ChemNanoMat

Spatial Patterning of Micromotor Aggregation and Flux
Rivas DP, Sokolich M and Das S
Using a spatially varying light pattern with light activated semi-conductor based magnetic TiO micromotors, we study the difference in micromotor flux between illuminated and non-illuminated regions in the presence and absence of an applied magnetic field. We find that the magnetic field enhances the flux of the motors which we attribute to a straightening of the micromotor trajectories which decreases the time they spend in the illuminated region. We also demonstrate spatially patterned light-induced aggregation of the micromotors and study its time evolution at various micromotor concentrations. Although light induced aggregation has been observed previously, spatial patterning of aggregation demonstrates a further means of control which could be relevant to swarm control or self-assembly applications. Overall, these results draw attention to the effect of trajectory shape on the flux of active colloids as well as the concentration dependence of aggregation and its time dependence within a spatially patterned region, which is not only pertinent to self-assembly and swarm control, but also provides insight into the behavior of active matter systems with spatially varying activity levels.
Electrospun Nanofibers for Wound Management
John JV, McCarthy A, Karan A and Xie J
Electrospun nanofibers show great potential in biomedical applications. This mini review article traces the recent advances in electrospun nanofibers for wound management various approaches. Initially, we provide a short note on the four phases of wound healing, including hemostasis, inflammation, proliferation, and remodeling. Then, we state how the nanofiber dressings can stop bleeding and reduce the pain. Following that, we discuss the delivery of therapeutics and cells using different types of nanofibers for enhancing cell migration, angiogenesis, and re-epithelialization, resulting in the promotion of wound healing. Finally, we present the conclusions and future perspectives regarding the use of electrospun nanofibers for wound management.
Nanotechnology Toolkit for Combating COVID-19 and Beyond
Muthiah G, Sarkar A, Roy S, Singh P, Kumar P, Bhardwaj K and Jaiswal A
The outbreak of SARS-CoV-2 is unlikely to be contained anytime soon with conventional medical technology. This beckons an urgent demand for novel and innovative interventions in clinical protocols, diagnostics, and therapeutics; to manage the current "disease X" and to be poised to counter its successor of like nature if one were to ever arise. To meet such a demand requires more attention to research on the viral-host interactions and on developing expeditious solutions, the kinds of which seem to spring from promising domains such as nanotechnology. Inducing activity at scales comparable to the viruses themselves, nanotechnology-based preventive measures, diagnostic tools and therapeutics for COVID-19 have been rapidly growing during the pandemic. This review covers the recent and promising nanomedicine-based solutions relating to COVID-19 and how some of these are possibly applicable to a wider range of viruses and pathogens. We also discuss the type, composition, and utility of nanostructures which play various roles specifically under prevention, diagnosis, and therapy. Further, we have highlighted the adoption and commercialization of some the solutions by large and small corporations alike, as well as providing herewith an exhaustive list on nanovaccines.
Phytotoxic effect of sub-3-nm crystalline ceria nanoparticles on the hydroponic growth of Daikon radish microgreens
Both AK, Shaker E and Cheung CL
Cerium oxide nanoparticles (ceria NPs) have been widely used in many industrial applications. They have been proposed as a potential remedy for reducing oxidative stress in biological systems. General concerns over the toxicity of engineered ceria NPs have led to studies of their phytotoxicity in plants. Most of these plant growth studies were conducted in soil using grain crops and commercial ceria NPs of sizes from 6 nm to 100's nm. In this paper, we report our evaluation of the phytotoxicity and uptake of sub-3-nm crystalline ceria NPs by exposing Daikon radish () microgreens to these NPs with environmentally relevant concentrations under hydroponic growth conditions. Aqueous suspensions of different concentrations of these ceria NPs (0.1 ppm, 1 ppm, and 10 ppm) were applied to these microgreens for the last 7 days of the 12-day growth period. Our results revealed the uptake of cerium by plant roots and the translocation of cerium to the stems and the cotyledons (seed leaves). The accumulation of cerium was found to be maximum at the roots, followed by the cotyledons and the stems of the plants. Even at the lowest concentration (0.1 ppm) of the sub-3-nm ceria NPs, the accumulation of cerium at the roots significantly stunted the root growth. However, these NP treatments did not show significant changes to the distributions of macro-minerals (Mg, K, and Ca) and micro-minerals (Zn and Cu) in the microgreens at the end of the 12-day growth period. The phytotoxic effect of sub-3-nm crystalline ceria nanoparticles on the hydroponic growth of Daikon radish microgreens was studied. The cerium uptake by the plant and its effect on the bioavailability of major macro-minerals and micro-minerals within the plant were examined.
