Phosphate Elimination and Recovery Lightweight (PEARL) membrane: A sustainable environmental remediation approach.

Aqueous phosphate pollution can dramatically impact ecosystems, introducing a variety of environmental, economic, and public health problems. While novel remediation tactics based on nanoparticle binding have shown considerable promise in nutrient recovery from water, they are challenging to deploy at scale. To bridge the gap between the laboratory-scale nature of these nanostructure solutions and the practical benchmarks for deploying an environmental remediation tool, we have developed a nanocomposite material. Here, an economical, readily available, porous substrate is dip coated using scalable, water-based processes with a slurry of nanostructures. These nanomaterials have tailored affinity for specific adsorption of pollutants. Our Phosphate Elimination and Recovery Lightweight (PEARL) membrane can selectively sequester up to 99% of phosphate ions from polluted waters at environmentally relevant concentrations. Moreover, mild tuning of pH promotes at will adsorption and desorption of nutrients. This timed release allows for phosphate recovery and reuse of the PEARL membrane repeatedly for numerous cycles. We combine correlative microscopy and spectroscopy techniques to characterize the complex microstructure of the PEARL membrane and to unravel the mechanism of phosphate sorption. More broadly, through the example of phosphate pollution, this work describes a platform membrane approach based on nanostructures with specific affinity coated on a porous structure. Such a strategy can be tuned to address other environmental remediation challenges through the incorporation of other nanomaterials.

Polymer Analog Memristive Synapse with Atomic-Scale Conductive Filament for Flexible Neuromorphic Computing System.

With the advent of artificial intelligence (AI), memristors have received significant interest as a synaptic building block for neuromorphic systems, where each synaptic memristor should operate in an analog fashion, exhibiting multilevel accessible conductance states. Here, we demonstrate that the transition of the operation mode in poly(1,3,5-trivinyl-1,3,5-trimethyl cyclotrisiloxane) (pV3D3)-based flexible memristor from conventional binary to synaptic analog switching can be achieved simply by reducing the size of the formed filament. With the quantized conductance states observed in the flexible pV3D3 memristor, analog potentiation and depression characteristics of the memristive synapse are obtained through the growth of atomically thin Cu filament and lateral dissolution of the filament via dominant electric field effect, respectively. The face classification capability of our memristor is evaluated via simulation using an artificial neural network consisting of pV3D3 memristor synapses. These results will encourage the development of soft neuromorphic intelligent systems.

Windowless Observation of Evaporation-Induced Coarsening of Au-Pt Nanoparticles in Polymer Nanoreactors.

The interactions between nanoparticles and solvents play a critical role in the formation of complex, metastable nanostructures. However, direct observation of such interactions with high spatial and temporal resolution is challenging with conventional liquid-cell transmission electron microscopy (TEM) experiments. Here, a windowless system consisting of polymer nanoreactors deposited via scanning probe block copolymer lithography (SPBCL) on an amorphous carbon film is used to investigate the coarsening of ultrafine (1-3 nm) Au-Pt bimetallic nanoparticles as a function of solvent evaporation. In such reactors, homogeneous Au-Pt nanoparticles are synthesized from metal-ion precursors in situ under electron irradiation. The nonuniform evaporation of the thin polymer film not only concentrates the nanoparticles but also accelerates the coalescence kinetics at the receding polymer edges. Qualitative analysis of the particle forces influencing coalescence suggests that capillary dragging by the polymer edges plays a significant role in accelerating this process. Taken together, this work (1) provides fundamental insight into the role of solvents in the chemistry and coarsening behavior of nanoparticles during the synthesis of polyelemental nanostructures, (2) provides insight into how particles form via the SPBCL process, and (3) shows how SPBCL-generated domes, instead of liquid cells, can be used to study nanoparticle formation. More generally, it shows why conventional models of particle coarsening, which do not take into account solvent evaporation, cannot be used to describe what is occurring in thin film, liquid-based syntheses of nanostructures.

Design Rules for Template-Confined DNA-Mediated Nanoparticle Assembly.

