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Conjugated polyelectrolyte copolymers containing 2,1,3-benzothiadiazole- (BT) and oligo(ethylene oxide)-substituted fluorene and phenylene units have been designed and synthesized. The phenylene pendent groups also have carboxylic acid functionalities, which allow probing the effect of pH on optical properties. The BT content in the backbone can be regulated at the synthesis stage. Dynamic light scattering studies show that polymers aggregate in water at low pH. Increased interchain contacts give rise to a lowering of the photoluminescence (PL) efficiency via self-quenching when the BT units are absent and increased levels of FRET from the phenylene-fluorene segments to BT. Furthermore, the PL efficiency of BT increases in the aggregated structures. Examination of solvent effects indicates that the increased BT efficiencies are likely due to decreased contact with water. The changes in PL efficiencies are reversible, showing that the aggregates are dynamic and not kinetically constrained.

A novel class of monodisperse conjugated polymer nanoparticles have been readily prepared by the facile reprecipitation of poly{1,3-bis[2-(3-alkylthienyl)]azulene} or poly{1,3-bis[2-(3-alkoxythienyl)]azulene}. The multicomponent poly(bithiophene-alt-azulene) macromolecules were efficiently self-assembled into a wide range of size-tunable nanoparticles from a few tens to five hundred nanometers via the hydrophobic and pi-stacking effects in the mixed chloroform/methanol solutions. Electronically altered polymer structures with different alkyl or alkoxy substitutes exhibited variable self-assembling behaviors to precisely tune the size and the optical/electronic properties of nanoparticles. A strong size dependence of continuous bathochromic absorption and significant enhanced emission were observed with the increase of particle size. A linear relationship between the absorption or fluorescence intensities and the particle size was demonstrated as well, and this is very useful to probe the intermolecular interactions and the size evolutions of conjugated polymer nanoparticles. After the size-dependent optical and electronic properties are created, they can be further optimized to improve the performance of materials prior to the use in novel organic nanodevices in a cost-effective way.

Strong field enhancement and confinement in plasmonic nanostructures provide suitable conditions for nonlinear optics in ultracompact dimensions. Despite these enhancements, second-harmonic generation (SHG) is still inefficient due to the centrosymmetric crystal structure of the bulk metals used, e.g., Au and Ag. Taking advantage of symmetry breaking at the metal surface, one could greatly enhance SHG by engineering these metal surfaces in regions where the strong electric fields are localized. Here, we combine top-down lithography and bottom-up self-assembly to lodge single rows of 8 nm diameter Au nanoparticles into trenches in a Au film. The resultant "double gap" structures increase the surface-to-volume ratio of Au colocated with the strong fields in ∼2 nm gaps to fully exploit the surface SHG of Au. Compared to a densely packed arrangement of AuNPs on a smooth Au film, the double gaps enhance SHG emission by 4200-fold to achieve an effective second-order susceptibility χ((2)) of 6.1 pm/V, making it comparable with typical nonlinear crystals. This patterning approach also allows for the scalable fabrication of smooth gold surfaces with sub-5 nm gaps and presents opportunities for optical frequency up-conversion in applications that require extreme miniaturization.

Inorganic ions may direct the self-assembly of biomacromolecules into nanostructures which can further be used as a reactant and matrix for nanomaterials synthesis and assembly. Here we use bone mineral and filamentous bacteriophage as a model to demonstrate this concept. Divalent calcium ions are found to trigger the electrostatic self-assembly of anionic nanofiber-like bacteriophages into bundle structures where calcium ions are pre-organized between bacteriophage nanofibers. The resultant Ca 2+ -bacteriophage bundles can be separated and purified from the aqueous solution. The nanostructures of the bundles are verified by zeta potential analysis, small angle x-ray scattering and transmission electron microscopy. Because of the transcription of the bacteriophage chiral surface to the periodic alignment of pre-loaded Ca 2+ , the Ca 2+ -bacteriphage bundles can serve as both Ca sources and biotemplates to initiate the oriented nucleation and growth of nanocrystalline hydroxyapatite in phosphate solution or in simulated body fluid. This work provides new insights into biomineralization and represents a new approach to the fabrication of biomolecular-inorganic hybrid layered nanostructures.Biomolecule-directed mineralization can lead to the formation of biomineralized hybrid structures with improved performance in nature. For example, bone is a hierarchically structured composite material, containing multiple levels of hierarchical organization.1 The lowest level of hierarchy is the organization of collagen fibrils mineralized with plate-like hydroxyapatite (HAP) nanocrystals. The collagen fibrils are self-assembled from collagen molecules with three intertwined polypeptide chains, and HAP crystals are nucleated and grown within these fibrils with their c-axis preferentially parallel to the collagen fibrils.2 -4 Therefore, to fabricate a biomaterial mimicking some features of bone structures, it is highly desired to mimic both the chemical composition and the orientation of HAP crystals with respect to bio/organic scaffolds. Previous studies have demonstrated that the oriented biominerals in mineralized tissues might originate from organized assemblies of biomacromolecules.5 -8 Bio/organic macromolecules or scaffolds such as collagen,9 , 10 biopolymers,11 , 12 synthetic polymers,13 -16 and spider silks,17 , 18 have been investigated to nucleate HAP or promote HAP crystal growth. These bio/organic macromolecules are involved in directing HAP mineralization by acting as templates through self-assembly.2 , 19 However, these systems lack one dimensionally (1D) nanostructures and precise organization of functional groups or amino acids. To the best of our knowledge, except for HAP mineralization on synthetic self-assembling peptide amphiphiles reported by Stupp et al,20 no naturally occurring systems that posses 1D nanostructure and periodically * To whom correspondence should be addressed. Tel.: . cbmao@ou.edu. Supporting Information AvailableDetailed experimental description, protein sequences, structure and ...

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Due to the unique hybrid structures and physical properties of polyhedral oligomeric silsesquioxanes (POSSs), hybridation with POSS has been demonstrated to be an important approach to build high-performance organic optoelectronic materials for applications in organic light-emitting diodes (OLEDs), liquid crystal display, sensors and electrochromic devices.

Biomaterials is an exciting and dynamic field, which uses a collection of diverse materials to achieve desired biological responses. While there is constant evolution and innovation in materials with time, biomaterials research has been hampered by the relatively long development period required. In recent years, driven by the need to accelerate materials development, the applications of machine learning in materials science has progressed in leaps and bounds. The combination of machine learning with high‐throughput theoretical predictions and high‐throughput experiments (HTE) has shifted the traditional Edisonian (trial and error) paradigm to a data‐driven paradigm. In this review, each type of biomaterial and their key properties and use cases are systematically discussed, followed by how machine learning can be applied in the development and design process. The discussions are classified according to various types of materials used including polymers, metals, ceramics, and nanomaterials, and implants using additive manufacturing. Last, the current gaps and potential of machine learning to further aid biomaterials discovery and application are also discussed.