A New Material for High‐Temperature Lead‐Free Actuators

Unimorph cantilevers are made from 0.5BaTiO₃‐0.5Sm₂O₃ (BTO‐SmO) self‐assembled vertical heteroepitaxial nanocomposite thin films, grown by PLD on (001) SrTiO₃ single crystal substrates. The films remain piezoelectric up to at least 250 °C without losing any actuation. The longitudinal piezoelectric coefficient, d₃₃, is ≈45 to 50 pm V^?1 measured from room temperature to 250 °C. The transverse piezoelectric coefficient, d₃₁, a key parameter of actuator performance, exceeds PZT (Pb_1–xZr_xTiO₃) films at >200 pm V^?1. Since the d₃₁ coefficient was found to be positive, this opens up exciting new applications opportunities. The possible reasons for d₃₁ > 0 are discussed in the light of 3D strain control in the nanocomposites.     

Supramolecular Surface Chemistry: Substrate‐Independent,Phosphate‐Driven Growth of Polyamine‐Based Multifunctional Thin Films

The ability to engineer surfaces at the supramolecular level by controlled integration of specific chemical units through substrate‐independent methodologies represents one of the new paradigms of contemporary materials science. Here, a method is reported to form multifunctional supramolecular coatings through simple dip‐coating of substrates in an aqueous solution of polyamine in the presence of phosphate anions. The chemical richness and versatility of polyamines are exploited as phosphate receptors to form thin functional films on a broad variety of substrates, ranging from metal to carbonaceous surfaces. It is shown that the simple derivatization of pendant amino groups of polyallylamine precursors with different chemical groups can endow films with predefined responsiveness or multiple functions—this translates into one‐pot and one‐step preparation of substrate‐adherent films displaying built‐in functions. It is believed that the flexibility, speed, and versatility with which this method provides such robust functional films make it very attractive for preparing samples of fundamental and technological interest.     

Nanostructures from Single Amino Acid‐Based Molecules: Stability,Fibrillation, Encapsulation,and Fabrication of Silver Nanoparticles

The small‐sized molecules that have been developed from single hydrophobic amino acids (Phe, Trp, Tyr and Leu) by suitably protecting the –NH₂ and –CO₂H groups generate diverse nanoscopic structures – such as nanorods, nanofibrils, nanotubes, and nanovesicles – depending upon the protection parameters and solvent polarity. The vesicular structures get disrupted in the presence of various salts, such as KCl, CaCl₂, (NH₄)₂SO₄ and N(n‐Bu)₄Br. Insertion of unnatural (o/m/p)‐aminobenzoic acids as a protecting group and the lack of conventional peptide bonds in the molecules give the nanostructures proteolytic stability. The nanostructures also show significant thermal stability along with a morphological transformation upon heat treatment. Our in vitro studies reveal that the addition of micromolar concentration “curcumin” significantly reduces the formation of amyloid‐like fibrils. These diverse nanostructures are used as a template for fabricating silver nanoparticles on their outer surfaces as well as in the inner part, followed by calcination in air which helps to obtain a 1D silver nanostructure. Furthermore, the nanovesicles are observed to encapsulate a potent drug (curcumin) and other biologically important molecules, which could be released through salt‐triggered disruption of vesicles.     

Evolution‐Based Design of an Injectable Hydrogel

A new class of simple, linear, amphiphilic peptides are developed that have the ability to undergo triggered self‐assembly into self‐supporting hydrogels. Under non‐gelling aqueous conditions, these peptides exist in a random coil conformation and peptide solutions have the viscosity of water. On the addition of a buffered saline solution, the peptides assemble into a β‐sheet rich network of fibrils, ultimately leading to hydrogelation. A family of nine peptides is prepared to study the influence of peptide length and amino acid composition on the rate of self‐assembly and hydrogel material properties. The amino acid composition is modulated by varying residue hydrophobicity and hydrophilicity on the two opposing faces of the amphiphile. The conformation of peptides in their soluble and gel state is studied by circular dichroism (CD), while the resultant material properties of their gels is investigated using oscillatory sheer rheology. One weight percent gels formed under physiological conditions have storage modulus (G′) values that vary from ≈20 to ≈800 Pa, with sequence length and hydrophobic character playing a dominant roll in defining hydrogel rigidity. Based on the structural and functional data provided by the nine‐peptide family members, an optimal sequence, namely LK13, is evolved. LK13 (LKLKLKLKLKLKL‐NH₂) undergoes triggered self‐assembly, affording the most rigid gel of those studied (G′=797 ± 105). It displays shear thin‐recovery behavior, allowing its delivery by syringe and is cytocompatibile as assessed with murine C3H10t1/2 mesenchymal stem cells.     

