Hybrid EuIII Coordination Luminophore Standing on Two Legs on Silica Nanoparticles for Enhanced Luminescence

In this study, we have demonstrated a two-legged, upright molecular design method for monochromatic and bright red luminescent Ln^III-silica nanomaterials. A novel Eu^III-silica hybrid nanoparticle was developed by using a doubly binding TPPO−Si(OEt)₃ (TPPO: triphenyl phosphine oxide) linker. The TPPO−Si(OEt)₃ was confirmed by ¹H, ³¹P, ²⁹Si NMR spectroscopy and single-crystal X-ray analysis. Luminescent Eu(hfa)₃ and Eu(tfc)₃ moieties (hfa: hexafluoroacetylacetonate, tfc: 3-(trifluoromethylhydroxymethylene)camphorate) were fixed onto TPPO−Si(OEt)₃-modified silica nanoparticles, producing Eu(hfa)₃(TPPO−Si)₂-SiO₂ and Eu(tfc)₃(TPPO−Si)₂-SiO₂, respectively. Eu(hfa)₃(TPPO−Si)₂−SiO₂ exhibited the higher intrinsic luminescence quantum yield (93 %) and longer emission lifetime (0.98 ms), which is much larger than those of previously reported Eu^III-based hybrid materials. Eu(tfc)₃(TPPO−Si)₂−SiO₂ showed an extra-large intrinsic emission quantum yield (54 %), although the emission quantum yield for the precursor Eu(tfc)₃(TPPO−Si(OEt)₃)₂ was found to be 39 %. These results confirmed that the TPPO−Si(OEt)₃ linker is a promising candidate for development of Eu^III-based luminescent materials.     

Large electro‐optic activity and enhanced temporal stability of methacrylate‐based crosslinking hyperbranched nonlinear optical polymer

A methacrylate‐based crosslinking hyperbranced polymers have been synthesized through initiator‐fragment incorporation radical polymerization and used for the temperature stable electro‐optic (EO) polymer application. This polymer consists of methyl methacrylate, 2‐metacryloxyethyl isocyanate, and ethylene glycol dimethacrylate (EGDMA) monomers. The use of EGDMA as a bifunctional unit resulted in the solvent‐soluble crosslinking hyperbranched chain, so that the EO polymer enhanced glass transition temperatures. A phenyl vinylene thiophene vinylene bridge nonlinear optical chromophore was attached to the polymer backbone as the side‐chain by a post‐functionalization reaction. The loading concentration of the chromophore was varied between 30 and 50 wt % by simply changing the mixing ratio of the precursor polymer to the chromophore. The synthesized EO polymers produced optical quality films with a light propagation loss of 0.61 dB/cm in a slab waveguide at 1.31 μm. The electrically poled film had an EO coefficient (r₃₃) of 139 pm/V at 1.31 μm. The EO crosslinking hyperbranced polymer had a high‐glass transition temperature of 170 °C, and exhibited excellent temporal stability of the EO activity at 85 °C for 500 h. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of poly(ethylene glycol)‐based hydrogels and their swelling/shrinking response to molecular recognition

To synthesize the novel molecular‐ and pH‐stimulus‐responsive hydrogel, we prepared poly(ethylene glycol)‐based hydrogel containing ionic groups. We evaluated the fundamental swelling/shrinking properties of the hydrogels synthesized by various conditions. Decreasing the molecular weight of a crosslinker provided the increasing of the equilibrium swelling ratio. Also, the equilibrium swelling ratio was changed by the introduction of functional ionic monomers and its compositions. Furthermore, the swelling/shrinking behaviors of the hydrogels were affected by the environmental condition of aqueous solution, in fact the hydrogels were considerably shrunk (to one‐fifth volume) using a di‐ionic solute in the aqueous solution through the ionic interactions between the hydrogel and the solutes. Additionally, the specific shrinking to diamine compounds was also observed in response to pH change. These results clearly show the swelling/shrinking responsibility of the hydrogels toward the molecular recognitions and its pH conditions. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3153–3158     

Fluorine in Shark Teeth: Its Direct Atomic‐Resolution Imaging and Strengthening Function

Atomic‐resolution imaging of beam‐sensitive biominerals is extremely challenging, owing to their fairly complex structures and the damage caused by electron irradiation. Herein, we overcome these difficulties by performing aberration‐corrected electron microscopy with low‐dose imaging techniques, and report the successful direct atomic‐resolution imaging of every individual atomic column in the complex fluorapatite structure of shark tooth enameloid, which can be of paramount importance for teeth in general. We demonstrate that every individual atomic column in shark tooth enameloid can be spatially resolved, and has a complex fluorapatite structure. Furthermore, ab initio calculations show that fluorine atoms can be covalently bound to the surrounding calcium atoms, which improves understanding of their caries‐reducing effects in shark teeth.     

