Retraction: Soft nanotubes acting as confinement effecters and chirality inducers for achiral polythiophenes.

Retraction of 'Soft nanotubes acting as confinement effecters and chirality inducers for achiral polythiophenes' by Naohiro Kameta et al., Chem. Commun., 2016, 52, 1346-1349, https://doi.org/10.1039/C5CC08035E.

Retraction: Biologically responsive, sustainable release from metallo-drug coordinated 1D nanostructures.

Retraction of 'Biologically responsive, sustainable release from metallo-drug coordinated 1D nanostructures' by Naohiro Kameta et al., J. Mater. Chem. B, 2013, 1, 276-283, https://doi.org/10.1039/C2TB00101B.

Retraction: Qualitative/chiral sensing of amino acids by naked-eye fluorescence change based on morphological transformation and hierarchizing in supramolecular assemblies of pyrene-conjugated glycolipids.

Retraction of 'Qualitative/chiral sensing of amino acids by naked-eye fluorescence change based on morphological transformation and hierarchizing in supramolecular assemblies of pyrene-conjugated glycolipids' by Naohiro Kameta et al., Chem. Commun., 2015, 51, 11104-11107, https://doi.org/10.1039/C5CC03843J.

Retraction: Two-step naked-eye detection of lectin by hierarchical organization of soft nanotubes into liquid crystal and gel phases.

Retraction of 'Two-step naked-eye detection of lectin by hierarchical organization of soft nanotubes into liquid crystal and gel phases' by Naohiro Kameta et al., Chem. Commun., 2015, 51, 6816-6819, https://doi.org/10.1039/C5CC01464F.

Soft-Matter Nanotubes: A Platform for Diverse Functions and Applications.

Self-assembled organic nanotubes made of single or multiple molecular components can be classified into soft-matter nanotubes (SMNTs) by contrast with hard-matter nanotubes, such as carbon and other inorganic nanotubes. To date, diverse self-assembly processes and elaborate template procedures using rationally designed organic molecules have produced suitable tubular architectures with definite dimensions, structural complexity, and hierarchy for expected functions and applications. Herein, we comprehensively discuss every functions and possible applications of a wide range of SMNTs as bulk materials or single components. This Review highlights valuable contributions mainly in the past decade. Fifteen different families of SMNTs are discussed from the viewpoints of chemical, physical, biological, and medical applications, as well as action fields (e.g., interior, wall, exterior, whole structure, and ensemble of nanotubes). Chemical applications of the SMNTs are associated with encapsulating materials and sensors. SMNTs also behave, while sometimes undergoing morphological transformation, as a catalyst, template, liquid crystal, hydro-/organogel, superhydrophobic surface, and micron size engine. Physical functions pertain to ferro-/piezoelectricity and energy migration/storage, leading to the applications to electrodes or supercapacitors, and mechanical reinforcement. Biological functions involve artificial chaperone, transmembrane transport, nanochannels, and channel reactors. Finally, medical functions range over drug delivery, nonviral gene transfer vector, and virus trap.

Observing the Kinetic Pathway of Nanotube Formation from Bolaamphiphiles by Time-Resolved Small-Angle X-ray Scattering.

We investigated the formation kinetics of a single monolayer nanotube from bolaamphiphiles (consisting of a sugar residue, an alkyl chain, and an amino group) in solution. In this bolaamphiphile, a transition from a monomerically dispersed state to the nanotube takes place by changing the solvent condition. This transition was induced by fast mixing with a stopped-flow apparatus. From just after the mixing, this transition process was monitored in situ by time-resolved small-angle X-ray scattering. In this manner, we were able to derive the direct structural information as a function of time during the nanotube formation. The results revealed that disklike aggregates initially formed, which then grew and closed to produce a tubular structure.

Encapsulation of Albumin in Organic Nanotube Channel: Structural Investigation by Small-Angle X-ray Scattering.

Rationally designed bolaamphiphiles are known to self-assemble into nanotube structures. Herein, we report the formation of an inclusion complex between a nanotube and bovine serum albumin (BSA). This complex formation was confirmed by ultraviolet (UV) absorbance and electrophoretic light scattering (ELS). The structure for different mixing ratios of BSA to the nanotube was also investigated by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). The structural analysis with our proposed model has revealed that the BSA molecules were contained within the internal space of the nanotube with maintenance of its tubular structure.

Cross-sectional structures of a molecular monolayer nanotube explored with SAXS: evidence for the parallel orientation of the headgroups in asymmetric bolaamphiphiles.

We investigated the cross-sectional structure of a molecular monolayer nanotube self-assembled from asymmetric bolaamphiphiles having two different hydrophilic headgroups. Small-angle X-ray scattering measurements clarified that the glucose and amino headgroups form the exterior and interior surfaces of the nanotube, respectively.

