Chirality-dependent Properties Research Articles

Hydrogel Composition Effects on Performance as Single-Walled Carbon Nanotube Purification Media.

Hydrogel microsphere media allows for postsynthetic purification of single-walled carbon nanotubes (SWNTs), affording characterization and application of their unique (n,m) chirality-dependent properties. This work reports the characterization of five hydrogel resins, Sephacryl S-100, S-200, S-300, S-400, and S-500, and the implementation of each as a SWNT purification medium. The physiochemical properties of each resin were explored spectroscopically through elemental analyses and with both light and electron microscopy. Both surface porosity and hydrogel swelling ratio were found to increase as the concentration of component allyl dextran (aDEX) decreased, each with an increasing Sephacryl S-number. Conversely, invariant properties included a hydrogel microsphere size distribution and concentrations of components methylenebisacrylamide and ammonium persulfate. When employed within gel-based SWNT purification schemes in overloading conditions, Sephacryl formulations of larger S-number adsorbed fewer SWNTs, but the chirality dependence of SWNT adsorption and elution was approximately consistent across all resins. In underloading conditions, approximately one-third of introduced SWNTs passed through each resin unabsorbed, while the resins showed varying chirality-dependent adsorption efficiencies. These observations collectively identify aDEX-rich gel regions as being responsible for SWNT purification, along with a SWNT-exclusive parameter other than chirality (speculated as length) that convolutes the effectiveness of gel-based single-chirality purification.

Atomic-Scale Evidence of Catalyst Evolution for the Structure-Controlled Growth of Single-Walled Carbon Nanotubes.

ConspectusKnowing how nanomaterials nucleate and dynamically evolve at the nanoscale is crucial to understanding and in turn controlling the structure and properties of a wide variety of materials, among which single-walled carbon nanotubes (SWCNTs) with chirality-dependent properties is a typical example. Catalyst takes a central role in guiding the SWCNT growth. An in-depth understanding of the growth mechanism of SWCNTs requires knowledge of the catalyst dynamic behavior during the chemical vapor deposition process, where real-time atomic-scale observations are needed. The high spatial, temporal, and energy resolution makes the state-of-the-art aberration-corrected environmental transmission electron microscope (ETEM) a superior tool for tracking the catalyst evolution and the SWCNT growth.Several key factors and processes, including the catalyst stability, carbon diffusion pathway, nucleation site, and growth modes of nanotubes, greatly influence the structure of SWCNTs. This Account summarizes our recent progress in the ETEM investigation of the dynamic catalyst behavior and nucleation of SWCNTs. We first compare the different growth modes of SWCNTs on two types of catalyst-stable solid intermetallic Co7W6 and unstable monometallic catalysts. Then we address the origin of different growth modes and chirality selectivity by revealing the atomic-scale stability and evolution of catalysts under carbon feed conditions and the observation of the in situ growth of SWCNTs on catalysts. We also discuss the catalyst-support interaction and the possible influence on SWCNT growth. In the end, we summarize the present achievements and future challenges.We carefully compare the difference in the ordinary Co catalyst and Co7W6 catalyst which has shown great chirality selectivity in SWCNT growth. Direct imaging by ETEM demonstrated that solid catalysts initiated the growth of SWCNTs with diameters smaller (dNT) than those of the catalyst particles (dNP) (dNT < dNP), whereas molten catalyst nanoparticles produced SWCNTs with similar diameters (dNT ≈ dNP). ETEM combined with in situ synchrotron X-ray absorption spectroscopy demonstrated that the Co7W6 catalyst maintained a solid stable structure under carbon feed conditions at 700-1000 °C, demonstrating the feasibility in acting as a structure template to grow SWCNTs. By contrast, the state and composition of the Co catalyst were changing during SWCNT growth. The near-surface lattice spacings of Co7W6 remained unchanged under carbon feed condition with carbon diffusion on the surface, whereas the solid Co catalyst underwent dynamic expansion and contraction due to carbon penetration into and precipitation out of Co nanoparticles. These two different pathways of carbon diffusion on or in catalysts indicate the distinctly different growth mechanisms of SWCNTs: the epitaxial growth of SWCNTs with specified chirality on the facets of Co7W6 nanocrystals and the nonselective growth of SWCNTs by the Co catalyst with Co/CoC3 as the active species. Besides the SWCNT-catalyst interface, the catalyst-support interface is also of importance in SWCNT growth. The atomic-scale information on catalyst dynamics provides a deep mechanistic understanding of SWCNT growth and will boost the development of the structure-controlled synthesis of SWCNTs and other nanomaterials.