Enzymatic Delivery of Magnetic Nanoparticles into Mitochondria of Live Cells
He H, Guo J and Xu B
Delivering magnetic nanoparticles (MNPs) into mitochondria provide a facile approach to manipulate cell life because mitochondria play essential roles in cell survival and death. Here we report the use of enzyme-responsive peptide assemblies to deliver MNPs into mitochondria of live cells. The mitochondria-targeting peptide (Mito-Flag), as the substrate of enterokinase (ENTK), assembles with MNPs in solution. The MNPs that are encapsulated by Mito-Flag peptides selectively accumulate to the mitochondria of cancer cells, rather than normal cells. The mitochondrial localization of MNPs reduces the viability of the cancer cells, but hardly affects the survival of the normal cell. This work demonstrates a new and facile strategy to specifically transport MNPs to the mitochondria in cancer cells for exploring the applications of MNPs as the targeted drug for biomedicine and cancer therapy.
Flexible and Stretchable PEDOT-Embedded Hybrid Substrates for Bioengineering and Sensory Applications
Fallahi A, Mandla S, Kerr-Phillip T, Seo J, Rodrigues RO, Jodat YA, Samanipour R, Hussain MA, Lee CK, Bae H, Khademhosseini A, Travas-Sejdic J and Shin SR
Herein, we introduce a flexible, biocompatible, robust and conductive electrospun fiber mat as a substrate for flexible and stretchable electronic devices for various biomedical applications. To impart the electrospun fiber mats with electrical conductivity, poly(3,4-ethylenedioxythiophene) (PEDOT), a conductive polymer, was interpenetrated into nitrile butadiene rubber (NBR) and poly(ethylene glycol) dimethacrylate (PEGDM) crosslinked electrospun fiber mats. The mats were fabricated with tunable fiber orientation, random and aligned, and displayed elastomeric mechanical properties and high conductivity. In addition, bending the mats caused a reversible change in their resistance. The cytotoxicity studies confirmed that the elastomeric and conductive electrospun fiber mats support cardiac cell growth, and thus are adaptable to a wide range of applications, including tissue engineering, implantable sensors and wearable bioelectronics.
Impurity Segregation and Nanoparticle Reorganization of Indium Doped MgO Cubes
Niedermaier M, Taniteerawong C, Schwab T, Zickler G, Bernardi J and Diwald O
Metal oxide nanocomposites are non-equilibrium solids and promising precursors for functional materials. Annealing of such materials can provide control over impurity segregation and, depending on the level of consolidation, represents a versatile approach to engineer free surfaces, particle-particle interfaces and grain boundaries. Starting with indium-magnesium-oxide nanoparticle powders obtained via injection of an indium organic precursor into the magnesium combustion flame and subsequent particle quenching in argon, we investigated the stability of the trivalent In ions in the host lattice of MgO nanoparticles by determining grain growth, morphology evolution and impurity segregation. The latter process is initiated by vacuum annealing at 873 K and can be tracked at 1173 K on a time scale of minutes. In the first instance the surface segregated indium wets the nanoparticle interfaces. After prolonged annealing indium evaporates and leaves the powder via the gas phase. Resulting MgO nanocubes are devoid of residual indium, regain their high morphological definition and show spectroscopic fingerprints (UV Diffuse Reflectance and Photoluminescence emission) that are characteristic of electronically unperturbed MgO cube corner and edge features. The results of this combined XRD, TEM, and spectroscopy study reveal the parameter window within which control over indium segregation is used to introduce a semiconducting metal oxide component into the intergranular region between insulating MgO nanograins.