Supramolecular Self-Assembly into Biofunctional Soft Nanotubes: From Bilayers to Monolayers.

The inner and outer surfaces of bilayer-based lipid nanotubes can be hardly modified selectively by a favorite functional group. Monolayer-based nanotubes display a definitive difference in their inner and outer functionalities if bipolar wedge-shaped amphiphiles, so-called bolaamphiphiles, as a constituent of the monolayer membrane pack in a parallel fashion with a head-to-tail interface. To exclusively form unsymmetrical monolayer lipid membranes, we focus herein on the rational molecular design of bolaamphiphiles and a variety of self-assembly processes into tubular architectures. We first describe the importance of polymorph and polytype control and then discuss diverse methodologies utilizing a polymer template, multiple hydrogen bonds, binary and ternary coassembly, and two-step self-assembly. Novel biologically important functions of the obtained soft nanotubes, brought about only by completely unsymmetrical inner and outer surfaces, are discussed in terms of protein refolding, drug nanocarriers, lectin detection, a chiral inducer for achiral polymers, the tailored fabrication of polydopamine, and spontaneous nematic alignment.

Effect of Photoinduced Size Changes on Protein Refolding and Transport Abilities of Soft Nanotubes.

Self-assembly of azobenzene-modified amphiphiles (Glyn Azo, n=1-3) in water at room temperature in the presence of a protein produced nanotubes with the protein encapsulated in the channels. The Gly2 Azo nanotubes (7 nm internal diameter [i.d.]) promoted refolding of some encapsulated proteins, whereas the Gly3 Azo nanotubes (13 nm i.d.) promoted protein aggregation. Although the 20 nm i.d. channels of the Gly1 Azo nanotubes were too large to influence the encapsulated proteins, narrowing of the i.d. to 1 nm by trans-to-cis photoisomerization of the azobenzene units of the Gly1 Azo monomers packed in the solid bilayer membranes led to a squeezing out of the proteins into the bulk solution and simultaneously enhanced their refolding ratios. In contrast, photoinduced transformation of the Gly2 Azo nanotubes to short nanorings (<40 nm) with a large i.d. (28 nm) provided no further refolding assistance. We thus demonstrate that pertubation by the solid bilayer membrane wall of the nanotubes is important to accelerate refolding of the denatured proteins during their transport in the narrow nanotube channels.

Molecular-Level Understanding of the Encapsulation and Dissolution of Poorly Water-Soluble Ibuprofen by Functionalized Organic Nanotubes Using Solid-State NMR Spectroscopy.

A comprehensive study of the encapsulation and dissolution of the poorly water-soluble drug ibuprofen (IBU) using two types of organic nanotubes (ONT-1 and ONT-2) was conducted. ONT-1 and ONT-2 had similar inner and outer diameters, but these surfaces were functionalized with different groups. IBU was encapsulated by each ONT via solvent evaporation. The amount of IBU in the ONTs was 9.1 and 29.2 wt % for ONT-1 and ONT-2, respectively. Dissolution of IBU from ONT-1 was very rapid, while from ONT-2 it was slower after the initial burst release. One-dimensional (1D) (1)H, (13)C, and two-dimensional (2D) (1)H-(13)C solid-state NMR measurements using fast magic-angle spinning (MAS) at a rate of 40 kHz revealed the molecular state of the encapsulated IBU in each ONT. Extremely mobile IBU was observed inside the hollow nanosapce of both ONT-1 and ONT-2 using (13)C MAS NMR with a single pulse (SP) method. Interestingly, (13)C cross-polarization (CP) MAS NMR demonstrated that IBU also existed on the outer surface of both ONTs. The encapsulation ratios of IBU inside the hollow nanospaces versus on the outer surfaces were calculated by waveform separation to be approximately 1:1 for ONT-1 and 2:1 for ONT-2. Changes in (13)C chemical shifts showed the intermolecular interactions between the carboxyl group of IBU and the amino group on the ONT-2 inner surface. The cationic ONT-2 could form the stronger electrostatic interactions with IBU in the hollow nanosapce than anionic ONT-1. On the other hand, 2D (1)H-(13)C NMR indicated that the hydroxyl groups of the glucose unit on the outer surface of the ONTs interacted with the carboxyl group of IBU in both ONT-1 and ONT-2. The changes in peak shape and chemical shift of the ONT glucose group after IBU encapsulation were larger in ONT-2 than in ONT-1, indicating a stronger interaction between IBU and the outer surface of ONT-2. The smaller amount of IBU encapsulation and rapid IBU dissolution from ONT-1 could be due to the weak interactions both at the outer and inner surfaces. Meanwhile, the stronger interaction between IBU and the inner surface of ONT-2 could suppress IBU dissolution, although the IBU on the outer surface of ONT-2 was released soon after dispersal in water. This study demonstrates that the encapsulation amount and the dissolution rates of poorly water-soluble drugs, a class which makes up the majority of new drug candidates, can be controlled using the functional groups on the surfaces of ONTs by considering the host-guest interactions.

