Plasmonic nanoparticles assemblies templated by helical bacteria and resulting optical activity.

Plasmonic nanoparticles (NPs) adsorbing onto helical bacteria can lead to formation of NP helicoids with micron scale pitch. Associated chiroptical effects can be utilized as bioanalytical tool for bacterial detection and better understanding of the spectral behavior of helical self-assembled structures with different scales. Here, we report that enantiomerically pure helices with micron scale of chirality can be assembled on Campylobacter jejuni, a helical bacterium known for severe stomach infections. These organisms have right-handed helical shapes with a pitch of 1-2 microns and can serve as versatile templates for a variety of NPs. The bacteria itself shows no observable rotatory activity in the visible, red, and near-IR ranges of electromagnetic spectrum. The bacterial dispersion acquires chiroptical activity at 500-750 nm upon plasmonic functionalization with Au NPs. Finite-difference time-domain simulations confirmed the attribution of the chiroptical activity to the helical assembly of gold nanoparticles. The position of the circular dichroism peaks observed for these chiral structures overlaps with those obtained before for Au NPs and their constructs with molecular and nanoscale chirality. This work provides an experimental and computational pathway to utilize chiroplasmonic particles assembled on bacteria for bioanalytical purposes.

Design and synthesis of metal hydroxide three-dimensional inorganic cationic frameworks.

Three-dimensional (3D) cationic frameworks are rare but crucial host materials with vast industrial applications. However, the controlled synthesis of 3D inorganic cationic framework (ICF) materials still remains a challenge. Here, we develop a new strategy to construct 3D inorganic cationic frameworks by octahedral metal-hydroxide (M(OH)6) unit induced reconstruction of layered rare-earth hydroxides. Based on this strategy, a large family (>187 members) of 3D-ICF with a general formula: RE12(OH)18((RE1-x-y,MxM'y)(OH)6)4·ACl6 (RE = Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y; M = Al, Cr; M' = Mg, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn; A = Na, K) were achieved. This newly constructed strategy would greatly promote the development of 3D inorganic cationic materials. Furthermore, the discovery of this new family of cationic frameworks would pave the way for the potential application of cationic materials in different sorts of fields.

Assembly of mesoscale helices with near-unity enantiomeric excess and light-matter interactions for chiral semiconductors.

Semiconductors with chiral geometries at the nanoscale and mesoscale provide a rich materials platform for polarization optics, photocatalysis, and biomimetics. Unlike metallic and organic optical materials, the relationship between the geometry of chiral semiconductors and their chiroptical properties remains, however, vague. Homochiral ensembles of semiconductor helices with defined geometries open the road to understanding complex relationships between geometrical parameters and chiroptical properties of semiconductor materials. We show that semiconductor helices can be prepared with an absolute yield of ca 0.1% and an enantiomeric excess (e.e.) of 98% or above from cysteine-stabilized cadmium telluride nanoparticles (CdTe NPs) dispersed in methanol. This high e.e. for a spontaneously occurring chemical process is attributed to chiral self-sorting based on the thermodynamic preference of NPs to assemble with those of the same handedness. The dispersions of homochiral self-assembled helices display broadband visible and near-infrared (Vis-NIR) polarization rotation with anisotropy (g) factors approaching 0.01. Calculated circular dichroism (CD) spectra accurately reproduced experimental CD spectra and gave experimentally validated spectral predictions for different geometrical parameters enabling de novo design of chiroptical semiconductor materials. Unlike metallic, ceramic, and polymeric helices that serve predominantly as scatterers, chiroptical properties of semiconductor helices have nearly equal contribution of light absorption and scattering, which is essential for device-oriented, field-driven light modulation. Deconstruction of a helix into a series of nanorods provides a simple model for the light-matter interaction and chiroptical activity of helices. This study creates a framework for further development of polarization-based optics toward biomedical applications, telecommunications, and hyperspectral imaging.

Multiscale deformations lead to high toughness and circularly polarized emission in helical nacre-like fibres.

Nacre-like composites have been investigated typically in the form of coatings or free-standing sheets. They demonstrated remarkable mechanical properties and are used as ultrastrong materials but macroscale fibres with nacre-like organization can improve mechanical properties even further. The fiber form or nacre can, simplify manufacturing and offer new functional properties unknown yet for other forms of biomimetic materials. Here we demonstrate that nacre-like fibres can be produced by shear-induced self-assembly of nanoplatelets. The synergy between two structural motifs--nanoscale brick-and-mortar stacking of platelets and microscale twisting of the fibres--gives rise to high stretchability (>400%) and gravimetric toughness (640 J g(-1)). These unique mechanical properties originate from the multiscale deformation regime involving solid-state self-organization processes that lead to efficient energy dissipation. Incorporating luminescent CdTe nanowires into these fibres imparts the new property of mechanically tunable circularly polarized luminescence. The nacre-like fibres open a novel technological space for optomechanics of biomimetic composites, while their continuous spinning methodology makes scalable production realistic.

Microwave Enabled One-Pot, One-Step Fabrication and Nitrogen Doping of Holey Graphene Oxide for Catalytic Applications.

The unique properties of a holey graphene sheet, referred to as a graphene sheet with nanoholes in its basal plane, lead to wide range of applications that cannot be achieved by its nonporous counterpart. However, the large-scale solution-based production requires graphene oxide (GO) or reduced GO (rGO) as the starting materials, which take hours to days for fabrication. Here, an unexpected discovery that GO with or without holes can be controllably, directly, and rapidly (tens of seconds) fabricated from graphite powder via a one-step-one-pot microwave assisted reaction with a production yield of 120 wt% of graphite is reported. Furthermore, a fast and low temperature approach is developed for simultaneous nitrogen (N) doping and reduction of GO sheets. The N-doped holey rGO sheets demonstrate remarkable electrocatalytic capabilities for the electrochemical oxygen reduction reaction. The existence of the nanoholes provides a "short cut" for efficient mass transport and dramatically increases edges and surface area, therefore, creates more catalytic centers. The capability of rapid fabrication and N-doping as well as reduction of holey GO can lead to development of an efficient catalyst that can replace previous coin metals for energy generation and storage, such as fuel cells and metal-air batteries.

Engineering the surface of perovskite La(0.5)Sr(0.5)MnO3 for catalytic activity of CO oxidation.

A simple treatment of La0.5Sr0.5MnO3 with diluted HNO3 creates more B-sites (rich) on the terminated perovskite surface and improves its catalytic activity toward CO oxidation, and the perovskite catalyst possesses a higher ratio of Mn(4+)/Mn(3+) and thus enhances the O2 adsorption capability, favourable for CO oxidation and catalytic activity.

Light-induced self-assembly of nanofibers inside liposomes.

Spatially confined self-assembly of peptide amphiphile nanofibers inside liposomes is triggered by light.