Template-based strategies are becoming increasingly important for controlling the position of nanoparticle-based (NP-based) structures on surfaces for a wide variety of encoding and device fabrication strategies. Thus, there is an increasing need to understand the behavior of NPs in confined spaces. Herein, a systematic investigation of the diffusion and adsorption properties of DNA-modified NPs is presented in lithographically defined, high-aspect-ratio pores using a template-confined, DNA-mediated assembly. Leveraging the sequence-specific binding affinity of DNA, it is discovered that although NP adsorption in deep polymer pores follows a traditional Langmuir adsorption model when under thermodynamic control, such NPs kinetically follow Fick's classical law of diffusion. Importantly, these observations allow one to establish design rules for template-confined, DNA-mediated NP assembly on substrates based on pore dimensions, NP size and shape, NP concentration, temperature, and time. As a proof-of-concept example, these design rules are used to engineer a vertical, four-layer assembly consisting of individual octahedral NPs stacked on top of one another, with in-plane positioning defined by pores generated by e-beam lithography.

Structural Evolution of Three-Component Nanoparticles in Polymer Nanoreactors.

Recent developments in scanning probe block copolymer lithography (SPBCL) enable the confinement of multiple metal precursors in a polymer nanoreactor and their subsequent transformation into a single multimetallic heterostructured nanoparticle through thermal annealing. However, the process by which multimetallic nanoparticles form in SPBCL-patterned nanoreactors remains unclear. Here, we utilize the combination of PEO-b-P2VP and Au, Ag, and Cu salts as a model three-component system to investigate this process. The data suggest that the formation of single-component Au, Ag, or Cu nanoparticles within polymer nanoreactors consists of two stages: (I) nucleation, growth, and coarsening of the particles to yield a single particle in each reactor; (II) continued particle growth by depletion of the remaining precursor in the reactor until the particle reaches a stable size. Also, different aggregation rates are observed for single-component particle formation (Au > Ag > Cu). This behavior is also observed for two-component systems, where nucleation sites have greater Au content than the other metals. This information can be used to trap nanoparticles with kinetic structures. High-temperature treatment ultimately facilitates the structural evolution of the kinetic particle into a particle with a fixed structure. Therefore, with multicomponent systems, a third stage that involves elemental redistribution within the particle must be part of the description of the synthetic process. This work not only provides a glimpse at the mechanism underlying multicomponent nanoparticle formation in SPBCL-generated nanoreactors but also illustrates, for the first time, the utility of SPBCL as a platform for controlling the architectural evolution of multimetallic nanoparticles in general.

The Structural Fate of Individual Multicomponent Metal-Oxide Nanoparticles in Polymer Nanoreactors.

Multicomponent nanoparticles can be synthesized with either homogeneous or phase-segregated architectures depending on the synthesis conditions and elements incorporated. To understand the parameters that determine their structural fate, multicomponent metal-oxide nanoparticles consisting of combinations of Co, Ni, and Cu were synthesized by using scanning probe block copolymer lithography and characterized using correlated electron microscopy. These studies revealed that the miscibility, ratio of the metallic components, and the synthesis temperature determine the crystal structure and architecture of the nanoparticles. A Co-Ni-O system forms a rock salt structure largely owing to the miscibility of CoO and NiO, while Cu-Ni-O, which has large miscibility gaps, forms either homogeneous oxides, heterojunctions, or alloys depending on the annealing temperature and composition. Moreover, a higher-ordered structure, Co-Ni-Cu-O, was found to follow the behavior of lower ordered systems.

Tip-Directed Synthesis of Multimetallic Nanoparticles.

