Production of Noble-Metal Nanohelices Based on Nonlinear Dynamics in Electrodeposition of Binary Copper Alloys.

Spatiotemporal pattern formation is dynamic self-organization widely observed in nature and drives various functions. Among these functions, chirality plays a central role. The relationship between dynamic self-organization and chirality has been an open question; therefore, the production of chiral nanomaterials by dynamic self-organization has not been achieved. Here, we show that the confinement of a two-dimensional spatiotemporal micropattern via the electrodeposition of a binary Cu alloy into a nanopore induces mirror symmetry breaking to produce a helical nanostructure of the noble-metal component although it is still not yet possible to control the handedness at this stage. This result suggests that spatiotemporal symmetry breaking functions as a mirror symmetry breaking if cylindrical pores are given as the boundary condition. This study can be a model system of how spatiotemporal symmetry breaking plays a role in mirror symmetry breaking, and it proposes a new approach to producing helical nanomaterials through dynamic self-organization.

Chiral Perovskite Nanocrystal Growth inside Helical Hollow Silica Nanoribbons.

Helical perovskite nanocrystals (H-PNCs) were prepared using nanometric silica helical ribbons as platforms for the in situ growth of the crystals using the supersaturated recrystallization method. The H-PNCs grow inside nanometric helical porous silica, and their handedness is determined by the handedness of porous silica templates. They show both strong induced circular dichroism (CD) and strong induced circularly polarized luminescence (CPL) signals, with high dissymmetry g-factors. Right-handed and left-handed PNCs show respectively positive and negative CD and CPL signals, with a dissymmetry g-factor (abs and lum) of ∼±2 × 10-2. Simulations based on the boundary element method demonstrate that the circular dichroism originates from the chiral shape of H-PNCs.

Chirality induction to achiral molecules by silica-coated chiral molecular assemblies.

Hybrid silica-organic nanohelices are used to organize a large variety of nonchiral small organic molecules or inorganic anions to nanometer-sized assemblies. Such chiral organization of achiral molecules induces chiroptical properties as detected by vibrational or electronic circular dichroism (CD), as well as from circularly polarized luminescence (CPL).

Optically Active Perovskite CsPbBr3 Nanocrystals Helically Arranged on Inorganic Silica Nanohelices.

Perovskite nanocrystals (PNCs) exhibit excellent absorption and luminescent properties. Inorganic silica right (or left) handed nanohelices are used as chiral templates to induce optically active properties to CsPbBr3 PNCs grafted on their surfaces. In suspension, PNCs grafted on the nanohelices do not show any detectable chiroptical properties. In contrast, in a dried film state, they show large circular dichroism (CD) and circularly polarized luminescence (CPL) signals with dissymmetric factor up to 6 × 10-3. Grazing incidence X-ray scattering, tomography, and cryo-electron microscopy (EM) have shown closely and helically packed PNCs on the dried helices and much more loosely organized PNCs on helices in suspension. Simulations based on the coupled dipole method (CDM) demonstrate that the CD comes from the dipolar interaction between PNC assembled into a chiral structure and the CD decreases with the interparticle distance.

Hierarchical chirality expression of gemini surfactant aggregates via equilibrium between chiral nucleotide and nonchiral mono-anions.

The assembling behaviors of nonchiral dicationic amphiphilic molecules (gemini) in the presence of the mixture of chiral anionic nucleotides and nonchiral anions are investigated. We demonstrate that subtle balance of various physico-chemical parameters and the competition between chiral and nonchiral anions at the interface of gemini assemblies influences the expression of molecular chirality at the micrometer scale through the hierarchical molecular assembly.

Mitigating Human IAPP Amyloidogenesis In Vivo with Chiral Silica Nanoribbons.