Gold-Nanoparticle-Based Chiral Plasmonic Nanostructures and Their Biomedical Applications.

As chiral antennas, plasmonic nanoparticles (NPs) can enhance chiral responses of chiral materials by forming hybrid structures and improving their own chirality preference as well. Chirality-dependent properties of plasmonic NPs broaden application potentials of chiral nanostructures in the biomedical field. Herein, we review the wet-chemical synthesis and self-assembly fabrication of gold-NP-based chiral nanostructures. Discrete chiral NPs are mainly obtained via the seed-mediated growth of achiral gold NPs under the guide of chiral molecules during growth. Irradiation with chiral light during growth is demonstrated to be a promising method for chirality control. Chiral assemblies are fabricated via the bottom-up assembly of achiral gold NPs using chiral linkers or guided by chiral templates, which exhibit large chiroplasmonic activities. In describing recent advances, emphasis is placed on the design and synthesis of chiral nanostructures with the tuning and amplification of plasmonic circular dichroism responses. In addition, the review discusses the most recent or even emerging trends in biomedical fields from biosensing and imaging to disease diagnosis and therapy.

(Invited, Digital Presentation) Optoelectronic Processes in Single-Chirality Carbon Nanotube Thin Films

Much understanding exists regarding chirality-dependent properties of single-wall carbon nanotubes (SWCNTs), primarily obtained through single-tube studies. However, macroscopic manifestations of chirality dependence have been limited, especially in electronic transport. Here, recent progress in our optical and electronic transport studies of single-chirality SWCNT thin films will be reviewed. We observed pronounced chirality-dependent electronic localization in temperature and magnetic field dependent conductivity measurements on macroscopic films of single-chirality SWCNTs [1]. We also performed optical absorption measurements in aligned single-chirality (6,5) SWCNT films, and through comparison with detailed theoretical calculations based on the Boltzmann scattering equation, we demonstrated that the background absorption is due to phonon-assisted transitions from the semiconductor vacuum to finite-momentum continuum states of excitons [2]. Furthermore, we conducted terahertz emission and photocurrent studies on films of aligned single-chirality semiconducting SWCNTs and found that excitons autoionize, i.e., spontaneously dissociate into electrons and holes [3]. Some of these studies were enabled by our recent improvement of the controlled vacuum filtration technique [4,5], which allows us to fabricate wafer-scale aligned SWCNTs with extremely anisotropic optical properties [6-9]. W. Gao et al., “Band Structure Dependent Electronic Localization in Macroscopic Films of Single-Chirality Single-Wall Carbon Nanotubes,” Carbon 183, 774 (2021).S. Dal Forno et al., “Origin of the Background Absorption in Carbon Nanotubes: Phonon-Assisted Excitonic Continuum,” Carbon 186, 465 (2021).F. R. G. Bagsican et al., “Terahertz Excitonics in Carbon Nanotubes: Exciton Autoionization and Multiplication,” Nano Letters 20, 3098 (2020).X. He et al., “Wafer-Scale Monodomain Films of Spontaneously Aligned Single-Walled Carbon Nanotubes,” Nature Nanotechnology 11, 633 (2016).W. Gao and J. Kono, “Science and Applications of Wafer-Scale Crystalline Carbon Nanotube Films Prepared through Controlled Vacuum Filtration,” Royal Society Open Science 6, 181605 (2019).F. Katsutani et al., “Direct Observation of Cross-Polarized Excitons in Aligned Single-Chirality Single-Wall Carbon Nanotubes,” Physical Review B 99, 035426 (2019).W. Gao et al., “Macroscopically Aligned Carbon Nanotubes as a Refractory Platform for Hyperbolic Thermal Emitters,” ACS Photonics 6, 1602 (2019).N. Komatsu et al., “Groove-Assisted Global Spontaneous Alignment of Carbon Nanotubes in Vacuum Filtration,” Nano Letters 20, 2332 (2020).A. Baydin et al., “Giant Terahertz Polarization Rotation in Ultrathin Films of Aligned Carbon Nanotubes,” Optica 8, 760 (2021).

