Ferromagnetic liquid droplets with adjustable magnetic properties.

The assembly and jamming of magnetic nanoparticles (NPs) at liquid-liquid interfaces is a versatile platform to endow structured liquid droplets with a magnetization, i.e., producing ferromagnetic liquid droplets (FMLDs). Here, we use hydrodynamics experiments to probe how the magnetization of FMLDs and their response to external stimuli can be tuned by chemical, structural, and magnetic means. The remanent magnetization stems from magnetic NPs jammed at the liquid-liquid interface and dispersed NPs magneto-statically coupled to the interface. FMLDs form even at low concentrations of magnetic NPs when mixing nonmagnetic and magnetic NPs, since the underlying magnetic dipole-driven clustering of magnetic NP-surfactants at the interface produces local magnetic properties, similar to those found with pure magnetic NP solutions. While the net magnetization is smaller, such a clustering of NPs may enable structured liquids with heterogeneous surfaces.

Shape-Reconfigurable Ferrofluids.

Ferrofluids (FFs) can adapt their shape to a magnetic field. However, they cannot maintain their shape when the magnetic field is removed. Here, with a magneto-responsive and reconfigurable interfacial self-assembly (MRRIS) process, we show that FFs can be structured by a magnetic field and maintain their shape, like solids, after removing the magnetic field. The competing self-assembly of magnetic and nonmagnetic nanoparticles at the liquid interface endow FFs with both reconfigurability and structural stability. By manipulating the external magnetic field, we show that it is possible to "write" and "erase" the shape of the FFs remotely and repeatedly. To gain an in-depth understanding of the effect of MRRIS on the structure of FFs, we systematically study the shape variation of these liquids under both the static and dynamic magnetic fields. Our study provides a simple yet novel way of manipulating FFs and opens opportunities for the fabrication of all-liquid devices.

Manipulating Dispersions of Magnetic Nanoparticles.

Dispersions of magnetic nanoparticles (MNPs) can exhibit paramagnetic ferrofluid or ferromagnetic liquid behavior. By modifying the surface functionality of MNPs, ferrofluids have been used to fabricate novel magnetically actuated devices. If the surface-functionalized MNPs interact with complementary ligands at a fluid-fluid interface, MNP surfactants form and in situ assemble at the interface. When jammed interfacially, MNP surfactants give rise to ferromagnetic behavior of the liquid (droplet), which is endowed with permanent magnetic dipoles while maintaining all of the characteristics of a fluid system. Here, we give a brief overview of the developments in the dispersion of MNPs in liquids from ferrofluids to ferromagnetic liquid droplets, their responses to external fields, and the manipulation of these responses for end uses. The reversible room-temperature para-to-ferro transformation of magnetic liquids is highlighted. We discuss challenges in the synthesis and characterization of these unusual liquids along with potential technological applications.

The Buckling Spectra of Nanoparticle Surfactant Assemblies.

Fine control over the mechanical properties of thin sheets underpins transcytosis, cell shape, and morphogenesis. Applying these principles to artificial, liquid-based systems has led to reconfigurable materials for soft robotics, actuation, and chemical synthesis. However, progress is limited by a lack of synthetic two-dimensional membranes that exhibit tunable mechanical properties over a comparable range to that seen in nature. Here, we show that the bending modulus, B, of thin assemblies of nanoparticle surfactants (NPSs) at the oil-water interface can be varied continuously from sub-kBT to 106kBT, by varying the ligands and particles that comprise the NPS. We find extensive departure from continuum behavior, including enormous mechanical anisotropy and a power law relation between B and the buckling spectrum width. Our findings provide a platform for shape-changing liquid devices and motivate new theories for the description of thin-film wrinkling.

Mechanical Properties of Solidifying Assemblies of Nanoparticle Surfactants at the Oil-Water Interface.

The effect of polymer surfactant structure and concentration on the self-assembly, mechanical properties, and solidification of nanoparticle surfactants (NPSs) at the oil-water interface was studied. The surface tension of the oil-water interface was found to depend strongly on the choice of the polymer surfactant used to assemble the NPSs, with polymer surfactants bearing multiple polar groups being the most effective at reducing interfacial tension and driving the NPS assembly. By contrast, only small variations in the shear modulus of the system were observed, suggesting that it is determined largely by particle density. In the presence of polymer surfactants bearing multiple functional groups, NPS assemblies on pendant drop surfaces were observed to spontaneously solidify above a critical polymer surfactant concentration. Interfacial solidification accelerated rapidly as polymer surfactant concentration was increased. On long timescales after solidification, pendant drop interfaces were observed to spontaneously wrinkle at sufficiently low surface tensions (approximately 5 mN m-1). Interfacial shear rheology of the NPS assemblies was elastic-dominated, with the shear modulus ranging from 0.1 to 1 N m-1, comparable to values obtained for nanoparticle monolayers elsewhere. Our work paves the way for the development of designer, multicomponent oil-water interfaces with well-defined mechanical, structural, and functional properties.

