Yingying Duan

Synthesis of chiral TiO 2 nanofibre with electron transition-based optical activity

The optical chirality induced at the absorption bands due to electronic exciton coupling of the transition dipole moments between chromophores in close proximity is ubiquitous in helical organic materials. However, inorganic materials with optical activity resulting from electronic transitions have not been explored. Here we report the synthesis of chiral TiO2 fibres via transcription of the helical structure of amino acid-derived amphiphile fibres through coordination bonding interactions between the organics and the TiO2 source. Upon calcination, the as-prepared amorphous TiO2 double-helical fibres with a pitch length of ~100 nm were converted to double-helical crystalline fibres with stacks of anatase nanocrystals in an epitaxial helical relationship. Both the amorphous and anatase crystalline helical TiO2 fibres exhibited optical response to circularly polarized light at the absorption edge around ~350 nm. This was attributed to the semiconductor TiO2-based electronic transitions from the valence band to the conduction band under an asymmetric electric field.

Silica Biomineralization via the Self‐Assembly of Helical Biomolecules

The biomimetic synthesis of relevant silica materials using biological macromolecules as templates via silica biomineralization processes attract rapidly rising attention toward natural and artificial materials. Biomimetic synthesis studies are useful for improving the understanding of the formation mechanism of the hierarchical structures found in living organisms (such as diatoms and sponges) and for promoting significant developments in the biotechnology, nanotechnology and materials chemistry fields. Chirality is a ubiquitous phenomenon in nature and is an inherent feature of biomolecular components in organisms. Helical biomolecules, one of the most important types of chiral macromolecules, can self-assemble into multiple liquid-crystal structures and be used as biotemplates for silica biomineralization, which renders them particularly useful for fabricating complex silica materials under ambient conditions. Over the past two decades, many new silica materials with hierarchical structures and complex morphologies have been created using helical biomolecules. In this review, the developments in this field are described and the recent progress in silica biomineralization templating using several classes of helical biomolecules, including DNA, polypeptides, cellulose and rod-like viruses is summarized. Particular focus is placed on the formation mechanism of biomolecule-silica materials (BSMs) with hierarchical structures. Finally, current research challenges and future developments are discussed in the conclusion.

Optically Active Nanostructured ZnO Films

Inorganic nanomaterials endowed with hierarchical chirality could open new horizons in physical theory and applications because of their fascinating properties. Here, we report chiral ZnO films coated on quartz substrates with a hierarchical nanostructure ranging from atomic to micrometer scale. Three levels of hierarchical chirality exist in the ZnO films: helical ZnO crystalline structures that form primary helically coiled nanoplates, secondary helical stacking of these nanoplates, and tertiary nanoscale circinate aggregates formed by several stacked nanoplates. These films exhibited optical activity (OA) at 380 nm and in the range of 200-800 nm and created circularly polarized luminescence centered at 510 nm and Raman OA at 50-1400 cm(-1) , which was attributed to electronic transitions, scattering, photoluminescent emission, and Raman scattering in a dissymmetric electric field. The unprecedented strong OA could be attributed to multiple light scattering and absorption-enhanced light harvesting in the hierarchical structures.

Growth of Optically Active Chiral Inorganic Films through DNA Self-Assembly and Silica Mineralisation

The circularly polarized reflection of nature is due to their distinct azimuthally twisted or helical character in the nanostructure of the surface films. Although many chiral inorganic powders have been successfully synthesised, the artificial synthesis of chiral inorganic films is rare. Herein, we reported a facile synthetic route for the growth of monolayered chiral film on the quaternary ammonium-modified silicon substrate. The films grew on the substrate surface because of the strong electrostatic interaction between positively charged quaternary ammonium groups and negatively charged phosphate groups of DNA, with subsequent growth to right-handed, vertically aligned, impeller-like helical architectures with left-handed two-dimensional square p4mm-structured DNA chiral packing. The DNA–silica composite films exhibited strong optical activity at 295 nm and in the range of 400–800 nm, corresponding to DNA chiral packing (absorption) and to the helical blade in the impeller (scattering), respectively. Upon removal of DNA templates, the pure inorganic impeller-like helical morphology was maintained; consequently, the scattering-based optical response was blue-shifted approximately 200 nm as a result of a decrease in the effective average refractive index. The hierarchical structures were reflected from the surfaces by cross-polarised light, which confirmed that the films were strongly birefringent, with long-range anisotropy.