Amyloid fibrils generally display chirality, a feature which has rarely been exploited in the development of therapeutics against amyloid diseases. This study reports, for the first time, the use of mesoscopic chiral silica nanoribbons against the in vivo amyloidogenesis of human islet amyloid polypeptide (IAPP), the peptide whose aggregation is implicated in type 2 diabetes. The thioflavin T assay and transmission electron microscopy show accelerated IAPP fibrillization through elimination of the nucleation phase and shortening of the elongation phase by the nanostructures. Coarse-grained simulations offer complementary molecular insights into the acceleration of amyloid aggregation through their nonspecific binding and directional seeding with the nanostructures. This accelerated IAPP fibrillization translates to reduced toxicity, especially for the right-handed silica nanoribbons, as revealed by cell viability, helium ion microscopy, as well as zebrafish embryo survival, developmental, and behavioral assays. This study has implicated the potential of employing chiral nanotechnologies against the mesoscopic enantioselectivity of amyloid proteins and their associated diseases.

Direct Observation of Siloxane Chirality on Twisted and Helical Nanometric Amorphous Silica.

Synthesis of chiral inorganic or hybrid nanomaterials through sol-gel transcription of chiral organic templates has attracted a great deal of interest for more than a decade. However, the chiral nature of these inorganic matrices has never been directly observed. For the first time, we report a direct evaluation of chirality on noncrystalline silica chiral nanoribbons by vibrational circular dichroism (VCD) measurements. Strong Cotton effect around 1150-1000 cm-1 from Si-O-Si asymmetric stretching vibration was observed. Surprisingly, calcination of these hybrid nanoribbons doubled the intensity of Cotton effects. On the basis of transmission electron microscopy observations, IR, VCD, NMR, and Raman spectroscopies, we demonstrate that the silica chirality originates from twisted siloxane network composed of chiral arrangement of the Si-O-Si bonds. Our findings clearly prove the presence of chiral organization of amorphous silica network, making them very promising chiral platforms for chiral recognition, optical applications, or asymmetric catalysis.

Induction of Strong and Tunable Circularly Polarized Luminescence of Nonchiral, Nonmetal, Low-Molecular-Weight Fluorophores Using Chiral Nanotemplates.

A new strategy is described for generating strong circularly polarized luminescence with highly tunable emission bands through chiral induction in nonchiral, totally organic, low-molecular-weight fluorescent dyes by chiral nanotemplate systems. Our approach allows the first systematic investigation to clarify the correlation between the circular dichroism and circularly polarized luminescence intensities. As a result, a dilute solution system with the highest circularly polarized luminescence intensity achieved to date and a dissymmetry factor of over 0.1 was identified.

Fractionation of beech wood cell walls into digestible cellulose-rich residues and photoluminescent lignin-rich precipitates via semi-flow hot-compressed water treatment with 2-naphthol.

Utilization of cell wall components of woody biomass has attracted attention as alternatives for fossil fuels towards a sustainable society. A semi-flow hydrothermal treatment was used to fractionate the beech (Fagus crenata) wood into cellulose-rich residues and lignin-rich precipitates. The enzymatic saccharification of the cellulose component in the residue was enhanced significantly because the preferential delignification from the secondary wall increased enzyme accessibility. Meanwhile, the precipitated lignin was soluble in organic solvent and exhibited clear photoluminescence (PL) according to the chromophore distances. Furthermore, the carbocation scavenger, 2-naphthol, was impregnated into the beech wood to inhibit the lignin re-condensation reaction. As a result, the digestibility of the cellulose component in the residue increased because unproductive enzymatic binding of lignin and lignin re-condensation were both suppressed. In addition, the PL intensity of the precipitates was significantly enhanced, indicating that 2-naphthol bound to the lignin molecules influenced the PL properties. Overall, fractionation using a semi-flow hydrothermal treatment efficiently uses both polysaccharides and lignin, especially the impregnation of 2-naphthol provided advantages for both saccharides and lignin. Monosaccharides can be converted into valuable products via a sugar platform, and the lignin precipitates exhibit useful PL properties that give them significant potential as a feedstock for numerous valuable materials, such as fluorescence reagents and spectral conversion agents. The results presented herein provide insights that are crucial for the comprehensive utilization of cell wall components for sustainable biorefinery systems.

Modulation of circularly polarized luminescence by swelling of microgels functionalized with enantiopure [Ru(bpy)3]2+ luminophores.