Near-IR Luminescent YbIII Coordination Polymers Composed of Pyrene Derivatives for Thermostable Oxygen Sensors

Oxygen-sensitive and near-infrared (NIR) luminescent Yb^III coordination polymers incorporating ligands based on pyrene derivatives were synthesized: Yb^III–TBAPy and Yb^III–TIAPy (TBAPy: 1,3,6,8-tetrakis(p-benzoate)pyrene; TIAPy: 1,3,6,8-tetrakis(3,5-isophthalic acid)pyrene). The coordination structures of these materials have been characterized by means of electrospray ionization mass spectrometry, X-ray diffraction analysis, and thermogravimetric analysis. Moreover, the porous structure of Yb^III–TIAPy has been evaluated by measuring its N₂ adsorption isotherm. The NIR luminescence properties of Yb^III–TBAPy and Yb^III–TIAPy have been examined by acquiring emission spectra and determining emission lifetimes under air or argon and in vacuo. Yb^III–TIAPy exhibited high thermal stability (with a decomposition temperature of 400 °C), intense luminescence (with an emission quantum yield under argon of 6.6 %), and effective oxygen-sensing characteristics. These results suggest that NIR luminescent Yb^III coordination polymers prepared using pyrene derivatives could have applications in novel thermo-stable oxygen sensors.     

Enhancement of Light Absorption Ability of Synthetic Chlorophyll Derivatives by Conjugation with a Difluoroboron Diketonate Group

The enhancement of the light absorption ability of synthetic chlorophyll derivatives is demonstrated. Chlorophyll derivatives directly conjugated with a difluoroboron 1,3‐diketonate group at the C3 position were synthesized from methyl pyropheophorbide‐d through Barbier acylmethylation of the C3‐formyl moiety, oxidation of the C3‐carbinol, and difluoroboron complexation of the diketonate. Electronic absorption spectra in a diluted solution showed that the synthetic conjugates gave an absorption band at λ=400–500 nm, with a Qy band shifted to a longer wavelength of λ≈700 nm. DFT calculations demonstrated that the absorption bands and redshifts were ascribable to the coupling of the LUMO of chlorin with that of the difluoroboron diketonate moiety. The introduction of a pyrenyl group at the C3³‐position of the conjugate afforded an additional charge‐transfer band over λ=500 nm, producing a pigment that bridged the green gap in standard chlorophylls.     

Acceleration of Proliferative Response of Mouse Fibroblasts by Short-Time Pretreatment with Polyphenols

Under the hypothesis that photo-irradiated proanthocyanidin could accelerate wound healing through reactive oxygen species (ROS) formation, we examined the effect of proanthocyanidin on 3T3-L1 mouse fibroblasts with or without photo-irradiation. As a result, irrespective of presence or absence of photo-irradiation, only 1 min exposure of the cells to proanthocyanidin resulted in accelerated proliferation of the cells in a concentration-dependent manner. Similarly to proanthocyanidin, 1 min pretreatment with catechin, caffeic acid, and chlorogenic acid accelerated the proliferative response, but gallic acid, epicatechin gallate, epigallocatechin, and epigallocatechin gallate failed. If incorporated active ingredient such as proanthocyanidin for such a short time as 1 min accelerates the proliferation response, a bioassay was conducted by utilizing antioxidant potential of proanthocyanidin. That is, intracellular oxidation of 2′,7′-dichlorodihydrofluorescin induced by H₂O₂ was significantly inhibited when the cells were pretreated with proanthocyanidin for 1 min, suggesting that incorporated proanthocyanidin into the cells exerted antioxidant effect. This was also supported by a liquid chromatography/mass spectrometry analysis in which incorporation of proanthocyanidin components such as catechin monomers and dimers into the cells within 1 min was confirmed. These results suggest that active polyphenolic compounds such as proanthocyanidin, catechin, caffeic acid, and chlorogenic acid incorporated into the cells in such a short time as 1 min could accelerate the proliferative response of the cells.