One-dimensional Alignment Research Articles

One-dimensional C60 arrays in noncovalent benzidine networks

Face-centered cubic packing is typically observed for pristine C60 in the solid state, and one-dimensional alignment structures of pristine C60 in the solid state are extremely rare. This study presents the synthesis of novel one-dimensional aligned C60 in single-cocrystal nanosheets, formed from C60 and N,N,N′,N′-tetraphenylbenzidine (TPB). In C60/TPB, which exhibits ambipolar charge transport characteristics, TPB serves as a molecular receptor to facilitate the formation of noncovalent networks wherein C60 organizes into one-dimensional arrays. The resulting C60/TPB nanosheets give rise to a distinct absorption band in the near-infrared region, suggesting the occurrence of charge-transfer interactions between the C60 and TPB frameworks within the cocrystals.

A Double-walled Noncovalent Carbon Nanotube by Columnar Packing of Nanotube Fragments.

Herein, we report the synthesis of double-walled noncovalent carbon nanotubes (CNTs) through host-guest complexation of nanotube fragments and tube-forming crystal engineering. As the smallest fragment of double-walled CNTs, a host-guest complex of perfluorocycloparaphenylene (PFCPP) and carbon nanobelt (CNB) was synthesized by mixing them in solvents. The immediate complexation of the PF[12]CPP⸧(6,6)CNB complex with a remarkably high association constant (Ka) of 2×105 L/mol was observed. Time-dependent 1H NMR and thermogravimetry measurements revealed that the stability of (6,6)CNB was significantly improved by encapsulation. X-ray crystallography confirmed the robust belt-in-ring structure of this complex. As indicated by the short distance between PF[12]CPP and (6,6)CNB (2.8 Å), intermolecular orbital interactions exist between the belt and the ring, which were further supported by theoretical calculation and phosphorescence quenching experiments. While the PF[12]CPP⸧(6,6)CNB complex adopts various crystal packing structures, chloroform was discovered to be a magic "glue" solvent inducing one-dimensional alignment of the PF[12]CPP⸧(6,6)CNB complex to build an unprecedented double-walled noncovalent CNT structure.

Pulsation waves along the Ciona heart tube reverse by bimodal rhythms expressed by a remote pair of pacemakers.

The heart of ascidians (marine invertebrate chordates) has a tubular structure, and heartbeats propagate from one end to the other. The direction of pulsation waves intermittently reverses in the heart of ascidians and their relatives; however, the underlying mechanisms remain unclear. We herein performed a series of experiments to characterize the pacemaker systems in isolated hearts and their fragments, and applied a mathematical model to examine the conditions leading to heart reversals. The isolated heart of Ciona robusta autonomously generated pulsation waves at ∼20 to 25beatsmin-1 with reversals at ∼1 to 10 min intervals. Experimental bisections of isolated hearts revealed that independent pacemakers resided on each side and also that their beating frequencies periodically changed as they expressed bimodal rhythms, which comprised an ∼1.25 to 5.5min acceleration/deceleration cycle of a beating rate of between 0 and 25beatsmin-1. Only fragments including 5% or shorter terminal regions of the heart tube maintained autonomous pulsation rhythms, whereas other regions did not. Our mathematical model, based on FitzHugh-Nagumo equations applied to a one-dimensional alignment of cells, demonstrated that the difference between frequencies expressed by the two independent terminal pacemakers determined the direction of propagated waves. Changes in the statuses of terminal pacemakers between the excitatory and oscillatory modes as well as in their endogenous oscillation frequencies were sufficient to lead to heart reversals. These results suggest that the directions of pulsation waves in the Ciona heart reverse according to the changing rhythms independently expressed by remotely coupled terminal pacemakers.

Slanted Structure of Blue Phase II Self-Aligned on One-Dimensional Patterned Surfaces.