Zeolite‐Coated Porous Arrays: A Novel Strategy for Enzyme Encapsulation

Zeolite Beta‐coated stainless steel supports with gradient porosity are employed as filter‐panels for lipase encapsulation. Enzyme encapsulation on the stainless steel porous discs is achieved via vacuum infiltration. Subsequently, two lipase‐encapsulated zeolite Beta‐coated stainless steel discs are attached using an adhesive. The zeolite Beta layer on the stainless steel discs largely prevents lipase leaching in comparison to the stainless steel discs without a zeolite layer. The activity of the lipase‐encapsulated, attached zeolite Beta‐coated stainless steel porous discs depends on the thickness of the zeolite Beta layer. It is shown that the biocatalytic performance of the lipase‐encapsulated, attached zeolite Beta‐coated stainless steel supports with a zeolite Beta layer thickness of ≈0.7–1 μm is better than the lipase‐encapsulated, attached zeolite Beta‐coated stainless steel supports with a zeolite Beta layer thickness of ≈2–3 μm in the lipase‐catalyzed transesterification of vinyl propionate with 1‐butanol using n‐hexane as solvent.     

Composite Colloidal Gels Made of Bisphosphonate‐Functionalized Gelatin and Bioactive Glass Particles for Regeneration of Osteoporotic Bone Defects

Injectable composite colloidal gels are developed for regeneration of osteoporotic bone defects through a bottom‐up assembly from bisphosphonate‐functionalized gelatin and bioactive glass particles. Upon bisphosphonate functionalization, gelatin nanoparticles show superior adhesion toward bioactive glass particles, resulting in elastic composite gels. By tuning their composition, these composite colloidal gels combine mechanical robustness with self‐healing ability. The composite colloidal gels support cell proliferation and differentiation in vitro without requiring any osteogenic supplement. In vivo evaluation of the composite colloidal gels reveals their capacity to support the regeneration of osteoporotic bone defects. Furthermore, the bisphosphonate modification of gelatin induces a therapeutic effect on the peri‐implantation region by enhancing the bone density of the osteoporotic bone tissue. Consequently, these composite colloidal gels offer new therapeutic opportunities for treatment of osteoporotic bone defects.     

High‐Nanofiller‐Content Graphene Oxide–Polymer Nanocomposites via Vacuum‐Assisted Self‐Assembly

Highly ordered, homogeneous polymer nanocomposites of layered graphene oxide are prepared using a vacuum‐assisted self‐assembly (VASA) technique. In VASA, all components (nanofiller and polymer) are pre‐mixed prior to assembly under a flow, making it compatible with either hydrophilic poly(vinyl alcohol) (PVA) or hydrophobic poly(methyl methacrylate) (PMMA) for the preparation of composites with over 50 wt% filler. This process is complimentary to layer‐by‐layer assembly, where the assembling components are required to interact strongly (e.g., via Coulombic attraction). The nanosheets within the VASA‐assembled composites exhibit a high degree of order with tunable intersheet spacing, depending on the polymer content. Graphene oxide–PVA nanocomposites, prepared from water, exhibit greatly improved modulus values in comparison to films of either pure PVA or pure graphene oxide. Modulus values for graphene oxide–PMMA nanocomposites, prepared from dimethylformamide, are intermediate to those of the pure components. The differences in structure, modulus, and strength can be attributed to the gallery composition, specifically the hydrogen bonding ability of the intercalating species     

