Aggregation-induced enhanced fluorescence emission of chiral Zn(II) complexes coordinated by Schiff-base type binaphthyl ligands.

A pair of novel chiral Zn(II) complexes coordinated by Schiff-base type ligands derived from BINOL (1,1'-bi-2-naphthol), R-/S-Zn, were synthesized. X-ray crystallography revealed the presence of two crystallographically independent complexes; one has a distorted trigonal-bipyramidal structure coordinated by two binaphthyl ligands and one disordered methanol molecule (molecule A), while the other has a distorted tetrahedral structure coordinated by two binaphthyl ligands (molecule B). Numerous CH⋯π and CH⋯O interactions were identified, contributing to the formation of a 3-dimensional rigid network structure. Both R-/S-Zn exhibited fluorescence in both CH2Cl2 solutions and powder samples, with the photoluminescence quantum yields (PLQYs) of powder samples being twice as large as those in solutions, indicating aggregation-induced enhanced emission (AIEE). The AIEE properties were attributed to the restraint of the molecular motion arising from the 3-dimensional intermolecular interactions. CD and CPL spectra were observed for R-/S-Zn in both solutions and powders. The dissymmetry factors, gabs and gCPL values, were within the order of 10-3 to 10-4 magnitudes, comparable to those reported for chiral Zn(II) complexes in previous studies.

Synthesis and Characterization of Quinone Compounds Derived from Doubly and Triply Linked Diporphyrins and Tuning of Their Absorption Properties.

Porphyrins are attracting increasing attention in materials science and photochemistry owing to their unique properties and diverse applications. This study focuses on modifying and tuning the absorption properties of porphyrins, specifically those of quinoidal porphyrins, to extend their spectral range into the near-infrared (NIR) region. We report the synthesis and structural and physical properties of quinone compounds derived from doubly and triply linked diporphyrins and their metal complexes. Doubly linked diporphyrinquinone exhibits broad panchromatic absorption properties in solution owing to its low symmetry. Metal complexation markedly extends its absorption range into the near-infrared region. In contrast, the metal complexes of the triply linked diporphyrinquinones exhibit sharp and strong absorption bands in the visible to near-infrared region owing to their higher symmetry. The longest absorption wavelength of the triply linked diporphyrinquinones was approximately 1500 nm, which was significantly more red-shifted than that of the doubly linked ones.

Structurally well-defined conjugated meso-aminoporphyrin oligomers analogous to polyanilines.

Polyaniline, which is formed by the oxidative polymerization of aniline, is a widely explored conducting polymer with several stable oxidation states, and can be applied in advanced materials, including sensing devices and electrochemical catalysts. The marriage of polyanilines with the diverse chemistry of porphyrins is expected to confer new properties, including a combination of electrical, optical, magnetic and chemical properties. Herein, we demonstrate that meso-aminodiarylporphyrin, a porphyrin analogue of aniline, undergoes oxidative oligomerization in an acidic solution under an oxygen atmosphere to yield stable oligomeric products that are analogous to fully oxidized polyanilines. The so-formed oligomers are composed of the same number of electron-rich porphyrinoid and electron-deficient quinoid moieties, and they exhibit a broad electronic absorption band in the near infrared (NIR) region, which is attributable to intramolecular charge transfer (ICT) transition from electron-rich porphyrinoid moieties to electron-deficient quinoid ones. The quinoid moieties in the oligomers could be reversibly reduced using sodium ascorbate to obtain all-porphyrinoid oligomers that resemble fully reduced polyanilines. The fully reduced oligomers do not exhibit the NIR ICT band. Furthermore, three types of partially reduced tetramers consisting of a single quinoid moiety were also obtained, among which two interconverted in solution. Their interconversion was significantly accelerated in the presence of a protic solvent. This result is consistent with the high electron conductivity of partially oxidized polyanilines following their protonation.

Aggregation-induced circularly polarized phosphorescence of Pt(II) complexes with an axially chiral BINOL ligand.

A pair of chiral Pt(II) complexes coordinated by simple BINOL and bipyridine ligands displaying aggregation-induced phosphorescence and circularly polarized luminescence were characterized by X-ray crystallography and absorption and emission spectroscopies. The emission of the powder sample was reddish whereas the thin film dispersed in PMMA (fPf = 1 wt%) exhibited a white emission.