Chemoresponsive microgels functionalized with enantiomeric Δ- or Λ-[Ru(bpy)3]2+ showed tunable chiroptical properties upon swelling and shrinking. The tuning is triggered by a modulation of the local mobility of [Ru(bpy)3]2+ upon addition of fructose, controlling interactions and distances between [Ru(bpy)3]2+ and phenylboronic acid.

Solubilization of sulfuric acid lignin by ball mill treatment with excess amounts of organic compounds.

In order to improve the solubility of sulfuric acid lignin (SL) in N,N-dimethylformamide (DMF), dry ball milling with excess amounts of additives such as l-tartaric acid was performed. Although the ball-milled SL without any additives was not soluble in DMF, when the SL was ball milled with an excessive amount of l-tartaric acid (the concentration of SL to be 0.1%), the dispersion and solubility of SL in DMF detected by the dynamic light scattering was greatly improved. Furthermore, the DMF solution showed clear photoluminescence, indicating that the distance between luminophores was modulated due to dispersion on the nanoscale. The structural analysis of the isolated lignin showed a decrease in molecular weight and the introduction of carboxylic acid groups. In other words, the introduction of hydrophilic functional groups into the lignin and simultaneously decrease in the molecular weight due to the cleavage of lignin linkages is considered to result in good dispersion in DMF on both the micro and macro scales. Similar effects were observed with the other chemicals containing several hydrophilic groups such as citric acid, d-glucose, and polyacrylic acid. Furthermore, this method is applicable to various lignins other than SL, and it is expected to utilize unused lignin resources.

Controlled packing of chiral assembly scaffolds to promote chiral J-aggregation of carbocyanine dyes.

Controlled aggregation of dyes is crucial to achieve their desired optical and electronic properties. Here, we report the induction of chiral J-aggregation of carbocyanine dyes by using lysine-derived amphiphile assemblies as scaffolds in water. The molecular structure of the amphiphiles affected the packing of the assembly. The tight packing with some flexibility promoted the formation of J-aggregates of the dyes with strong chiroptical properties.

Sequential chiral induction between organic and inorganic supramolecular helical assemblies for the in situ formation of chiral carbon dots.

Self-organised helical bilayers of dicationic gemini surfactants confined in helical silica nanospace were transformed in situ to carbon dots (CDots) via pyrolysis. These water-dispersible CDots exhibit electronic absorption spanning the UV and visible range and possess symmetrical circular dichroism (CD) signals, the sign of which depends on the handedness of the helices.

Tunable Light Emission from Lignin: Various Photoluminescence Properties Controlled by the Lignocellulosic Species, Extraction Method, Solvent, and Polymer.

This report describes the tunable light emission from lignin, which was achieved by carefully selecting the lignocellulosic species, extraction method, solvent, and polymer. Lignins comprising various taxonomic species with distinct primary structures exhibited diverse photoluminescence (PL) intensities and spectral patterns. Investigations probing how the solvent affects the PL properties revealed that the PL quenching phenomenon originated from the decreasing distance between aromatic moieties (luminophores). Therefore, polymers can play key roles as media to modulate the distance between luminophores, and the PL intensity can be enhanced by employing a relatively stiff polymer. In terms of the emission color, the PL spectral pattern can be tuned by changing the lignin primary structures or by deprotonating the phenolic hydroxyl groups. By modulating these influencing factors, various light emissions were obtained from lignins in solutions and transparent solid materials.

Cooperative interaction between organic and inorganic moieties in hybrid silica nanohelices for enantioselective interaction.

Hybrid nanometric helical structures formed by the molecular assemblies of dicationic gemini surfactants with tartrate counterions covered with helical silica walls interact differently with matching or mismatching enantiomers of the tartrate. The difference of the interaction is based on the cooperativity between the chiral crystalline gemini surfactant molecular organization/conformation and the rigid chiral nanospace formed by the helical silica wall.

Significance of boost radiotherapy in early invasive ductal breast cancer with ductal carcinoma in situ component under negative surgical margins.

