Stimuli-Responsive Molecular Photon Upconversion

The addition of stimuli-responsiveness to anti-Stokes emission provides a unique platform for biosensing and chemosensing. Particularly, stimuli-responsive photon upconversion based on triplet–triplet annihilation (TTA-UC) is promising due to its occurrence at low excitation intensity with high efficiency. This Minireview summarizes the recent developments of TTA-UC switching by external stimuli such as temperature, oxygen, chemicals, light, electric field, and mechanical force. For the systematic understanding of the underlying general mechanisms, the switching mechanisms are categorized into four types: 1) aggregation-induced UC; 2) assembly-induced air-stable UC; 3) diffusion-controlled UC; and 4) energy-transfer-controlled UC. The development of stimuli-responsive smart TTA-UC systems would enable sensing with unprecedented sensitivity and selectivity, and expand the scope of TTA-UC photochemistry by combination with supramolecular chemistry, materials chemistry, mechanochemistry, and biochemistry.     

Strategic multi-store opening under financial constraint

This paper analyzes strategic store openings in a situation in which firms can open multiple stores depending on the financial constraints of the firm. Specifically, given any upper limit of the number of store openings that two potentially symmetric firms can open, they sequentially determine the number of store openings, including their locations, to maximize their profits. As a result of our analysis in a microeconomic framework, we show that the equilibrium strategy can be wholly classified into only two following opposite strategies according to the level of their financial constraints involved. When firms can afford to invest significant amounts of money in the market, the leader chooses “segmentation strategy,” in which a part of the market can be monopolized by opening a chain of multiple stores and deterring the follower’s entry. In contrast, when the leader has a severe financial constraint so that it can only monopolize less than half of the market, the leader chooses “minimum differentiation strategy,” where firms open each of their stores at exactly the same point as the rival’s. Under this strategy, the leader necessarily captures just half of the market. Furthermore, we show that regardless of potential symmetry between firms, both first and second mover advantages in terms of profit can occur in the equilibrium.     

Preparation of Polymeric Analogs of Tetramethylurea and Their Use as Liquid-Liquid Phase-Transfer Catalysts

Polymeric analogs of tetramethylurea were prepared by free-radical polymerization of N,N,N'-trimethyl-N'-p-vinylbenzylurea and copolym-erization of this monomer with styrene. These polymers are soluble in toluene and have the ability to extract alkali metal ions such as lithium, sodium, and potassium. Moreover, these polymers act as phase-transfer catalysts for typical S _N 2 reactions, although the monomeric analogs tetramethylurea and N,N,N'-trimethyl-N'-benzylurea do not. A plausible mechanism for these catalytic reactions is proposed.     

The effect of additional autopolyploidization in a slow growing cellulase hyperproducer of Trichoderma

M14-2 is a cellulase hyperproducer derived from Trichderma recesei QM 6a, but with a growth rate lower than that of the original strain. When M14-2 was autopolyploidized followed by haploidization and selection, the strain with both a higher cellulase productivity per mycelia and a higher growth rate could be obtained as M14-2B. This strain seemed to be constructed using gene sources amplified by additional autopolyploidization.     

(2,2′‐Biquinoline‐κ2N,N′)dichloropalladium(II), ‐copper(II) and ‐zinc(II)

In the three title complexes, namely (2,2′‐biquinoline‐κ²N,N′)dichloro­palladium(II), [PdCl₂(C₁₈H₁₂N₂)], (I), and the corresponding copper(II), [CuCl₂(C₁₈H₁₂N₂)], (II), and zinc(II) complexes, [ZnCl₂(C₁₈H₁₂N₂)], (III), each metal atom is four‐coordinate and bonded by two N atoms of a 2,2′‐biquinoline molecule and two Cl atoms. The Pd^II atom has a distorted cis‐square‐planar coordination geometry, whereas the Cu^II and Zn^II atoms both have a distorted tetra­hedral geometry. The dihedral angles between the N—M—N and Cl—M—Cl planes are 14.53 (13), 65.42 (15) and 85.19 (9)° for (I), (II) and (III), respectively. The structure of (II) has twofold imposed symmetry.     