Comparative transcript profiling reveals the mechanism of female sterility associated with seedless Ponkan mandarin (Citrus reticulata Blanco).

Seedlessness is a highly desirable trait in citrus varieties. Sterility is the key determination for seedlessness formation. However, the molecular basis for female sterility in seedless mandarin remains unclear. Thus, a seedless Ponkan mandarin (Citrus reticulata Blanco 'Lipeng No.2'), considered the bud mutation of normal seedy Ponkan, was collected to identify candidate genes involved in seedless variation. Suppression subtractive hybridization (SSH) screened 1091 uniESTs related to seedy and seedless Ponkan (727 singlets and 364 contigs), which mainly governed catalytic activity, transferase activity, and oxygen binding. By using RNA-Seq technology, 106 differentially expressed genes (DEGs) were captured, of which 74 were up-regulated and 32 were down-regulated. Gene Ontology and pathway analysis showed that six DEGs were enriched in the biosynthesis of secondary metabolite, whereas five DEGs were enriched in the signaling of plant hormones. The combined results of SSH and RNA-Seq indicated the importance of amino acid metabolism in seedless Ponkan. Our findings revealed that the mechanism of seedless Ponkan generation may be related to gene regulation, signal cascade, and hormone levels. This study provided a solid foundation for functional gene identification in seedless Ponkan and a good reference for relevant research on molecular mechanisms of female sterility in Ponkan mandarin.

Adaptive Structured Pickering Emulsions and Porous Materials Based on Cellulose Nanocrystal Surfactants.

Taking advantage of the formation and assembly of cellulose nanocrystal surfactants (CNCSs) at the water-oil interface, where polar cellulose nanocrystals (CNCs) and end-functionalized polymer chains interact, the preparation and stability of emulsions prepared with CNCSs were investigated. The packing density of CNCSs at the interface can be adjusted by tuning parameters such as pH, ionic strength, and concentration/molecular weight of the end-functionalized polymer ligands. Stable non-spherical emulsions are obtained during homogenization, as a result of the interfacial jamming of CNCSs, with pH-triggered reconfigurability. Porous materials are prepared by freeze-drying creamed, CNCS-stabilized emulsions. The cells of the porous materials have a controlled pore size and shape that are commensurate with the droplets in the emulsion and are responsive to pH. The behavior of the adaptive, reconfigurable supracolloidal system is coupled to its internal and surrounding environment.

Liquid Tubule Formation and Stabilization Using Cellulose Nanocrystal Surfactants.

Structured liquids, generated by the interfacial formation, assembly, and jamming of nanoparticle (NP)-surfactants at liquid/liquid interfaces, maintain all the desirable characteristics of each liquid, while providing a spatially structured framework. Herein, we show that rod-like cellulose nanocrystal (CNC)-based NP-surfactants, termed CNC-surfactants, are formed rapidly at the liquid/liquid interface, assemble into a monolayer, and, when jammed, offer a robust assembly with exceptional mechanical properties. Plateau-Rayleigh (PR) instabilities of a free-falling jet of an aqueous medium containing the CNCs into a toluene solution of amine end-functionalized polystyrene are completely suppressed, allowing the jetting of aqueous tubules that are stabilized when the CNC-surfactants are jammed at the interface. These results open a new platform for the additive manufacturing techniques, for example, three-dimensional (3D) printing, of all-liquid constructs.

An Extraordinary Sulfonated-Graphenal-Polymer-Based Electrolyte Separator for All-Solid-State Supercapacitors.

Sulfonated graphenal polymers can be assembled up by poly(vinyl alcohol) adhesion. The porous assembly structure results in a remarkably improved ionic conductivity and thus enhances electrochemical performances such as specific capacitance, capacitance retention, and cycling stability.

Bioremediation potential of the hard clam Mercenaria mercenaria as an intensive shrimp aquaculture pond polyculture condidate.

Polyculture practices are important for achieving sustainable aquaculture development. Recently, hard clams polyculture in intensive shrimp ponds has been encouraged because bivalves can consume excess nutrients in aquaculture systems and sequester carbon. To evaluate the bioremediation potential of hard clams polyculture in intensive shrimp ponds, this study built an assessment model based on individual growth models and estimated the potential for nitrogen and phosphorus removal as well as CO2 fixation by hard clams. Firstly, key parameters required for model construction were obtained through field surveys and physiological experiments. Subsequently, an individual growth model for the hard clam Mercenaria mercenaria was developed based on the Dynamic Energy Budget (DEB) theory. Fitting of the growth data indicated that the model accurately replicated the growth patterns of hard clams, with relative root mean square errors of 9.87 % for shell length and 5.02 % for dry tissue weight. Finally, the assessment model for the bioremediation potential of hard clams demonstrated that, over 110 days in the intensive shrimp mariculture pond, the net removal of nitrogen and phosphorus by hard clams were 3.68 kg ha-1 and 0.81 kg ha-1, respectively, and CO2 fixation was 507.00 kg ha-1. These findings suggested that the DEB model is an effective tool for evaluating bivalve ecological remediation potential and can aid in selecting species for sustainable polyculture.