Charge-four Weyl point: Minimum lattice model and chirality-dependent properties

Topological Weyl semimetals have been attracting broad interest. Recently, a new type of Weyl point with topological charge of $4$, termed as charge-4 Weyl point (C-4 WP), was proposed in spinless systems. Here, we show the minimum symmetry requirement for C-4 WP is point group $T$ together with ${\cal T}$ symmetry or point group $O$. We establish a minimum tight-binding model for C-4 WP on a cubic lattice with time-reversal symmetry and without spin-orbit coupling effect. This lattice model is a two-band one, ontaining only one pair of C-4 WPs with opposite chirality around Fermi level. Based on both the low-energy effective Hamiltonian and the minimum lattice model, we investigate the electronic, optical and magnetic properties of C-4 WP. Several chirality-dependent properties are revealed, such as chiral Landau bands, quantized circular photogalvanic effect and quadruple-helicoid surface arc states. Furthermore, we predict that under symmetry breaking, various exotic topological phases can evolve out of C-4 WPs. Our work not only reveals several interesting phenomena associate to C-4 WPs, but also provides a simple and ideal lattice model of C-4 WP, which will be helpful for the subsequent study on C-4 WPs.

Band structure dependent electronic localization in macroscopic films of single-chirality single-wall carbon nanotubes

Significant understanding has been achieved over the last few decades regarding chirality-dependent properties of single-wall carbon nanotubes (SWCNTs), primarily through single-tube studies. However, macroscopic manifestations of chirality dependence have been limited, especially in electronic transport, despite the fact that such distinct behaviors are needed for many applications of SWCNT-based devices. In addition, developing reliable transport theory is challenging since a description of localization phenomena in an assembly of nanoobjects requires precise knowledge of disorder on multiple spatial scales, particularly if the ensemble is heterogeneous. Here, we report an observation of pronounced chirality-dependent electronic localization in temperature and magnetic field dependent conductivity measurements on macroscopic films of single-chirality SWCNTs. The samples included large-gap semiconducting (6,5) and (10,3) films, narrow-gap semiconducting (7,4) and (8,5) films, and armchair metallic (6,6) films. Experimental data and theoretical calculations revealed Mott variable-range-hopping dominated transport in all samples, while localization lengths fall into three distinct categories depending on their band gaps. Armchair films have the largest localization length. Our detailed analyses on electronic transport properties of single-chirality SWCNT films provide significant new insight into electronic transport in ensembles of nanoobjects, offering foundations for designing and deploying macroscopic SWCNT solid-state devices.

Chirality-dependent properties of domain walls in a U-shaped Permalloy nanostrip

Transverse domain walls (DWs) in a U-shaped ferromagnetic nanostrip possess many dynamic properties different from those in flat nanostrip. By breaking the top–bottom symmetry, the U-shaped strip endows DWs with chirality-dependent structures, mobilities and Walker breakdown fields. More interestingly, Walker breakdown in U-shaped nanostrip is hierarchy, with two different modes. Micromagnetic simulations predicted that DWs with different chiralities have different robustness and (anti)vortex dynamics in Walker breakdown. Our results provide a method for manipulating DW chirality.

Chirality-Enriched Carbon Nanotubes for Next-Generation Computing.

For the past half century, silicon has served as the primary material platform for integrated circuit technology. However, the recent proliferation of nontraditional electronics, such as wearables, embedded systems, and low-power portable devices, has led to increasingly complex mechanical and electrical performance requirements. Among emerging electronic materials, single-walled carbon nanotubes (SWCNTs) are promising candidates for next-generation computing as a result of their superlative electrical, optical, and mechanical properties. Moreover, their chirality-dependent properties enable a wide range of emerging electronic applications including sub-10 nm complementary field-effect transistors, optoelectronic integrated circuits, and enantiomer-recognition sensors. Here, recent progress in SWCNT-based computing devices is reviewed, with an emphasis on the relationship between chirality enrichment and electronic functionality. In particular, after highlighting chirality-dependent SWCNT properties and chirality enrichment methods, the range of computing applications that have been demonstrated using chirality-enriched SWCNTs are summarized. By identifying remaining challenges and opportunities, this work provides a roadmap for next-generation SWCNT-based computing.

Heterochiral Doped Supramolecular Coordination Networks for High-Performance Optoelectronics.