Alloy nanoparticles are important in many fields, including catalysis, plasmonics, and electronics, due to the chemical and physical properties that arise from the interactions between their components. Typically, alloy nanoparticles are made by solution-based synthesis; however, scanning-probe-based methods offer the ability to make and position such structures on surfaces with nanometer-scale resolution. In particular, scanning probe block copolymer lithography (SPBCL), which combines elements of block copolymer lithography with scanning probe techniques, allows one to synthesize nanoparticles with control over particle diameter in the 2-50 nm range. Thus far, single-element structures have been studied in detail, but, in principle, one could make a wide variety of multicomponent systems by controlling the composition of the polymer ink, polymer feature size, and metal precursor concentrations. Indeed, it is possible to use this approach to synthesize alloy nanoparticles comprised of combinations of Au, Ag, Pd, Ni, Co, and Pt. Here, such structures have been made with diameters deliberately tailored in the 10-20 nm range and characterized by STEM and EDS for structural and elemental composition. The catalytic activity of one class of AuPd alloy nanoparticles made via this method was evaluated with respect to the reduction of 4-nitrophenol with NaBH4. In addition to being the first catalytic studies of particles made by SPBCL, these proof-of-concept experiments demonstrate the potential for SPBCL as a new method for studying the fundamental science and potential applications of alloy nanoparticles in areas such as heterogeneous catalysis.

Apertureless cantilever-free pen arrays for scanning photochemical printing.

A novel, apertureless, cantilever-free pen array can be used for dual scanning photochemical and molecular printing. Serial writing with light is enabled by combining self-focusing pyramidal pens with an opaque backing between pens. The elastomeric pens also afford force-tuned illumination and simultaneous delivery of materials and optical energy. These attributes make the technique a promising candidate for maskless high-resolution photopatterning and combinatorial chemistry.

Formation mechanism of high-index faceted Pt-Bi alloy nanoparticles by evaporation-induced growth from metal salts.

Nanoparticles with high-index facets are intriguing because such facets can lend the structure useful functionality, including enhanced catalytic performance and wide-ranging optical tunability. Ligand-free solid-state syntheses of high index-facet nanoparticles, through an alloying-dealloying process with foreign volatile metals, are attractive owing to their materials generality and high yields. However, the role of foreign atoms in stabilizing the high-index facets and the dynamic nature of the transformation including the coarsening and facet regulation process are still poorly understood. Herein, the transformation of Pt salts to spherical seeds and then to tetrahexahedra, is studied in situ via gas-cell transmission electron microscopy. The dynamic behaviors of the alloying and dealloying process, which involves the coarsening of nanoparticles and consequent facet regulation stage are captured in the real time with a nanoscale spatial resolution. Based on additional direct evidence obtained using atom probe tomography and density functional theory calculations, the underlying mechanisms of the alloying-dealloying process are uncovered, which will facilitate broader explorations of high-index facet nanoparticle synthesis.

Magnetic Nanostructure-Loaded Bicontinuous Nanospheres Support Multicargo Intracellular Delivery and Oxidation-Responsive Morphological Transitions.

Magnetic nanostructures (MNS) have a wide range of biological applications due to their biocompatibility, superparamagnetic properties, and customizable composition that includes iron oxide (Fe3O4), Zn2+, and Mn2+. However, several challenges to the biomedical usage of MNS must still be addressed, such as formulation stability, inability to encapsulate therapeutic payloads, and variable clearance rates in vivo. Here, we enhance the utility of MNS during controlled delivery applications via encapsulation within polymeric bicontinuous nanospheres (BCNs) composed of poly(ethylene glycol)-block-poly(propylene sulfide) (PEG-b-PPS) copolymers. PEG-b-PPS BCNs have demonstrated versatile encapsulation and delivery capabilities for both hydrophilic and hydrophobic payloads due to their unique and highly organized cubic phase nanoarchitecture. MNS-embedded BCNs (MBCNs) were thus coloaded with physicochemically diverse molecular payloads using the technique of flash nanoprecipitation and characterized in terms of their structure and in vivo biodistribution following intravenous administration. Retention of the internal aqueous channels and cubic architecture of MBCNs were verified using cryogenic transmission electron microscopy and small-angle X-ray scattering, respectively. MBCNs demonstrated improvement in magnetic resonance imaging (MRI) contrast enhancement (r2 relaxivity) as compared to free MNS, which in combination with scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy evidenced the clustering and continued access to water of MNS following encapsulation. Furthermore, MBCNs were found to be noncytotoxic and able to deliver their hydrophilic and hydrophobic small-molecule payloads both in vitro and in vivo. Finally, the oxidation sensitivity of the hydrophobic PPS block allowed MBCNs to undergo a unique, triggerable transition in morphology into MNS-bearing micellar nanocarriers. In summary, MBCNs are an attractive platform for the delivery of molecular and nanoscale payloads for diverse on-demand and sustained drug delivery applications.