Orientation analysis of liquid crystal (LC) devices is important for understanding and controlling light propagation behavior in these devices. Blue phases (BPs)─unique LC phases that self-organize into three-dimensional helical structures─are candidate materials for LC-based reflective diffractors. We realized BPII deflectors with large diffraction angles using one-dimensional surface alignment patterns. We analyzed the BPII lattice arrangement in the deflector based on Bragg reflections and demonstrated that the lattice structure was slanted with respect to the substrate, which was confirmed using transmission electron microscopy. In addition, we calculated the similarity between the alignment pattern on the substrate surface and the director arrangement of BPII near the interface, confirming that the structure observed experimentally matched the most probable calculated structure. Thus, this study contributes to the optical design of BPII deflectors and provides information on the orientation mechanism in high-order self-organizing soft matter structures.

Multi-landmark alignment of genomic signals reveals conserved expression patterns across transcription start sites

The prevalent one-dimensional alignment of genomic signals to a reference landmark is a cornerstone of current methods to study transcription and its DNA-dependent processes but it is prone to mask potential relations among multiple DNA elements. We developed a systematic approach to align genomic signals to multiple locations simultaneously by expanding the dimensionality of the genomic-coordinate space. We analyzed transcription in human and uncovered a complex dependence on the relative position of neighboring transcription start sites (TSSs) that is consistently conserved among cell types. The dependence ranges from enhancement to suppression of transcription depending on the relative distances to the TSSs, their intragenic position, and the transcriptional activity of the gene. Our results reveal a conserved hierarchy of alternative TSS usage within a previously unrecognized level of genomic organization and provide a general methodology to analyze complex functional relationships among multiple types of DNA elements.

One-dimensional alignment of defects in a flexible metal-organic framework.

Crystalline materials are often considered to have rigid periodic lattices, while soft materials are associated with flexibility and nonperiodicity. The continuous evolution of metal-organic frameworks (MOFs) has erased the boundaries between these two distinct conceptions. Flexibility, disorder, and defects have been found to be abundant in MOF materials with imperfect crystallinity, and their intricate interplay is poorly understood because of the limited strategies for characterizing disordered structures. Here, we apply advanced nuclear magnetic resonance spectroscopy to elucidate the mesoscale structures in a defective MOF with a semicrystalline lattice. We show that engineered defects can tune the degree of lattice flexibility by combining both ordered and disordered compartments. The one-dimensional alignment of correlated defects is the key for the reversible topological transition. The unique matrix is featured with both rigid framework of nanoporosity and flexible linkage of high swellability.

An Inorganic-Organic Hybrid Framework Composed of Polyoxotungstate and Long-Chained Bolaamphiphile.

Surfactants are functional molecules utilized in various situations. The self-assembling property of surfactants enables several molecular arrangements that can be employed to build up nanometer-sized architectures. This is beneficial in the construction of functional inorganic-organic hybrids holding the merits of both inorganic and organic components. Among several surfactants, bolaamphiphile surfactants with two hydrophilic heads are effective, as they have multiple connecting or coordinating sites in one molecule. Here, a functional polyoxotungstate inorganic anion was successfully hybridized with a bolaamphiphile to form single crystals with anisotropic one-dimensional alignment of polyoxotungstate. Keggin-type metatungstate ([H2W12O40]6-, H2W12) was employed as an inorganic anion, and 1,12-dodecamethylenediammonium (C12N2) derived from 1,12-dodecanediamine was combined as an organic counterpart. A simple and general ion-exchange reaction provided a hybrid crystal consisting of H2W12 and C12N2 (C12N2-H2W12). Single crystal X-ray structure analyses revealed a characteristic honeycomb structure in the C12N2-H2W12 hybrid crystal, which is possibly effective for the emergence of conductivity due to the dissociative protons of C12N2.

Complexation study of a 1,3-phenylene-bridged cyclic hexa-naphthalene with fullerenes C60 and C70 in solution and 1D-alignment of fullerenes in the crystals.

