The Hammett correlation between distyrylbenzene substituents and chemiluminescence efficiency providing various ρ-values for peroxyoxalate chemiluminescence of several oxalates

Peroxyoxalate chemiluminescence (PO-CL) was investigated using eight oxalates with various phenol moieties and the distyrylbenzene (DSB) fluorophores with various substituents. The ρ-values in the Hammett correlation between the substituent constants (σp+) of the DSBs and the singlet chemiexcitation yields (ΦS) for the PO-CL reactions varied from −0.50 to −1.01 depending on the oxalate structure, and the reactive oxalates tended to afford the higher absolute ρ-values but with a few exceptions. Based on the CIEEL mechanism, these experimental observations suggest that the aryloxy groups still remain in the 1,2-dioxetanones (DOTs), which are the postulated high-energy intermediates, and control the electronic properties of DOTs as electron-acceptors. The LUMO energies of the DOTs calculated by the ab initio method with a B3LYP/6-31g(d) basis set reveal that the lower the DOT-LUMO energies, the higher the absolute ρ-values were provided for the corresponding oxalates, as predicted by the frontier molecular orbital (FMO) theory. Thus, the chemical species interacting with the DSBs would be not unitary and will be DOTs.ArticleJournal of Photochemistry and Photobiology A: Chemistry. 252:222-231 (2013)journal articl

Symmetry-adapted HAM/3 method and its application to some symmetric molecules

The semiempirical HAM/3 method developed by Lindholm and coworkers about two decades ago has been known to have a deficiency that splits energies for the degenerate energy states. We have recently proposed a group-theoretical approach to remedy the internally broken symmetry of the HAM/3 Hamiltonians. In this paper, we present some results of its application to various small molecules with symmetry Td, C3v, and D3h. The proposed scheme gives correct degeneracy for these molecules.O método semi-empírico HAM/3, desenvolvido por Lindholm e colaboradores há mais de duas décadas, tem uma deficiência. As energias de excitação calculadas por HAM/3 para estados degenerados são desdobradas. Recentemente foi proposto um método para corrigir esta deficiência. Apresentamos aqui resultados de aplicações deste novo método para algumas moléculas com simetria Td, C3v e D3h. O esquema proposto apresenta a degenerescência correta para as moléculas estudadas.445449Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Chromatographic formation of a triadic band of lithium in hydrated LTA zeolite: An investigation on lithium isotope separation effects by ion exchange

published online 12 April 2017Lithium concentrations [Li] and isotopic ratios [Li-7]/[Li-6] were measured for effluent fractions from a biphasic zeolite column. The biphasic state was ascribed to a mixture of hydrated Linde Type A (LTA) zeolites, [Li-0.008(NH4)(0.92)]A and [Li-0.33(NH4)(0.67)]A, which were formed by Li ion exchange from hydrated ammonium in the form (NH4)(12)[Al12Si12O48]center dot nH(2)O (NH(4)A). The biphasic Li band of the column was displaced by ion exchange with a solution of NH4NO3. A constant [Li] with a much lower level than the concentration of NHt(4)(_)(+) in the displacer (NH4NO3) was observed for the effluent from a short column. This constant lower level of [Li] was attributable to the biphasic state. On this [Li] plateau of the effluent, the level of [Li-7] shifted higher than the original isotopic composition of the Li feed, whereas Li-6 was concentrated on the biphasic zeolite solid. The accumulation of Li-6 in the zeolite proceeded by a mechanism of differential elution of Li-7 from the biphasic zeolite. For the long column experiment, a significant enrichment of Li-6 in the zeolite was observed, whereby a triadic band of Li was probably formed in the column. Two monophasic and a biphasic state were assigned. The biphasic band was deemed to push the monophasic bands forward, thereby enriching the monophasic bands with Li-7, while Li-6 accumulated at the end of the biphasic band. The trio structure of the Li band and isotopic discrimination in the band were analyzed. (C) 2017 Elsevier Inc. All rights reserved.ArticleMICROPOROUS AND MESOPOROUS MATERIALS. 248:115-121 (2017)journal articl

Exophiala dermatitidis infection in non-cystic fibrosis bronchiectasis

SummaryA 54-year-old female presented with an exacerbation of right middle lobe bronchiectasis. A bronchoscopic bronchial washing and repeated trials of sputum culture consistently recovered no other infectious agent except Exophiala dermatitidis. Her illness was improved by administrations of intravenous miconazole and nebulized amphotericin B when sputum cultures yielded no fungi, demonstrating a pathogenic role of the fungi. The present case illustrates E. dermatitidis as a pathogenic agent in non-cystic fibrosis bronchiectasis

Anatomic double-bundle anterior cruciate ligament reconstruction, using CT-based navigation and fiducial markers

