligomeric silsesquioxanes (POSS) having epoxy functional groups were also used. The concentration dependence of different nanomaterials, containing epoxy functional group for HBA/D230 adhesives, was studied. The tensile strength increased with the addition of nanomaterials having glycidyl epoxy group; however, the dependence varied with the size, the number of functional groups, and the amount of the addition. HBA/D230 adhesives containing different amounts of nanomaterials, whose compositions are similar to that of granite, were applied to the Korean granite and the results were compared with those obtained by using commercial adhesives, which have the problem of significant color change and high viscosity. The mechanical properties of HBA/D230 adhesives, containing POSS having glycidyl epoxy group, are found to be similar to those of commercial adhesives. Besides, it has low viscosity and long-term color stability.     

Development of Two-Dimensional Nanomaterials Based Electrochemical Biosensors on Enhancing the Analysis of Food Toxicants

In recent times, food safety has become a topic of debate as the foodborne diseases triggered by chemical and biological contaminants affect human health and the food industry’s profits. Though conventional analytical instrumentation-based food sensors are available, the consumers did not appreciate them because of the drawbacks of complexity, greater number of analysis steps, expensive enzymes, and lack of portability. Hence, designing easy-to-use tests for the rapid analysis of food contaminants has become essential in the food industry. Under this context, electrochemical biosensors have received attention among researchers as they bear the advantages of operational simplicity, portability, stability, easy miniaturization, and low cost. Two-dimensional (2D) nanomaterials have a larger surface area to volume compared to other dimensional nanomaterials. Hence, researchers nowadays are inclined to develop 2D nanomaterials-based electrochemical biosensors to significantly improve the sensor’s sensitivity, selectivity, and reproducibility while measuring the food toxicants. In the present review, we compile the contribution of 2D nanomaterials in electrochemical biosensors to test the food toxicants and discuss the future directions in the field. Further, we describe the types of food toxicity, methodologies quantifying food analytes, how the electrochemical food sensor works, and the general biomedical properties of 2D nanomaterials.     

One-dimensional organic-inorganic hybrid nanomaterials

This feature article presents the current research activities that concentrate on one-dimensional (1D) organic-inorganic hybrid nanostructures such as nanowires, nanorods, and nanotubes. The combination of organic and inorganic components in a 1D manner has been an increasingly expanding research field because the synergistic behavior of organic-inorganic materials is bound directly to the charming characteristics of 1D nanomaterials. These are responsible for the many novel optical and electrical properties, hierarchical superstructures, functions, and versatile applications that have been achieved. In this article, after justifying the interest in developing 1D organic-inorganic hybrid nanomaterials, we classify 1D hybrid nanostructures and review construction strategies that have been adopted, with a special focus on template-directed synthesis. In summary, we provide our personal perspectives on the future emphasis of the research on 1D organic-inorganic hybrid nanostructures.     

Cytotoxicity screening of 23 engineered nanomaterials using a test matrix of ten cell lines and three different assays

Background

The most common causes of granulomatous inflammation are persistent pathogens and poorly-degradable irritating materials. A characteristic pathological reaction to intratracheal instillation, pharyngeal aspiration, or inhalation of carbon nanotubes is formation of epithelioid granulomas accompanied by interstitial fibrosis in the lungs. In the mesothelium, a similar response is induced by high aspect ratio nanomaterials, including asbestos fibers, following intraperitoneal injection. This asbestos-like behaviour of some engineered nanomaterials is a concern for their potential adverse health effects in the lungs and mesothelium. We hypothesize that high aspect ratio nanomaterials will induce epithelioid granulomas in nonadherent macrophages in 3D cultures.

