Selective encapsulation of carboxylic acid dimers within a size-regulable resorcinarene-based hemicarcerand.

A cavity within a resorcinarene-based hemicarcerand was contracted and expanded through conformational changes induced by the complexation and decomplexation, allowing self-sorting of homo- and heterodimeric carboxylic acid pairs.

Insertions of the striated muscles in the skin and mucosa: a histological study of fetuses and cadavers.

Striated muscle insertions into the skin and mucosa are present in the head, neck, and pelvic floor. We reexamined the histology of these tissues to elucidate their role in transmission of the force. We examined histological sections of 25 human fetuses (gestational ages of ~11-19 weeks and ~26-40 weeks) and 6 cadavers of elderly individuals. Facial muscle insertion or terminal almost always formed as an interdigitation with another muscle or as a circular arrangement in which muscle fiber insertions were sandwiched and mechanically supported by other muscle fibers (like an in-series muscle). Our examination of the face revealed some limited exceptions in which muscle fibers that approached the dermis were always in the nasalis and mentalis muscles, and often in the levator labii superioris alaeque nasi muscle. The buccinator muscle was consistently inserted into the basement membrane of the oral mucosa. Parts of the uvulae muscle in the soft palate and of the intrinsic vertical muscle of the tongue were likely to direct toward the mucosa. In contrast, the pelvic floor did not contain striated muscle fibers that were directed toward the skin or mucosa. Although 'cutaneous muscle' is a common term, the actual insertion of a muscle into the skin or mucosa seemed to be very rare. Instead, superficial muscle insertion often consisted of interdigitated muscle bundles that had different functional vectors. In this case, the terminal of one muscle bundle was sandwiched and fixed mechanically by other bundles.

Application of Exciton Coupling for Characterization of Nanographene Edges.

The front cover artwork is provided by Prof. Haino's group at Hiroshima University. The image shows the mirror image circular dichroism spectra of nanographenes carrying chiral chromophores. Read the full text of the Research Article at 10.1002/cphc.202300740.

Kinetic Resolution of Secondary Alcohols Catalyzed at the Exterior of Chiral Coordinated Capsules.

Confined spaces inside molecular hosts can function as reaction vessels. However, this concept significantly limits the scope of reactants. When the exterior of molecular hosts is used instead, we can ease the restriction because reactants are not necessary to be trapped inside molecular hosts, although studies along this line have not been reported. As a proof-of-concept of enantioselective reactions at the exterior of chiral molecular hosts, we utilized host-guest complexes of enantiomerically enriched Cu-coordinated capsules and guests possessing a catalytic center to realize the kinetic resolution of secondary alcohols. Under suitable reaction conditions, a selectivity factor of 2.6 was realized, demonstrating that the reactions occur at the exterior of the capsules. A series of experiments indicated that the substituents on the 2,2'-bipyridyl arms and the alkyl chains on the lower rim contributed to the enantioselectivity of the reactions.

Application of Exciton Coupling for Characterization of Nanographene Edge.

The structural characterization of nonstoichiometric nanographene (NG)-organic hybrid materials is usually difficult. The number of substituents on the edge and their arrangements are frequently questioned but are difficult to answer. Since the number of functional groups is closely related to the distance between the nearest neighbors (dISD ), the extraction of dISD from spectroscopic data could provide important information on their structural characterization. We show that exciton coupling, which is a theoretical prediction of the absolute structures of discrete molecules, is a possible candidate to address this issue. The comparison of the calculated CD spectra of the chiral chromophores extracted from the model NG edge with the observed edge spectra indicated a dISD of ca. 8 Å; this corresponded to substitution on every other armchair edge. Furthermore, an up-up-down-down alternate orientation was found to be a possible edge structure. Although the procedure was limited to NGs carrying chiral substituents, our method could facilitate the detailed structural characterization of NG-organic hybrid materials.

Intermediate Color Emission via Nanographenes with Organic Fluorophores.

Photoluminescence (PL) color can be tuned by mixing fluorophores emitting the three primary colors in an appropriate ratio. When color tuning is achieved on a single substrate, we can simplify device structures. We demonstrated that nanographenes (NGs), which are graphene fragments with a size of tens of nanometers, could be utilized as carriers of fluorophores. The addition of red- and blue-light-emitting fluorophores on the edge successfully reproduced the purple light. The relative PL intensities of the fluorophores could be regulated by the excitation wavelength, enabling multicolor emission between blue and red light. Owing to the triphenylamine units of the fluorophores, the NGs showed PL enhancement due to aggregation. This characteristic was valuable for the fabrication of solid polymer materials. Specifically, the functionalized NGs can be dispersed into polyvinylidene difluoride. The resultant polymer films emitted red, blue, and purple color. Our study demonstrated the potential applicability of NGs for fluorophore carriers capable of reproducing intermediate colors of light.