Homopolymer self-assembly of poly(propylene sulfone) hydrogels via dynamic noncovalent sulfone-sulfone bonding.

Natural biomolecules such as peptides and DNA can dynamically self-organize into diverse hierarchical structures. Mimicry of this homopolymer self-assembly using synthetic systems has remained limited but would be advantageous for the design of adaptive bio/nanomaterials. Here, we report both experiments and simulations on the dynamic network self-assembly and subsequent collapse of the synthetic homopolymer poly(propylene sulfone). The assembly is directed by dynamic noncovalent sulfone-sulfone bonds that are susceptible to solvent polarity. The hydration history, specified by the stepwise increase in water ratio within lower polarity water-miscible solvents like dimethylsulfoxide, controls the homopolymer assembly into crystalline frameworks or uniform nanostructured hydrogels of spherical, vesicular, or cylindrical morphologies. These electrostatic hydrogels have a high affinity for a wide range of organic solutes, achieving >95% encapsulation efficiency for hydrophilic small molecules and biologics. This system validates sulfone-sulfone bonding for dynamic self-assembly, presenting a robust platform for controllable gelation, nanofabrication, and molecular encapsulation.

Quantifying Polymer Chain Orientation in Strong and Tough Nanofibers with Low Crystallinity: Toward Next Generation Nanostructured Superfibers.

Advanced fibers revolutionized structural materials in the second half of the 20th century. However, all high-strength fibers developed to date are brittle. Recently, pioneering simultaneous ultrahigh strength and toughness were discovered in fine (<250 nm) individual electrospun polymer nanofibers (NFs). This highly desirable combination of properties was attributed to high macromolecular chain alignment coupled with low crystallinity. Quantitative analysis of the degree of preferred chain orientation will be crucial for control of NF mechanical properties. However, quantification of supramolecular nanoarchitecture in NFs with low crystallinity in the ultrafine diameter range is highly challenging. Here, we discuss the applicability of traditional as well as emerging methods for quantification of polymer chain orientation in nanoscale one-dimensional samples. Advantages and limitations of different techniques are critically evaluated on experimental examples. It is shown that straightforward application of some of the techniques to sub-wavelength-diameter NFs can lead to severe quantitative and even qualitative artifacts. Sources of such size-related artifacts, stemming from instrumental, materials, and geometric phenomena at the nanoscale, are analyzed on the example of polarized Raman method but are relevant to other spectroscopic techniques. A proposed modified, artifact-free method is demonstrated. Outstanding issues and their proposed solutions are discussed. The results provide guidance for accurate nanofiber characterization to improve fundamental understanding and accelerate development of nanofibers and related nanostructured materials produced by electrospinning or other methods. We expect that the discussion in this review will also be useful to studies of many biological systems that exhibit nanofilamentary architectures and combinations of high strength and toughness.

Engineered Theranostic Magnetic Nanostructures: Role of Composition and Surface Coating on Magnetic Resonance Imaging Contrast and Thermal Activation.

Magnetic nanostructures (MNS) have emerged as promising functional probes for simultaneous diagnostics and therapeutics (theranostic) applications due to their ability to enhance localized contrast in magnetic resonance imaging (MRI) and heat under external radio frequency (RF) field, respectively. We show that the "theranostic" potential of the MNS can be significantly enhanced by tuning their core composition and architecture of surface coating. Metal ferrite (e.g., MFe2O4) nanoparticles of ∼8 nm size and nitrodopamine conjugated polyethylene glycol (NDOPA-PEG) were used as the core and surface coating of the MNS, respectively. The composition was controlled by tuning the stoichiometry of MFe2O4 nanoparticles (M = Fe, Mn, Zn, ZnxMn1-x) while the architecture of surface coating was tuned by changing the molecular weight of PEG, such that larger weight is expected to result in longer length extended away from the MNS surface. Our results suggest that both core as well as surface coating are important factors to take into consideration during the design of MNS as theranostic agents which is illustrated by relaxivity and thermal activation plots of MNS with different core composition and surface coating thickness. After optimization of these parameters, the r2 relaxivity and specific absorption rate (SAR) up to 552 mM(-1) s(-1) and 385 W/g were obtained, respectively, which are among the highest values reported for MNS with core magnetic nanoparticles of size below 10 nm. In addition, NDOPA-PEG coated MFe2O4 nanostructures showed enhanced biocompatibility (up to [Fe] = 200 µg/mL) and reduced nonspecific uptake in macrophage cells in comparison to other well established FDA approved Fe based MR contrast agents.

