Design of Photostable,Activatable Near‐Infrared Photoacoustic Probes Using Tautomeric Benziphthalocyanine as a Platform

Near‐infrared (NIR) imaging techniques have attracted significant attention for biological and medicinal applications due to the ability of NIR to penetrate deeply into tissues. However, there are very few stable, activatable molecular probes that can utilize NIR light in the wavelength range beyond 800 nm. Herein, we report a new activatable NIR system for photoacoustic imaging based on tautomeric benziphthalocyanines (BPcs). We found that the existence of a free hydroxyl group is crucial for NIR absorption of BPcs. Synthesized water‐soluble hydroxy BPcs exhibited high photostability and no fluorescence, which are desirable features for photoacoustic imaging. We synthesized BPcs in which the free hydroxyl group was masked by an esterase‐labile or an H₂O₂‐labile group. The photoacoustic signals of these hydroxy‐masked BPcs were increased upon NIR excitation at 880 nm in the presence of esterase or H₂O₂, respectively. These are rare examples of activatable probes utilizing NIR light at around 900 nm.     

Ring-Opened Hemiporphyrazines: Helical Molecules Exhibiting Circularly Polarized Luminescence

We designed and synthesized a new type of small helical molecule exhibiting intense circularly polarized luminescence (CPL) ( 1_2H ) by modifying a 20π-electron hemiporphyrazine with a large transition magnetic dipole moment. The hemiporphyrazine ring was opened and one additional pyridine unit was introduced, resulting in an overlap of two pyridine rings. X-ray structure analysis confirmed that 1_2H and its zinc complex ( 1_Zn ) adopt a helical geometry. A racemic mixture of 1_Zn was resolved into two enantiomers ((P)- and (M)- 1_Zn ), which exhibited CPL with a high luminescence dissymmetry factor (g_lum) value of ±2.1×10⁻². The origin of the large g_lum value was rationalized by means of DFT calculations. Helical structures could be formed in a diastereoselective manner by covalently attaching chiral units to the skeleton ( 1’_2H and 1’_Zn ). 1_Zn was found to possess chiral recognition ability for amines.     

Characterization of atmospheric tritiated water concentration in the vicinity of the fukushima daiichi nuclear power plant

Journal of Radioanalytical and Nuclear Chemistry - This paper discusses the spatiotemporal variation in atmospheric tritiated water (HTO) concentration near the Fukushima Daiichi Nuclear Power...     

Synthesis and electronic structures of D2h-symmetry tetrabenzoporphyrins

A novel low-symmetry tetrabenzoporphine with D_2h symmetry (1) and its zinc complex (2) were prepared via mixed condensation reaction of 5,6-dimethyl phthalimide and 4,5,6,7-tetraphenyl phthalimide with sodium acetate in the presence of zinc acetate. The zinc complex 2 exhibited a split Q band at 640 and 623 nm and a single Soret band at 435 nm. The absorption spectra of 1 and 2 were calculated and analyzed using Hartree-Fock theory based on INDO/S Hamiltonian.     

Optical resolution, absolute configuration, and chiroptical properties of three-layered [3.3]paracyclophane

A racemic mixture of three-layered [3.3]paracyclophane ([3.3]PCP), 1, has been resolved into two enantiomers, and their absolute configuration was determined from a comparison of experimental chiroptical properties and density functional theory (DFT) calculations. A simple model comprising two p-xylenes and 1,2,4,5-tetramethylbenzene (durene) was used to explain the origin of the chiroptical properties of the three-layered cyclophane system.     

Partial pair correlation functions of low-density supercritical water determined by neutron diffraction with the H/D isotopic substitution method

Neutron diffraction measurements were carried out on H/ D isotopically substituted water in the low-density supercritical condition (T = 673 K, P = 26.3 MPa, and rho = 0.0068 molecules.A-3) in order to obtain direct information on the intermolecular partial structure functions, gHH inter(r), gOH inter(r), and gOO inter(r). In correspondence to the high-density supercritical water previously reported, the intermolecular nearest neighbor peaks in gHH inter(r), gOH inter(r), and gOO inter(r) are diffuse compared with the ambient ones. The nearest neighbor O...O distance (3.3 A) and its coordination number (2.6) were determined from the observed gOO inter(r). These results indicate that the orientational correlation between neighboring water molecules is considerably lost in low-density supercritical water. Small clusters involving a few water molecules are preferentially formed in low-density supercritical water, which is consistent with results obtained by previous IR and NMR studies.     

Nonlinear magneto-optical effects and photomagnetism of electrochemically synthesized molecule-based magnets

This article describes novel optical functionalities such as photomagnetic effects and magnetization-induced second harmonic generation (MSHG) in several cyano-bridged metal assemblies. Single crystal- and film-types of a cyano-bridged Cu–Mo bimetallic assembly, , were electrochemically prepared. When this compound was irradiated with light, spontaneous magnetization with a Curie temperature (T _C) of 23 K was observed. Electrochemically prepared Fe^II[Cr^III(CN)₆]_2/3·5H₂O thin film, which was a ferromagnet with T _C=21 K, showed photoreduced magnetization. This photomagnetism is due to the change of ferromagnetic coupling between Fe^II and Cr^III. MSHG was observed in Cs^ICo^II[Cr^III(CN)₆]·0.5H₂O. This -type Prussian blue analog-based magnet is proven to be a piezoelectric ferromagnet, i.e., condensed matter with both piezoelectric and ferromagnetism. This MSHG is due to the coupling between a piezoelectric structure of and ferromagnetism with a T _C of 46 K.

Alternating Copolymerization of Ethylene and 5‐Hexen‐1‐ol with [Ethylene(1‐indenyl)(9‐fluorenyl)]‐zirconium Dichloride/Methylaluminoxane as the Catalyst

The copolymerization of ethylene and 5‐hexen‐1‐ol pretreated with trimethylaluminium was performed using [ethylene(1‐indenyl)(9‐fluorenyl)]zirconium dichloride/methylaluminoxane as the catalyst. The 5‐hexen‐1‐ol unit in the copolymer could be increased to about 50 mol‐% with increasing [5‐hexen‐1‐ol/ethylene[ ratio. ¹³C NMR analysis proved that the poly(ethylene‐co‐(5‐hexen‐1‐ol)) containing 50 mol‐% of 5‐hexen‐1‐ol units is an almost alternating copolymer.     

Preparation of Monodisperse Polylactide Microspheres by Dispersion Polymerization Using a Polymeric Stabilizer with Hydroxy Groups

Monodisperse poly(D ,L ‐lactide) (PDLLA) microspheres have been prepared by dispersion polymerization of D ,L ‐lactide with a synthetic polymeric stabilizer. The polymerization is carried out in xylene/heptane (1:2, v/v) at 368 K for 3 h with poly[(dodecyl methacrylate)‐co‐(2‐hydroxyethyl methacrylate)] (P(DMA‐co‐HEMA)). P(DMA‐co‐HEMA) has hydroxy groups as an initiation group for pseudoanionic dispersion polymerization. The particle diameter and the coefficient of variation concerning the diameter distribution of the obtained PDLLA microspheres are 3.9 µm and 4.3%, respectively. In addition, from the results of dynamic light scattering measurements, it is found that P(DMA‐co‐HEMA) and the PDLLA‐grafted copolymer form a micellar structure in solution.