Particle‐Stabilized Materials: Dry Oils and (Polymerized) Non‐Aqueous Foams

Oil (liquids with low surface tension and practically immiscible with water) drops can be dispersed in air if relatively oleophobic particles are available. However, such particles with oil‐repellent surfaces cannot simply be prepared by controlling the particle surface chemistry alone. Herein the preparation of oil‐in‐air materials (oil marbles, dry oils) by changing the wetting behavior of particles by tuning the oil properties, which allows the formation of the metastable Cassie–Baxter wetting state of particle assemblies on oil drop surfaces, is presented. The oil‐in‐air materials can be converted to air‐in‐oil materials (non‐aqueous foams) by tailoring the oil properties, as the robustness of the metastable Cassie–Baxter state of the particle assemblies critically depends on the particle wettability. This conversion implies the phase inversion of dispersed systems consisting of air and oils. It is also shown that particle‐stabilized non‐aqueous foams can be utilized as template to produce macroporous polymers.     

Hierarchically Structured,Double‐Periodic Inverse Composite Opals

A versatile colloidal templating strategy to fabricate hierarchically structured inverse opals is investigated. A sequence of infiltration and pyrolysis steps provides access to a range of material combinations such as SiO₂, Al₂O₃, or TiO₂. The experimental results also document the feasibility of this method to fabricate porous polymer films with a double periodic pore lattice.     

Programmable Arrays of “Micro‐Bubble” Constructs via Self‐Encapsulation

The fabrication of ordered arrays of self‐encapsulated “micro‐bubble” material constructs based on the capillary‐driven collapse of flexible silk fibroin sheets during propagation of the diffusion front of the encapsulated material is demonstrated. The individual micro‐bubbles of different shapes are composed of a sacrificial material encapsulated within the ultrathin silk coating, which covers and seals the inner material during dissolution of supporting layer. The array of microscopic rectangular multi‐layer silk sheets on supporting polymer layers can be selectively dissolved along the edges to initiate their self‐encapsulation. The resulting micro‐bubble morphology, shape, and arrangements can be readily pre‐programmed by controlling the geometry of the silk sheets, such as thickness, dimension, and aspect ratio. These micro‐bubble constructs can be utilized for encapsulation of various materials as well as nanoparticles in a single or multi compartmental manner. These biocompatible and biodegradable micro‐bubble constructs present a promising platform for one‐shot spatial and controllable loading and locking material arrays with addressable abilities.     

Hindering the Oxidation of Silicene with Non‐Reactive Encapsulation

The chemical stability of buckled silicene, i.e., the silicon counterpart of graphene, is investigated then resulting in a low reactivity with O₂ when dosing up to 1000 L and in a progressive oxidation under ambient conditions. The latter drawback is addressed by engineering ad hoc Al‐ and Al₂O₃‐based encapsulations of the silicene layer. This encapsulation design can be generally applied to any silicene configuration, irrespective of the support substrate, and it leads to the fabrication of atomically sharp and chemically intact Al/silicene and Al₂O₃/silicene interfaces that can be functionally used for ex situ characterization as well as for gated device fabrication.     

Self‐Assembled Heteroepitaxial Oxide Nanocomposite Thin Film Structures: Designing Interface‐Induced Functionality in Electronic Materials

Achieving self‐assembling/self‐organizing systems is the holy grail of nanotechnology. Spontaneous organization is not unique to the physical sciences since nature has been producing such systems for millions of years. In biological systems global patterns emerge from numerous interactions among lower‐level components of the system. The same is true for physical systems. In this review, the self‐assembly mechanisms of oxide nanocomposite films, as well as the advantageous functionalities that arise from such ordered structures, are explored.     

Cooperative Switching in Large‐Area Assemblies of Magnetic Janus Particles

Magnetic Janus particles (MJPs) have received considerable attention for their rich assembly behavior and their potential technological role in applications ranging from simple magnetophoretic displays to smart cloaking devices. However, further progress is hampered by the lack of predictive understanding of the cooperative self‐assembly behavior of MJPs and appropriate dynamic control mechanisms. In this paper, a detailed experimental and theoretical investigation into the magnetically directed spatiotemporal self‐assembly and switching of MJPs is presented. For this purpose, a novel type of MJPs with defined hemispherical compartments carrying superparamagnetic iron oxide nanoparticles as well as a novel simulation model to describe their cooperative switching behavior is established. Combination of the theoretical and experimental work culminates in a simple method to direct assemblies of MJPs, even at high particle concentrations. In addition, a magnetophoretic display with switchable MJPs is developed on the basis of the theoretical findings to demonstrate the potential usefulness of controlled large‐area assemblies of magnetic Janus particles.     

