Keratin Microspheres as Promising Tool for Targeting Follicular Growth.

Skin is the body barrier that constrains the infiltration of particles and exogenous aggression, in which the hair follicle plays an important role. Recent studies have shown that small particles can penetrate the skin barrier and reach the hair follicle, making them a potential avenue for delivering hair growth-related substances. Interestingly, keratin-based microspheres are widely used as drug delivery carriers in various fields. In this current study, we pursue the effect of newly synthesized 3D spherical keratin particles on inducing hair growth in C57BL/6 male mice and in human hair follicle dermal papilla cells. The microspheres were created from partially sulfonated, water-soluble keratin. The keratin microspheres swelled in water to form spherical gels, which were used for further experiments. Following topical application for a period of 20 days, we observed a regrowth of hair in the previously depleted area on the dorsal part of the mice in the keratin microsphere group. This observation was accompanied by the regulation of hair-growth-related pathways as well as changes in markers associated with epidermal cells, keratin, and collagen. Interestingly, microsphere keratin treatment enhanced the cell proliferation and the expression of hair growth markers in dermal papilla cells. Based on our data, we propose that 3D spherical keratin has the potential to specifically target hair follicle growth and can be employed as a carrier for promoting hair growth-related agents.

Poly(lactic acid) stereocomplex microspheres as thermally tolerant optical resonators.

Thermally tolerant polymer optical resonators are fabricated from a stereocomplex of poly(L-lactic acid) and poly(D-lactic acid) through the oil-in-water miniemulsion method. The thermal stability of the microspheres of the stereocomplex poly(lactic acid) (SC-PLA) is superior to that of the homochiral poly(lactic acid) (HC-PLA). As a result of the high thermal stability, the optical resonator properties of the SC-PLA microspheres are preserved at an elevated temperature of up to 230 °C, which is 70 °C higher than that of microspheres formed from HC-PLA.

Pathway Complexity in Nanotubular Supramolecular Polymerization: Metal-Organic Nanotubes with a Planar-Chiral Monomer.

Here, we report an anomalous pathway complexity in the supramolecular polymerization of a chiral monomer, which displays an unusual chiroptical feature that does not follow any of the known stereochemical rules such as "chiral self-sorting" and "majority rule". We newly developed a planar-chiral ferrocene-cored tetratopic pyridyl monomer FcL, which underwent AgBF4-mediated supramolecular polymerization to give nanotubes FcNTs composed of metal-organic nanorings FcNRs. Although FcNRs must be homochiral because of a strong geometrical constraint, FcNRs were formed even efficiently from racemic FcL and AgBF4. Detailed studies revealed the presence of two competing pathways for producing homochiral FcNRs as the constituents of FcNTs: (i) spontaneous cyclization of initially formed acyclic polymers -[FcL-Ag+]n- and (ii) template (FcNR)-assisted cyclization via a Ag+···Ag+ metallophilic interaction. The dominance of the two pathways changes depending on the %ee of chiral FcL. Namely, when the %ee of FcL is high, -[FcL-Ag+]n- must contain sufficiently long homochiral sequences that can be readily cyclized into FcNRs. Meanwhile, when the %ee of FcL is low, the homochiral sequences in -[FcL-Ag+]n- must be short and therefore are hardly eligible for spontaneous cyclization. Why were FcNRs formed? Even though the probability is very low, homochiral -[FcL-Ag+]n- can be statistically generated and undergo spontaneous cyclization to give FcNRs minutely. We found that FcNRs can be amplified by heterochirally templating their own synthesis using metallophilic interaction. Because of this stereochemical preference, the growth of FcNRs into FcNTs via the template-assisted mechanism occurs only when both (R,R)FcL and (S,S)FcL are present in the polymerization system.

Molecular and Supramolecular Designs of Organic/Polymeric Micro-photoemitters for Advanced Optical and Laser Applications.