To investigate the host ability of a simple macrocycle, 1,3-phenylene-bridged naphthalene hexamer N6, we evaluated the complexation of N6 with fullerenes in toluene and in the crystals. The complexes in the solid-state demonstrate the one-dimensional alignment of fullerenes. The single-crystals of the C60@N6 composite have semiconductive properties revealed by photoconductivity measurements.

Ligand Modified and Light Switched On/Off Single-Chain Magnets of {Fe 2 Co} Coordination Polymers via Metal-to-Metal Charge Transfer

Ligand Modified and Light Switched On/Off Single-Chain Magnets of {Fe ₂ Co} Coordination Polymers via Metal-to-Metal Charge Transfer

Highly Anisotropic Thermal Conductivity of Three-Dimensional Printed Boron Nitride-Filled Thermoplastic Polyurethane Composites: Effects of Size, Orientation, Viscosity, and Voids.

Extrusion-based three-dimensional (3D) printing techniques usually exhibit anisotropic thermal, mechanical, and electric properties due to the shearing-induced alignment during extrusion. However, the transformation from the extrusion to stacking process is always neglected and its influence on the final properties remains ambiguous. In this work, we adopt two different sized boron nitride (BN) sheets, namely, small-sized BN (S-BN) and large-sized BN (L-BN), to explore their impact on the orientation degree, morphology, and final anisotropic thermal conductivity (TC) of thermoplastic polyurethane (TPU) composites by fused deposition modeling. The transformation from one-dimensional axial alignment in the extruded filament to two-dimensional alignment (horizontal and vertical alignment) in the stacking filament of BN sheets is observed, and its impact on anisotropic TC in three directions is clarified. It is found that L-BN/TPU composites show a high TC of 6.45 W m-1 K-1 at 60 wt % BN content along the printing direction, while at a lower content (<40 wt %), S-BN/TPU composites exhibit a higher TC than L-BN/TPU composites. Effects of orientation, viscosity, and voids are comprehensively considered to elucidate such differences. Finally, heat dissipation tests demonstrate the great potential of 3D printed BN/TPU composites to be used in thermal management applications.

Unidirectional Alignment of Surface-Grafted ZnO Nanorods in Micrometer-Thick Cells Using Low-Molecular-Weight Liquid Crystals.

Inorganic nanomaterials such as nanotubes and nanorods have attracted great attention due to their anisotropic properties. Although the alignment control of inorganic nanomaterials is key to the development of functional devices utilizing their fascinating properties, there is still difficulty in achieving uniform alignment over a large area with a micrometer thickness. To overcome this problem, we focused on liquid crystals (LCs) to promote the alignment of anisotropic nanomaterials, taking advantage of the cooperative motion of LCs. We present the uniform, one-dimensional alignment of ZnO nanorods along the direction of LCs in micrometer-thick cells by grafting nematic LC polymers from the nanorod surfaces to provide miscibility with the host LCs. Polarized optical microscopy and polarized UV–visible absorption spectroscopy revealed the unidirectional alignment of nematic LC polymer-grafted ZnO nanorods parallel to the nematic host LCs.

Self-Aligned Assembly of a Poly(2-vinylpyridine)-b-Polystyrene-b-Poly(2-vinylpyridine) Triblock Copolymer on Graphene Nanoribbons.

