Assessment of the Crystallization Process of CaO-Al2O3-SiO2 Glass Probed with Tb3+ Luminescence.

The ratio of the intensity of Tb3+ fluorescence at 543 nm because of an electric dipole transition (5D4-7F5) relative to that at 437 nm due to a magnetic dipole transition (5D3-7F4) was determined to be proportional to the amount of metastable CaAl2Si2O8 crystals precipitated in CaO-Al2O3-SiO2 glass. The present results indicate that Tb3+ luminescence can be used as a probe to evaluate the crystallization of glass.

Temperature-Dependent Electronic Ground-State Charge Transfer in van der Waals Heterostructures.

Electronic charge rearrangement between components of a heterostructure is the fundamental principle to reach the electronic ground state. It is acknowledged that the density of state distribution of the components governs the amount of charge transfer, but a notable dependence on temperature is not yet considered, particularly for weakly interacting systems. Here, it is experimentally observed that the amount of ground-state charge transfer in a van der Waals heterostructure formed by monolayer MoS2 sandwiched between graphite and a molecular electron acceptor layer increases by a factor of 3 when going from 7 K to room temperature. State-of-the-art electronic structure calculations of the full heterostructure that accounts for nuclear thermal fluctuations reveal intracomponent electron-phonon coupling and intercomponent electronic coupling as the key factors determining the amount of charge transfer. This conclusion is rationalized by a model applicable to multicomponent van der Waals heterostructures.

Rhodium-Catalyzed Alkylation of C-H Bonds in Aromatic Amides with Non-activated 1-Alkenes: The Possible Generation of Carbene Intermediates from Alkenes.

The alkylation of C-H bonds (hydroarylation) in aromatic amides with non-activated 1-alkenes using a rhodium catalyst and assisted by an 8-aminoquinoline directing group is reported. The addition of a carboxylic acid is crucial for the success of this reaction. The results of deuterium-labeling experiments indicate that one of deuterium atoms in the alkene is missing, suggesting that the reaction does not proceed through the commonly accepted mechanism for C-H alkylation reactions. Instead the reaction is proposed to proceed through a carbene mechanism. The carbene mechanism is also supported by preliminary DFT calculations.

Widely Dispersed Intermolecular Valence Bands of Epitaxially Grown Perfluoropentacene on Pentacene Single Crystals.

Strong intermolecular electronic coupling and well-ordered molecular arrangements enable efficient transport of both charge carriers and excitons in semiconducting π-conjugated molecular solids. Thus, molecular heteroepitaxy to form crystallized donor-acceptor molecular interfaces potentially leads to a novel strategy for creating efficient organic optoelectronic devices via the concomitance of these two requirements. In the present study, the crystallographic and electronic structures of a heteroepitaxial molecular interface, perfluoropentacene (PFP, C22F14) grown on pentacene single crystals (Pn-SCs, C22H14), were determined by means of grazing-incidence X-ray diffraction (GIXD) and angle-resolved ultraviolet photoelectron spectroscopy (ARUPS), respectively. GIXD revealed that PFP uniquely aligned its primary axis along the [11̅0] axis of crystalline pentacene to form well-crystallized overlayers. Valence band dispersion (at least 0.49 eV wide) was successfully resolved by ARUPS. This indicated a significant transfer integral between the frontier molecular orbitals of the nearest-neighbor PFP molecules.

Electronic structure of dipeptides in the gas-phase and as an adsorbed monolayer.

Peptide-based molecular electronic devices are promising due to the large diversity and unique electronic properties of biomolecules. These electronic properties can change considerably with peptide structure, allowing diverse design possibilities. In this work, we explore the effect of the side-chain of the peptide on its electronic properties, by using both experimental and computational tools to detect the electronic energy levels of two model peptides. The peptides include 2Ala and 2Trp as well as their 3-mercaptopropionic acid linker which is used to form monolayers on an Au surface. Specifically, we compare experimental ultraviolet photoemission spectroscopy measurements with density functional theory based computational results. By analyzing differences in frontier energy levels and molecular orbitals between peptides in gas-phase and in a monolayer on gold, we find that the electronic properties of the peptide side-chain are maintained during binding of the peptide to the gold substrate. This indicates that the energy barrier for the peptide electron transport can be tuned by the amino acid compositions, which suggests a route for structural design of peptide-based electronic devices.

