Extraordinary Acceleration of an Electrophilic Reaction Driven by the Polar Surface of 2D Aluminosilicate Nanosheets.

To increase chemical reaction rates, general solutions include increasing the concentration/temperature and introducing catalysts. In this study, the rate constant of an electrophilic metal coordination reaction is accelerated 23-fold on the surface of layered aluminosilicate (LAS), where the reaction substrate (ligand molecule) induces dielectric polarization owing to the polar and anionic surface. According to the Arrhenius plot, the frequency factor (A) is increased by almost three orders of magnitude on the surface. This leads to the conclusion that the collision efficiency between the ligands and metal ions is enhanced on the surface due to the dielectric polarization. This is surprising because one side of the ligand is obscured by the surface, so the collision efficiency is expected to be decreased. This unique method to accelerate the chemical reaction is expected to expand the range of utilization of LASs, which are chemically inert, abundant, and environmentally friendly. The concept is also applicable to other metal oxides which have polar surfaces, which will be useful for various chemical reactions in the future.

On-surface synthesis of disilabenzene-bridged covalent organic frameworks.

Substituting carbon with silicon in organic molecules and materials has long been an attractive way to modify their electronic structure and properties. Silicon-doped graphene-based materials are known to exhibit exotic properties, yet conjugated organic materials with atomically precise Si substitution have remained difficult to prepare. Here we present the on-surface synthesis of one- and two-dimensional covalent organic frameworks whose backbones contain 1,4-disilabenzene (C4Si2) linkers. Silicon atoms were first deposited on a Au(111) surface, forming a AuSix film on annealing. The subsequent deposition and annealing of a bromo-substituted polyaromatic hydrocarbon precursor (triphenylene or pyrene) on this surface led to the formation of the C4Si2-bridged networks, which were characterized by a combination of high-resolution scanning tunnelling microscopy and photoelectron spectroscopy supported by density functional theory calculations. Each Si in a hexagonal C4Si2 ring was found to be covalently linked to one terminal Br atom. For the linear structure obtained with the pyrene-based precursor, the C4Si2 rings were converted into C4Si pentagonal siloles by further annealing.

Postsynthetic Modification of a Covalent Organic Framework Achieved via Strain-Promoted Cycloaddition.

Two-dimensional covalent organic frameworks (2D COFs) are layered, structurally regular, and permanently porous macromolecules. When reactive groups are embedded into a COF structure, subsequent chemical reactions can be performed following polymerization. As such, a postsynthetic modification (PSM) strategy provides diverse materials from a single set of COF monomers and polymerization protocols. Here, we report the synthesis of an asymmetric dibenzocyclooctyne-containing imine-linked 2D COF, which readily undergoes strain-promoted azide-alkyne cycloaddition (SPAAC) reactions without catalyst under mild and dilute conditions. This approach was used to quantitatively decorate the COF lattice with alkyl chains and amines, all without the need for exogenous species. Functionalization may result in spontaneous delamination of bulk COF materials into solution-stable sheets, demonstrating the utility of this technique. As such, this platform is useful for postsynthetic functionalization with sensitive chemical functionalities that are not amenable to direct polymerization or existing PSM strategies.

Revealing the Local Electronic Structure of a Single-Layer Covalent Organic Framework through Electronic Decoupling.

Covalent organic frameworks (COFs) are molecule-based 2D and 3D materials that possess a wide range of mechanical and electronic properties. We have performed a joint experimental and theoretical study of the electronic structure of boroxine-linked COFs grown under ultrahigh vacuum conditions and characterized using scanning tunneling spectroscopy on Au(111) and hBN/Cu(111) substrates. Our results show that a single hBN layer electronically decouples the COF from the metallic substrate, thus suppressing substrate-induced broadening and revealing new features in the COF electronic local density of states (LDOS). The resulting sharpening of LDOS features allows us to experimentally determine the COF band gap, bandwidths, and the electronic hopping amplitude between adjacent COF bridge sites. These experimental parameters are consistent with the results of first-principles theoretical predictions.

Materials nanoarchitectonics at two-dimensional liquid interfaces.