Directed self-assembly (DSA) of block copolymers is one of the most promising patterning techniques for patterning sub-10 nm features. However, at such small feature sizes, it is becoming increasingly difficult to fabricate the guiding pattern for the DSA process, and it is necessary to explore alternative guiding methods for DSA to achieve long-range ordered alignment. Here, we report the self-aligned assembly of a triblock copolymer, poly(2-vinylpyridine)-b-polystyrene-b-poly(2-vinylpyridine) (P2VP-b-PS-b-P2VP) on neutral graphene nanoribbons with the gap consisting of a P2VP-preferential silicon oxide (SiO2) substrate via solvent vapor annealing. The assembled P2VP-b-PS-b-P2VP demonstrated long-range, one-dimensional alignment on the graphene substrate in a direction perpendicular to the boundary of the graphene and substrate with a half-pitch size of 8 nm, which greatly alleviates the lithography resolution required for traditional chemoepitaxy DSA. A wide processing window is demonstrated with the gap between graphene stripes varying from 10 to 100 nm, overcoming the restriction on widths of guiding patterns to have commensurate domain spacing. When the gap was reduced to 10 nm, P2VP-b-PS-b-P2VP formed a straight-line pattern on both the graphene and the substrate. Monte Carlo simulations showed that the self-aligned assembly of the triblock copolymer on the graphene nanoribbons is guided at the boundary of parallel and perpendicular lamellae on graphene and SiO2, respectively. Simulations also indicate that the swelling of a system allows for rapid rearrangement of chains and quickly anneal any misaligned grains and defects. The effect of the interaction strength between SiO2 and P2VP on the self-assembly is systematically investigated in simulations.

Biofunctionalization of carbon nanotubes for reversible site-specific protein immobilization

Carbon nanotubes (CNTs) emerge as biosensors due to their extraordinary electrical transport properties. Such applications depend on interfacing proteins with CNTs in an oriented manner while maintaining their structural and functional integrity, opening versatile opportunities for one-dimensional alignment and high-sensitivity sensing of protein interactions and conformational dynamics. Here, we devised a novel surface architecture for reversible protein immobilization on CNTs via a short peptide tag for fabrication of reusable biosensors for multiple protein analysis. To this end, we conjugated pyrene-poly(ethylene glycol) with tris-nitrilotriacetic acid (Py-PEG-tris-NTA) for site-specific immobilization of oligohistidine(His)-tagged proteins. We demonstrate spontaneous self-assembly of Py-PEG-tris-NTA on CNTs and graphene, as well as specific capturing of His-tagged green fluorescent protein after loading the NTA chelators with Ni(II) ions. The protein binding capacity of tris-NTA-functionalized CNTs could be restored by an imidazole wash, allowing for repeated immobilization cycles. Reflectance interference spectroscopy and fluorescence lifetime analysis confirmed a specific and reversible binding of proteins on CNT-coated silica substrates as well as close interfacing to the CNT surface.

Subwavelength liquid crystal gratings for polarization-independent phase shifts in the terahertz spectral range

A polarization-independent terahertz (THz) phase shifter was proposed using a liquid crystal (LC) grating with subwavelength periodic alignment. The LC grating was constructed with one-dimensional periodic planar alignment and was designed based on the effective medium theory. The phase of the transmitted wave was theoretically independent of the polarization state and the phase was shifted by transition from a periodic planar alignment to a homeotropic alignment. The LC grating was fabricated using a nematic LC and photoalignment layers. The easy axes of the photoalignment layers were periodically regulated using a grating photomask with a subwavelength pitch. There was minimal dependence of the obtained phase shift on the polarization state, and the results were in agreement with the theoretical calculations.

Long-lasting field-free alignment of large molecules inside helium nanodroplets

Molecules with their axes sharply confined in space, available through laser-induced alignment methods, are essential for many current experiments, including ultrafast molecular imaging. For these applications the aligning laser field should ideally be turned-off, to avoid undesired perturbations, and the strong alignment should last long enough that reactions and dynamics can be mapped out. Presently, this is only possible for small, linear molecules and for times less than 1 picosecond. Here, we demonstrate strong, field-free alignment of large molecules inside helium nanodroplets, lasting >10 picoseconds. One-dimensional or three-dimensional alignment is created by a slowly switched-on laser pulse, made field-free through rapid pulse truncation, and retained thanks to the impeding effect of the helium environment on molecular rotation. The opportunities field-free aligned molecules open are illustrated by measuring the alignment-dependent strong-field ionization yield of dibromothiophene oligomers. Our technique will enable molecular frame experiments, including ultrafast excited state dynamics, on a variety of large molecules and complexes.