ConspectusFor optical and electronic applications of supramolecular assemblies, control of the hierarchical structure from nano- to micro- and millimeter scale is crucial. Supramolecular chemistry controls intermolecular interactions to build up molecular components with sizes ranging from several to several hundreds of nanometers using bottom-up self-assembly process. However, extending the supramolecular approach up to a scale of several tens of micrometers to construct objects with precisely controlled size, morphology, and orientation is challenging. Especially for microphotonics applications such as optical resonators and lasers, integrated optical devices, and sensors, a precise design of a micrometer-scale object is required. In this Account, we review the recent progress on precise control of microstructures from π-conjugated organic molecules and polymers, which work as micro-photoemitters and are suitable for optical applications.After the introduction on the importance of the control of the hierarchical structures from molecular assembly, we review supramolecular methodology for assembling molecules and supramolecules to form microstructures such as spheres and polygons with precisely controlled morphology and molecular orientations. The resultant microstructures act as anisotropic emitters of circularly polarized luminescence. We report that synchronous crystallization of π-conjugated chiral cyclophanes forms concave hexagonal pyramidal microcrystals with homogeneous size, morphology, and orientation, which clearly paves the way for the precise control of skeletal crystallization under kinetic control. Furthermore, we show microcavity functions of the self-assembled micro-objects. The self-assembled π-conjugated polymer microspheres work as whispering gallery mode (WGM) optical resonators, where the photoluminescence exhibits sharp and periodic emission lines. The spherical resonators with molecular functions act as long-distance photon energy transporters, convertors, and full-color microlasers. Fabrication of microarrays with photoswitchable WGM microresonators by the surface self-assembly technique realizes optical memory with physically unclonable functions of WGM fingerprints. All-optical logic operations are demonstrated by arranging the WGM microresonators on synthetic and natural optical fibers, where the photoswitchable WGM microresonators act as a gate for light propagation via a cavity-mediated energy transfer cascade. Meanwhile, the sharp WGM emission line is appropriate for utilization as optical sensors for monitoring the mode shift and mode splitting. The resonant peaks sensitively respond to humidity change, absorption of volatile organic compounds, microairflow, and polymer decomposition by utilizing structurally flexible polymers, microporous polymers, nonvolatile liquid droplets, and natural biopolymers as media of the resonators. We further construct microcrystals from π-conjugated molecules with rods and rhombic plates, which act as WGM laser resonators with light-harvesting function. Our developments, precise design and control of organic/polymeric microstructures, form a bridge between nanometer-scale supramolecular chemistry and bulk materials and pave the way toward flexible micro-optics applications.

Degradable optical resonators as in situ microprobes for microscopy-based observation of enzymatic hydrolysis.

Optical resonators work as precise physical and chemical sensors. Here, we assemble a whispering gallery mode resonator from a natural polymer, fibroin protein, and successfully observe its catalytic degradation reaction as a spectral shift. This methodology will contribute to the precise in situ observation of biological reactions by optical microscopy.

Functions and fundamentals of porous molecular crystals sustained by labile bonds.

Organic molecules favour dense packing so that they can maximise the enthalpic gain upon solidification. Multidentate organic molecules that can form reticular bonding networks have been considered essential to overcome this tendency and assemble the molecules in a porous manner. Meanwhile, contrary to this understanding, a few organic molecules have been found to form porous molecular crystals by simply stacking with each other via van der Waals forces or analogous very weak noncovalent interactions. Although the porous molecular crystals were relatively rare in the 2000s due to the difficulty in the synthesis, their number has increased in the last decade, and their functional uniqueness has been unveiled eventually. This article reviews the recent advances in such functional porous molecular crystals. Particularly, thermal stability, processability, structural dynamicity, reactivity, and self-healing ability are highlighted. In addition, fundamental principles behind their functionalities, including the history, energetics, and the effect of crystallization solvent, are also reviewed.

Synchronous assembly of chiral skeletal single-crystalline microvessels.

Skeletal or concave polyhedral crystals appear in a variety of synthetic processes and natural environments. However, their morphology, size, and orientation are difficult to control because of their highly kinetic growth character. We report a methodology to achieve synchronous, uniaxial, and stepwise growth of micrometer-scale skeletal single crystals from planar-chiral double-decker molecules. Upon drop-casting of a heated ethanol solution onto a quartz substrate, the molecules spontaneously assemble into standing vessel-shaped single crystals uniaxially and synchronously over the wide area of the substrate, with small size polydispersity. The crystal edge is active even after consumption of the molecules and resumes stereoselective growth with successive feeding. The resultant morphology can be packed into polycyclic aromatic hydrocarbon-like microarchitectures and behaves as a microscopic container.

Polymer Optical Microcavity Sensor for Volatile Organic Compounds with Distinct Selectivity toward Aromatic Hydrocarbons.