[2.2]Paracyclophane-Based Chiral Platforms for Circularly Polarized Luminescence Fluorophores and Their Chiroptical Properties: Past and Future.

Quality of CPL fluorophore is defined by the vectors of electric dipole transition moment and imaginary magnetic dipole transition moment. The aim of this review is to introduce readers to a chiral moiety applicable to CPL studies focusing on chiral cyclophanes because the rigid cyclophanes are able to hold the vector directions of electric dipole transition moment and imaginary magnetic dipole transition moment.

Synthesis of Porphyrinquinone and Doubly-Fused Diporphyrin Quinone Through Oxidation of Diarylporphyrins Using a Hypervalent Iodine Compound.

Treatment of a meso-diarylporphyrin with PhI(OAc)2 in the presence of BF3 ⋅ OEt2 and propionic acid affords the corresponding porphyrinquinone in a high yield (91%). A novel quinone derived from meso-meso ß-ß doubly-fused diporphyrin was obtained as the sole byproduct (16% yield), which exhibits strong panchromatic absorption between 300 and 1000 nm. It has a low HOMO-LUMO gap owing to expanded and low-symmetry π-planes.

Photovoltaic Properties and Long-Term Durability of Porphyrin-Sensitized Solar Cells with Silicon-Based Anchoring Groups.

Anchoring groups for dye-sensitized solar cells (DSSCs) play a decisive role in high-power conversion efficiency (η) and long-term cell durability. To date, a carboxylic acid is the most widely used anchoring group for DSSCs. However, the carboxylic acid tends to dissociate from a TiO2 surface during the cell operation as well as in the presence of water. Considering that the dye dissociation from TiO2 leads to a decrease in the cell performance, stable anchoring groups are highly desirable to achieve long-term durability of DSSCs toward their practical application. In this study, we designed and synthesized a series of porphyrin dyes with the triethoxysilyl anchoring groups, ZnPSi1, ZnPSi2, and ZnPSi3, to evaluate the effects of the silicon-based anchoring group on cell durability and photovoltaic properties. The DSSCs based on ZnPSi1, ZnPSi2, and ZnPSi3 exhibited moderate η-values of 2.2, 4.7, and 2.3%, respectively. It is noteworthy that the η-value of the DSSC based on ZnPSi2 (4.7%) is the highest among DSSCs based on porphyrin dyes with silicon-based anchoring groups. The moderate η-values are mainly attributed to the low charge collection efficiency originating from the low surface coverage and plausible tilted geometry of the dyes on TiO2. More importantly, we demonstrated that the DSSC based on ZnPSi2 revealed higher long-term cell durability under illumination than that based on reference porphyrin YD2 -o -C8 having a conventional carboxylic acid anchoring group.

Unsymmetrically Substituted Donor-π-Acceptor-Type 5,15-Diazaporphyrin Sensitizers: Synthesis, Optical and Photovoltaic Properties.

The first examples of unsymmetrical ß-substituted donor-π-acceptor (D-π-A)-type 5,15-diazaporphyrin (DAP) sensitizers with both p-aminophenyl and p-carboxyphenyl groups at their peripheral 3-, 7-, 13-, and/or 17-positions have been synthesized for use in dye-sensitized solar cells (DSSCs). UV/Vis absorption and emission spectroscopy, electrochemical measurements, and DFT calculations revealed that these D-π-A dyes exhibit high light-harvesting properties over the whole visible range because of the intrinsic charge-transfer character of their electronic transitions. The cell performances of TiO2 -based DSSCs fabricated with the newly prepared DAP derivatives were evaluated under standard AM1.5 conditions. Among the four dyes examined, 13,17-bis(p-carboxyphenyl)-3,7-bis[p-(N,N-dimethylamino)phenyl]-DAP showed the highest power conversion efficiency (2.0 %), which was 20 times larger than that obtained with 3-(p-carboxyphenyl)-DAP. These results show that the DAP chromophore could be used as the electron-accepting π unit in various types of functional dyes.

Metal-Free Synthesis of meso-Aminoporphyrins through Reduction of meso-Azidoporphyrins Generated in Situ by Nucleophilic Substitution Reactions of meso-Bromoporphyrins.