Results

Carbon black particles (Printex 90) and crocidolite asbestos fibers were used as well-characterized reference materials and compared with three commercial samples of multiwalled carbon nanotubes (MWCNTs). Doses were identified in 2D and 3D cultures in order to minimize acute toxicity and to reflect realistic occupational exposures in humans and in previous inhalation studies in rodents. Under serum-free conditions, exposure of nonadherent primary murine bone marrow-derived macrophages to 0.5 μg/ml (0.38 μg/cm²) of crocidolite asbestos fibers or MWCNTs, but not carbon black, induced macrophage differentiation into epithelioid cells and formation of stable aggregates with the characteristic morphology of granulomas. Formation of multinucleated giant cells was also induced by asbestos fibers or MWCNTs in this 3D in vitro model. After 7-14 days, macrophages exposed to high aspect ratio nanomaterials co-expressed proinflammatory (M1) as well as profibrotic (M2) phenotypic markers.

Conclusions

Induction of epithelioid granulomas appears to correlate with high aspect ratio and complex 3D structure of carbon nanotubes, not with their iron content or surface area. This model offers a time- and cost-effective platform to evaluate the potential of engineered high aspect ratio nanomaterials, including carbon nanotubes, nanofibers, nanorods and metallic nanowires, to induce granulomas following inhalation.     

One-dimensional self-assembly of planar pi-conjugated molecules: adaptable building blocks for organic nanodevices

In general, fabrication of well-defined organic nanowires or nanobelts with controllable size and morphology is not as advanced as for their inorganic counterparts. Whereas inorganic nanowires are widely exploited in optoelectronic nanodevices, there remains considerable untapped potential in the one-dimensional (1D) organic materials. This Account describes our recent progress and discoveries in the field of 1D self-assembly of planar pi-conjugated molecules and their application in various nanodevices including the optical and electrical sensors. The Account is aimed at providing new insights into how to combine elements of molecular design and engineering with materials fabrication to achieve properties and functions that are desirable for nanoscale optoelectronic applications. The goal of our research program is to advance the knowledge and develop a deeper understanding in the frontier area of 1D organic nanomaterials, for which several basic questions will be addressed: (1) How can one control and optimize the molecular arrangement by modifying the molecular structure? (2) What processing factors affect self-assembly and the final morphology of the fabricated nanomaterials; how can these factors be controlled to achieve the desired 1D nanomaterials, for example, nanowires or nanobelts? (3) How do the optoelectronic properties (e.g., emission, exciton migration, and charge transport) of the assembled materials depend on the molecular arrangement and the intermolecular interactions? (4) How can the inherent optoelectronic properties of the nanomaterials be correlated with applications in sensing, switching, and other types of optoelectronic devices? The results presented demonstrate the feasibility of controlling the morphology and molecular organization of 1D organic nanomaterials. Two types of molecules have been employed to explore the 1D self-assembly and the application in optoelectronic sensing: one is perylene tetracarboxylic diimide (PTCDI, n-type) and the other is arylene ethynylene macrocycle (AEM, p-type). The materials described in this project are uniquely multifunctional, combining the properties of nanoporosity, efficient exciton migration and charge transport, and strong interfacial interaction with the guest (target) molecules. We see this combination as enabling a range of important technological applications that demand tightly coupled interaction between matter, photons, and charge. Such applications may include optical sensing, electrical sensing, and polarized emission. Particularly, the well-defined nanowires fabricated in this study represent unique systems for investigating the dimensional confinement of the optoelectronic properties of organic semiconductors, such as linearly polarized emission, dimensionally confined exciton migration, and optimal pi-electronic coupling (favorable for charge transport). Combination of these properties will make the 1D self-assembly ideal for many orientation-sensitive applications, such as polarized light-emitting diodes and flat panel displays.     

Two-dimensional nanomaterials for photocatalytic water disinfection: recent progress and future challenges

