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Specimens of the largescale dwarf flounder, Engyprosopon macrolepis (Regan, 1908) (Pleuronectiformes: Bothidae), were collected from the fishery landing of Chi-kan, Peng-hu Islands, western Taiwan. Although this species has been recorded from western Pacific Ocean including the Philippines and Japan, it has never been recorded from Taiwanese waters. Therefore, our specimens represent the first record for Taiwanese waters and fill a gap in the distribution of this species between the two countries. A detailed description of the specimens, including coloration of the fresh condition is provided and compared to the data of specimens collected in other regions. With the addition of E. macrolepis, a total of 11 species of Engyprosopon are recorded from Taiwanese waters, and we suggest that more species are expected to occur off Taiwan.

Two specimens of the rare Amarsipa fish, Amarsipus carlsbergi, were collected from Pratas Island in the northern South China Sea. They represent the first record of Taiwanese EEZ and fill the distribution gap in the northwestern Pacific Ocean between Japan (East China Sea) and Vietnam. The two specimens were identified based on their diagnostic characteristics, including no pharyngeal sacs, a pelvic fin well in front of the pectoral fin, a slender body and other morphology. Detailed data and descriptions of these two specimens, including a description of otolith morphology, are provided.

A new pineapple fish is described based on 26 type and 80 non-type specimens collected from Taiwan, Vanuatu, the Solomon Islands, and Queensland, Australia. This new species is sympatric with and similar to Monocentris japonica but can be distinguished from the latter in having only 6 or 7 scales on the third scale row below the lateral line; excisura notched and a small pseudo-excisura present on the sagittal otolith; consistently greater head depth, body depth, postorbital length, dorsal-fin-pelvic-fin length, and dorsal-fin-pectoral-fin length in proportion to standard length. A detailed description and designation of neotype are provided for M. japonica. DNA barcoding analysis supports the distinction of the new species with an estimated average COI gene divergence of 3.6 % from M. japonica.

A graded fullerene derivative thin film was used as a dual-functional electron transport layer (ETL) in CH 3 NH 3 PbI 3 (MAPbI 3 ) solar cells, to improve the fill factor (FF) and device stability. The graded ETL was made by mixing phenyl-C 61 -butyric acid methyl ester (PCBM) molecules and C 60 -diphenylmethanofullerene-oligoether (C 60 -DPM-OE) molecules using the spin-coating method. The formation of the graded ETLs can be due to the phase separation between hydrophobic PCBM and hydrophilic C 60 -DPM-OE, which was confirmed by XPS depth-profile analysis and an electron energy-loss spectroscope. Comprehensive studies were carried out to explore the characteristics of the graded ETLs in MAPbI 3 solar cells, including the surface properties, electronic energy levels, molecular packing properties and energy transfer dynamics. The elimination of the s-shape in the current density-voltage curves results in an increase in the FF, which originates from the smooth contact between the C 60 -DPM-OE and hydrophilic MAPbI 3 and the formation of the more ordered ETL. There was an improvement in device stability mainly due to the decrease in the photothermal induced morphology change of the graded ETLs fabricated from two fullerene derivatives with distinct hydrophilicity. Consequently, such a graded ETL provides dual-functional capabilities for the realization of stable high-performance MAPbI 3 solar cells.

In this study, the electrochemical behavior of zinc meso-substituted porphyrins in the presence of imidazole is examined by using both cyclic voltammetry (CV) and density functional theory (DFT) methods. The results show that the first half-wave oxidation potentials (1st E 1/2 ) of zinc porphyrins complexed with imidazole all move to the negative side, while the second ones (2nd E 1/2 ) move to the positive side, resulting in larger half-wave oxidation potential splittings of the two oxidation states (ΔE = second E 1/2 - first E 1/2 ) comparing with the zinc porphyrins. By employing DFT calculations, we have found that both sterically controlled inter π-conjugation between porphyrin rings and meso-substituted phenyl groups and deformation of porphyrin rings do play important roles in contributing to the half-wave oxidation potentials. Imidazole exhibits strong effects on the deformation of porphyrin rings which is dominant in determining the first E 1/2 while the inter π-conjugation between porphyrin rings and meso-substituted phenyl groups mainly contributes to the second E 1/2 . Without imidazole, the inter π-conjugation between porphyrin rings and meso-substituted phenyl groups is the only important criterion which effects both first E 1/2 and second E 1/2 of zinc porphyrins.