A facile and metal-free method for the preparation of free base meso-aminodiarylporphyrins from readily available meso-bromodiarylporphyrins is described. Simple treatment of meso-bromoporphyrins with sodium azide and sodium ascorbate in DMF affords the corresponding meso-aminoporphyrins in very good yields. This method involves the aromatic nucleophilic substitution (SNAr) of a bromo group with an azido group and the subsequent in situ reduction of the introduced azido group by sodium ascorbate. This amination reaction can be scaled up to gram scale without any decrease of the product yield. The amination reaction of free base meso-dibromoporphyrin affords a monoaminated product selectively, whereas that of the Ni(II) complex furnishes a diaminated product that is oxidized by air under ambient conditions but isolable as a trifluoroacetyl ester. Metal-insertion reactions of the obtained free base aminoporphyrins afford the corresponding metal complexes (Ni(II), Cu(II), Zn(II), and Pd(II)) all in good yields except the Pd(II) complex. Synthetic methods for the preparation of N-mono- or dialkylaminoporphyrins from the free base meso-aminoporphyrins have been also established.

Effects of Bulky Substituents of Push-Pull Porphyrins on Photovoltaic Properties of Dye-Sensitized Solar Cells.

To evaluate the effects of substituent bulkiness around a porphyrin core on the photovoltaic properties of porphyrin-sensitized solar cells, long alkoxy groups were introduced at the meso-phenyl group (ZnPBAT-o-C8) and the anchoring group (ZnPBAT-o-C8Cn, n = 4, 8) of an asymmetrically substituted push-pull porphyrin with double electron-donating diarylamino groups and a single electron-withdrawing carboxyphenylethynyl anchoring group. The spectroscopic and electrochemical properties of ZnPBAT-o-C8 and ZnPBAT-o-C8Cn were found to be superior to those of a push-pull porphyrin reference (YD2-o-C8), demonstrating their excellent light-harvesting and redox properties for dye-sensitized solar cells. A power conversion efficiency (η) of the ZnPBAT-o-C8-sensitized solar cell (η = 9.1%) is higher than that of the YD2-o-C8-sensitized solar cell (η = 8.6%) using iodine-based electrolyte due to the enhanced light-harvesting ability of ZnPBAT-o-C8. In contrast, the solar cells based on ZnPBAT-o-C8Cn, possessing the additional alkoxy chains in the anchoring group, revealed the lower η values of 7.3% (n = 4) and 7.0% (n = 8). Although ZnPBAT-o-C8Cn exhibited higher resistance at the TiO2-dye-electrolyte interface by virtue of the extra alkoxy chains, the reduced amount of the porphyrins on TiO2 by excessive addition of coadsorbent chenodeoxycholic acid (CDCA) for mitigating the aggregation on TiO2 resulted in the low η values. Meanwhile, the ZnPBAT-o-C8-sensitized solar cell showed the lower η value of 8.1% than the YD2-o-C8-sensitized solar cell (η = 9.8%) using cobalt-based electrolyte. The smaller η value of the ZnPBAT-o-C8-sensitized solar cell may be attributed to the insufficient blocking effect of the bulky substituents of ZnPBAT-o-C8 under the cobalt-based electrolyte conditions. Overall, the alkoxy chain length and substitution position around the porphyrin core are important factors to affect the cell performance.

Molecular Design and Syntheses of Tetracyano-5,10-porphyrinquinodimethane Showing Stabilized LUMO.

An isomer of tetracyanoporphyrinquinodimethane (TCPQ), 5,10-TCPQ, was designed, synthesized, and structurally characterized, and its basic properties were discussed with emphasis on comparison with those of reported 5,15-TCPQ. The title compound was synthesized by a convenient cascade reaction involving a catalyst-free aromatic nucleophilic substitution reaction and the Uno-Takahashi reaction. The obtained π-expanded redox molecule acted as a Wurster-type redox molecule that underwent not only reduction but also oxidation processes. Furthermore, its absorption spectrum showed a large bathochromic shift that extended to the near-IR region, approximately 1150 nm.

Tropolone as a High-Performance Robust Anchoring Group for Dye-Sensitized Solar Cells.

A tropolone group has been employed for the first time as an anchoring group for dye-sensitized solar cells (DSSCs). The DSSC based on a porphyrin, YD2-o-C8T, with a tropolone moiety exhibited a power-conversion efficiency of 7.7 %, which is only slightly lower than that observed for a reference porphyrin, YD2-o-C8, with a conventional carboxylic group. More importantly, YD2-o-C8T was found to be superior to YD2-o-C8 with respect to DSSC durability and binding ability to TiO2 . These results unambiguously demonstrate that tropolone is a highly promising dye-anchoring group for DSSCs in terms of device durability as well as photovoltaic performance.