We hypothesize that there is a risk of ipsilateral breast tumor recurrence (IBTR) in surgical margin-free invasive ductal carcinoma (IDC) in the presence of ductal carcinoma in situ (DCIS) component affecting surgical margins in early stage. From 1990 to 2014, 343 patients with IDC in which the DCIS component constitute have received radiotherapy (RT) following breast-conserving surgery (BCS). All patients received whole breast irradiation with a prescribed dose of 50 Gy in 20 fractions (four times a week). This one-arm cohort with boost RT (253 patients) was compared for IBTR with a non-cohort group receiving no boost RT because of freedom from positive margins (90 patients). Median observation months were 98 (boost group) vs 119 (no boost group), respectively. The 15-year local recurrence-free survival (LRFS) rates were 98.5% and 85.6% in the boost and no boost groups, respectively (Cox proportional hazards model univariate analysis; p = 0.013, HR 0.13). Similarly, for other background factors, there was a significant difference in the LRFS between age groups. The 15-year LRFS rate was 91.8% in patients aged 45 years or younger and 94.6% in patients older than 46 years (p = 0.031, HR 0.21), respectively. Only these two factors were independently significant in Cox proportional hazards model multivariate analysis. IBTR risk in margin-free IDC with DCIS component was independently decreased by boost RT in the cohort setting. Tumor size, extensive intraductal component (EIC), boost dose, the presence of lymph node (LN) metastasis and hormonal therapy were not IBTR risk factors in this study.

Chiral optical scattering from helical and twisted silica nanoribbons.

Helical and twisted silica nanoribbons, deposited in an in-plane direction and with a random orientation, on a quartz substrate showed chiral optical scattering, and the helical nanoribbons had a g-factor of the order of 10-2 below 250 nm. Their signs depend on the handedness of the nanohelices. The effect of the morphology and the orientation of the helices on the chiral optical scattering were investigated with simulations via the boundary element method.

Chirality Induction to CdSe Nanocrystals Self-Organized on Silica Nanohelices: Tuning Chiroptical Properties.

CdSe nanocrystals (NCs) were grafted on chiral silica nanoribbons, and the mechanism of resulting chirality induction was investigated. Because of their chiral organization, these NCs show optically active properties that depend strongly on their grafting densities and sizes of the NCs. The effect of the morphology of the chiral silica templates between helical (cylindrical curvature) vs twisted (saddle like curvature) ribbons was investigated. The g-factor of NCs-silica helical ribbons is larger than that of the NCs-silica twisted ribbons. Finally, rod-like NCs (QR) with different lengths were grafted on the twisted silica ribbons. Interestingly, their grafting direction with respect to the helix surface changed from side-grafting for short QR to tip-grafting for long rods and the corresponding CD spectra switched signs.

Lanthanide ion-doped silica nanohelix: a helical inorganic network acts as a chiral source for metal ions.

We demonstrate that lanthanide ions doped in nanometrical silica helices with a chirally arranged siloxane network without any organic mediates show induced chiroptical properties such as circular dichroism and circularly polarized luminescence.

Lessons for pharmacogenomics studies: association study between CYP2D6 genotype and tamoxifen response.

We earlier reported a significant association between the cytochrome P450 2D6 (CYP2D6) genotype and the clinical outcome in 282 Japanese breast cancer patients receiving tamoxifen monotherapy. Although many research groups have provided evidence indicating the CYP2D6 genotype as one of the strongest predictors of tamoxifen response, the results still remain controversial. We hypothesized that concomitant treatment was one of the causes of these controversial results. We then studied 167 breast cancer patients who received tamoxifen-combined therapy to evaluate the effects of concomitant treatment on the association analysis and observed no significant association between CYP2D6 genotype and recurrence-free survival (P=0.44, hazard ratio: 0.64, 95% confidential interval: 0.20-1.99 in patients with two variant alleles vs. patients without a variant allele). When we carried out two subgroup analyses for nodal status and tumor size, we observed a positive association between the CYP2D6 genotype and the clinical outcome only in patients who received tamoxifen monotherapy. This study explained a part of the discrepancies among the reported results.