Construction of a Database Aimed at Complementing Information by Presenting Time Series of Scattered Regional Business Records in the Edo period

The Saga Prefectural Library and Saga University have in their collections the “Nikki" of the Saga clan and its branch clans, as well as a collection of business journals known as the “Nikki Mokuroku," which are summarized titles of these journals. This collection also includes private records equivalent to jounals kept in the homes of the feudal lord's officials. In order to gain an integrated understanding of the political and economic movements within and outside the domain at the time from these historical documents, the Saga University's Center for Regional Culture and History has constructed a "Time-series Database of ’Nikki' Materials Related to the Saga Domain," which allows users to reference 11 different journals surviving in the Saga Prefecture area, with journal images from the same date in parallel. In addition, the daily articles in the “Ogi-han Nikki Database" are also supported. As a result, records of various events and weather conditions on a given date complement each other, making it possible to collect information in an integrated manner. This paper presents an overview of the database and its current efforts, including potential applications such as machine learning.</p

Intramolecular Charge Transfer in a Star-Shaped Oligoarylamine

The intervalence (IV) states of the monocationic states of the star-shaped nonaamine (3) and the triamine (2) as the branched unit in 3 have been examined by electrochemical, spectroelectrochemical, and temperature-dependent ESR spectroscopy. The oligoarylamines 2 and 3 were synthesized by using the successive palladium-catalyzed amination reaction. The redox property of 3 was basically the same as that of 2. However, there exist small potential differences between the first three one-electron oxidations for 3, indicating electronic coupling among the peripherally substituted triamine moieties via the central 1,3,5-benzenetriyl bridging unit. The observed ESR spectral pattern for 2+ remained unchanged over the measured temperature range. From the spectral simulation analyses, it was concluded that the unpaired electron in 2+ is fully delocalized over the whole molecule on the ESR time scale. This conclusion was corroborated by comparison of its optical absorption spectrum with TD-DFT-calculated results. In contrast, the peak-to-peak ESR line width (ΔHPP) of 3+ exhibited temperature dependency. This behavior is ascribed to the thermally activated intramolecular charge transfer (ICT) among the branched three triamine moieties via the central 1,3,5-benzenetriyl bridging unit. From the spectral simulations based on the stochastic Liouville method, the first-order rate constant at each temperature and the parameters of the energy barrier for the ICT in 3+ were successfully determined

<i>N</i>-Methyl-Substituted Aza[1<i>_n</i>]metacyclophane: Preparation, Structure, and Properties

A series of aza[1n]metacyclophanes (n = 3−8), which correspond to the cyclic oligomers of poly(m-aniline), are obtained in one step by a Pd(0)-catalyzed amination reaction of 3-bromo-N-methylaniline. The most stable conformations of the cyclic trimer and tetramer are determined by density functional calculations. The theoretical results show that these new macrocyclic compounds can be regarded as precursors for cyclophane-based high-spin molecules. Moreover, we describe their spectroscopic and electrochemical properties in connection with the ring size of these cyclic oligomers

Isolation and Characterization of Persistent Radical Cation and Dication of 2,7-Bis(dianisylamino)pyrene

Orbital interaction between 2,7-pyrenylene and two nitrogen redox-active centers effectively reduces the energy difference between HOMO and HOMO–1, both of which were distributed over the two nitrogen centers. In fact, one- and two-electron oxidation of 2,7-bis­(dianisylamino)­pyrene <b>3</b> generated a persistent radical cation and a persistent dication, respectively, and we succeeded in the isolation and single crystal X-ray structural analyses of all three oxidation states. The radical cation was considered as a spin and charge delocalized mixed-valence compound with a semiquinoidal structure. The dication was in an open-shell singlet state with a small singlet–triplet energy gap. The molecular and electronic structures for all three oxidation states of <b>3</b> were studied in comparison with the data reported for each oxidation state of closely related bis­(triarylamine)­s, of which structures were determined by X-ray crystallography

Luminescent Superbenzene with Diarylamino and Diarylboryl Groups

Dianisylamino donor and dimesitylboryl acceptor substituents were introduced at the 2,11-positions of hexa-<i>peri</i>-hexabonzocoronene (HBC) to demonstrate an effective fluorescent enhancement of HBC as virtually nonfluorescent “superbenzene”. The present donor–acceptor substitution replaced the typical weak α-band with an intense intramolecular charge-transfer band in the absorption spectrum, thereby leading to a much larger fluorescence quantum yield (Φ_f = 0.56 in CH₂Cl₂) than any other HBC derivatives

Isolation and Characterization of Persistent Radical Cation and Dication of 2,7-Bis(dianisylamino)pyrene

Orbital interaction between 2,7-pyrenylene and two nitrogen redox-active centers effectively reduces the energy difference between HOMO and HOMO–1, both of which were distributed over the two nitrogen centers. In fact, one- and two-electron oxidation of 2,7-bis­(dianisylamino)­pyrene <b>3</b> generated a persistent radical cation and a persistent dication, respectively, and we succeeded in the isolation and single crystal X-ray structural analyses of all three oxidation states. The radical cation was considered as a spin and charge delocalized mixed-valence compound with a semiquinoidal structure. The dication was in an open-shell singlet state with a small singlet–triplet energy gap. The molecular and electronic structures for all three oxidation states of <b>3</b> were studied in comparison with the data reported for each oxidation state of closely related bis­(triarylamine)­s, of which structures were determined by X-ray crystallography