Galectin LEC-1 plays a defensive role against damage due to oxidative stress in Caenorhabditis elegans.

LEC-1 is a major galectin in Caenorhabditis elegans and contains two carbohydrate recognition domains (CRDs), N-CRD and C-CRD. To determine the role of LEC-1, we examined the phenotypes of a mutant C. elegans strain lacking lec-1. We observed negligible differences in embryogenesis, morphogenesis and egg laying at 20 °C between the mutant and the wild-type. Furthermore, the life spans of the mutant and the wild-type were equivalent at either 20 °C or 25 °C. However, the lec-1 mutant showed a greater susceptibility to H2O2 and paraquat than the wild-type. This result suggests an increased susceptibility to oxidative stress, with the phenotypes being similar to those of lec-10 deletion mutants as previously described. To understand the molecular mechanism underlying this phenotype, C. elegans proteins bound by either the LEC-1 N-CRD or C-CRD were isolated and identified using a nano liquid chromatography-tandem mass spectrometry technique. MIG-6 was identified as a major binding partner of LEC-1 with both N- and C-CRD. From these results and previous reports, we speculate that interaction of LEC-1 and MIG-6 in the pharynx may affect susceptibility to paraquat and that LEC-10 has different functions from LEC-1 in regulating H2O2 and paraquat resistance in the intestine.

Sperm proteasome degrades egg envelope glycoprotein ZP1 during fertilization of Japanese quail (Coturnix japonica).

At the time of fertilization, the extracellular matrix surrounding avian oocytes, termed the perivitelline membrane (pvm), is hydrolyzed by a sperm-borne protease, although the actual protease that is responsible for the digestion of the pvm remains to be identified. Here, we show evidence that the ubiquitin-proteasome system is functional in the fertilization of Japanese quail. The activities for the induction of the acrosome reaction and binding to ZP3 as revealed by ligand blotting of purified serum ZP1 are similar to those of pvm ZP1. Western blot analysis of purified ZP1 and ZP3 by the use of the anti-ubiquitin antibody showed that only pvm ZP1 was reactive to the antibody. In vitro penetration assay of the sperm on the pvm indicated that fragments of ZP1 and intact ZP3 were released from the pvm. Western blot analysis using the anti-20S proteasome antibody and ultrastructural analysis showed that immunoreactive proteasome was localized in the acrosomal region of the sperm. Inclusion of specific proteasome inhibitor MG132 in the incubation mixture, or depletion of extracellular ATP by the addition of apyrase, efficiently suppressed the sperm perforation of the pvm. These results demonstrate for the first time that the sperm proteasome is important for fertilization in birds and that the extracellular ubiquitination of ZP1 might occur during its transport via blood circulation.

Catalyst-free aromatic nucleophilic substitution of meso-bromoporphyrins with azide anion: efficient synthesis and structural analyses of meso-azidoporphyrins.

meso-Mono- or diazidoporphyrins were readily obtained in high yields by the catalyst-free aromatic nucleophilic reaction of the corresponding bromoporphyrins with azide anions under mild conditions. The molecular structures of the obtained azides were unambiguously determined by X-ray crystallographic analysis.

Sugar-binding properties of the two lectin domains of LEC-1 with respect to the Galß1-4Fuc disaccharide unit present in protostomia glycoconjugates.

Galß1-4Fuc disaccharide unit was recently reported to be the endogenous structure recognized by the galectin LEC-6 isolated from the nematode Caenorhabditis elegans. LEC-1, which is another major galectin from this organism, is a tandem repeat-type galectin that contains two carbohydrate recognition domains, the N-terminal lectin domain (LEC-1Nh) and the C-terminal lectin domain (LEC-1Ch), and was also found to have an affinity for the Galß1-4Fuc disaccharide unit. In the present study, we compared the binding strengths of LEC-1, LEC-1Nh, and LEC-1Ch to Galß1-4Fuc, Galß1-3Fuc, and Galß1-4GlcNAc units as well as to LEC-6-ligand N-glycans by using frontal affinity chromatography (FAC) analysis. The two lectin domains of LEC-1 exhibited the highest affinity for Galß1-4Fuc, though sugar-binding properties differed somewhat between LEC-1Nh and LEC-1Ch. Furthermore, these two domains had significantly lower affinities for the LEC-6-binding glycans. These results suggest that the endogenous recognition unit of LEC-1 is likely to be Galß1-4Fuc, and that the endogenous ligands for LEC-1 are different from those for LEC-6.

