Self-Aggregation, Enhanced Guest-Binding Behavior, and Anion-Induced Agglutination of Cyclophane Dimers Linked with Florescent Perylene Diimide.

Cationic, anionic, and nonionic cyclophane dimers, , , and , covalently linked with fluorescent perylene diimide were synthesized, respectively, as a host for aggregation-induced multivalent effects on guest-binding. These PDI-linked cyclophane dimers and , especially , formed self-aggregates in HO-rich solvents through π-stacking interactions. Critical aggregation concentrations of , , and in HO were 4.

Diet, Food Intake, and Exercise Mixed Interventions (DEMI) in the Enhancement of Wellbeing among Community-Dwelling Older Adults in Japan: Systematic Review and Meta-Analysis of Randomized Controlled Trials.

This systematic review and meta-analysis discusses the available data on the efficacy of diet, food intake, and exercise mixed interventions (DEMI) for community-dwelling older adults in Japan and assesses the evidence level. We searched the literature regarding the research questions using electronic and hand-searching methods. To ensure the reliability and quality of the evidence, we used the Cochrane risk of bias tool and GRADE system.

A Computational Study on the Mechanism of Catalytic Cyclopropanation Reaction with Cobalt N-Confused Porphyrin: The Effects of Inner Carbon and Intramolecular Axial Ligand.

The factors that affect acceleration and high / selectivity in the catalytic cyclopropanation reaction of styrene with ethyl diazoacetate by cobalt N-confused porphyrin (NCP) complexes were investigated using density functional theory calculations. The reaction rate was primarily related to the energy gap between the cobalt-carbene adduct intermediates, and , which was affected by the NCP skeletons and axial pyridine ligands more than the corresponding porphyrin complex. In addition, high / stereoselectivity was determined at the and, in part, in the isomerization process at the carbon-centered radical intermediates, and .

Ruthenium(iv) N-confused porphyrin μ-oxo-bridged dimers: acid-responsive molecular rotors.

Ruthenium(iv) N-confused porphyrin μ-oxo-bridged complexes were synthesized oxidative dimerization of a ruthenium(ii) N-confused porphyrin complex using 2,2,6,6-tetramethylpiperidine 1-oxyl. The deformed core planes in the dimers conferred a relatively high ring rotational barrier of 16 kcal mol. Rotation of the complexes was controlled by protonating the peripheral nitrogen.

Synthesis and Guest-Binding Properties of pH/Reduction Dual-Responsive Cyclophane Dimer.

A water-soluble cyclophane dimer having two disulfide groups as a reduction-responsive cleavable bond as well as several acidic and basic functional groups as a pH-responsive ionizable group was successfully synthesized. It was found that showed pH-dependent guest-binding behavior. That is, strongly bound an anionic guest, 6--toluidinonaphthalene-2-sulfonate (TNS) with binding constant (/M) for 1:1 host-guest complexes of 9.

Heptacene: Synthesis and Its Hole-Transfer Property in Stable Thin Films.

Heptacene (1) has been produced via a monoketone precursor, 2, which was prepared from 1,2,4,5-tetrabromobenzene in nine steps in a total yield of 10 %. Compound 2 was converted to 1 quantitatively by heating at 202 °C. Heptacene exhibited high thermal stability in the solid state without any observable change over two months.

Quantum calculations of the photoelectron spectra of the OH·NH anion: implications for OH + NH→ HO + NH reaction dynamics.

We present the results of quantum dynamics calculations for analyzing the experimentally measured photoelectron spectra of the OH·NH anion complex. Detachment of an excess electron of OH·NH initially produces a molecular arrangement, which is close to the transition-state structure of the neutral OH + NH→ HO + NH hydrogen abstraction reaction due to the Franck-Condon principle, and thus finally leads to the OH + NH or HO + NH asymptotic channel. We used both the path integral method and the reduced-dimensionality quantum wave packet method to simulate the photoelectron spectra of the OH·NH anion.

Theoretical Analysis of the Formylmethylene Anion Photoelectron Spectrum: Importance of Wolff Rearrangement Dynamics.

