Exploring the Role of Central Metals in Bulky Phthalocyanines for Dye-Sensitized Solar Cells.

Two series of metallo-(Zn(II), Mg(II), and Ru(II)) and free-base phthalocyanines (Pcs) with a carboxyl anchoring group and well-established bulky peripheral substituents (either tert-butyl or bulky 2,6-diisopropylphenoxy) were synthesized and tested as sensitizers in dye-sensitized solar cells (DSSCs). The trend of photovoltaic efficiencies (PCEs) for free-base and metallo Pcs followed the order Zn(II)Pc > Mg(II)Pc >> H2Pc ≈ Ru(II)Pc regardless of the peripheral substitution. Higher efficiencies (4.95 versus. 3.63 for the Zn(II) derivatives) were achieved with Pcs bearing the bulkier 2,6-diisopropylphenoxy group, indicating a lower aggregation and more suitable HOMO-LUMO levels. Furthermore, these derivatives showed a more relevant influence of the metal on the PCE (from the highest value of 4.95 for the Zn(II)Pc to the lowest value of 0.23 for the Ru(II)Pc. In both series, the best PCEs observed with the Zn(II) derivatives were mainly due to their highest Jsc values. The lowest efficiencies found for the free-bases and Ru(II) derivatives were attributed to a mismatch between their LUMO levels and the conduction band of the TiO2 and lower light-harvesting capabilities, respectively. In conclusion, Zn(II) derivatives are still the best Pc candidates to use as sensitizers in molecular photovoltaics.

Attention-deficit hyperactivity symptoms and risk of alcohol use relapse.

AIM: Alcohol use disorder (AUD) is frequently accompanied by comorbid attention-deficit hyperactivity disorder (ADHD). Comorbid ADHD has been reported to increase the severity of AUD. We investigated whether ADHD severity also influences AUD relapse risk at baseline and after inpatient treatment. METHODS: In this study, 187 AUD patients admitted to Narimasu Kosei Hospital from October 2019 to March 2021 were included in the analysis. According to the Adult ADHD Self-Report Scale (ASRS), participants were divided into two groups: ASRS+ with ADHD characteristics (n = 43) and ASRS- with low/no ADHD characteristics (n = 144). Groups were compared for AUD relapse risk at the start of treatment (baseline) and before hospital discharge using the multidimensional Alcohol Relapse Risk Scale (ARRS). The change in relapse risk during hospitalization was also compared by assessment of the interaction between groups (ASRS+ vs. ASRS-) and time (at discharge vs. baseline). RESULTS: The total ARRS score and dimension subscores for stimulus-induced vulnerability and emotionality problems were significantly higher in the ASRS+ group at baseline and before discharge compared to the ASRS- group. There was a significant group × time interaction indicating less improvement of stimulus-induced vulnerability during inpatient treatment among the ASRS+ group compared to the ASRS- group. CONCLUSIONS: Our findings suggest that AUD patients with ADHD characteristics have a higher risk of relapse both at baseline and after inpatient treatment. Stimulus-induced vulnerability to relapse is less likely to improve with treatment in patients with ADHD characteristics.

Phosphorescence emission from spatial stacks of phenanthrene units in oligo(9,10-phenanthrene)s.

The covalent linkage of phenanthrene units at 9 and 10 positions resulted in a broadening of the absorption band and a red-shift of the fluorescence band in ethanol compared with its monomer. Spatial stacking of phenanthrene units also altered the spectral shape of phosphorescence emission, and the oligomer film emitted phosphorescence at room temperature.

Phenanthroline-Fused Phthalocyanine Analogues Having a Monovalent Corrole Inner Perimeter and 4nπ Nonaromatic Properties.

Condensation of 4,5-bis(4-tert-butyl-2,6-dimethylphenoxy)phthalonitrile with 2,9-diamino-1,10-phenanthroline in the presence of M(OAc)2 (M = Ni, Pd, Zn) afforded a series of phenanthroline-fused phthalocyanine analogues with a 16 π-electron skeleton. While the arrangement of elements along the inner perimeter of these macrocycles is the same as that of the hitherto reported trivalent corroles, they represent the first example of porphyrinoids possessing a monovalent corrole inner perimeter and nonaromatic characteristics as revealed by their spectroscopic data and theoretical studies.

Boron(III) Carbazosubphthalocyanines: Core-Expanded Antiaromatic Boron(III) Subphthalocyanine Analogues.