Molecular Recognition Process in Resorcinarene-based Coordination Capsules.

Cu and Ag capsules can take up various organic molecules. Their molecular recognition possibly involves partial dissociation and slippage. We investigated molecular recognition processes in the Cu and Ag capsules by CD and 1 H NMR spectroscopy and employed 4,4'-diacetoxy biphenyl carrying two benzothiadiazole groups as a probe. CD and 1 H NMR measurements reveal that the host-guest complexation proceeds under second-order reactions and that these capsules undergo the partial dissociation to take up the probe in [D1 ]chloroform and [D8 ]THF. The slippage also contributes to host-guest complexation for a Cu capsule that carries p-methoxyphenyl groups on the 2,2'-bipyridiyl arms. DFT calculations suggest that π/π stacking interactions between the electron-rich p-methoxyphenyl group and the electron-poor 2,2'-bipyridyl arm elongate the capsule, allowing the guest to access the cavity without the partial dissociation.

Induction of Chirality on Nanographenes.

Chirality induction is an important topic in studies of nanographenes (NGs). We report chirality enhancements of NGs through postsynthetic chemical modifications of NGs with pyrene and m-terphenyl groups. These substituents were installed into N-(p-bromophenylethyl)imides on the edges of the NGs with Pd-catalyzed cross-coupling reactions. Circular dichroism (CD) spectra demonstrated that these bulky substituents improved the induced CD signal of the NGs compared to those previously reported and suggested that they induced the opposite chirality. Density functional theory calculations indicated possible edge structures for the NGs and indicated that π/π and CH/π interactions among the neighboring substituents influenced the orientations of the imides. These imides distorted the edges, and the distorted edges eventually generated the chiral environments of the NGs. The interactions among the substituents are, therefore, likely to allow detection of the CD signals in the visible region and induction of the opposite chirality.

Substituent-Induced Supramolecular Aggregates of Edge Functionalized Nanographenes.

Precisely controlled molecular assemblies often display intriguing morphologies and/or functions arising from their structures. The application of the concept of the self-assembly for controlling the aggregation of nanographenes (NGs) is challenging. The title NGs are those carrying both long alkyl chains and tris(phenylisoxazolyl)benzene (TPIB) on the edge. The former group secures the affinity of NGs for organic solvents, and the latter group drives the 1D arrangement of NGs through the interactions between the TPIB units. The concentration-dependent and temperature variable 1 H NMR, UV-vis, and PL spectra demonstrate the aggregation of NGs in 1,2-dichloroethane, and the aggregation is controllable by the regulation of the solvent polarity. AFM images give the stacked structures of the NGs, and these aggregates turn out to be network polymeric structures at a high concentration. These observations demonstrate that the synergy of the face-to-face interactions between the surfaces and the interactions between the TPIB units are effective for controlling the self-assembly of the NGs.

Effects of Edge Functionalization of Nanographenes with Small Aromatic Systems.

Regulation of the physical properties of nanographenes (NGs) by edge functionalization is an active research area. We conducted a computational study of the effects of edge functionalization on the physical properties of NGs. The computed NGs were models of experimentally obtained NGs and composed of a C174 carbon framework with one to four 3,5-dimethylnaphthalene units on the edge. The effects were assessed structurally, magnetically, and electronically by the least square planarity index, harmonic oscillator model of aromaticity, nucleus-independent chemical shift, and HOMO-LUMO (H-L) gaps. Density functional theory calculations indicate that although the structures of the model NGs are not very sensitive to edge functionalization, but the magnetic and electronic properties are. The installed substituents narrowed the H-L gap and induced a redshift of the photoluminescence (PL) band by the π conjugation between NG and the substituent. These results are consistent with the extension of the absorption band and the redshift of the PL bands of the experimentally modified NGs. Furthermore, the calculations confirmed the contribution of the charge transfer character to the absorption spectra.

Computational Studies on the Structures of Nanographenes with Various Edge Functionalities.

Computational studies have often been carried out on hydrogen-terminated nanographenes (NGs). These structures are, however, far from those deduced from experimental observations, which have suggested armchair edges with two carboxy groups on the edges as dominant. We conducted computational studies on NGs consisting of C42 , C60 , C78 , C96 , C142 , and C174 carbon atoms with hydrogen, carboxy, and N-methyl imide-terminated armchair edges. DFT calculations inform distorted basal planes and similar HOMO-LUMO gaps, indicating that the edge oxidation and functionalization do not very influence the electronic structure. Comparison of observed UV-vis spectra of carboxy- and N-octadecyl chain terminated NGs with calculated spectra of model NGs informs the contribution of π-π* transitions on the basal plane to the absorptions in the visible region. A dimeric structure of NG and octadecyl-installed NG demonstrate that both the distorted basal planes and the steric contacts among the functional groups widen the surface-to-surface distance thereby allowing the invasion of solvent molecules between the surfaces. This picture is consistent with the improved solubility of edge-modified NGs.