Photoelectron spectroscopy of a molecular anion is very useful for investigating the transition state and intermediate regions on the reactive potential energy surfaces of a neutral system. In this work, we theoretically analyzed the previously measured photoelectron spectrum of the formylmethylene anion, HCCHO. We simulated the photoelectron spectra for both the singlet and triplet states using the semiclassical method with quantum nuclear densities and Franck-Condon factor calculations with harmonic vibrational analysis.

Spin-inversion mechanisms in O binding to a model heme compound: A perspective from nonadiabatic wave packet calculations.

Spin-inversion dynamics in O binding to a model heme complex, which consisted of Fe(II)-porphyrin and imidazole, were studied using nonadiabatic wave packet dynamics calculations. We considered three active nuclear degrees of freedom in the dynamics, including the motions along the Fe-O distance, Fe-O-O angle, and Fe out-of-plane distance. Spin-free potential energy surfaces for the singlet, triplet, quintet, and septet states were developed using density functional theory calculations, and spin-orbit coupling elements were obtained from CASSCF-level electronic structure calculations.

Positron-electron correlation-polarization potential model for positron binding in polyatomic molecules.

Positron binding energies (PBEs) of 41 polyatomic molecules were calculated using the positron-electron correlation-polarization potential (CPP) approach and compared with experimentally measured values. In this approach, the short-range positron-electron potential is modeled using the density-functional expression, whereas the long-range potential is approximated by the attractive polarization potential. The positron-electron CPP model based on local-density approximation yields larger PBEs than experimental values; however, the calculated values can be substantially improved by introducing generalized gradient approximation.

Reduced-Dimensionality Quantum Dynamics Study of the Fe(CO) + H FeH(CO) Spin-inversion Reaction.

Many chemical reactions of transition metal compounds involve a change in spin state via spin inversion, which is induced by relativistic spin-orbit coupling. In this work, we theoretically study the efficiency of a typical spin-inversion reaction, Fe(CO) + H FeH(CO). Structural and vibrational information on the spin-inversion point, obtained through the spin-coupled Hamiltonian approach, is used to construct three degree-of-freedom potential energy surfaces and to obtain singlet-triplet spin-orbit couplings.

Ruthenium N-Confused Porphyrins: Selective Reactivity for Ambident 2-Heteroatom-Substituted Pyridines Serving as Axial Ligands.

Three types of ruthenium(II) N-confused porphyrin (NCP) complexes bearing an axial 2-thiopyridine, 2-pyridone, and 2-iminopyridine moiety at the inner carbon atom, respectively, were synthesized. The unique reactivity of the 2-substituted pyridine derivatives (2-X-pyridine; X=SH, OH, NH ) toward the inner carbon atom of the NCP allows the formation of two types of coordinated products (i. e.

Theoretical Study on the Spectroscopic Observation of Intersystem Crossing between B and A States of GeH Using the GeH (B) Anion.

We performed nonadiabatic quantum wave packet dynamics calculations to simulate the photodetachment spectrum of the GeH (B) anion. We developed the (4 × 4) diabatic potential energy surfaces to describe the intersystem crossing transitions between the neutral A and B states induced by spin-orbit interactions based on ab initio calculations. The spin-orbit coupling matrix elements were calculated using the Breit-Pauli Hamiltonian with the spin-free states obtained from the multireference configuration interaction method.

Nuclear quantum effects in the direct ionization process of pure helium clusters: path-integral and ring-polymer molecular dynamics simulations on the diatomics-in-molecule potential energy surfaces.

The direct photoionization of pure helium clusters, He (n = 100, 200 and 300), and its subsequent short-time process have been studied by path integral molecular dynamics (PIMD) and ring-polymer molecular dynamics (RPMD) simulations that can effectively describe the nuclear quantum effects in large systems. The modified diatomics-in-molecule (DIM) model [Calvo et al., J.

Synthesis and physical properties of brominated hexacene and hole-transfer properties of thin-film transistors.

A halide-substituted higher acene, 2-bromohexacene, and its precursor with a carbonyl bridge moiety were synthesized. The precursor was synthesized through 7 steps in a total yield of 2.5%.