In this study, the electrochemical behavior of free base and zinc meso-substituted porphyrins is examined by cyclic voltammetry (CV) and density functional theory (DFT). The results show that the half-wave oxidation potential splitting of the two oxidation states (ΔE= second E1/2 - first E1/2) of tetraphenylporphyrin (H2TPP) and its zinc complex (ZnTPP) are higher than those of porphyrins and their zinc complexes with meso-substituted five-membered heterocylic rings. The ΔE values follow the trend of TPP > T(3'-thienyl)P > T(3'-furyl)P > T(2'-thienyl)P for both meso-porphyrins and their respective zinc complexes. By employing DFT calculations, we have found that the trend of ΔE values is consistent with that of highest spin density (HSD) distribution and HOMO-LUMO energy gaps of cationic radicals as well as the π-conjugation between central porphyrin and meso-substituted rings. Also, they exhibit the better resonance between the porphyrin ring with meso-substituted rings as moving from porphyrins and their zinc complexes with phenyl rings to five-membered heterocyclic rings. A good agreement between calculated and experimental results indicates that cationic radicals, especially their spin density distribution, do play an important role in half-wave oxidation potential splitting of meso-porphyrins and their zinc complexes.

The first observation of the photothermoelectric effect in a nanoporous silicon (NPSi) device indicates that the photocurrent is dependent on the position of light-induced local heating from illumination at the Au-electrode/NPSi interface., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A series of straight-chain oligoarylamines were synthesized and examined by electrochemical, spectroelectrochemical, electron paramagnetic resonance techniques, and density functional theory (DFT) calculation. Depending on their electrochemical characteristics, these oligoarylamines were classified into two groups: one containing an odd number and the other an even number of redox centers. In the systems with odd redox centers (N1, N3, and N5), each oxidation was associated with the loss of one electron. As for the systems with even redox centers (N2, N4, and N6), oxidation occurred by taking N2 as a unit. Absorption spectra of linear oligoarylamines at various oxidative states were obtained to investigate their charge transfer behaviors. Moreover, DFT-computed isotropic hyperfine coupling constants and spin density were in accordance with the EPR experiment, and gave a close examination of oligoarylamines at charged states.

Investigations on the transfer of the ligand, imidazole (HIm), between two covalently linked redox centres--zinc porphyrin and phenylenediamine (PD)--and the influence of the length of the linker are reported. Since the binding affinity of the ligand with zinc porphyrin is different from that of the ligand with the phenylenediamine moiety, the transfer of the ligand could be electrochemically controlled by adjusting the oxidation potentials. Changes in cyclic voltammograms and absorption spectra of the complexes revealed the site of ligand binding in the various oxidation states of the modified zinc porphyrins. Binding constants of the modified zinc porphyrins in various oxidation states were also determined by photometric titration with the ligand and digital simulations. Evidence for the delocalization of the electron from the zinc porphyrin to the phenylenediamine moiety and the influence of the delocalization on them were obtained from EPR studies.

By increasing the number of amino substituents on triarylamine, the extent of hydrogen bonding between the oxidized form of triarylamine and imidazole could be electrochemically controlled. Three behaviors, depending on the interaction between oxidized amine and imidazole, were obtained in CV patterns. DFT calculation was used to confirm that the electron density of protons of the amino group decreased as the amino moiety increased.

The N-phenyl-substituted hexaaza[1(6)]paracyclophane (3, hexamer) has been synthesized successfully in two steps and the noncoplanar conformation was calculated by gaussian program. The electrochemical properties exhibited lots of interesting results and each overlapping oxidative wave contained two-electron transfer.

Electrochemical properties of substituted free base meso-tetraphenylporphyrins (H(2)T(o,o'-X)PP, H(2)T(o-X)PP, and H(2)T(p-X)PP, where X = OCH(3), CH(3), H, F, or Cl on the phenyl rings) are examined by cyclic voltammetry. When a substituent is located only at the para position of the meso-phenyl group, the difference between the first and second oxidation potentials (ΔE(ox), i.e., E(2)(ox) - E(1)(ox)), is generally significantly smaller than those of the H(2)TPPs with bulky o,o'-substituents on the phenyl group. This trend is elucidated with density functional theory calculations and attributed mainly to the sterically controlled π-conjugation of the meso-phenyl groups to the central porphyrin ring, rather than the often discussed deformation of porphyrin.

In electrochemical oxidations, the second oxidation potential of phenylenediamines (PD) varies because of hydrogen-bonding formation for PD(+•) with pyridines. A linear relationship was obtained for the potential shift as a function of pK(a) of the protonated pyridines and potential inversion could be observed. The oxidized PD(+•) could also form hydrogen bonding with alcohols and the shift of potential exhibits a different pattern.