Amino Acid Based Self-assembled Nanostructures: Complex Structures from Remarkably Simple Building Blocks
Chakraborty P and Gazit E
Amino acids are the simplest biological building blocks capable of forming discreet nanostructures by supramolecular self-assembly. The understanding of the process of organization of amino acid nanostructures is of fundamental importance for the study of metabolic diseases as well as for materials science applications. Although peptide self-assembled structures have been the topic of many review articles, much less attention has been devoted to the ability of amino acid building blocks, both natural and synthetic, to form ordered assemblies with defined architectures and notable physical properties, by the process of self-association. Herein, we try to shed light on amino acid based nanostructures, their fabrication and implications. We discuss self-assembled nanostructures, including hydrogels with nanoscale order, obtained from both modified and unmodified single amino acids. We also envision some future prospects in this emerging field.
Targetable Mechanical Properties by Switching between Self-Sorting and Co-assembly with Formed Tripodal Ketoenamine Supramolecular Hydrogels
Foster JS, Prentice AW, Forgan RS, Paterson MJ and Lloyd GO
A new family of supramolecular hydrogelators are introduced in which self-sorting and co-assembly can be utilised in the tuneability of the mechanical properties of the materials, a property closely tied to the nanostructure of the gel network. The reactivity of the components of the gelators allows for system chemistry concepts to be applied to the formation of the gels and shows that molecular properties, and not necessarily the chemical identity, determines some gel properties in these family of gels.
Maskless Spatioselective Functionalization of Silicon Nanowires
Veerbeek J and Huskens J
Spatioselective functionalization of silicon nanowires was achieved without using a masking material. The designed process combines metal-assisted chemical etching (MACE) to fabricate silicon nanowires and hydrosilylation to form molecular monolayers. After MACE, a monolayer was formed on the exposed nanowire surfaces. A second MACE step was expected to elongate the nanowires, thus creating two different segments. When monolayers of 1-undecene or 1-tetradecyne were formed on the upper segment, however, the second MACE step did not extend the nanowires. In contrast, nanowires functionalized with 1,8-nonadiyne were elongated, but at an approximately 8 times slower etching rate. The elongation resulted in a contrast difference in high-resolution scanning electron microscopy (HR-SEM) images, which indicated the formation of nanowires that were covered with a monolayer only at the top parts. Click chemistry was successfully used for secondary functionalization of the monolayer with azide-functionalized nanoparticles. The spatioselective presence of 1,8-nonadiyne gave a threefold higher particle density on the upper segment functionalized with 1,8-nonadiyne than on the lower segment without monolayer. These results indicate the successful spatioselective functionalization of silicon nanowires fabricated by MACE.
Structural Determinants of the Stability of Enzyme-Responsive Polyion Complex Nanoparticles Targeting 's Elastase
Insua I, Petit M, Blackman LD, Keogh R, Pitto-Barry A, O'Reilly RK, Peacock AFA, Krachler AM and Fernandez-Trillo F
Here, we report how the stability of polyion complex (PIC) particles containing 's elastase (LasB) degradable peptides and antimicrobial poly(ethylene imine) is significantly improved by careful design of the peptide component. Three LasB-degradable peptides are reported herein, all of them carrying the LasB-degradable sequence -GLA- and for which the number of anionic amino acids and cysteine units per peptide were systematically varied. Our results suggest that while net charge and potential to cross-link via disulfide bond formation do not have a predictable effect on the ability of LasB to degrade these peptides, a significant effect of these two parameters on particle preparation and stability is observed. A range of techniques has been used to characterize these new materials and demonstrates that increasing the charge and cross-linking potential of the peptides results in PIC particles with better stability in physiological conditions and upon storage. These results highlight the importance of molecular design for the preparation of PIC particles and should underpin the future development of these materials for responsive drug delivery.