Integration of Nanographenes and Organic Chemistry - Toward Nanographene-based Two-dimensional Materials.

The front cover artwork is provided by Takeharu Haino's group. The image shows the fragmentation of a graphene sheet by chemical oxidation, producing nanographenes. The quantum size effect opens the band gap of nanographenes, allowing them to emit photoluminescence in the visible region. Read the full text of the Concept at 10.1002/cphc.202200311.

Metal Nanoparticles on Lipophilic Nanographenes.

Utilization of graphitic domains on nanographenes (NGs) for anchoring metal nanoparticles (NPs) can open the door for their applications in catalysis. Reported examples employ hydrophilic graphene oxides as substrates, making it difficult to coexist with organic substrates in organic solvents. The title NGs are metal NP-doped lipophilic NGs (M-NG1). Various metal cations form NPs with a diameter of a few to tens of nanometers on the basal plane. Owing to the lipophilic nature of NG1, M-NG1 is prepared by the reduction of the basal plane with sodium in THF followed by the addition of metal salts. Au-NPs on NG1 allow anchoring an organic thiol carrying an anthracene fluorophore, which is a proof of concept of composite materials utilizing the surface of NGs. The assessment of the catalytic function of Pd-NG1 reveals that chlorobenzene and bromobenzene yield a coupling product, and fluorobenzene also undergoes the reactions, demonstrating the catalytic function of Pd-NG1.

Goiter in a 6-year-old patient with novel thyroglobulin gene variant (Gly145Glu) causing intracellular thyroglobulin transport disorder: Correlation between goiter size and the free T3 to free T4 ratio.

Thyroglobulin gene abnormalities cause thyroid dyshormonogenesis. A 6-yr-old boy of consanguineous parents presented with a large goiter and mild hypothyroidism (thyroid-stimulating hormone [TSH] 7.2 µIU/mL, free T3 [FT3] 3.4 pg/mL, free T4 [FT4] 0.6 ng/dL). Despite levothyroxine (LT4) administration and normal TSH levels, the goiter progressed slowly and increased rapidly in size at the onset of puberty. Thyroid scintigraphy revealed a remarkably high 123I uptake of 75.2%, with a serum thyroglobulin level of 13 ng/ml, which was disproportionately low for the goiter size. DNA sequencing revealed a novel homozygous missense variant, c.434G>A [p.Gly145Glu], in the thyroglobulin gene. Goiter growth was suppressed by increasing the LT4 dose. Thyroidectomy was performed at 17-yr-of-age. Thyroglobulin analysis of the thyroid tissue detected mutant thyroglobulin present in the endoplasmic reticulum, demonstrating that thyroglobulin transport from the endoplasmic reticulum to the Golgi apparatus was impaired by the Gly145Glu variant. During the clinical course, an elevated FT3/FT4 ratio was observed along with thyroid enlargement. A high FT3/FT4 ratio and goiter seemed to be compensatory responses to impaired hormone synthesis. Thyroglobulin defects with goiter should be treated with LT4, even if TSH levels are normal.

Chirality Induction on a Coordination Capsule for Circularly Polarized Luminescence.

By utilizing a confined space inside a coordination capsule consisting of achiral components, we achieve trimeric structures composed of acetic acid and 2,3-disubstituted tartaric acid derivatives. Steric and electronic interactions between the substituents on the tartaric acid and 2,2'-bipyridyl arms of the capsule permit the transfer of the chirality of the tartaric acid to the capsule, resulting in diastereoenrichment of the host-guest complexes of up to 92 % de. The chiral templates can be washed away with diethyl ether, leaving an enantiomerically enriched capsule. The resulting capsule biases the dynamic axial chirality of a 4,4'-diacetoxybiphenyl guest carrying benzothiadiazole units, demonstrating guest-to-capsule and capsule-to-guest chirality transfer. The induced chirality on the bound guest enables it to emit circularly polarized luminescence in the NIR region, demonstrating the application of induced chirality for confined spaces for the generation of chiroptical properties.

Integration of Nanographenes and Organic Chemistry - Toward Nanographene-based Two-Dimensional Materials.

Graphene and its relatives have received considerable attention from the fields of physics and chemistry since the isolation of pristine graphene sheets. Nanographenes (NGs) are graphene fragments that are a few to tens of nanometers in diameter. Compared to graphene and its relatives, such as graphene oxides, NGs can be handled more easily, and their large π surface and oxygen functional groups on the edge allow postsynthetic modifications. The study of NGs is gradually shifting from the development of synthetic procedures to postsynthetic modification. From the structural point of view, NGs can be regarded as two-dimensional carbon polymers. Their unique structures and affinity for organic molecules make NGs excellent scaffolds for two-dimensional materials, which are now an important topic in organic and polymer chemistry. In this conceptual article, we introduce the position of NGs from the perspective of two-dimensional substances and briefly review both the structural features of NGs and the effects of functionalization on their physical properties. These are valuable when producing reasonable strategies for their postsynthetic modifications.