Regio- and Diastereocontrol in Carbonyl Allylation by 1-Halobut-2-enes with Tin(II) Halides

Regio- and diastereoselective carbonyl allylations of 1-halobut-2-enes with tin(II) halides are described. Tin(II) bromide in a dichloromethane−water biphasic system is an effective reagent for unusual α-regioselective carbonyl allylation of 1-bromobut-2-ene to produce 1-substituted pent-3-en-1-ols. The addition of tetrabutylammonium bromide (TBABr) to the biphasic system produces 1-substituted 2-methylbut-3-en-1-ols via usual γ-addition which is opposite to the α-addition without TBABr. The γ-addition to aromatic aldehydes exhibits anti-diastereoselectivity, while that to aliphatic aldehydes is not diastereoselective. The allylation of benzaldehyde by 1-chlorobut-2-ene in 1,3-dimethylimidazolidin-2-one (DMI) does not occur with tin(II) chloride or bromide but does proceed with tin(II) iodide and exhibits γ-syn selectivity which is unusual for a Barbier-type carbonyl allylation. In the carbonyl allylation by 1-chlorobut-2-ene with any tin(II) halide, the addition of tetrabutylammonium iodide (TBAI) accelerates the reaction and enhances γ-syn selectivity. The use of tin(II) iodide and TBAI produces 2-methyl-1-phenylbut-3-en-1-ol with high yield and high syn-diastereoselectivity. The syn-diastereoselective carbonyl allylation of 1-chlorobut-2-ene using tin(II) iodide, a catalytic amount of TBAI, and NaI in DMI−H2O is applied to various aldehydes

Spin-Delocalization in Charged States of <i>para</i>-Phenylene-Linked Dendritic Oligoarylamines

Two kinds of basic dendritic (or starburst) all-para-phenylene-linked oligotriarylamines, which are generated from para-phenylenediamine and triphenylamine as core units, respectively, were prepared, and the electrochemical, spectroelectrochemical, ESR spectroscopic measurements were carried out with respect to their application as hole transport materials in optoelectronic devices such as organic light-emitting devices. The prepared dendritic oligoarylamines exhibits the multiredox-active properirs, and are stably oxidizable up to tetra- or hexacations. According to the degree of oxidation, it was suggested that the charge distribution of the charged states gradually change so as to reduce the electrostatic repulsion between increased charges on the basis of the spectroelectrochemical studies. Moreover, the stability of the generated radical cations and the spin distribution in their radical cations were confirmed by the ESR measurements

<i>Meta</i>–<i>Para</i>-Linked Octaaza[1₈]cyclophanes and Their Polycationic States

Octaazacyclophanes, octaaza­[1₈]<i>m</i>,<i>p</i>,<i>m</i>,<i>p</i>,<i>m</i>,<i>p</i>,<i>m</i>,<i>p</i>-cyclophane (<b>2</b>) and octaaza­[1₈]<i>m</i>,<i>p</i>,<i>p</i>,<i>p</i>,<i>m</i>,<i>p</i>,<i>p</i>,<i>p</i>-cyclophane (<b>3</b>), as ring-size extended congeners of tetraaza­[1₄]<i>m</i>,<i>p</i>,<i>m</i>,<i>p</i>-cyclophane were synthesized, and the electronic states of their polycationic species were investigated by quantum chemical calculations, electrochemical measurements (cyclic voltammetry (CV) and differential pulse voltammetry (DPV)), UV–vis–NIR spectroelectrochemical measurements, and pulsed electron spin resonance (ESR) spectroscopy. These octaazacyclophanes exhibited multiredox activities depending on different linkage patterns along the macrocyclic molecular skeletons, and both molecules were oxidizable up to their respective octacations. Spectroelectrochemical measurements demonstrated that <i>p</i>-phenylenediamine (PD) moieties in <b>2</b> could be converted from the semiquinoidal structure to the quinoidal sturcture with increasing oxidation number, whereas higher oxidation states of <b>3</b> did not show definite quinoidal deformation of PD moieties. A pulsed ESR spectrum gave evidence about formation of the almost pure spin-triplet state for <b>3</b>²⁺, whereas the high-spin states of <b>2</b>²⁺ and <b>2</b>⁴⁺ are virtually degenerate with the competing low-spin states even at low temperatures, probably due to the fragility of spin-coupling pathway caused by facile conformational changes

A Genetically Encoded FRET Probe to Detect Intranucleosomal Histone H3K9 or H3K14 Acetylation Using BRD4, a BET Family Member

Acetylation is a well-characterized histone modification, which plays important roles in controlling epigenetic gene expression, and its malfunction is tightly associated with cancer. By taking advantage of the specific binding of BRD4 to acetylated lysine residues, we developed a FRET-based probe for visualizing histone H3 acetylation in living cells. BRD4, a protein known to be involved in acute myeloid leukemia and nuclear protein in testis midline carcinoma, recognizes the acetylation of histone H3 via its bromodomains. The probe exhibited a significant change in FRET signaling that was dependent on histone H3 acetylation. Mutagenesis studies revealed that an increase in the emission ratio reflected the acetylation of either K9 or K14 of histone H3 within the probe. Since BRD4 has increasingly drawn attention as a new anticancer drug target, we demonstrated that the developed fluorescent probe will also serve as a powerful tool to evaluate BRD4 inhibitors in living cells