Condensation of 1,8-diamino-3,6-dichlorocarbazole with a series of disubstituted 1,3-diiminoisoindolines, followed by treatment with BF3 ⋅OEt2 led to the formation of the corresponding core-expanded boron(III) subphthalocyanine analogues. These air-stable π-conjugated boron(III) carbazosubphthalocyanines possess two boron-containing seven-membered-ring units and a 16 π-electron skeleton, and represent the first examples of antiaromatic boron(III) subphthalocyanine analogues as supported by spectroscopic and theoretical studies. The molecular structure of one of these compounds was unambiguously determined by single-crystal X-ray diffraction analysis. In contrast to typical boron(III) subphthalocyanines, which adopt a cone-shaped structure, the π skeleton of this compound is almost planar.

Increased Light-Harvesting in Dye-Sensitized Solar Cells through Förster Resonance Energy Transfer within Supramolecular Dyad Systems.

Novel pyridine-substituted subphthalocyanines were prepared for an additional harvesting of a green spectral region of the solar light spectrum for zinc phthalocyanine-based dye-sensitized solar cells. These compounds can bind with the central metal of zinc phthalocyanines to form the corresponding supramolecular complexes as monitored by the absorption and fluorescence spectral changes. The stability constants of these complexes were altered by the number and position of pyridine units in the pyridine-substituted subphthalocyanines. On the basis of fluorescence titration study, the complexes efficiently transfer energy from the subphthalocyanine to zinc phthalocyanine. The solar cells using TiO2 electrodes stained with the supramolecular complexes, composed of zinc phthalocyanine sensitizer and pyridine-substituted subphthalocyanines, showed panchromatic responses, and the photocurrent generation in the range of 500-600 nm is attributed to the efficient Förster resonance energy transfer from subphthalocyanine to zinc phthalocyanine on the TiO2 surface.

Cross-sectional survey of diabetic neuropathy in Kanagawa and clinical significance of a touch test using tissue paper.

UNLABELLED: Aims/Introduction: The prevalence of diabetes mellitus is increasing rapidly in Japan, and diabetic neuropathy is a major factor decreasing diabetic patients' quality of life, as well as a risk factor for sudden death. The present study aimed to determine the prevalence of diabetic neuropathy and raise awareness about it among patients and their physicians. MATERIALS AND METHODS: Diabetic outpatients (N = 5077) at 249 medical institutions within Kanagawa Prefecture, Japan, were surveyed by questionnaire and underwent foot examinations. The questionnaire included 10 questions about sensory abnormalities of both feet, muscle cramps and autonomic symptoms. Foot examinations included testing for vibratory perception of the medial malleolus, Achilles tendon reflexes and touch sensation of the bottom of the great toe using tissue paper. RESULTS: Of the 5077 patients surveyed, 70.4% reported symptoms. Overall, 75.4% of the patients underwent vibratory perception testing, of whom 44.9% had abnormal thresholds (≤10 s). On the tissue paper touch test, performed in 94.6% of patients, 11.9% had no touch sensation. Of the 2803 type 2 diabetic patients with known background factors who underwent foot examinations, 49.4% had diabetic neuropathy. There was a high prevalence of diabetic neuropathy (36.1%) in patients with <5-year history. Of the patients with no touch sensation on the tissue paper test, 81.3% had diabetic neuropathy. CONCLUSIONS: The present study identified the prevalence of diabetic neuropathy in Kanagawa Prefecture. The tissue paper test is a simple and excellent method of evaluating decreased superficial sensation that can help evaluate the severity of diabetic neuropathy. (J Diabetes Invest, doi: 10.1111/j.2040-1124.2011.00174.x, 2011).

Appropriate spoon form for feeding of liquids in infant feeding development.

Feeding development in infants is important not only for of the purpose of acquiring nutrition but also for developing the ability to intake liquids. Our previous study showed that the introduction of a straw was appropriate after an infant has acquired the ability to sip liquid from a spoon and/or cup. In this study, we investigated the effect of a bowlshaped spoon on liquid intake. The aim of this study was to determine the appropriate form of spoon for infant feeding development. Eleven healthy infants (3 girls and 8 boys, 10-18 months old, mean age: 13.3 months) were recruited with their guardians' consent. We made 3 types of prototype spoon: A, oval (a standard renge soup spoon); B, flared-out (with the margin of the bowl flared out); and C, hemispherical (with a hemispherical bottom, and smaller than type A or B). We observed infants taking liquid supported by their mothers and evaluated the following responses: 1) confusion with regard to lip position, 2) spillage and 3) choking. Type C showed statistically less confusion with regard to lip position than type A or B (p<0.01), and B showed less than type A (p<0.05). No statistically significant differences were observed in spillage or choking among the three types of spoon. The renge soup spoon is often used to smooth the transition from breast/bottle to cup feeding. In this study, we demonstrated the appropriate spoon form for infant feeding development.