Reconfigurable Magnetic Liquid Building Blocks for Constructing Artificial Spinal Column Tissues.

All-liquid molding can be used to transform a liquid into free-form solid constructs, while maintaining internal fluidity. Traditional biological scaffolds, such as cured pre-gels, are normally processed in solid state, sacrificing flowability and permeability. However, it is essential to maintain the fluidity of the scaffold to truly mimic the complexity and heterogeneity of natural human tissues. Here, this work molds an aqueous biomaterial ink into liquid building blocks with rigid shapes while preserving internal fluidity. The molded ink blocks for bone-like vertebrae and cartilaginous-intervertebral-disc shapes, are magnetically manipulated to assemble into hierarchical structures as a scaffold for subsequent spinal column tissue growth. It is also possible to join separate ink blocks by interfacial coalescence, different from bridging solid blocks by interfacial fixation. Generally, aqueous biomaterial inks are molded into shapes with high fidelity by the interfacial jamming of alginate surfactants. The molded liquid blocks can be reconfigured using induced magnetic dipoles, that dictated the magnetic assembly behavior of liquid blocks. The implanted spinal column tissue exhibits a biocompatibility based on in vitro seeding and in vivo cultivating results, showing potential physiological function such as bending of the spinal column.

Packing bimodal magnetic particles to fabricate highly dense anisotropic rare earth bonded permanent magnets.

Highly dense and magnetically anisotropic rare earth bonded magnets have been fabricated via packing bimodal magnetic particles using a batch extrusion process followed by compression molding technology. The bimodal feedstock was a 96 wt% magnet powder mixture, with 40% being anisotropic Sm-Fe-N (3 µm) and 60% being anisotropic Nd-Fe-B (100 µm) as fine and coarse particles, respectively; these were blended with a 4 wt% polyphenylene sulfide (PPS) polymer binder to fabricate the bonded magnets. The hybrid bonded magnet with an 81 vol% magnet loading yielded a density of 6.15 g cm-3 and a maximum energy product (BH)m of 20.0 MGOe at 300 K. Scanning electron microscopy (SEM) indicated that the fine-sized Sm-Fe-N particles filled the gap between the large Nd-Fe-B particles. Rietveld analysis of the X-ray diffraction data showed that the relative contents of the Nd2Fe14B and Sm2Fe17N3 phases were 61% and 39%, respectively, in the hybrid bonded magnet. The PPS binder coated most of the magnetic particles homogeneously. Compared with the magnetic properties of the initial Nd-Fe-B and Sm-Fe-N powders, the reduction in the remanence, from the demagnetization curve, is ascribed to the dilution effect of the binder, the non-perfect alignment, and the internal magnetic stray field.

Perspective: Ferromagnetic Liquids.

Mechanical jamming of nanoparticles at liquid-liquid interfaces has evolved into a versatile approach to structure liquids with solid-state properties. Ferromagnetic liquids obtain their physical and magnetic properties, including a remanent magnetization that distinguishes them from ferrofluids, from the jamming of magnetic nanoparticles assembled at the interface between two distinct liquids to minimize surface tension. This perspective provides an overview of recent progress and discusses future directions, challenges and potential applications of jamming magnetic nanoparticles with regard to 3D nano-magnetism. We address the formation and characterization of curved magnetic geometries, and spin frustration between dipole-coupled nanostructures, and advance our understanding of particle jamming at liquid-liquid interfaces.

Building Reconfigurable Devices Using Complex Liquid-Fluid Interfaces.

Liquid-fluid interfaces provide a platform both for structuring liquids into complex shapes and assembling dimensionally confined, functional nanomaterials. Historically, attention in this area has focused on simple emulsions and foams, in which surface-active materials such as surfactants or colloids stabilize structures against coalescence and alter the mechanical properties of the interface. In recent decades, however, a growing body of work has begun to demonstrate the full potential of the assembly of nanomaterials at liquid-fluid interfaces to generate functionally advanced, biomimetic systems. Here, a broad overview is given, from fundamentals to applications, of the use of liquid-fluid interfaces to generate complex, all-liquid devices with a myriad of potential applications.

Reconfigurable ferromagnetic liquid droplets.