Communication: Switched wave packets with spectrally truncated chirped pulses.

A new technique for obtaining switched wave packets using spectrally truncated chirped laser pulses is demonstrated experimentally and numerically by one-dimensional alignment of both linear and asymmetric top molecules. Using a simple long-pass transmission filter, a pulse with a slow turn-on and a rapid turn-off is produced. The degree of alignment, characterized by ⟨cos2 θ2D⟩, rises along with the pulse intensity and reaches a maximum at the peak of the pulse. After truncation, ⟨cos2 θ2D⟩ drops sharply but exhibits pronounced half and full revivals. The experimental alignment dynamics trace agrees very well with a numerically calculated trace based on the solution of the time-dependent Schrödinger equation. However, the extended periods of field-free alignment of asymmetric tops following pulse truncation reported previously are not reproduced in our work.

Communication: Gas-phase structural isomer identification by Coulomb explosion of aligned molecules

The gas-phase structures of four difluoroiodobenzene and two dihydroxybromobenzene isomers were identified by correlating the emission angles of atomic fragment ions created, following femtosecond laser-induced Coulomb explosion. The structural determinations were facilitated by confining the most polarizable axis of each molecule to the detection plane prior to the Coulomb explosion event using one-dimensional laser-induced adiabatic alignment. For a molecular target consisting of two difluoroiodobenzene isomers, each constituent structure could additionally be singled out and distinguished.

Automated quantification of one-dimensional nanostructure alignment on surfaces

A method for automated quantification of the alignment of one-dimensional (1D) nanostructures from microscopy imaging is presented. Nanostructure alignment metrics are formulated and shown to be able to rigorously quantify the orientational order of nanostructures within a two-dimensional domain (surface). A complementary image processing method is also presented which enables robust processing of microscopy images where overlapping nanostructures might be present. Scanning electron microscopy (SEM) images of nanowire-covered surfaces are analyzed using the presented methods and it is shown that past single parameter alignment metrics are insufficient for highly aligned domains. Through the use of multiple parameter alignment metrics, automated quantitative analysis of SEM images is shown to be possible and the alignment characteristics of different samples are able to be quantitatively compared using a similarity metric. The results of this work provide researchers in nanoscience and nanotechnology with a rigorous method for the determination of structure/property relationships, where alignment of 1D nanostructures is significant.

One-dimensionality in atomic nuclei: A candidate for linear-chainαclustering inC14

The clustering of $\ensuremath{\alpha}$ particles in atomic nuclei results in the self-organization of various geometrical arrangements at the femtometer scale. The one-dimensional alignment of multiple $\ensuremath{\alpha}$ particles is known as linear-chain structure, evidence of which has been highly elusive. We show via resonant elastic and inelastic $\ensuremath{\alpha}$ scattering of a radioactive $^{10}\mathrm{Be}$ beam that excited states in the neutron-rich nucleus $^{14}\mathrm{C}$ agree with recent predictions of linear-chain structure based on an antisymmetrized molecular dynamics model.

Alignment enhancement of molecules embedded in helium nanodroplets by multiple laser pulses

We show experimentally that field-free one-dimensional (1D) alignment of 1,4-diiodobenzene molecules embedded in helium nanodroplets, induced by a single, linearly polarized 200-fs laser pulse, can be significantly enhanced by using two or four optimally synchronized laser pulses. The strongest degree of 1D alignment is obtained with four pulses and gives $\ensuremath{\langle}{cos}^{2}\ensuremath{\theta}\ensuremath{\rangle}&gt;0.60$. Besides the immediate implications for molecular frame studies, our results pave the way for more general manipulation of rotational motion of molecules in He droplets.