Lipid Nanotube Tailored Fabrication of Uniquely Shaped Polydopamine Nanofibers as Photothermal Converters.

Helically coiled and linear polydopamine (PDA) nanofibers were selectively fabricated with two different types of lipid nanotubes (LNTs) that acted as templates. The obtained coiled PDA-LNT hybrid showed morphological advantages such as higher light absorbance and photothermal conversion effect compared to a linear counterpart. Laser irradiation of the coiled PDA-LNT hybrid induced a morphological change and subsequent release of the encapsulated guest molecule. In cellular experiments, the coiled PDA-LNT efficiently eliminated HeLa cells because of its strong affinity with the tumor cells. This work illustrates the first approach to construct characteristic morphologies of PDA nanofibers using LNTs as simple templates, and the coiled PDA-LNT hybrid exhibits attractive photothermal features derived from its unique coiled shape.

Soft nanotubes acting as confinement effecters and chirality inducers for achiral polythiophenes.

Depending on their nanochannel sizes, soft nanotubes were able to not only control the conformation and aggregation state of encapsulated achiral polythiophene boronic acids but also induce chirality in the polythiophene chains that exhibit chiral recognition abilities for D, L-sugars.

Qualitative/chiral sensing of amino acids by naked-eye fluorescence change based on morphological transformation and hierarchizing in supramolecular assemblies of pyrene-conjugated glycolipids.

Supramolecular assemblies of fluorescent glycolipids exhibited molecular packing rearrangement as well as morphological transformation, in response to amino acid analytes. Naked-eye detectable fluorescence color changes and hydrogel formation as the result of the amplification of the molecular- and nanometer-scaled changes enabled not only qualitative analysis but also chiral sensing of a specific amino acid among 20 amino acids.

Photoinduced morphological transformations of soft nanotubes.

In water, synthetic amphiphiles composed of a photoresponsive azobenzene moiety and an oligoglycine hydrogen-bonding moiety selectively self-assembled into nanotubes with solid bilayer membranes. The nanotubes underwent morphological transformations induced by photoisomerization of the azobenzene moiety within the membranes, and the nature of the transformation depended on the number of glycine residues in the oligoglycine moiety (i.e., on the strength of intermolecular hydrogen bonding). Upon UV-light irradiation of nanotubes prepared from amphiphiles with the diglycine residue, trans-to-cis isomerization induced a transformation from nanotubes (inner diameter (i.d.) 7 nm), several hundreds of nanometers to several tens of micrometers in length, to imperfect nanorings (i.d. 21-38 nm). The cis-to-trans isomerization induced by continuous visible-light irradiation resulted in the stacking of the imperfect nanorings to form nanotubes with an i.d. of 25 nm and an average length of 310 nm, which were never formed by a self-assembly process. Time-lapse fluorescence microscopy enabled us to visualize the transformation of nanotubes with an i.d. of 20 nm (self-assembled from amphiphiles with the monoglycine residue) to cylindrical nanofibers with an i.d. of 1 nm; shrinkage of the hollow cylinders started at the two open ends with simultaneous elongation in the direction of the long axis.

Two-step naked-eye detection of lectin by hierarchical organization of soft nanotubes into liquid crystal and gel phases.

Depending on the concentration of a lectin analyte, supramolecular soft nanotubes, bearing recognition sites immobilized on the outer surface through ethylene glycol chains, hierarchically organized into naked-eye-detectable liquid crystals and hydrogels.

Spontaneous nematic alignment of a lipid nanotube in aqueous solutions.

The dispersibility and liquid crystal formation of a self-assembled lipid nanotube (LNT) was investigated in a variety of aqueous solutions. As the lipid component, we chose a bipolar lipid with glucose and tetraglycine headgroups, which self-assembled into an LNT with a small outer diameter of 16 to 17 nm and a high axial ratio of more than 310. The LNT gave a stable colloidal dispersion in its dilute solutions and showed spontaneous liquid crystal (LC) alignment at relatively low concentrations and in a pH region including neutral pH. The LNT samples with shorter length distributions were prepared by sonication, and the relationship between the LNT axial ratio and the minimum LC formation concentration was examined. The robustness of the LNT made the liquid crystal stable in mixed solvents of water/ethanol, water/acetone, and water/tetrahydrofuran (1:1 by volume) and at a temperature of up to 90 °C in water. The observed colloidal behavior of the LNT was compared to those of similar 1D nanostructures such as a phospholipid tubule.