Much attention has been paid to the synthesis of low-dimensional materials from small units such as functional molecules. Bottom-up approaches to create new low-dimensional materials with various functional units can be realized with the emerging concept of nanoarchitectonics. In this review article, we overview recent research progresses on materials nanoarchitectonics at two-dimensional liquid interfaces, which are dimensionally restricted media with some freedoms of molecular motion. Specific characteristics of molecular interactions and functions at liquid interfaces are briefly explained in the first parts. The following sections overview several topics on materials nanoarchitectonics at liquid interfaces, such as the preparation of two-dimensional metal-organic frameworks and covalent organic frameworks, and the fabrication of low-dimensional and specifically structured nanocarbons and their assemblies at liquid-liquid interfaces. Finally, interfacial nanoarchitectonics of biomaterials including the regulation of orientation and differentiation of living cells are explained. In the recent examples described in this review, various materials such as molecular machines, molecular receptors, block-copolymer, DNA origami, nanocarbon, phages, and stem cells were assembled at liquid interfaces by using various useful techniques. This review overviews techniques such as conventional Langmuir-Blodgett method, vortex Langmuir-Blodgett method, liquid-liquid interfacial precipitation, instructed assembly, and layer-by-layer assembly to give low-dimensional materials including nanowires, nanowhiskers, nanosheets, cubic objects, molecular patterns, supramolecular polymers, metal-organic frameworks and covalent organic frameworks. The nanoarchitecture materials can be used for various applications such as molecular recognition, sensors, photodetectors, supercapacitors, supramolecular differentiation, enzyme reactors, cell differentiation control, and hemodialysis.

Removal of GenX and Perfluorinated Alkyl Substances from Water by Amine-Functionalized Covalent Organic Frameworks.

Per- and polyfluorinated alkyl substances (PFAS), such as perfluorooctanoic acid (PFOA), perfluorooctanesulfonate (PFOS), and ammonium perfluoro-2-propoxypropionate (GenX), contaminate ground and surface waters throughout the world. The cost and performance limitations of current PFAS removal technologies motivate efforts to develop selective and high-affinity adsorbents. Covalent organic frameworks (COFs) are unexplored yet promising adsorbents because of their high surface area and tunable pore sizes. Here we show that imine-linked two-dimensional (2D) COFs bearing primary amines adsorb GenX rapidly at environmentally relevant concentrations. COFs with partial amine incorporation showed the highest capacity and fastest removal, suggesting that the synergistic combination of the polar group and hydrophobic surfaces are responsible for GenX binding. A COF with 28% amine loading also removed more than 90% of 12 out of 13 PFAS. These results demonstrate the promise of COFs for PFAS removal and suggest design criteria for maximizing adsorbent performance.

Development and Performance Characterization of a Polyimine Covalent Organic Framework Thin-Film Composite Nanofiltration Membrane.

Two-dimensional covalent organic frameworks (COFs) were used to create the first asymmetric, thin-film composite (TFC) nanofiltration (NF) membrane with a COF active layer. NF membrane active layers of polyimine COF were synthesized via the interfacial polymerization (IP) of terephthalaldehyde and tris(4-aminophenyl)benzene monomers on top of a poly(ether sulfone) (PES) ultrafiltration membrane support. Rutherford backscattering spectrometry and Fourier transform infrared spectroscopy analyses confirmed the presence of an imine-linked film with a thickness of ∼10 nm that was formed reproducibly. The rejection efficiencies of the COF NF membrane for a model organic compound, Rhodamine-WT, and a background electrolyte, NaCl, were higher than those of the PES support without the COF film. This enhanced solute rejection is the first successful demonstration of a TFC membrane with a thin COF active layer. However, this work also demonstrates the need for COF NF membranes with smaller active layer pores and alternative support materials. The former should result in greater solute rejection, and the latter is key because the PES used for support in the COF membranes is incompatible with the organic solvents used for the COF IP process.

Exceptionally High Electric Double Layer Capacitances of Oligomeric Ionic Liquids.