Hybrid magnetic nanostructures (MNS) for magnetic resonance imaging applications.

The development of MRI contrast agents has experienced its version of the gilded age over the past decade, thanks largely to the rapid advances in nanotechnology. In addition to progress in single mode contrast agents, which ushered in unprecedented R(1) or R(2) sensitivities, there has also been a boon in the development of agents covering more than one mode of detection. These include T(1)-PET, T(2)-PET T(1)-optical, T(2)-optical, T(1)-T(2) agents and many others. In this review, we describe four areas which we feel have experienced particular growth due to nanotechnology, specifically T(2) magnetic nanostructure development, T(1)/T(2)-optical dual mode agents, and most recently the T(1)-T(2) hybrid imaging systems. In each of these systems, we describe applications including in vitro, in vivo usage and assay development. In all, while the benefits and drawbacks of most MRI contrast agents depend on the application at hand, the recent development in multimodal nanohybrids may curtail the shortcomings of single mode agents in diagnostic and clinical settings by synergistically incorporating functionality. It is hoped that as nanotechnology advances over the next decade, it will produce agents with increased diagnostics and assay relevant capabilities in streamlined packages that can meaningfully improve patient care and prognostics. In this review article, we focus on T(2) materials, its surface functionalization and coupling with optical and/or T(1) agents.

High-performance nanostructured MR contrast probes.

Magnetic resonance imaging (MRI) has become a powerful technique in biological molecular imaging and clinical diagnosis. With the rapid progress in nanoscale science and technology, nanostructure-based MR contrast agents are undergoing rapid development. This is in part due to the tuneable magnetic and cellular uptake properties, large surface area for conjugation and favourable biodistribution. In this review, we describe our recent progress in the development of high-performance nanostructured MR contrast agents. Specifically, we report on Gd-enriched nanostructured probes that exhibit T(1) MR contrast and superparamagnetic Fe(3)O(4) and CoFe(2)O(4) nanostructures that display T(2) MR contrast enhancement. The effects of nanostructure size, shape, assembly and surface modification on relaxivity are described. The potential of these contrast agents for in vitro and in vivo MR imaging with respect to colloidal stability under physiological conditions, biocompatibility, and surface functionality are also evaluated.

Imaging nanoparticles in cells by nanomechanical holography.

Nanomaterials have potential medical applications, for example in the area of drug delivery, and their possible adverse effects and cytotoxicity are curently receiving attention. Inhalation of nanoparticles is of great concern, because nanoparticles can be easily aerosolized. Imaging techniques that can visualize local populations of nanoparticles at nanometre resolution within the structures of cells are therefore important. Here we show that cells obtained from mice exposed to single-walled carbon nanohorns can be probed using a scanning probe microscopy technique called scanning near field ultrasonic holography. The nanohorns were observed inside the cells, and this was further confirmed using micro Raman spectroscopy. Scanning near field ultrasonic holography is a useful technique for probing the interactions of engineered nanomaterials in biological systems, which will greatly benefit areas in drug delivery and nanotoxicology.

Nanoscale imaging of buried structures via scanning near-field ultrasound holography.

A nondestructive imaging method, scanning near-field ultrasound holography (SNFUH), has been developed that provides depth information as well as spatial resolution at the 10- to 100-nanometer scale. In SNFUH, the phase and amplitude of the scattered specimen ultrasound wave, reflected in perturbation to the surface acoustic standing wave, are mapped with a scanning probe microscopy platform to provide nanoscale-resolution images of the internal substructure of diverse materials. We have used SNFUH to image buried nanostructures, to perform subsurface metrology in microelectronic structures, and to image malaria parasites in red blood cells.