Photocatalysis has received ever-growing attention as a promising alternative to traditional water treatment technologies for waterborne biohazard inactivation. Due to unique optical, electronic, physicochemical properties and feasibility of functional architecture assembly, two-dimensional (2D) nanomaterials have become important in developing novel photocatalysts. This review summarizes the recent progress in configuring nanostructures with 2D materials as building blocks for photocatalytic water disinfection. In this review, five categories of 2D nanomaterials, that is, graphene, graphitic carbon nitride, 2D metal oxides and metallates, metal oxyhalides and transition metal dichalcogenides, for photocatalytic pathogen inactivation are introduced. First, the synthesis process, nanostructure engineering and disinfection performance of 2D-based photocatalysts are reviewed in categories. In the following section, the bacteria destruction mechanism based on the generation and roles of reactive species (RSs) is presented. Moreover, the effects of the chemical characteristics of the water matrix on photocatalytic bactericidal performance are discussed. Finally, the challenges regarding the development and application of 2D-based photocatalysts for highly efficient water sterilization are highlighted. © 2018 Society of Chemical Industry     

House of Cards Nanostructuring of Graphene Oxide and Montmorillonite Clay for Oil–Water Separation

Noncovalent interactions are ubiquitous in our daily living. Nature employs hydrophobic effects, π–π interactions, hydrogen bonding, van der Waals forces, and electrostatic interactions in many biological processes such as protein folding. In the same manner, scientists exploit this plethora of inherently reversible noncovalent interactions as dials to design robust and smart materials. Electrostatic interaction is particularly interesting due to the simplicity of its concept, i.e., opposite charges attract. However, to our knowledge, the electrostatic interaction between two different 2D nanomaterials has not been investigated in literature. A myriad of natural and synthetic 2D nanomaterials should be explored for what may be an exciting cocktail of synergistic and tunable properties brought about by their charges and physical properties. This contribution highlights an interesting phenomena when organic, negatively charged graphene oxide and inorganic, positively charged montmorillonite (MMT) clay edges are brought into contact.     

Examination of Surfactant Protein D as a Biomarker for Evaluating Pulmonary Toxicity of Nanomaterials in Rat

This work studies the relationship between lung inflammation caused by nanomaterials and surfactant protein D (SP-D) kinetics and investigates whether SP-D can be a biomarker of the pulmonary toxicity of nanomaterials. Nanomaterials of nickel oxide and cerium dioxide were classified as having high toxicity, nanomaterials of two types of titanium dioxides and zinc oxide were classified as having low toxicity, and rat biological samples obtained from 3 days to 6 months after intratracheal instillation of those nanomaterials and micron-particles of crystalline silica were used. There were different tendencies of increase between the high- and low-toxicity materials in the concentration of SP-D in bronchoalveolar-lavage fluid (BALF) and serum and in the expression of the SP-D gene in the lung tissue. An analysis of the receiver operating characteristics for the toxicity of the nanomaterials by SP-D in BALF and serum showed a high accuracy of discrimination from 1 week to 3 or 6 months after exposure. These data suggest that the differences in the expression of SP-D in BALF and serum depended on the level of lung inflammation caused by the nanomaterials and that SP-D can be biomarkers for evaluating the pulmonary toxicity of nanomaterials.     

3D Conformal Surface Engineering of Continuous Fibers with Porous Microstructures for 1D Advanced Functional Materials

One-dimensional (1D) continuous advanced functional materials and devices with inherent flexibility for complex deformations facilitate a broad range of applications in wearable technology. This communication presents a new electrostatic self-assembly strategy for controllable assembly of nanomaterials to fabricate 1D continuous materials with customizable functions based on a kind of continuous fiber fully surface-engineered with 3D conformal porous microstructures (F@3CPMs) by a unique self-assembly approach of breath figure using water microdroplet arrays. Through gently rubbing the modified fibers with suitable triboelectric materials, either positively or negatively charged F@3CPMs can be rationally prepared with adjustable triboelectric charge intensity. Besides showing superiority in incorporating desired components, such kind of F@3CPMs are demonstrated to have general applicability and enhanced performance in controllable self-assembly of polymeric, metal, and carbon nanomaterials for customizable functionalizations. Moreover, taking advantages of continuous fibers that can deform largely, functional F@3CPMs are further applied for development of 1D flexible motion sensing devices by twisting directly, which can be either used as 1D freestanding devices for straightforward integration with conventional fabrics or woven as a fabric structure integrity for a kind of self-powered interactive textiles without additional battery as power resources to detect and monitor the body motions of human beings.     