Accurate placement of separate anteromedial and posterolateral bundle bone tunnels is crucial for anatomic, double-bundle anterior cruciate ligament (ACL) reconstruction. However, identifying the anatomic footprint at which to make the tibial and femoral bone tunnels is not a straightforward procedure. To overcome this problem, we used a CT-based navigation technique with a registration procedure based on fiducial markers (FMs). Preoperatively, 10 FM points were placed on skin around knee joint and scanned with CT. Imaging data of the knee were recorded on the computer system for preoperative registration and surgical planning. Intraoperatively, with a reference frame fixed to the distal medial aspect of femur and tibia, paired-point matching registration was performed with the use of points marked on skin through FM center holes. During tibial tunnel guide wire placement, tibial aiming guide with tracking device fed back the position of tip and direction of the guide wire on the three-dimensional (3D) tibia bone surface image and multiple image planes in real time. For the femoral side, the navigation pointer was placed at the footprint center with visual guidance of 3D image of lateral wall sagittal view on navigation monitor and marked with navigation awl. The average registration accuracy of 22 consecutive patients was 0.7 +/- A 0.2 mm and 0.6 +/- A 0.2 mm for femoral and tibial bone, respectively. Most of the bone tunnel positions evaluated with 3D-CT image were confirmed to be accurately placed in reference to the preoperative plan. There was no damage to femoral condyle cartilage and no other complication. This new CT-based computer navigation system opens the possibility for surgeons to plan bone tunnel positioning preoperatively and control it during technically demanding anatomic double-bundle ACL reconstruction.ArticleKNEE SURGERY SPORTS TRAUMATOLOGY ARTHROSCOPY. 19(3):378-383 (2011)journal articl

A comparison of nephrotoxicity between patients with a solitary-functioning kidney and those with bilateral-functioning kidneys in cisplatin-based chemotherapy for advanced urothelial carcinoma: a Japanese retrospective multi-institutional study

BackgroundTo compare the prevalence of nephrotoxicity between patients with a solitary-functioning kidney versus those with bilateral-functioning kidneys during the administration of cisplatin-based chemotherapy for advanced urothelial carcinoma.MethodsWe retrospectively analyzed 244 advanced urothelial carcinoma patients treated with cisplatin-based chemotherapy between 2004 and 2010 at 17 institutes in Japan. The 24 h creatinine clearance, Cockcroft–Gault formula, and estimated glomerular filtration rate equation (eGFR), were compared before all chemotherapies. The urinary tract function status was determined based on the data of nephroureterectomy, hydronephrosis, and relief of upper urinary tract obstruction. A total of 244 patients were divided into four groups according to their urinary tract functioning status and eGFR results, including bilateral-functioning kidneys with pretreatment eGFR ≥60 mL/min/1.73 m2 group (n = 83, 34.0%); a solitary-functioning kidney with pretreatment eGFR ≥60 mL/min/1.73 m2 group (n = 36, 14.8%); bilateral-functioning kidneys with pretreatment eGFR  10% and 30% from baseline in the post-third-course of chemotherapy was significantly higher in patients with bilateral-functioning kidneys than in those with a solitary-functioning kidney, among patients with pretreatment eGFR  20% from baseline were significantly higher in patients with bilateral-functioning kidneys than those with a solitary-functioning kidney among patients with pretreatment eGFR < 60 mL/min/1.73 m2 (p = 0.034), whereas no significant difference was observed among patients with pretreatment eGFR ≥60 mL/min/1.73 m2.ConclusionsThe results suggest that cisplatin-based chemotherapy may have more nephrotoxicity in patients with bilateral-functioning kidneys than in those with a solitary-functioning kidney

Significance and development of Urine uroplakin III mRNA measurement in vesicoureteral reflux

科学研究費補助金研究成果報告書研究種目: 基盤研究(C)研究期間: 2005～2006課題番号: 17591673研究代表者: 上仁 数義（滋賀医科大学・医学部・助手）研究分担者: 吉貴 達寛（滋賀医科大学・医学部・助教授）研究分担者: 成田 充弘（滋賀医科大学・医学部・講師）研究分担者: 影山 進（滋賀医科大学・医学部・助手）研究分担者: 坂野 祐司（滋賀医科大学・医学部・助手

Long-Term Prostate-Specific Antigen Response on a Low-Dose Cabazitaxel Regimen for Metastatic Castration-Resistant Prostate Cancer : A Case Report.

BACKGROUND:Cabazitaxel is a second-generation taxane approved for patients with metastatic castration-resistant prostate cancer (CRPC). Although cabazitaxel improves overall survival when used following docetaxel chemotherapy, duration of the clinical response is relatively short, and few patients achieve a long-term response.CASE REPORT:A 71-year-old man with prostate adenocarcinoma with an initial prostate-specific antigen (PSA) level of 4956 ng/ml, Gleason score 4+5 and cTxN0M1b was referred to our department for treatment. Several therapeutic approaches, including androgen deprivation therapy, with a combination of bicalutamide and a luteinizing hormone-releasing hormone analogue, and 4 sequential hormonal therapies including flutamide, estramustine, enzalutamide, and abiraterone, all failed to prevent disease progression. Subsequently, after 5 cycles of docetaxel chemotherapy were also ineffective, cabazitaxel chemotherapy at a dose of 20 mg/m² together with prednisone and pegfilgrastim was initiated. The patient developed grade 4 thrombocytopenia during the first 4 cycles, and the dosage of cabazitaxel had to be tapered to 12.5 mg/m² by the fifth cycle. In subsequent cycles, the treatment was continued without grade 4 thrombocytopenia or any other toxicities ³grade 3. The patient achieved a long-term clinical response over 4 years and his PSA level continued to decrease, from 29.8 ng/ml at treatment initiation to a nadir of 2.0 ng/ml after the 60th cycle.CONCLUSIONS:The present case is a rare example of a sustained response to low-dose cabazitaxel, and suggests its potential as a treatment option for metastatic CRPC patients. In our patient, this approach achieved a good clinical response with manageable toxicity over the long term