Electric double layer (EDL) capacitors are promising as next-generation energy accumulators if their capacitances and operation voltages are both high. However, only few electrolytes can simultaneously fulfill these two requisites. Here we report that an oligomeric ionic liquid such as IL4TFSI with four imidazolium ion units in its structure provides a wide electrochemical window of ∼5.0 V, similar to monomeric ionic liquids. Furthermore, electrochemical impedance measurements using Au working electrodes demonstrated that IL4TFSI exhibits an exceptionally high EDL capacitance of ∼66 µF/cm2, which is ∼6 times as high as those of monomeric ionic liquids so far reported. We also found that an EDL-based field effect transistor (FET) using IL4TFSI as a gate dielectric material and SrTiO3 as a channel material displays a very sharp transfer curve with an enhanced carrier accumulation capability of ∼64 µF/cm2, as determined by Hall-effect measurements.

Rapid, Low Temperature Formation of Imine-Linked Covalent Organic Frameworks Catalyzed by Metal Triflates.

Imine-linked two-dimensional covalent organic frameworks (2D COFs) are crystalline polymer networks with enhanced stability compared to boronate ester-linked systems and with broad monomer scope. They are traditionally prepared by condensing polyfunctional aldehydes and amines at elevated temperature in a mixture of organic solvents and aqueous CH3CO2H, which catalyzes imine formation and exchange. Here we employ metal triflates, which are water-tolerant Lewis acids, to accelerate 2D imine-linked COF synthesis and improve their materials quality. Low catalyst loadings provide crystalline polymer networks in nearly quantitative yields. These conditions are demonstrated for several COFs, including heteroatom-containing systems of interest for optoelectronic applications.

Ultrahigh-throughput exfoliation of graphite into pristine 'single-layer' graphene using microwaves and molecularly engineered ionic liquids.

Graphene has shown much promise as an organic electronic material but, despite recent achievements in the production of few-layer graphene, the quantitative exfoliation of graphite into pristine single-layer graphene has remained one of the main challenges in developing practical devices. Recently, reduced graphene oxide has been recognized as a non-feasible alternative to graphene owing to variable defect types and levels, and attention is turning towards reliable methods for the high-throughput exfoliation of graphite. Here we report that microwave irradiation of graphite suspended in molecularly engineered oligomeric ionic liquids allows for ultrahigh-efficiency exfoliation (93% yield) with a high selectivity (95%) towards 'single-layer' graphene (that is, with thicknesses <1 nm) in a short processing time (30 minutes). The isolated graphene sheets show negligible structural deterioration. They are also readily redispersible in oligomeric ionic liquids up to ~100 mg ml(-1), and form physical gels in which an anisotropic orientation of graphene sheets, once induced by a magnetic field, is maintained.

Supramolecular ferroelectrics.

Supramolecular chemistry uses non-covalent interactions to coax molecules into forming ordered assemblies. The construction of ordered materials with these reversible bonds has led to dramatic innovations in organic electronics, polymer science and biomaterials. Here, we review how supramolecular strategies can advance the burgeoning field of organic ferroelectricity. Ferroelectrics - materials with a spontaneous and electrically reversible polarization - are touted for use in non-volatile computer memories, sensors and optics. Historically, this physical phenomenon has been studied in inorganic materials, although some organic examples are known and strong interest exists to extend the search for ferroelectric molecular systems. Other undiscovered applications outside this regime could also emerge. We describe the key features necessary for molecular and supramolecular dipoles in organic ferroelectrics and their incorporation into ordered systems, such as porous frameworks and liquid crystals. The goal of this Review is to motivate the development of innovative supramolecular ferroelectrics that exceed the performance and usefulness of known systems.

An animal model for late onset chronic demyelination disease caused by failed terminal differentiation of oligodendrocytes.