A whispering-gallery mode (WGM) optical resonance sensor for volatile organic compounds (VOCs) is developed from polystyrene (PS) microspheres doped with fluorescent ß-cyano-appended oligo(p-phenylenevinylene) (ß-COPV). The ß-COPV-doped PS microspheres (MSCOPV) are formed by the miniemulsion method in a binary solvent. MSCOPV expand upon permeation of VOCs into the PS matrix and exhibit a spectral shift of the WGM resonance peak. The permeation efficiency is highly dependent on the chemical affinity between the analyte and the polymer matrix, with exceptionally high selectivity toward aromatic hydrocarbons such as benzene, toluene, and xylenes (BTXs). The high selectivity and sensitivity of MSCOPV are in clear contrast to those of conventional WGM sensors that just detect VOCs nonpreferentially through adsorption onto the surface.

Intraspecific variations of the cytoplasmic male sterility genes orf108 and orf117 in Brassica maurorum and Moricandia arvensis, and the specificity of the mRNA processing.

The mitochondrial gene orf108, which is co-transcribed with atp1 and causes cytoplasmic male sterility in Brassica crops, is widely distributed across wild species and genera of Brassicaceae. However, to date, intraspecific variations in the presence of orf108 have not yet been studied, and the mechanisms underlying the wide distribution of the gene remain unclear. We analyzed the presence and sequence variations of orf108 in two wild species, Brassica maurorum and Moricandia arvensis. After polymerase chain reaction amplification of the 5' region of atp1 and the coding sequence of orf108, we determined the DNA sequences. Brassica maurorum and M. arvensis showed variations in the presence of orf108 or orf117 (orf108V117) both between and within accessions and were not fixed to the mitochondrial type with the male sterile genes. Sequencing of the amplicons showed that B. maurorum had orf108V117 instead of orf108. Sequencing also indicated mitochondrial heteroplasmy in the two species; in particular, in B. maurorum, one plant possessed both orf108 and orf108V117 sequences. These results suggest that substoichiometric shifting of mitochondrial genomes leads to the acquisition or loss of orf108. Furthermore, fertility restorer genes of the two species were involved in the processing of the mRNA of male sterility genes at different sites.

Robust Angular Anisotropy of Circularly Polarized Luminescence from a Single Twisted-Bipolar Polymeric Microsphere.

It has long been surmised that the circular polarization of luminescence (CPL) emitted by a chiral molecule or a molecular assembly should vary with the direction in which the photon is emitted. Despite its potential utility, this anisotropic CPL has not yet been demonstrated at the level of single molecules or supramolecular assemblies. Here we show that conjugated polymers bearing chiral side chains self-assemble into solid microspheres with a twisted bipolar interior, which are formed via liquid-liquid phase separation and subsequent condensation into a cholesteric lyotropic liquid crystalline mesophase. The resultant microspheres, when dispersed in methanol, exhibit CPL with a glum value as high as 0.23. The microspheres are mechanically robust enough to be handled with a microneedle under ambient conditions, allowing comprehensive examination of the angular anisotropy of CPL. The single microsphere is found to exhibit distinct angularly anisotropic birefringence and CPL with glum up to ∼0.5 in the equatorial plane, which is 2.5-fold greater than that along the polar axis. Such optically anisotropic solid materials are important for the application to next-generation microlight-emitting and visualizing devices as well as for fundamental optics studies of chiral light-matter interaction.

A single nucleotide substitution in the coding region of Ogura male sterile gene, orf138, determines effectiveness of a fertility restorer gene, Rfo, in radish.

Cytoplasmic male sterility (CMS) observed in many plants leads defect in the production of functional pollen, while the expression of CMS is suppressed by a fertility restorer gene in the nuclear genome. Ogura CMS of radish is induced by a mitochondrial orf138, and a fertility restorer gene, Rfo, encodes a P-type PPR protein, ORF687, acting at the translational level. But, the exact function of ORF687 is still unclear. We found a Japanese variety showing male sterility even in the presence of Rfo. We examined the pollen fertility, Rfo expression, and orf138 mRNA in progenies of this variety. The progeny with Type H orf138 and Rfo showed male sterility when their orf138 mRNA was unprocessed within the coding region. By contrast, all progeny with Type A orf138 were fertile though orf138 mRNA remained unprocessed in the coding region, demonstrating that ORF687 functions on Type A but not on Type H. In silico analysis suggested a specific binding site of ORF687 in the coding region, not the 5' untranslated region estimated previously, of Type A. A single nucleotide substitution in the putative binding site diminishes affinity of ORF687 in Type H and is most likely the cause of the ineffectiveness of ORF687. Furthermore, fertility restoration by RNA processing at a novel site in some progeny plants indicated a new and the third fertility restorer gene, Rfs, for orf138. This study clarified that direct ORF687 binding to the coding region of orf138 is essential for fertility restoration by Rfo.