The first and second generation of zinc porphyrin core dendrimers (3 and 4) with triarylamine as dendron have been synthesized via Ullmann coupling reaction. Their absorption and emission spectra indicate that there are strong interactions between zinc porphyrin core and triarylamine dendrons. Zinc porphyrin links with triarylamine causes Soret band broadening and Q band shift as compared with ZnTPP. Because of the antenna effect on these dendrimers, the fluorescence quantum yields were strongly enhanced when more triarylamine moieties were linked. Cyclic voltammetry and spectroelectrochemical methods were used to investigate the redox properties of dendrimers. Axial ligation of zinc porphyrin with N-methylimidazole is useful in differentiating the oxidation site of dendrimers. For the first generation dendrimer (3), porphyrin ring oxidation potential shifts cathodically because the periphery dendrons are strong electron-donating groups. On the other hand, the dendrons of the second generation (4) are oxidized first and generate an atmosphere of eight positive charges. The porphyrin ring core is then oxidized with an anodic shift in potential due to the electron-withdrawing effect of the oxidized substituents.

Multi-(5-phenyl-1,3,4-oxadiazo-2-yl)benzenes show emission in organic solvents from ultraviolet to blue (339-447 nm). The reduction potentials E(1/2)(red) cover a large range of -2.11 V for 2,5-diphenyl-1,3,4-oxadiazole to -0.76 V for 1,2,3,4,5,6-hexa(5-phenyl-1,3,4-oxadiazo-2-yl)benzene. An unexpectedly wide spectral range of the oxadiazole (OXD) exciplex emissions in PVK is observed, ranging from 406 to 603 nm. The OXDs also exhibit similar electroluminescence (EL) when blended into polyvinylcarbazole (PVK). A linear correlation between the lambda(max) of the electroluminescence and photoluminescence is observed, implying that the emission mechanisms in both processes are similar. In addition, the linear correlation between the E(1/2)(red) versus lambda(max) of EL (eV) reflected that the term of the charge-transfer configuration of the contact electron-hole pair plays a major role in the exciplex emission. The exciplex EL of 1,2,5-tri(5-phenyl-1,3,4-oxadiazo-2-yl)benzene (5) could be as high as 1.0 cd/A. Since the exciplex emission usually has a large Stokes shift, this provides a window for us to generate duo emissions for near white light EL with high efficiency. Among the devices we tried, the device of PVK/2-tert-butylphenyl-5-biphenyl-1,3,4-oxadiazole/5/2,5,8,11-tetra-tert-butylperylene (100:40:40:4) gave EL with good current efficiency of 1.63 cd/A.

ZnTMP-PD was synthesized and fully characterized; by using electrochemical and spectroelectrochemical methods, ligand shuttling between the zinc porphyrin and the meso-phenylenediamine substituent could be monitored; EPR results indicated that the charge was delocalized on ZnTMP-PD.

The fluorescence and phosphorescence of 2,2'-bis(5-phenyl-1,3,4-oxadiazol-2-yl)biphenyl shows good spectral matching with the absorption spectra of the MLCT1 and MLCT3 transitions of Ir(ppy)3. The red-shift of the 0-0 band in the phosphorescence at 77 K is due to the intramolecular pi-pi interactions between the oxadiazole side chains. Maximum brightness of 43,000 cd/m2 with an efficiency of 26 cd/A at 200 cd/m2 was achieved when BOBP was used as the host material for Ir(ppy)3 in the PHOLED study. [structure: see text].

A new series of pi-conjugated donor-acceptor compounds (1-6) with inherent redox centers have been prepared and studied with respect to their electronic properties. The photophysical characteristics of these compounds have been studied in relation to their structures. Cyclic voltammetry and UV-vis spectroelectrochemistry were used to probe the ground-state electronic properties of the neutral and charged species. The observed electronic absorption properties of the neutral and charged molecules are explained with the help of frontier orbital structures and electrostatic potential maps obtained from density functional theory (DFT, B3LYP/6-31G) calculations. Electrochemiluminescence (ECL) of this series of donor-substituted phenylethynylanthronitriles with different donors was also studied. The structure-property relationship of all of the compounds is discussed.

Substituent effects on the photophysical and electrochemical properties of 1,7-diaryl-substituted perylene diimides (1,7-Ar(2)PDIs) have been carefully explored. Progressive red-shifts of the absorption and emission maxima were observed when the electron-donating ability of these substituents was increased. Linear Hammett correlations of 1/lambda(max) versus sigma(+) were observed in both spectral analyses. The positive slopes of the Hammett plots suggested that the electronic transitions carry certain amounts of photoinduced intramolecular charge-transfer (PICT) character from the aryl substituents to the perylene diimide core which leads to the reduction of the electron density on the substituents. The substituent electronic effects originated mainly from the perturbation of the core PDI HOMO energy level by the substituents. This conclusion was supported by PM3 analyses and confirmed by cyclic voltammetry experiments. More interestingly, the Ph(2)NC(6)H(4)-substituted PDI, 4i, showed an unusual dual-band absorption that spans from 450 to 750 nm. We tentatively assigned these two bands as the charge-transfer band and the PDI core absorption, respectively.

[reaction: see text] The diphenylamino group is an effective handle for electropolymerization to give electron donor-acceptor conjugated polymers. In addition, interesting electrochromic and photoresponsive behavior of 13 has been investigated.

