The function of Chalcogenophene in the Cyclomatelated Ring of the Cycloruthenated Dyes applied in Dye-Sensitized Solar Cell.

Three thiocyanate-free cycloruthenated complexes, DUY24-O, DUY24, and DUY24-Se containing furan, thiophene, and selenophene, respectively, as a part of the cycloruthenated ring, were designed to reveal the function of the chalcogen atom on the physicochemical and photovoltaic performance of the cycloruthenated sensitizers applied in dye-sensitized solar cells (DSCs). The three sensitizers have a similar molecular size; therefore, the effect of molecular dimensions on their photovoltaic performance can be negligible. NMR data, electron-donating resonance effects, optical properties, and the energy levels of the frontier orbitals reveal that the physical/photovoltaic properties of the three sensitizers were affected significantly by the chalcogen atom on the cyclometalated chalcogenophene ring. The λmax (both in ethanol and adsorbed on TiO2), frontier orbital level, and dye loading of thiophene- and selenophene-containing dyes are very close. Nevertheless, DUY24-Se has a higher molar absorption coefficient compared to DUY24; therefore, the DSC based on DUY24-Se has higher efficiency (8.4% under AM1.5 G one-sun and 26% under T5-light at ca. 6000 lux) than that sensitized with the DUY24 dye. These efficiencies are also higher than those (7.9 and 21.6%, respectively) of the cell dyed with N719, fabricated using the same conditions. The better performance of the device sensitized with DUY24-Se compared to DUY24-based cells suggests that selenophene is as good as (or even better than) thiophene to be a part of the cyclometalated ring for thiocyanate-free cycloruthenated sensitizers applied in DSCs. Furan-containing DUY24-O has much worse photovoltaic performance compared to the other two dyes. This is not only because DUY24-O has the shortest λmax, the lowest molar absorption coefficient, and the highest HOMO level but also the lowest dye loading (because of the strong interaction between the oxygen in furan and TiO2, the array of DUY24-O occupies more surface when adsorbed on TiO2) and the fastest charge recombination. The physicochemical and photovoltaic properties as well as the adsorption behavior of the dye on the TiO2 anode for the cycloruthenated sensitizers affected significantly by the chalcogen atom of the chalcogenophene on the cyclometalated ring provide a new strategy to design high-efficiency NCS-free cyclometalated sensitizers for DSCs.

Successful live birth after repeated high-dose radiotherapy to the uterus.

RESEARCH QUESTION: It has been established that radiotherapy can increase the risk of adverse pregnancy outcomes. However, there is currently no consensus on the effective sterilizing dose of adulthood uterine radiotherapy. DESIGN: This is a case report of a 36-year-old women with three different cancer types who received repeated high-dose radiotherapy of 66 Gy and 50 Gy to the pelvis. The study used a dose-volume histogram, the most widely used tool to calculate the radiation distribution within a volume of interest in a patient during radiotherapy. It was determined that the current patient's uterus might have received the highest uterine radiation dosage for full-term live birth that has been reported in the current literature. RESULTS: Due to iatrogenic ovarian failure, the woman was only able to use donor eggs. After preparation of the endometrium for 18 days, it had reached 8.7 mm in thickness with a triple-line appearance. Two cleavage-stage embryos were transferred, one of which implanted successfully. The course of the pregnancy was uneventful. Finally, the patient gave birth to a healthy baby via Caesarean section at 38+5 weeks of gestation. CONCLUSIONS: The uterus may be more resistant to radiotherapy than previously understood. Uterine fertility preservation methods should be guided by the age of the patient receiving radiotherapy and the actual dose of radiation exposure of the uterus. Future studies should implement a dose-volume histogram to calculate the radiation exposure of the reproductive organs.

High-Efficiency Cycloruthenated Sensitizers for Dye-Sensitized Solar Cells.

Four thiocyanate-free ruthenium sensitizers (DUY24-DUY27) containing 2-thienylpyridine moiety as cyclometalating core were synthesized for dye-sensitized solar cell (DSC) application. To the best of our knowledge, DUY24-DUY27 are four best-efficiency sensitizers having 42%-65% higher efficiencies compared to those of the published sensitizers comprising the same type of the cyclometalating ancillary ligands. The significant characteristic of DUY24-DUY27 is their ß-lowest unoccupied spin orbital (ß-LUSO) distributes remarkably on the cyclometalating ligands, especially on the soft sulfur atom, which strengthens the interaction between the oxidized dye and iodide ion for efficient dye regeneration. The photovoltaic performance of DUY24-DUY27-based DSCs supports that the dye regeneration (therefore the short-circuit photocurrent density (JSC) of the cell) can be improved by not only lowering the highest occupied molecular orbital energy level of the dye molecule but also distributing the ß-LUSO properly on the soft atoms. The study provides an important new guide for designing high-efficiency ruthenium-based dyes for DSC application.

Delayed postcoital vaginal cuff dehiscence with small bowel evisceration after robotic-assisted staging surgery.

OBJECTIVE: We report a rare case of vaginal cuff dehiscence with small bowel evisceration at 7 months post robotic-staging surgery. CASE REPORT: A 41-year-old woman was sent to the emergency room with sudden onset of abdominal pain, vaginal bleeding, and vaginal protruding mass after sexual activity. She had a history of synchronous uterine and ovarian cancer treated with robotic-staging surgery 7 months before. Then she received six courses of postoperative adjuvant chemotherapy, and the last chemotherapy ended 1 month ago. At the operation room, some small bowel loops were noted in the vaginal tip with cuff dehiscence and bleeding. After repositioning of the small bowel, a 2.5-cm vaginal cuff dehiscence was repaired transvaginally. The patient recovered well, and is free of disease and has normal sexual activity 2 months after repairs. CONCLUSION: Unusual delayed-type vaginal cuff dehiscence hints the possibility that a combination of robotic surgery and postoperative chemotherapy might result in delayed healing of the vaginal cuff.