Fluorescence Switchable Conjugated Polymer Microdisk Arrays by Cosolvent Vapor Annealing.

Depositing minute light emitters into a regular array is a basic but essential technique in display technology. However, conventional lithographic methodologies involve multistep and energy-consuming processes. Here, we develop a facile method in which organic and polymeric fluorescent dyes spontaneously aggregate to form a patterned microarray. We find that a thin film of fluorescent π-conjugated polymer transforms into micrometer-sized aggregates when exposed to binary organic vapor at ambient temperature. The arrayed microaggregates can be formed over the whole substrate surface when using a quartz substrate that is prepatterned with regular hydrophilic boxes and hydrophobic grids. The resultant microarray is applicable to optical memories and displays when photoswitchable fluorophores are doped into the polymer matrix.

Long-wavelength visible to near infrared photoluminescence from carbon-bridged styrylstilbene and thiadiazole conjugates in organic and aqueous media.

Donor-acceptor-donor conjugates composed of electron-donating carbon-bridged styrylstilbene (COPV2) and electron-accepting thiadiazole derivatives equipped with carbazolyl (Cz) terminators, Cz-COPV2-A-COPV2-Cz (A = benzothiadiazole (BTz), naphthobis(thiadiazole) (NTz), or benzobis(thiadiazole) (BBTz)), were newly synthesized and found to serve as efficient and stable long-wavelength photoluminescent dyes in organic and aqueous media. In particular, Cz-COPV2-BBTz-COPV2-Cz showed photoluminescence in the near infrared region (895-927 nm) with a photoluminescence quantum yield (PLQY) of up to 0.19 in cyclohexane and of 0.02-0.03 in THF/water mixtures. Its analogues with weaker acceptors, Cz-COPV2-BTz-COPV2-Cz and Cz-COPV2-NTz-COPV2-Cz, showed yellow to deep-red emission in organic solvents, with PLQYs of up to 0.71 in organic solvents and 0.45 in THF/water mixtures.

Solvophobicity-directed assembly of microporous molecular crystals.

Dense packing is a universal tendency of organic molecules in the solid state. Typical porous crystals utilize reticular strong intermolecular bonding networks to overcome this principle. Here, we report a solvophobicity-based methodology for assembling discrete molecules into a porous form and succeed in synthesizing isostructural porous polymorphs of an amphiphilic aromatic molecule Py6Mes. A computational analysis of the crystal structure reveals the major contribution of dispersion interaction as the driving force for assembling Py6Mes into a columnar stacking while the columns are sterically salient and form nanopores between them. The porous packing is facilitated particularly in solvents with weak dispersion interaction due to the solvophobic effect. Conversely, solvents with strong dispersion interaction intercalate between Py6Mes due to the solvophilic effect and provide non-porous inclusion crystals. The solvophobicity-directed polymorphism is further corroborated by the polymorphs of Py6Mes-analogues, m-Py6Mes and Ph6Mes.

Molecular simulation on the stability and adsorption properties of choline-based ionic liquids/IRMOF-1 hybrid composite for selective H2S/CO2 capture.