Superexchange mediated energy transfer in zinc(II) porphyrin-free base porphyrin dimers: comparison of m- and p-bis(phenylethynyl) phenylene linked dimers.

The singlet-singlet energy transfer rate in a new zinc(II) porphyrin-free base porphyrin dimer, having a m-bis(phenylethynyl)phenylene bridge, was found to be slower than that in the corresponding p-bis(phenylethynyl)phenylene-bridged dimer, despite the shorter donor-acceptor distance and pathway. The slower rate is interpreted as evidence for a major contribution of the superexchange mechanism.

ß-galactosidases from jack bean and Streptococcus have different cleaving abilities towards fucose-containing sugars.

We examined the sugar-cleaving abilities of ß-galactosidases from jack bean and Streptococcus towards sugars containing fucose residues, and found that jack bean ß-galactosidase has an ability to cleave the ß1-3 linkage between galactose (Gal) and fucose (Fuc) residues, but not ß1-4 linkage. On the other hand, streptococcal ß-galactosidase was found to cleave the linkage in both Galß1-4Fuc and Galß1-3Fuc disaccharide units. Such a difference in sugar-cleaving abilities between these 2 ß-galactosidases will be useful for structural analysis of glycans, especially those from species belonging to Protostomia, such as Caenorhabditis elegans.

Manipulating double-decker molecules at the liquid-solid interface.

We have used a scanning tunneling microscope (STM) to manipulate heteroleptic phthalocyaninato, naphthalocyaninato, and porphyrinato double-decker (DD) molecules at the liquid-solid interface between 1-phenyloctane solvent and graphite. We employed nanografting of phthalocyanines with eight octyl chains to place these molecules into a matrix of heteroleptic DD molecules; the overlayer structure is epitaxial on graphite. We have also used nanografting to place DD molecules in matrices of single-layer phthalocyanines with octyl chains. Rectangular scans with a STM at low bias voltage resulted in the removal of the adsorbed DD molecular layer and substituted the DD molecules with bilayer-stacked phthalocyanines from phenyloctane solution. Single heteroleptic DD molecules with lutetium sandwiched between naphthalocyanine and octaethylporphyrin were decomposed with voltage pulses from the probe tip; the top octaethylporphyrin ligand was removed, and the bottom naphthalocyanine ligand remained on the surface. A domain of decomposed molecules was formed within the DD molecular domain, and the boundary of the decomposed molecular domain self-cured to become rectangular. We demonstrated a molecular "sliding block puzzle" with cascades of DD molecules on the graphite surface.

Zona pellucida protein ZP2 is expressed in the oocyte of Japanese quail (Coturnix japonica).

The avian perivitelline layer (PL), a vestment homologous to the zona pellucida (ZP) of mammalian oocytes, is composed of at least three glycoproteins. Our previous studies have demonstrated that the matrix's components, ZP3 and ZPD, are synthesized in ovarian granulosa cells. Another component, ZP1, is synthesized in the liver and is transported to the ovary by blood circulation. In this study, we report the isolation of cDNA encoding quail ZP2 and its expression in the female bird. By RNase protection assay and in situ hybridization, we demonstrate that ZP2 transcripts are restricted to the oocytes of small white follicles (SWF). The expression level of ZP2 decreased dramatically during follicular development, and the highest expression was observed in the SWF. Western blot and immunohistochemical analyses using the specific antibody against ZP2 indicate that the 80 kDa protein is the authentic ZP2, and the immunoreactive ZP2 protein is also present in the oocytes. Moreover, ultrastructural analysis demonstrated that the immunoreactive ZP2 localizes to the zona radiata, the perivitelline space, and the oocyte cytoplasm in the SWF. By means of western blot analysis and immunofluorescence microscopy, we detected a possible interaction of the recombinant ZP2 with ZP3 and that this interaction might lead to the formation of amorphous structure on the cell surface. These results demonstrate for the first time that the avian ZP gene is expressed in the oocyte, and that the ZP2 protein in the oocyte might play a role for the PL formation in the immature follicles of the ovary.