Chiral self-sorting has great potential for constructing new complex structures and determining chirality-dependent properties in multicomponent mixtures. However, it is still of great challenge to achieve high fidelity chiral self-discrimination. Besides, the researches on the coordination polymers or metal-organic frameworks for micro/nanooptoelectronics are still rare due to their low conductivity and difficulty in developing a rapid and simple scale-up synthetic method. Here, heterochiral supramolecular coordination networks (SCNs) were synthesized by the solvothermal reaction of naphthalene diimide enantiomers and cadmium iodide, using the chirality as a synthetic tuning parameter to control the morphologies. Intriguingly, heterochiral micro/nanocrystals exhibited photochromic and photodetecting properties. Furthermore, we also developed a simple and efficient doping method to enhance the conductivity and photoresponsivity of micro/nanocrystals using hydrazine. From experimental and theoretical studies, the mechanism was suggested as follows: the radicals in the singly occupied molecular orbital level of the ligands provide charge carriers that can undergo "through-space" transport between π-π stacked ligands and the electron transfer from adsorbed hydrazine to the SCNs results in reduction of energy gap, leading to increased conductivity. Our findings demonstrate a simple and powerful strategy for implementing coordination networks with redox ligands for micro/nanooptoelectronic applications.

Temperature and Chirality Dependent Mechanical Properties of Single-Walled Carbon Nanotube

Presented herein is an investigation into the stretching and fracture behavior of single-walled carbon nanotubes (SWCNT) subjected to axial tensile load at various temperatures. This study is carried out using molecular dynamics (MD) simulation at temperatures ranging from 200 K to 2200 K. The authors find that single-walled carbon nanotubes exhibit obvious temperature and chirality dependent properties. The values of tensile strain and tensile strength of zigzag (12, 0) and armchair (7, 7) SWCNTs with similar radii decrease with increase in temperature, but decline slightly on different slopes. The stress-strain curves of zigzag and armchair SWCNTs vary significantly when the temperature is more than 1200 K. Our studies suggest temperature and chirality play an important role in determining the tensile strength and tensile strain of SWCNT.

The effect of single wall carbon nanotube metallicity on genomic DNA-mediated chirality enrichment

Achieving highly enriched single wall carbon nanotubes (SWNTs) is one of the major hurdles today because their chirality-dependent properties must be uniform and predictable for use in nanoscale electronics. Due to the unique wrapping and groove-binding mechanism, DNA has been demonstrated as a highly specific SWNT dispersion and fractionation agent, with its enrichment capabilities depending on the DNA sequence and length as well as the nanotube properties. Salmon genomic DNA (SaDNA) offers an inexpensive and scalable alternative to synthetic DNA. In this study, SaDNA enrichment capabilities were tested on SWNT separation with varying degrees of metallicity that were formulated from mixtures of commercial metallic (met-) and semiconducting (sem-) abundant SWNTs. The results herein demonstrate that the degree of metallicity of the SWNT sample has a significant effect on the SaDNA enrichment capabilities, and this effect is modeled based on deconvolution of the near-infrared (NIR) absorption spectra and verified with photoluminescence emission (PLE) measurements. Using molecular dynamics and circular dichroism, the preferential SaDNA mediated separation of the (6, 5) sem-tube is shown to be largely influenced by the presence of met-SWNTs.

Chiral properties in a two-dimensional chiral polaritonic photonic crystal

We theoretically investigated a format of two-dimensional dielectric-chiral photonic crystal structure that is composed of a dispersive chiral medium embedded in a dielectric background. The photonic band structure shows distinctive dispersion relationship for circularly polarized electromagnetic waves, leading to a number of intriguing wave properties, namely chirality dependent “node switching,” polarization sensitive transmission and handedness dependent mode localization. All of these effects are attributed to the strong interaction between the local resonant modes around the dispersive chiral rods and the Bloch modes of the bulk waves. The chirality dependent properties can find tremendous applications in polarization based optoelectronics devices and rapid separation of chiral compounds in pharmaceutical industry.