Electroactive Amphiphiles for Addressable Supramolecular Nanostructures
Townsend EJ, Alotaibi M, Mills BM, Watanabe K, Seddon AM and Faul CFJ
In this focus review we aim to highlight an exciting class of materials, electroactive amphiphiles (EAAs). This class of functional amphiphilic molecules has been the subject of sporadic investigations over the last few decades, but little attempt has been made to date to gather or organise these investigations into a logical fashion. Here we attempted to gather the most important contributions, provide a framework in which to discuss them, and, more importantly, point towards the areas where we believe these EAAs will contribute to solving wider scientific problems and open new opportunities. Our discussions cover materials based on low molecular weight ferrocenes, viologens and anilines, as well as examples of polymeric and supramolecular EAAs. With the advances of modern analytical techniques and new tools for modelling and understanding optoelectronic properties, we believe that this area of research is ready for further exploration and exploitation.
Synthesis, Radiolabelling and In Vitro Imaging of Multifunctional Nanoceramics
Lledos M, Mirabello V, Sarpaki S, Ge H, Smugowski HJ, Carroll L, Aboagye EO, Aigbirhio FI, Botchway SW, Dilworth JR, Calatayud DG, Plucinski PK, Price GJ and Pascu SI
Molecular imaging has become a powerful technique in preclinical and clinical research aiming towards the diagnosis of many diseases. In this work, we address the synthetic challenges in achieving lab-scale, batch-to-batch reproducible copper-64- and gallium-68-radiolabelled metal nanoparticles (MNPs) for cellular imaging purposes. Composite NPs incorporating magnetic iron oxide cores with luminescent quantum dots were simultaneously encapsulated within a thin silica shell, yielding water-dispersible, biocompatible and luminescent NPs. Scalable surface modification protocols to attach the radioisotopes Cu (t=12.7 h) and Ga (t=68 min) in high yields are reported, and are compatible with the time frame of radiolabelling. Confocal and fluorescence lifetime imaging studies confirm the uptake of the encapsulated imaging agents and their cytoplasmic localisation in prostate cancer (PC-3) cells. Cellular viability assays show that the biocompatibility of the system is improved when the fluorophores are encapsulated within a silica shell. The functional and biocompatible SiO matrix represents an ideal platform for the incorporation of Cu and Ga radioisotopes with high radiolabelling incorporation.
Facile Morphology-Controlled Synthesis of Organolead Iodide Perovskite Nanocrystals Using Binary Capping Agents
Debroye E, Yuan H, Bladt E, Baekelant W, Van der Auweraer M, Hofkens J, Bals S and Roeffaers MBJ
Controlling the morphology of organolead halide perovskite crystals is crucial to a fundamental understanding of the materials and to tune their properties for device applications. Here, we report a facile solution-based method for morphology-controlled synthesis of rod-like and plate-like organolead halide perovskite nanocrystals using binary capping agents. The morphology control is likely due to an interplay between surface binding kinetics of the two capping agents at different crystal facets. By high-resolution scanning transmission electron microscopy, we show that the obtained nanocrystals are monocrystalline. Moreover, long photoluminescence decay times of the nanocrystals indicate long charge diffusion lengths and low trap/defect densities. Our results pave the way for large-scale solution synthesis of organolead halide perovskite nanocrystals with controlled morphology for future device applications.
Chirality Controls Reaction-Diffusion of Nanoparticles for Inhibiting Cancer Cells
Du X, Zhou J, Wang J, Zhou R and Xu B
Reaction-diffusion (RD) is the most important inherent feature of living organism, but it has yet to be used for developing biofunctional nanoparticles (NPs). Here we show the use of chirality to control the RD of NPs for selectively inhibiting cancer cells. We observe that L-phosphotyrosine (L-pY) decorated NPs (NP@L-pYs) are innocuous to cells, but D-pY decorated ones (NP@D-pYs) selectively inhibit cancer cells. Our study shows that alkaline phosphatases (ALP), presented in the culture and overexpressed on the cancer cells, dephosphorylates NP@L-pYs much faster than NP@D-pYs. Such a rate difference allows the NP@D-pYs to be mainly dephosphorylated on cell surface, thus adhering selectively on the cancer cells to result in poly(ADP-ribose)polymerase (PARP) hyperactivation mediated cell death. Without phosphate groups or being prematurely dephosphorylated before reaching cancer cells (as the case of NP@L-pYs), the NPs are innocuous to cells. Moreover, NP@D-pYs even exhibit more potent activity than cisplatin for inhibiting platinum-resistant ovarian cancer cells (e.g., A2780-cis). As the first example of chirality controlling RD process of NPs for inhibiting cancer cells, this work illustrates a fundamentally new way for developing nanomedicine based on RD processes and nanoparticles.