Optically active chiral Ag nanowires

Chiral Ag nanowires (CAgNWs), fabricated inside chiral carbon nanotubes (CCNTs), exhibit strong circular dichroism (CD) signals in the visible and near-IR regions. Enantiopure CCNTs were prepared by carbonization of the self-assembled chiral polypyrrole nanotubes according to our previous report. Ag ions could be easily introduced into the chiral pores of CCNTs due to the capillary phenomenon. After hydrogen reduction, the optically active CAgNWs formed inside the channels of the CCNTs. The helical channels in the CCNTs played a predominant effect on the chiral formation of the CAgNWs. This system provides new insight into the fabrication as well as the study of optical activity (OA) of chiral inorganic nanomaterials. Such novel chiral inorganic material will bring new opportunities in non-linear optics, biosensors and chiral recognition.中文摘要本文以手性碳纳米管为模板, 成功地在其内部形成了手性银纳米线. 由于手性排列的银纳米线之间的集合耦合效应, 在可见光区和近红外区产生了较强的手性圆二色信号. 根据我们先前报道的方法, 通过碳化处理自组装合成的手性吡咯碳纳米管得到了单一手性的碳纳米管. 由于毛细管效应, 银离子能够很容易地进入手性碳纳米管的手性孔道中, 然后再通过氢气高温还原, 在其管内得到了具有光学活性的手性银纳米线. 手性碳纳米管内的螺旋孔道对手性银纳米线的形成起模板作用. 该合成体系将有助于理解具有手性光学活性的无机材料的形成及其机理. 这种新颖的手性无机材料也将有机会应用到非线性光学器件、生物传感和手性识别等领域.

Water‐Dependent Optical Activity Inversion of Chiral DNA–Silica Assemblies

Chirality is widely found in nature and is expressed hierarchically in many organic-inorganic hybrid materials. Optical activity (OA) is the most fundamental attribute of these chiral materials. In this study, we found that the OA of impeller-like chiral DNA-silica assemblies (CDSAs) was inverted with the addition of water. The state of DNA under dry and wet conditions, and the dual chirality of chiral DNA layers and twisted helical arrays of opposite handedness in CDSAs were considered to exert predominant effects on the OAs. The circular dichroism (CD) responses for the dry CDSAs were mostly attributed to the chiral arrangement of DNA layers, whereas the opposite CD responses for the wet CDSAs primarily originated from twisted helical arrays of DNA molecules. The observed CD signals were a super-position of the two opposing OA responses. The increase in the longitudinal relation of DNA molecules due to the recovery of a double-helical structure of DNA in the presence of water was considered to be the reason for the increase in intensity of the CD signals that originated from the twisted helical array, which led to the inversion of OA of the CDSAs. The inversion of the plasmon-resonance-based OAs for the chiral-arranged achiral Ag nanoparticles (NPs) located in the channels of the CDSAs in dry and wet states further confirmed the dual chirality of DNA packing. Such research on DNA assemblies and metal NPs with dual, opposite chirality assists in the understanding of DNA hierarchical chirality in living systems and the creation of macroscopic ordered helical materials and biosensors.

Hard-templating of chiral TiO2 nanofibres with electron transition-based optical activity

Abstract The fabrication of optically active inorganic nanomaterials with chiral superstructures attracts attention because of their potential applications in chemical sensing and non-linear optics. Here, we present a facile way to prepare TiO2 nanofibres, in which the nanocrystals are helically arranged into a chiral superstructure. Notably, the chiral superstructure shows strong optical activity due to the difference of absorbing left- and right-handed circularly polarized light. This special optical activity resulted from electron transition from the valence band to the conduction band of TiO2 through a vicinal effect of helically arranged TiO2 nanocrystals.

Silver Films with Hierarchical Chirality

Physical fabrication of chiral metallic films usually results in singular or large-sized chirality, restricting the optical asymmetric responses to long electromagnetic wavelengths. The chiral molecule-induced formation of silver films prepared chemically on a copper substrate through a redox reaction is presented. Three levels of chirality were identified: primary twisted nanoflakes with atomic crystal lattices, secondary helical stacking of these nanoflakes to form nanoplates, and tertiary micrometer-sized circinates consisting of chiral arranged nanoplates. The chiral Ag films exhibited multiple plasmonic absorption- and scattering-based optical activities at UV/Vis wavelengths based on their hierarchical chirality. The Ag films showed chiral selectivity for amino acids in catalytic electrochemical reactions, which originated from their primary atomic crystal lattices.