The compatibility and performance of an Isoreticular Metal-Organic Frameworks (IRMOF-1) impregnated with choline-based ionic liquids (ILs) for selective adsorption of H2S/CO2, were studied by molecular dynamics (MD) simulation. Cholinium alanate ([Chl][Ala]) was nominated as the suitable IL for impregnation into IRMOF-1, consistent with the low RMSD values (0.546 nm, 0.670 nm, 0.776 nm) at three IL/IRMOF-1 w/w ratios (WIL/IRMOF-1 = 0.4, 0.8, and 1.2). The [Chl]+ and [Ala]- ion pair was located preferentially around the carboxylate group within the IRMOF-1 framework, with the latter interacting strongly with the host than the [Chl]+. Results of radius of gyration (Rg) and root mean square displacement (RMSD) revealed that a ratio of 0.4 w/w of IL/IRMOF-1 (Rg = 1.405 nm; RMSD = 0.546 nm) gave the best conformation to afford an exceptionally stable IL/IRMOF-1 composite. It was discovered that the IL/IRMOF-1 composite was more effective in capturing H2S and CO2 compared to pristine IRMOF-1. The gases adsorbed in higher quantities in the IL/IRMOF-1 composite phase compared to the bulk phase, with a preferential adsorption for H2S, as shown by the uppermost values of adsorption ( [Formula: see text] = 17.954 mol L-1 bar-1) and an adsorption selectivity ( [Formula: see text] = 43.159) at 35 IL loading.

Facile light-initiated radical generation from 4-substituted pyridine under ambient conditions.

Photochemical reactions that generate stable radical species under ambient conditions find unique applications in materials science. Here we present a facile photogeneration of a stable radical species from a 4-substituted pyridine derivative in the presence of water and air at room temperature. The radical generation reaction accompanies a visible colour change to green and is repeatable multiple times.

Single-Crystalline Optical Microcavities from Luminescent Dendrimers.

Microcrystallites are promising minute mirrorless laser sources. A variety of luminescent organic compounds have been exploited along this line, but dendrimers have been inapplicable owing to their fragility and extremely poor crystallinity. Now, a dendrimer family that overcomes these difficulties is presented. First-, second-, and third-generation carbazole (Cz) dendrimers with a carbon-bridged oligo(phenylenevinylene) (COPV2) core (GnCOPV2, n=1-3) assemble to form microcrystals. The COPV2 cores align uni/bidirectionally in the crystals while the Cz units in G2- and G3COPV2 align omnidirectionally. The dendrons work as light-harvesting antennas that absorb non-polarized light and transfer it to the COPV2 core, from which a polarized luminescence radiates. Furthermore, these crystals act as laser resonators, where the lasing thresholds are strongly coupled with the crystal morphology and the orientation of COPV2, which is in contrast with the conventional amorphous dendrimers.

Appearance of male sterile and black radishes in the progeny of cross between Raphanus raphanistrum and Raphanus sativus.

In addition to Ogura cytoplasmic male sterility (CMS), which is used extensively for F1 hybrid seed production in Brassicaceae crops, two other CMS systems, NWB CMS and DCGMS, have also been identified. The causal gene for the latter two CMS systems has been identified as a novel chimeric gene, orf463. We previously reported that orf463 is specific to black radish cultivars and that it is present in line 'RS-5' of Raphanus raphanistrum; however, the orf463 sequence in 'RS-5' differed from that of black radish cultivars. Though, R. raphanistrum with an orf463 sequence identical to that found in black radish cultivars was recently identified. We therefore sought to determine whether the orf463 gene in line 'RS-5' induces CMS in radishes. We crossed 'RS-5' as a female parent with a cultivated radish, 'Uchiki-Gensuke', as a male parent, and examined the gross plant morphology and pollen fertility of the resulting progeny. The F2 population contained both male sterile plants and plants with black roots. The findings showed that R. raphanistrum contains two types of orf463 genes that induce CMS, and that the origin of black radishes could be attributed to R. raphanistrum having orf463 gene.

Sigmoidally hydrochromic molecular porous crystal with rotatable dendrons.

Vapochromic behaviour of porous crystals is beneficial for facile and rapid detection of gaseous molecules without electricity. Toward this end, tailored molecular designs have been established for metal-organic, covalent-bonded and hydrogen-bonded frameworks. Here, we explore the hydrochromic chemistry of a van der Waals (VDW) porous crystal. The VDW porous crystal VPC-1 is formed from a novel aromatic dendrimer having a dibenzophenazine core and multibranched carbazole dendrons. Although the constituent molecules are connected via VDW forces, VPC-1 maintains its structural integrity even after desolvation. VPC-1 exhibits reversible colour changes upon uptake/release of water molecules due to the charge transfer character of the constituent dendrimer. Detailed structural analyses reveal that the outermost carbazole units alone are mobile in the crystal and twist simultaneously in response to water vapour. Thermodynamic analysis suggests that the sigmoidal water sorption is induced by the affinity alternation of the pore surface from hydrophobic to hydrophilic.