The dramatic influence of the location of bend and of lateral fluoro substitution on the mesomorphic properties of angular chiral esters based on a 1,3-disubstituted benzene ring

The synthesis and mesomorphic properties of a range of 3-ring and 4-ring chiral esters based on a 1,3-disubstituted benzene unit are detailed. These materials all deviate from the usual linear molecular architecture of liquid crystals, and hence are all angular in nature. Some of these materials have the bend right at the end of the molecule where the chain deviates from the normal linear arrangement, and hence a ‘hockey stick’ molecular architecture is perhaps an accurate description. Other materials have a genuine bent-core construction where the bend is towards the centre of the molecule, and hence are best termed as ‘boomerang’ shape. In all cases, interesting comparisons of mesophase morphology and transition temperatures were found, both between the various angular materials and with their linear analogues. In particular, the influence on transition temperatures of lateral fluoro substitution in the novel angular materials was found to be wholly different to that found in the known linear analogues. The work forms part of a larger on-going research programme to investigate the mesomorphic and chirality-dependent properties of angular liquid crystals. The research revealed that no mesomorphism in parent compounds is possible when the bend is close to the centre of the molecule, however, lateral fluoro substitution of such compounds facilitates the generation of liquid crystal phases. Where the molecular bend is as a consequence of the terminal unit at the end of the core, then surprisingly high clearing points resulted, and such materials were found to show the potential for a high tilt angle, and a strong tendency towards helical mesophases. Lateral fluoro substitution of these latter examples resulted consistently in significantly higher clearing points, which is in marked contrast to the behaviour reported previously in known liquid crystals of linear molecular architectures.

Mesophasic helical structures with high twisting power in optically active 3-methyladipic acid bis esters

A homologous series of novel twin molecules, (R)-3-methyladipic acid bis[4-(5-alkyl-2-pyrimidinyl)phenyl] ester, has been prepared and the physical properties investigated, where the chirality was generated in the system by introducing the chiral centre in the central region of the molecular structure. Heptyl and octyl members of the series show a monotropic cholesteric phase. The chirality-dependent properties of the series of the twin materials were compared with those of analogous ‘monomeric’ materials carrying a chiral centre in the peripheral aliphatic chain. Pitch measurements revealed that the twin materials induce a strong helical structure in both cholesteric and chiral smectic C phases. Furthermore, a chiral twin molecule possessing only one phenyl ring at each core part, i.e.(R)-3-methyladipic acid bis(4-octyloxyphenyl) ester, was prepared. The S*c pitch of this compound was found to be longer than that for the former series of twin materials. These results allow us to propose a possible model for producing the strong helical structure in the S*c phases where the chirality had been induced by the twin molecules. In addition, the strong desire for the twin materials to form a helical ordering in smectic phases was also found to induce an unusual smectic phase, in contact studies with an achiral liquid-crystalline material, where a texture similar to that reported for the twist grain boundary (TGB) phases was observed.

Inversion of chirality-dependent properties in helical liquid crystals: effects of structural modification

The effects of structural modification on the inversion of chirality-dependent properties in the helical mesophases of a number of terphenyls have been investigated. The occurrence of inversion phenomena are very sensitive to small changes in the molecular structure and subtle changes can often produce profound effects. Structural modification of the non-chiral or chiral terminal chains has been shown to destabilize the inversion of chirality-dependent properties; however, a stable room temperature ferroelectric smectic C* phase has been prepared. The inclusion of lateral fluoro-substituents in the aromatic core causes a large reduction in the melting points of the terphenyl materials and the stabilization of inversion phenomena in the cholesteric phase. Changes in the fluoro-substitution pattern results in a change in the direction of the molecular dipole and hence a change in the sign of the spontaneous polarization. Helical mesophases and therefore also inversion phenomena are suppressed in the non-fluorinated material.

Ferrielectric and antiferroelectric properties of a fluoro-substituted biphenyl ester

The material (R)-1-methylheptyl 4-(4′-n-dodecyloxybiphenyl-4-ylcarbonyloxy)-3-fluorobenzoate has been prepared and its liquid-crystalline properties investigated. This material was selected for synthesis because it was expected to exhibit a ferroelectric smectic C* phase with a large value for its spontaneous polarization. Moreover, as the material carries a terminal peripheral chiral 1-methylheptyl moiety it was also expected to exhibit strong chirality-dependent properties. Thus, the material was also found to possess ferrielectric and antiferroelectric modifications in addition to the normal ferroelectric phase. In particular, the ferrielectric phase was found to exhibit unusual behaviour in the presence of applied electric fields.