Cobalt(ii)-catalyzed chelation-assisted C-H iodination of aromatic amides with I2.

The cobalt-catalyzed chelation-assisted iodination of aromatic amides using molecular I2 as an iodinating reagent is reported. 8-Amino-5-chloroquinoline functions as an efficient directing group. This mild and air stable catalytic system shows a wide functional group tolerance and improved synthetic accessibility.

Rh(I)-Catalyzed Alkylation of ortho-C-H Bonds in Aromatic Amides with Maleimides.

An alkylation of C-H bonds with maleimides by a rhodium-catalyzed reaction of aromatic amides containing an 8-aminoquinoline moiety as the directing group is reported. Various N-substituents in the maleimide, including methyl, ethyl, cyclohexyl, benzyl, and phenyl groups and even H, are applicable to the reaction. The reaction is highly regioselective at the less hindered ortho-C-H bond when meta-substituted aromatic amides are used as substrates.

Cobalt-catalyzed chelation assisted C-H allylation of aromatic amides with unactivated olefins.

The cobalt-catalyzed chelation assisted ortho C-H allylation of aromatic amides with unactivated aliphatic alkenes is reported. The reaction proceeds in air under mild reaction conditions, providing allylated products in good to excellent yields with high E-selectivities. This operationally simple method shows a high functional group tolerance.

Rhodium-Catalyzed Alkylation of C-H Bonds in Aromatic Amides with Styrenes via Bidentate-Chelation Assistance.

Rhodium-catalyzed alkylation reactions of aromatic C-H bonds in aromatic amides with styrene derivatives have been developed by using an 8-aminoquinoline as a bidentate directing group. C-C bond formation selectively occurred between the ortho C-H bonds in aromatic amides and the terminal carbon of the styrene derivatives. The presence of an 8-aminoquinoline moiety is essential for the success of the reaction.

Diagnostic performance of ADC for Non-mass-like breast lesions on MR imaging.

We assessed the usefulness and limitations of utilizing apparent diffusion coefficient (ADC) values on diffusion-weighted imaging (DWI) for the differential diagnosis of benign and malignant non-mass-like breast lesions. We retrospectively reviewed 27 such lesions (16 malignant, 11 benign) detected on magnetic resonance (MR) imaging and analyzed the enhancing patterns of dynamic contrast-enhanced DCE-MRI (distribution and internal enhancement), kinetic curve patterns, and ADC values. All images were obtained with a 1.5-tesla MR unit, with patients supine. On DCE-MRI, malignant lesions tended to show either segmental or branching-ductal distribution, and when lesions with these patterns were considered malignant, sensitivity was 68.8%; specificity, 63.6%; positive predictive value (PPV), 73.3%; negative predictive value (NPV), 58.3%; and accuracy, 66.7%. Kinetic curve analysis did not reliably differentiate benign and malignant non-mass-like lesions. There was no significant difference between the mean ADC value of the malignant lesions, 0.968 × 10(-3) mm(2)/s at b=1000 s/mm(2), and that of benign lesions, 1.207 × 10(-3) mm(2)/s (P=0.109). Receiver operating characteristic (ROC) analysis revealed the most effective threshold of ADC value for differentiating tumors as 1.1 × 10(-3) mm(2)/s; values lower than this were observed more often in malignant than benign lesions (P=0.054). Us of this threshold yielded sensitivity of 68.8%; specificity, 72.7%; PPV, 78.6%; NPV, 61.5%; and accuracy, 70.4%. Combining the ADC value criteria with the analysis of DCE-MRI pattern increased sensitivity to 93.8%, negative predictive value (NPV) to 85.7%, and accuracy to 77.8% but decreased specificity to 54.5%. Use of ADC values does not adequately improve DCE-MRI performance for differential diagnosis of non-mass-like breast lesions, but adding the ADC value criteria to the DCE-MRI pattern analysis improves sensitivity, NPV, and accuracy.