Chirality Induction in a Hydrophilic Metallohelicate.

The title compound is a water-soluble triply stranded metallohelicate 1Fe composed of TEG-chain-installed calix[4]arene-based bis-bidentate ligands and Fe3+ cations. This compound can incorporate up to two molecules of small chiral cations (G1 and G2). Interestingly, G1 shows positive cooperativity for host-guest complexation, whereas G2 exhibits noncooperativity, despite having a greater affinity for 1Fe than G1. Density functional theory (DFT) calculations indicate the metallohelicate cavity expands upon encapsulation of the first guest. This conformational change facilitates the entrapment of the second guest and explains why the interaction parameters of G1 and G2 are larger than 1, despite electrostatic repulsion between the guests. The DFT calculation predicts an intermolecular interaction between the phenyl groups of G1 in the cavity, whereas no such interaction is found for G2. This difference can explain the distinct molecular recognition of G1 and G2. CD spectroscopy shows that both (R)-G1 and (R)-G2 induce (M)-helicity in 1Fe and vice versa. DFT calculations suggest that the chirality of the guests is transmitted to 1Fe via CH/O hydrogen bonds between the guest and the C=O bond on the calix[4]arene strand. The CD intensity of 1Fe is nonlinear in the ee% of (R)- and (S)-G1, indicating that the presence of the first guest increases the affinity of 1Fe toward a second guest with the same chirality due to preorganization by the first guest.

Electrochromism of Nanographenes in the Near-Infrared Region.

Nanographene (NG) is a potential candidate for organic EC materials because of its large π-conjugated system, chemical stability, absorption band covering the visible region, and tunable optical properties by postsynthetic modification. We show that NGs carrying redox-active triphenylamine (TPA) units covalently linked to the NG edge function as EC materials in the NIR region. The hybrid materials can be obtained by the installation of TPA units onto the NG edge and display changes in the absorption spectrum in the NIR region extending to a wavelength of over 2000 nm upon one-electron oxidation and reduction at low potentials (<1.1 V). Time-dependent unrestricted density functional theory calculation of a model NG at the UB3LYP/6-31G(d,p) level of theory suggests that a narrow energy gap between the basal plane and the oxidized TPA unit is responsible for the observed EC function in the NIR region.

Nanographene - A Scaffold of Two-Dimensional Materials.

Substances can be divided into 0D to 3D species based on the number of repeating units (atom, ion, and molecule) and their arrangements in space (point, linear, layer, and solid). Discrete substances belong to 0D species, polymers are examples of 1D species, and molecular crystals are 3D species. Most of the substances belong to one of these species. On the other hand, those categorized into 2D species wherein the repeating units organize a layer are less explored. 2D species have a surface and edges. The incorporation of these structural features into a molecular design can realize multifunctionalized systems that are difficult to achieve by conventional organic synthesis. The development of 2D species is, therefore, the frontier of organic, inorganic, and polymer chemistry. Nanographenes (NGs) are suitable scaffolds for realizing 2D species due to several factors, such as chemical stability and oxygen-containing functional groups on the surface and on the edge, allowing postsynthetic modifications. Our group has utilized NGs with tens of nanometers in diameters for developing 2D species. Carboxy groups on the edge enable us to install various substituents into NGs, offering NG-based functional materials. These studies demonstrate that the integration of NGs with organic chemistry can widen the scope of their applications other than optical materials that are a main application of NGs. We introduce our recent studies on the development of NG-based functional materials realized by postsynthetic modifications. We hope that this account will contribute to the development of the chemistry of 2D species.

Self-Assembly of Nanographenes.

Suitably decorated small aromatic systems can organize stacked structures that display interesting properties arising from their unique morphologies. Although nanographenes produced by top-down methods have graphitic domains and can in principle be applied for such supramolecular systems, to our knowledge, no such example has been reported thus far. This is partly because of their limited solubility in organic solvents and partly because of their wide lateral size distribution. To realize nanographene-based supramolecular aggregates, nanographenes carrying alkyl chains with narrow lateral size distributions are employed. We find that the nanographenes undergo self-assembly and that self-assembly is regulated by concentration, solvent polarity, temperature, and sonication. Optical measurements and AFM images indicate that stacked structures are possible candidates for aggregates. A molecular mechanics calculation models the interactions in the aggregates. The nanographenes showed concentration-dependent morphologies on mica, stacked structures at low concentrations and polymer-like network structures on mica at higher concentrations.