Enhanced Electrochemical Sensing with Carbon Nanotubes Modified with Bismuth and Magnetic Nanoparticles in a Lab-on-a-Chip
Jothimuthu P, Hsu JL, Chen R, Inayathullah M, Pothineni VR, Jan A, Gurtner GC, Rajadas J and Nicolls MR
Iron plays an especially important role in human physiological functions and pathological impairments. The superior properties of carbon nanotubes (CNTs) and their modification with bismuth and magnetic nanoparticles as developed in this work have led to an extraordinary and novel material to facilitate ultrasensitive detection in the nanomolar range. Here, we present the development of an electrochemical sensor for detection of ferrous (Fe) and ferric (Fe) iron by means of CNTs modified with bismuth and magnetic nanoparticles for higher sensitivity of detection. The sensor fabrication includes microfabrication methodologies, soft lithography, and electrodeposition. Cyclic voltammetry and differential pulse voltammetry are used for the electroanalytical studies and detection of the ions in samples. The sensor has a dynamic range of detection from 0.01 nm to 10 mm. The performance of the sensor with modified CNTs was explored for sensitivity and specificity. CNTs, modified with bismuth and magnetic nanoparticles by means of electrodeposition, enhanced the detection limit significantly down to 0.01 nm.
Cell surface engineering to control cellular interactions
Custódio CA and Mano JF
Cell surface composition determines all interactions of the cell with is environment, thus cell functions such as adhesion, migration and cell-cell interactions are likely to be controlled by engineering and manipulating cell membrane. Cell membranes present a rich repertoire of molecules, therefore a versatile ground for modification. However the complex and dynamic nature of the cell surface is also a major challenge for cell surface engineering that should also involve strategies compatible with cell viability. Cell surface engineering by selective chemical reactions or by the introduction of exogenous targeting ligands can be powerful tools for engineering novel interactions and control cell function. In addition to chemical conjugation and modification of functional groups, ligands of interest to modify the surface of cells include recombinant proteins, liposomes or nanoparticles. Here, we review recent efforts to perform changes to cell surface composition. We focus on the engineering of the cell surface with biological, chemical or physical methods to modulate cell functions and control cell-cell and cell-microenvironment interactions. Potential applications of cell surface engineering are also stated.
Biomimetic Crystallization of MnFeO Mediated by Peptide-Catalyzed Esterification at Low Temperature
Maeda Y, Wei Z, Ikezoe Y, Tam E and Matsui H
Enzymes are some of the most efficient catalysts in nature. If small catalytic peptides mimic enzymes, there is potential for broad applications from catalysis for new material synthesis to drug development, due to the ease of molecular design. Recently a hydrogel-based combinatory phage display library was developed and protease-mimicking peptides were identified. Here we advanced the previous discovery to apply one of these catalytic peptides for the synthesis of bimetal oxide nanocrystals through the catalytic ester-elimination pathway. Conventional bimetal oxide crystallization usually requires high temperatures above several hundred °C; however, this catalytic peptide could grow superparamagnetic MnFeO nanocrystals at 4°C. Superconducting quantum interference device (SQUID) analysis revealed that MnFeO nano-crystals grown by the catalytic peptide exhibit superpara-magnetism. This study demonstrates the usefulness of protease-mimicking catalytic peptides in the field of material synthesis.