Various animal models are available for studying human multiple sclerosis (MS). Most of them model the initial phase of MS,including the immune-triggered attack of the myelin membrane and/or oligodendrocytes and, occasionally, demonstrate there mission and relapsing phases. However, few mimic the late chronic demyelinating phase. Overexpression of the proteolipid protein gene (Plp) causes a unique demyelinating disorder in mice in which normal-appearing myelin forms early in life and chronic demyelination occurs later. We found that remyelination is severely affected in this late demyelinating phase, but is not caused by deprivation of oligodendrocyte progenitors expressing PDGF receptor alpha (PDGFRa) and Olig2, which are present at an even higher number in the demyelinated white matter of the mutants than in wild-type controls. Furthermore, mature oligodendrocytes containing PLP were observed, but failed to remyelinate. The ability of oligodendrocytes from older transgenic animals to produce a myelin membrane-like structure was not impaired when cultured in vitro, which indicates that the lack of remyelination is not simply caused by changes in the intrinsic properties of the oligodendrocytes. Glial activation also occurred much earlier than active demyelination in mutant mice. Thus, in addition to intrinsic mechanisms, extrinsic mechanisms might also have an important role in defects of remyelination. These features are also observed in patients at a late stage of MS, leading to chronic demyelinating lesions. Thus, this mouse model partly mimics the late stage of MS and can be used to study the cause of inhibition of remyelination.

A Japanese case of familial cardiac myxoma associated with a mutation of the PRKAR1alpha gene.

Familial cardiac myxoma is inherited as an autosomal dominant syndrome. Here, we report a Japanese case of familial cardiac myxoma identified as a genetic abnormality. The mother experienced multiple recurrence of tumors in the left atrium and left ventricle 40 months after surgical resection of a left atrial myxoma. All recurrent tumors were successfully resected. Her daughter also had a solitary myxoma in the left atrium, but she had no recurrence after the operation. Both patients had lentigines in their face but no endocrine abnormality. Molecular genetic analysis demonstrated involvement of a mutation in the PRKAR1alpha gene.

Intercalated duct cell is starting point in development of pancreatic ductal carcinoma?

BACKGROUND: Although it is well known that the pancreatic ductal carcinoma may develop having a relationship to the mucous gland hyperplasia (MGH) with atypia (PanIN-1B by PanIN system), the starting point of this atypical MGH is unclear. To know it, we examined the pancreas tissue using many methods described below. METHODS: 1. Twenty-seven surgically resected pancreas tissue specimens, including pancreatic ductal carcinomas (PDC), chronic pancreatitis and normal pancreas, were investigated using immunohistochemical stainings for MUC1, MUC6, 45M1, Ki67 and p53. 2. DNA extraction and analysis of K-ras mutation at codon 12 using microdissection method: The paraffin blocks with 16 regions including the intercalated duct cell (IC) adjacent to the atypical MGH were prepared for DNA extraction. Mutation of K-ras codon 12 was analyzed and compared in enriched polymerase chain reaction-enzyme-linked mini sequence assay (PCR-ELMA). RESULTS: 1. In the normal pancreas, although no positive cell was seen in 45M1, p53, Ki67, the cytoplasm of IC were always positive for MUC1 and sometimes positive for MUC6. In the pancreas with fibrosis or inflammation, MGH was positive for MUC6 and 45M1. And atypical MGH was positive for MUC1, MUC6 and 45M1. Some IC adjacent to the atypical MGH was positive for Ki67 as well as atypical MGH. The carcinoma cells in all cases of PDC were diffusely positive for MUC1, 45M1, p53 and Ki67, and focally positive for MUC6. 2. In K-ras mutation, we examined the regions including IC adjacent to the atypical MGH, because the immunohistochemical apomucin stainings of these regions resembled those of PDC as described above. And K-ras mutation was confirmed in 12 of 16 regions (75%). All mutations were a single mutation, in 6 regions GTT was detected, in 4 regions GAT was detected and in 2 region AGT was detected. CONCLUSION: Some intercalated duct cell may be the starting point of the pancreatic ductal carcinoma, because the exhibitions of mucin expressions, Ki67, p53 and K-ras mutation in some intercalated duct cell resembled those of mucous gland hyperplasia or pancreatic ductal carcinoma.

HtrA1 serine protease inhibits signaling mediated by Tgfbeta family proteins.