[reaction: see text] A series of novel 9,9-diarylfluorene-capped oligothiophenes were synthesized by Suzuki coupling reactions in good yields. The color of the emissions can be controlled by varying the conjugation length of the oligothiophene core. The bulky and rigid terminal groups of the resulting oligomers are significantly beneficial for their high morphological and thermal stability. These new oligothiophenes exhibit intriguing reversible oxidation and reduction redox behavior.

Background: Renal involvement in patients with systemic lupus erythematosus (SLE) varies from none to full-blown disease. Monocyte chemoattractant protein (MCP-1) is implicated in the activation of inflammatory cells and has been suggested to affect the progression of lupus nephritis (LN)., Methods: In the 5' flanking region of the MCP-1 gene, a guanine (G)/adenine (A) transition identified at position -2518 upstream from the transcription site was reported to be associated with circulating levels. We investigated whether the G/A polymorphism was associated with clinical manifestations of SLE in terms of renal involvement and the biological significance of this polymorphism., Results: Frequencies of MCP-1/-2518 polymorphisms were similar in patients and controls. Serum MCP-1 levels in patients with SLE were significantly greater than those of healthy controls, but amount of proteinuria did not correlate with serum MCP-1 level in patients. In AA homozygotes, patients with LN showed greater serum MCP-1 levels than patients without LN. In addition, urinary excretion of MCP-1 was greater in AA homozygotes compared with other genotypes in patients with LN. A positive correlation between urinary excretion of MCP-1 and proteinuria was observed in patients with SLE. Genetic constructs containing G at this site showed that G construct had lower activity (39%) than that shown by a construct containing A, and this response, which depended on MCP-1 genotype, was maintained after stimulation with tumor necrosis factor-alpha., Conclusion: These results suggest that a genetic polymorphism in the 5' flanking region of the MCP-1 gene would be associated with nephritis in lupus through modulating MCP-1 expression., (Copyright 2002 by the National Kidney Foundation, Inc.)

Novel ter(9,9-diarylfluorene)s were synthesized by a Suzuki-coupling reaction of 2-bromofluorene (1) and 2,7-fluorenediboronic ester derivatives (3) with high isolated yields (63-86%). The X-ray structure analysis of ter(9,9'-spirobifluorene) (4aa) revealed that the conjugated chromophore adopts a helical conformation. This conformation effectively releases the steric interaction between the fluorene moieties and prevents inter-chromophore interactions. The introduction of aryl groups at the C9 position of fluorene was highly beneficial to the thermal and morphological stability of these oligomers. These terfluorenes exhibit intense blue fluorescence with excellent quantum yields both in solution ( approximately 100%) and in solid state (66-90%), and possess interesting reversible redox properties. Highly efficient blue light-emitting OLED devices were fabricated using 4aa and 4cc as emitters as well as hole transporters. The devices exhibit low turn-on voltage ( approximately 3 V) and high EL external quantum efficiency (2.5-3%).

[reaction: see text] Conjugated oligomers with an alternating phenylene-pyrimidine structure have been synthesized by the successive Suzuki coupling reaction starting from 2-bromo-5-iodopyrimidine. The photoluminescence properties and quasi-reversible redox behavior of these oligomers make them applicable as an active material for a light-emitting device. Blue light-emitting electroluminescent devices with an external quantum efficiency up to 1.8% have been fabricated.

We have studied the oxidation of microperoxidase-8 (MP-8) by H2O2 and the subsequent reaction of the intermediates with substrate by stopped-flow experiments. Oxidation of MP-8 by H2O2 gives two intermediates, I and II. The observed rate constant for the formation of I is linearly dependent on [H2O2] and exhibits a bell-shaped dependence on pH with pKa values of 8.90 and 10.60, which are attributed to the deprotonation of MP-bound H2O2 and H2O, respectively. The observed rate constant for the conversion of I to II is independent of [H2O2], but increases sharply at pH>9.0. The predominant forms of the intermediate at pH 7.0 and 10.7 are I and II, respectively. Addition of substrate to the intermediates at pH 9.0 gives rise to three distinct stages, corresponding to the three steps (in decreasing order of rate): I-->II*, II-->MP, and II*-->MP. The rates of these steps are all linearly dependent on the substrate concentration and each individual rate constant has been determined. Substrate reactivity at pH 10.7 covers over two orders of magnitude, ranging from 1.36 x 10(7) M(-1) s(-1) for 1-naphthol to 4.03 x 10(4) M(-1) s(-1) for ferrocyanide. The substrate reactivity is linearly correlated with its reduction potential, indicating that an electron transfer process is involved in the rate-limiting step.

An efficient synthesis of 3,3'-diphenyl-2,2'-bithiophene based bis(triarylamines) and their physical properties are reported.