Solid ferromagnetic materials are rigid in shape and cannot be reconfigured. Ferrofluids, although reconfigurable, are paramagnetic at room temperature and lose their magnetization when the applied magnetic field is removed. Here, we show a reversible paramagnetic-to-ferromagnetic transformation of ferrofluid droplets by the jamming of a monolayer of magnetic nanoparticles assembled at the water-oil interface. These ferromagnetic liquid droplets exhibit a finite coercivity and remanent magnetization. They can be easily reconfigured into different shapes while preserving the magnetic properties of solid ferromagnets with classic north-south dipole interactions. Their translational and rotational motions can be actuated remotely and precisely by an external magnetic field, inspiring studies on active matter, energy-dissipative assemblies, and programmable liquid constructs.

Liquid Letters.

Using the interfacial jamming of cellulose nanocrystal (CNC) surfactants, a new concept, termed all-liquid molding, is introduced to produce all-liquid objects that retain the shape and details of the mold with high fidelity, yet remain all liquid and are responsive to external stimuli. This simple process, where the viscosity of the CNC dispersion can range from that of water to a crosslinked gel, opens tremendous opportunities for encapsulation, delivery systems, and unique microfluidic devices. The process described is generally applicable to any functionalized nanoparticles dispersed in one liquid and polymer ligands having complementary functionality dissolved in a second immiscible liquid. Such sculpted liquids retain all the characteristics of the liquids but retain shape indefinitely, very much like a solid, and provide a new platform for next-generation soft materials.

Reconfigurable Printed Liquids.

Liquids lack the spatial order required for advanced functionality. Interfacial assemblies of colloids, however, can be used to shape liquids into complex, 3D objects, simultaneously forming 2D layers with novel magnetic, plasmonic, or structural properties. Fully exploiting all-liquid systems that are structured by their interfaces would create a new class of biomimetic, reconfigurable, and responsive materials. Here, printed constructs of water in oil are presented. Both form and function are given to the system by the assembly and jamming of nanoparticle surfactants, formed from the interfacial interaction of nanoparticles and amphiphilic polymers that bear complementary functional groups. These yield dissipative constructs that exhibit a compartmentalized response to chemical cues. Potential applications include biphasic reaction vessels, liquid electronics, novel media for the encapsulation of cells and active matter, and dynamic constructs that both alter, and are altered by, their external environment.

Reducing and Uniforming the Co3 O 4 Particle Size by Sulfonated Graphenal Polymers for Electrochemical Applications.

A novel two-dimensional (2D) nanomaterial, namely sulfonated graphenal polymer (SGP), is used to tune the hydrothermal growth of Co3O4 nanoparticles. SGP provides abundant nucleation sites to grow Co3O4 nanoparticles and effectively reduces the particle size and dimension. As a result, with considering the improved size uniformity of Co3O4 and the tight wrapping of SGP around Co3O4 as well, the Co3O4/SGP hybrid electrode exhibits a high specific electrochemical capacitance of 234.28 F/g at a current density of 0.2 A/g, 237% higher than that of the pure Co3O4 electrode. By using the hybrid as the anode of an all-solid-state asymmetric supercapacitor, the capacitance can be well maintained up to 93% after 5000 cycles even at 2 A/g.

3D Structural Model of High-Performance Non-Fullerene Polymer Solar Cells as Revealed by High-Resolution AFM.

Rapid improvements in nonfullerene polymer solar cells (PSCs) have brought power conversion efficiencies to greater than 12%. To further improve device performance, a fundamental understanding of the correlations between structure and performance is essential. In this paper, based on a typical high-performance system consisting of J61(one donor-acceptor (D-A) copolymer of benzodithiophene and fluorine substituted benzotriazole) and ITIC (3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene), a 3D structural model is directly imaged by employing high-resolution atomic force microscopy (AFM). Hierarchical morphologies ranging from fiberlike crystallites, several nanometers in size, to a bicontinuous morphology, having domains tens of nanometers in size, are observed. A fibrillar interpenetrating networks of J61-rich domains embedded in a matrix comprised of a J61/ITIC is seen, reflecting the partial miscibility of J61 with ITIC. These hierarchical nanostructural characteristics are coupled to significantly enhanced exciton dissociation, and further contribute to photocurrent and final device performance.

High energy product developed from cobalt nanowires.

Cobalt nanowires with high aspect ratio have been synthesized via a solvothermal chemical process. Based on the shape anisotropy and orientation of the nanowire assemblies, a record high room-temperature coercivity of 10.6 kOe has been measured in Co nanowires with a diameter of about 15 nm and a mean length of 200 nm. As a result, energy product of the wires reaches 44 MGOe. It is discovered that the morphology uniformity of the nanowires is the key to achieving the high coercivity and high energy density. Nanowires of this type are ideal building blocks for future bonded, consolidated and thin film magnets with high energy density and high thermal stability.