Ultra‐Thin Self‐Assembled Protein‐Polymer Membranes: A New Pore Forming Strategy

Self‐assembled membranes offer a promising alternative for conventional membrane fabrication, especially in the field of ultrafiltration. Here, a new pore‐making strategy is introduced involving stimuli responsive protein‐polymer conjugates self‐assembled across a large surface area using drying‐mediated interfacial self‐assembly. The membrane is flexible and assembled on porous supports. The protein used is the cage protein ferritin and resides within the polymer matrix. Upon denaturation of ferritin, a pore is formed which intrinsically is determined by the size of the protein and how it resides in the matrix. Due to the self‐assembly at interfaces, the membrane constitutes of only one layer resulting in a membrane thickness of 7 nm on average in the dry state. The membrane is stable up to at least 50 mbar transmembrane pressure, operating at a flux of about 21 000–25 000 L m^?2 h^?1 bar^?1 and displayed a preferred size selectivity of particles below 20 nm. This approach diversifies membrane technology generating a platform for “smart” self‐assembled membranes.     

Highly Improved Rate Capability for a Lithium‐Ion Battery Nano‐Li4Ti5O12 Negative Electrode via Carbon‐Coated Mesoporous Uniform Pores with a Simple Self‐Assembly Method

A mesostructured spinel Li₄Ti₅O₁₂ (LTO)‐carbon nanocomposite (denoted as Meso‐LTO‐C) with large (>15 nm) and uniform pores is simply synthesized via block copolymer self‐assembly. Exceptionally high rate capability is then demonstrated for Li‐ion battery (LIB) negative electrodes. Polyisoprene‐block‐poly(ethylene oxide) (PI‐b‐PEO) with a sp²‐hybridized carbon‐containing hydrophobic block is employed as a structure‐directing agent. Then the assembled composite material is crystallized at 700 °C enabling conversion to the spinel LTO structure without loss of structural integrity. Part of the PI is converted to a conductive carbon that coats the pores of the Meso‐LTO‐C. The in situ pyrolyzed carbon not only maintains the porous mesostructure as the LTO is crystallized, but also improves the electronic conductivity. A Meso‐LTO‐C/Li cell then cycles stably at 10 C‐rate, corresponding to only 6 min for complete charge and discharge, with a reversible capacity of 115 mA h g^?1 with 90% capacity retention after 500 cycles. In sharp contrast, a Bulk‐LTO/Li cell exhibits only 69 mA h g^?1 at 10 C‐rate. Electrochemical impedance spectroscopy (EIS) with symmetric LTO/LTO cells prepared from Bulk‐LTO and Meso‐LTO‐C cycled in different potential ranges reveals the factors contributing to the vast difference between the rate‐capabilities. The carbon‐coated mesoporous structure enables highly improved electronic conductivity and significantly reduced charge transfer resistance, and a much smaller overall resistance is observed compared to Bulk‐LTO. Also, the solid electrolyte interphase (SEI)‐free surface due to the limited voltage window (>1 V versus Li/Li⁺) contributes to dramatically reduced resistance.     

Responsive Macroscopic Materials From Self‐Assembled Cross‐Linked SiO2‐PNIPAAm Core/Shell Structures