HtrA1, a member of the mammalian HtrA serine protease family, has a highly conserved protease domain followed by a PDZ domain. Because HtrA1 is a secretory protein and has another functional domain with homology to follistatin, we examined whether HtrA1 functions as an antagonist of Tgfbeta family proteins. During embryo development, mouse HtrA1 was expressed in specific areas where signaling by Tgfbeta family proteins plays important regulatory roles. The GST-pulldown assay showed that HtrA1 binds to a broad range of Tgfbeta family proteins, including Bmp4, Gdf5, Tgfbetas and activin. HtrA1 inhibited signaling by Bmp4, Bmp2, and Tgfbeta1 in C2C12 cells, presumably by preventing receptor activation. Experiments using a series of deletion mutants indicated that the binding activity of HtrA1 required the protease domain and a small linker region preceding it, and that inhibition of Tgfbeta signaling is dependent on the proteolytic activity of HtrA1. Misexpression of HtrA1 near the developing chick eye led to suppression of eye development that was indistinguishable from the effects of noggin. Taken together, these data indicate that HtrA1 protease is a novel inhibitor of Tgfbeta family members.

Nuclear transfer of adult bone marrow mesenchymal stem cells: developmental totipotency of tissue-specific stem cells from an adult mammal.

Recent studies have demonstrated that somatic stem cells have a flexible potential greater than previously expected when they are transplanted into different tissues. On the other hand, recent studies also have revealed that these potentials might occur because of spontaneous cell fusion with recipient cells. The nuclei of somatic cells could have been reprogrammed when they were artificially or spontaneously fused with mouse embryonic stem (ES) cells. The resultant hybrid cells acquired a developmental pluripotency that the original somatic cells did not have but that ES cells did. LaBarge and Blau (Cell 2002; 111:589-601) demonstrated that adult bone marrow-derived cells contributed to muscle tissue in a stepwise biological progression. This means that bone marrow-derived cells became satellite cells of mononucleate muscle stem cells after the first irradiation-induced damage to the mouse, and after the second irradiation-induced damage, multinucleate myofibers appeared from the bone marrow-derived cells. Considered together, the differentiation potential of the somatic stem cell nucleus itself remains unclear. Although the pluripotency of somatic stem cell populations has been evaluated, the developmental totipotency of the nuclei of somatic stem cells, whether or not they fused with other cells, has not been shown, except in only one study concerning fetal neural cells (never in adult stem cells). Here, we showed the developmental totipotency of adult bovine mesenchymal stem cells by nuclear transfer.

Cardiac hemangioma: a report of two cases and review of the literature.

Cardiac hemangioma is extremely rare. We encountered two patients with cardiac hemangioma detected by thoracic echocardiography during a medical checkup. In the first case, transthoracic echocardiography revealed a pedunculated tumor in the left ventricle. Selective left coronary angiography demonstrated that the main feeding artery of the tumor arose from the third diagonal branch of the left anterior descending coronary artery. In the second case, thoracic and transesophageal echocardiography showed an oval tumor arising from the right atrium. Both tumors were successfully resected. Histopathological examination revealed that one of the tumors was a capillary hemangioma and the other was a mixed capillary and cavernous hemangioma. After operation, both patients had an uneventful recovery without any complications.

Multiple esophagogastric granular cell tumors.

Multiple granular cell tumors of the esophagus and the stomach found in a 53-year-old man are reported. One lesion was detected within the lower thoracic esophagus and seven lesions were detected in the stomach. The esophageal tumor was resected endoscopically, and gastrectomy was performed for the multiple gastric lesions. Histologically, the tumors consisted of spindle or polyhedral cells and the cytoplasm contained punctated eosinophilic granules with positive immunohistochemical staining for S-100 protein. The tumors were mainly located in the submucosal layer. Some tumor cells were seen in the mucosae propria and the muscularis propria. The tumor cells were only slightly positive for p53- and Ki-67-immunohistochemical stainings. Based on these findings, we diagnosed the granular cell tumors as benign. Granular cell tumor is comparatively rare in clinical practice, but a few such tumors have been seen in the digestive tract. A few cases of multiple esophagogastric granular cell tumors have also been reported in the literature.