Copper(II) and zinc(II) complexes of pyridine‐2,6‐di­carboxyl­ic acid

The title compounds, bis­(pyridine‐2,6‐di­carboxyl­ato‐N,O,O′)copper(II) monohydrate, [Cu(C₇H₄NO₄)₂]·H₂O, andbis(pyridine‐2,6‐dicarboxylato‐N,O,O′)zinc(II) trihydrate, [Zn(C₇H₄NO₄)₂]·3H₂O, have distorted octahedral geometries about the metal centres. Both metal ions are bonded to four O atoms and two pyridyl‐N atoms from the two terdentate ligand mol­ecules, which are nearly perpendicular to each other. The copper(II) complex has twofold crystallographic symmetry and contains two different ligand mol­ecules, one of which is neutral and another doubly ionized. In contrast, the zinc(II) complex contains two identical singly ionized ligand mol­ecules. Both crystal structures are stabilized by O—H?O intermolecular hydrogen bonds between the complex and the water mol­ecules.     

catena‐Poly­[[di­aqua­lithium(I)]‐μ‐[9H‐purine‐2,6(1H,3H)‐dionato‐O2:N7]]

In the title compound, [Li(C₅H₃N₄O₂)(H₂O)₂]_n, the coordinate geometry about the Li⁺ ion is distorted tetrahedral and the Li⁺ ion is bonded to N and O atoms of adjacent ligand mol­ecules forming an infinite polymeric chain with Li—O and Li—N bond lengths of 1.901 (5) and 2.043 (6) Å, respectively. Tetrahedral coordination at the Li⁺ ion is completed by two cis water mol­ecules [Li—O 1.985 (6) and 1.946 (6) Å]. The crystal structure is stabilized both by the polymeric structure and by a hydrogen‐bond network involving N—H?O, O—H?O and O—H?N hydrogen bonds.     

Partial Protection of Carbohydrate Derivatives. Part 13.1 Chemical Conversion of Kanamycin A Into 2′-Deoxykanamycin A, 2′-Epi-Kanamycin A,and 2′-Epi-Kanamycin B

Abstract

Hydrazinolyses of hexa-0-benzoyl-tetra-N-benzyloxycarbonyl-and N-ethoxycarbonylkanamycin A were performed and found to be sufficiently regioselective to give the corresponding 2′-hydroxyl derivatives in good yields under controlled conditions. The products were converted into the corresponding 2′-triflates, which were then subjected to nucleophilic substitution reactions with sodium benzenethioxide, sodium benzoate, and sodium azide to give the corresponding d-mannopyranosyl derivatives in good yields. Deprotection of the phenylthio (10) and azido (12) derivatives, and hydrogenolysis, gave 2′-deoxykankmycin A and 2′-epi-kanamycin B, respectively. Moreover, deprotection of the benzoyl compound 11 gave 2′-epi-kanamycin A.     

Metallation of a cyclic chlorophyll hetero-dyad, and the optical properties of synthetic metallo-dyads

A cyclic chlorophyll hetero-dyad 1-H₂H₂, prepared by double ester linking of two structurally different pyropheophorbide-a moieties through 3-CH₂OCO-13²′ and 17²-COOCH₂-3′, was metallated with zinc and copper to give mono and di-metallated complexes 1-MH₂ or 1-H₂M and 1-MM. The metallation proceeded stepwise and regioselectively, with predominant synthesis of one of the two mono-metallated complexes 1-MH₂ as intermediate. The di-zinc complex produced, 1-ZnZn, was demetallated exclusively via the same mono-zinc complex 1-ZnH₂ as was the major intermediate during metallation. Visible and/or circular dichroism spectra of 1-H₂H₂, 1-MH₂, 1-H₂M, and 1-MM (M = Ni, Cu, or Zn) were measured in organic solvents. Intramolecular interaction of chlorin chromophores is discussed and compared with that of the corresponding monomeric species.     

Difference between low-volume and high-volume Andersen samplers in measuring atmospheric aerosols

The mass concentration and size distribution of aerosols in Tokaimura were investigated using a high-volume and a low-volume Andersen sampler. A difference was found using the two samplers： the concentration of total aerosols determined with the high-volume sampler is smaller than that of the low-volume sampler by 70-90% throughout the year. Compared to the high-volume sampler, low-volume sampler gave lower concentration for aerosols 〉7 μm, higher concentration for aerosols of 3.3-7.0 μm and 〈 1.1 μm, though similar results for aerosols of 1.1-3.3 μm. The low-volume sampler was found to have better separation efficiency and higher accuracy.