通过加成反应制备纳米材料的新方法

通过加成反应,结合再沉淀法,制备得到Ni(DMG)_2的单晶纳米结构,并且通过调节反应物浓度可实现不同形貌的可控生长,在浓度低的条件下,可得到六方纳米管材,而随着浓度的升高,逐渐变为实心的六方纳米棒,这种制备方法提供了一种潜在的新方法——即通过加成反应来制备纳米材料。     

Manufacturing of inorganic nanomaterials: concepts and perspectives

The present paper aims at extracting key physical and chemical concepts for the development of inorganic nanomaterials with controlled size, shape, and topology. In particular, efforts are made to identify general guiding principles for the rational design of 0D, 1D, 2D and 3D architectures, focusing on selected model systems as representative case studies. To this aim, different strategies and approaches are discussed, in an attempt to unify concepts and ideas common to solid-, liquid- and gas-phase synthetic routes. Furthermore, the importance of tailoring the nanomaterial composition, structure and morphology is also highlighted in relation to their eventual technological applications.     

Identification of a Steric Zipper Motif in the Amyloidogenic Core of Human Cystatin C and Its Use for the Design of Self-Assembling Peptides

Amyloid fibrils have been known for many years. Unfortunately, their fame stems from negative aspects related to amyloid diseases. Nevertheless, due to their properties, they can be used as interesting nanomaterials. Apart from their remarkable stability, amyloid fibrils may be regarded as a kind of a storage medium and as a source of active peptides. In many cases, their structure may guarantee a controlled and slow release of peptides in their active form; therefore, they can be used as a potential nanomaterial in drug delivery systems. In addition, amyloid fibrils display controllable stiffness, flexibility, and satisfactory mechanical strength. In addition, they can be modified and functionalized very easily. Understanding the structure and genesis of amyloid assemblies derived from a broad range of amyloidogenic proteins could help to better understand and use this unique material. One of the factors responsible for amyloid aggregation is the steric zipper. Here, we report the discovery of steric zipper-forming peptides in the sequence of the amyloidogenic protein, human cystatin C (HCC). The ability of short peptides derived from this fragment of HCC to form fibrillar structures with defined self-association characteristics and the factors influencing this aggregation are also presented in this paper.     

Hetero-structured semiconductor nanomaterials for photocatalytic applications

Photocatalyst represents alternative solutions for renewable energy generation and environmental remediation. For photocatalytic applications, semiconductor nanomaterials emerge as important materials due to their unique structures, chemical and physical properties. Herein, we illustrate a brief overview of the recent progress in the development of hetero-structure nanomaterial based photocatalysts. Particularly, we focus our discussions on various dimensional (0D, 1D, 2D, and 3D) hetero-nanostructure of semiconductors to solve essential problems that are visible light absorption, fast charge separation, effective cocatalyst for charge utilization, and photoelectrochemical stability.     

Direct pyrolysis to convert biomass to versatile 3D carbon nanotubes/mesoporous carbon architecture: conversion mechanism and electrochemical performance

The massive conversion of resourceful biomass to carbon nanomaterials not only opens a new avenue to effective and economical disposal of biomass, but provides a possibility to produce highly valued functionalized carbon-based electrodes for energy storage and conversion systems. In this work, biomass is applied to a facile and scalable one-step pyrolysis method to prepare three-dimensional (3D) carbon nanotubes/mesoporous carbon architecture, which uses transition metal inorganic salts and melamine as initial precursors. The role of each employed component is investigated, and the electrochemical performance of the attained product is explored. Each component and precise regulation of their dosage is proven to be the key to successful conversion of biomass to the desired carbon nanomaterials. Owing to the unique 3D architecture and integration of individual merits of carbon nanotubes and mesoporous carbon, the as-synthesized carbon nanotubes/mesoporous carbon hybrid exhibits versatile application toward lithium-ion batteries and Zn-air batteries. Apparently, a significant guidance on effective conversion of biomass to functionalized carbon nanomaterials can be shown by this work.