A way to obtain macroscopic responsive materials from silicon‐oxide polymer core/shell microstructures is presented. The microparticles are composed of a 60 nm SiO₂‐core with a random copolymer corona of the temperature responsive poly‐N‐isopropylacrylamide (PNIPAAm) and the UV‐cross‐linkable 2‐(dimethyl maleinimido)‐N‐ethyl‐acrylamide. The particles shrink upon heating and form a stable gel in both water and tetrahydrofuran (THF) at 3–5 wt% particle content. Cross‐linking the aqueous gel results in shrinkage when the temperature is increased above the lower critical solution temperature and it regains its original size upon cooling. By freeze drying with subsequent UV irradiation, thin stable layers are prepared. Stable fibers are produced by extruding a THF gel into water and subsequent UV irradiation, harnessing the cononsolvency effect of PNIPAAm in water/THF mixtures. The temperature responsiveness translates to the macroscopic materials as both films and fibers show the same collapsing behavior as the microcore/shell particle. The collapse and re‐swelling of the materials is related to the expelling and re‐uptake of water, which is used to incorporate gold nanoparticles into the materials by a simple heating/cooling cycle. This allows for future applications, as various functional particles (antibacterial, fluorescence, catalysis, etc.) can easily be incorporated in these systems.     

Multifunctional Nanoparticles Composed of A Poly( dl‐lactide‐coglycolide) Core and A Paramagnetic Liposome Shell for Simultaneous Magnetic Resonance Imaging and Targeted Therapeutics

A multifunctional nanoscale platform that is self‐assembled from a hydrophobic poly( dl ‐lactide‐coglycolide)(PLGA) core and a hydrophilic paramagnetic‐folate‐coated PEGylated lipid shell (PFPL; PEG=polyethylene glycol) is designed for simultaneous magnetic resonance imaging (MRI) and targeted therapeutics. The nanocomplex has a well‐defined core‐shell structure which is studied using confocal laser scanning microscopy (CLSM). The paramagnetic diethylenetriaminepentaacetic acid‐gadolinium (DTPA‐Gd) chelated to the shell layer exhibits significantly higher spin–lattice relaxivity (r₁) than the clinically used small‐molecular‐weight MRI contrast agent Magnevist^®. The PLGA core serves as a nanocontainer to load and release the hydrophobic drugs. From a drug‐release study, it is found that the modification of the PLGA core with a polymeric liposome shell can be a useful tool for reducing the drug‐release rate. Cellular uptake of folate nanocomplex is found to be higher than that of non‐folate‐nanocomplex due to the folate‐binding effect on the cell membrane. This work indicates that the multifunctional platform with combined characteristics applicable to MRI and drug delivery may have great potential in cancer chemotherapy and diagnosis.     

Spin‐Coated Periodic Mesoporous Organosilica Thin Films—Towards a New Generation of Low‐Dielectric‐Constant Materials

Periodic mesoporous organosilica (PMO) thin films have been produced using an evaporation‐induced self‐assembly (EISA) spin‐coating procedure and a cationic surfactant template. The precursors are silsesquioxanes of the type (C₂H₅O)₃Si–R–Si(OC₂H₅)₃ or R′–[Si(OC₂H₅)₃]₃ with R = methene (–CH₂–), ethylene (–C₂H₂–), ethene (–C₂H₄–), 1,4‐phenylene (C₆H₄), and R′ = 1,3,5‐phenylene (C₆H₃). The surfactant is successfully removed by solvent extraction or calcination without any significant Si–C bond cleavage of the organic bridging groups R and R′ within the channel walls. The materials have been characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X‐ray diffraction (PXRD), and ²⁹Si and ¹³C magic‐angle spinning (MAS) NMR spectroscopy. The d‐spacing of the PMOs is found to be a function of R. Nanoindentation measurements reveal increased mechanical strength and stiffness for the PMOs with R = CH₂ and C₂H₄ compared to silica. Films with different organic‐group content have been prepared using mixtures of silsesquioxane and tetramethylorthosilicate (TMOS) precursors. The dielectric constant (k) is found to decrease with organic content, and values as low as 1.8 have been measured for films thermally treated to cause a “self‐hydrophobizing” bridging‐to‐terminal transformation of the methene to methyl groups with concomitant loss of silanols. Increasing the organic content and thermal treatment also increases the resistance to moisture adsorption in 60 and 80 %‐relative‐humidity (RH) environments. Methene PMO films treated at 500 °C are found to be practically unchanged after five days exposure to 80 % RH. These low dielectric constants, plus the good thermal and mechanical stability and the hydrophobicity suggest the potential utility of these films as low‐k layers in microelectronics.