Synthesis, Optical Properties, and Electronic Structures of Tetrakis(pentafluorophenyl)tetrathiaisophlorin Dioxide.

The synthesis, structure, optical and redox properties, and electronic structure of tetrakis(pentafluorophenyl)tetrathiaisophlorin dioxide (12) are reported. Oxidation of tetrakis(pentafluorophenyl)tetrathiaisophlorin (11) with dimethyldioxirane afforded the oxidized product, which was the tetrathiaisophlorin with two thiophene 1-oxide moieties (12). More significant nonplanarity and greater bond length alternation in 12 than those of 11 were observed by X-ray structural analysis.

Multistep Electron Transfer Systems Containing [2.2]- or [3.3]Paracyclophane.

Paracyclophanes (PCPs), which exhibit interesting properties due to their transannular interactions, have been employed as a spacer in various electron transfer (ET) systems. In the present work, we investigated ET processes in dyads and triads containing [2.2]PCP or [3.

A gustatory second-order neuron that connects sucrose-sensitive primary neurons and a distinct region of the gnathal ganglion in the Drosophila brain.

Although the gustatory system provides animals with sensory cues important for food choice and other critical behaviors, little is known about neural circuitry immediately following gustatory sensory neurons (GSNs). Here, we identify and characterize a bilateral pair of gustatory second-order neurons (G2Ns) in Drosophila. Previous studies identified GSNs that relay taste information to distinct subregions of the primary gustatory center (PGC) in the gnathal ganglia (GNG).

Synthesis and electronic and photophysical properties of [2.2]- and [3.3]paracyclophane-based donor-donor'-acceptor triads.

Three types of the donor(D)-donor'(D')-acceptor(A) triads 1-6 with different D-A combinations, carbazole (Cz, D)-[n.n]PCP(D')-1,8-naphthalimide (NI, A) (1-3), 10H-phenothiazine (PTZ, D)-[n.n]PCP(D')-NI(A) (4, 5), and 10-methyl-10H-phenothiazine (Me-PTZ, D)-[2.

Visualization of the dynamic behavior of ribosomal RNA gene repeats in living yeast cells.

The ribosomal RNA (rRNA) gene forms an extremely large repeat (rDNA) in the chromosome. In budding yeast, Saccharomyces cerevisiae, the rDNA is located on chromosome XII and occupies approximately 60% (1.5 Mb) of the chromosome and 10% of the total genome.

Neural architecture of the primary gustatory center of Drosophila melanogaster visualized with GAL4 and LexA enhancer-trap systems.

Gustatory information is essential for animals to select edible foods and avoid poisons. Whereas mammals detect tastants with their taste receptor cells, which convey gustatory signals to the brain indirectly via the taste sensory neurons, insect gustatory receptor neurons (GRNs) send their axons directly to the primary gustatory center in the suboesophageal ganglion (SOG). In spite of this relatively simple architecture, the precise structure of the insect primary gustatory center has not been revealed in enough detail.

Abundance of ribosomal RNA gene copies maintains genome integrity.

The ribosomal RNA (rDNA) gene repeats are essential housekeeping genes found in all organisms. A gene amplification system maintains large cluster(s) of tandemly repeated copies in the chromosome, with each species having a specific number of copies. Yeast has many untranscribed rDNA copies (extra copies), and we found that when they are lost, the cells become sensitive to DNA damage induced by mutagens.

Olfactory sensory neurons expressing class I odorant receptors converge their axons on an antero-dorsal domain of the olfactory bulb in the mouse.

Vertebrate odorant receptor (OR) genes are divided phylogenetically into two distinct classes: the fish-like class I and the terrestrial-specific class II. In the present study, we systematically analysed mouse class I OR genes (42 subfamilies) to elucidate the expression profiles in the olfactory epithelium (OE) and the projection sites of their olfactory sensory neurons (OSNs) in the olfactory bulb (OB). In situ hybridization (ISH) revealed that most class I OR genes (36 subfamilies) were expressed in the dorso-medial zone (zone 1) of the OE.