Excited-State Dynamics of [Ru(S-Sbpy)(bpy)2]2+ to Form Long-Lived Localized Triplet States.

The novel photosensitizer [Ru(S-Sbpy)(bpy)2]2+ harbors two distinct sets of excited states in the UV/Vis region of the absorption spectrum located on either bpy or S-Sbpy ligands. Here, we address the question of whether following excitation into these two types of states could lead to the formation of different long-lived excited states from where energy transfer to a reactive species could occur. Femtosecond transient absorption spectroscopy identifies the formation of the final state within 80 fs for both excitation wavelengths. The recorded spectra hint at very similar dynamics following excitation toward either the parent or sulfur-decorated bpy ligands, indicating ultrafast interconversion into a unique excited-state species regardless of the initial state. Non-adiabatic surface hopping dynamics simulations show that ultrafast spin-orbit-mediated mixing of the states within less than 50 fs strongly increases the localization of the excited electron at the S-Sbpy ligand. Extensive structural relaxation within this sulfurated ligand is possible, via S-S bond cleavage that results in triplet state energies that are lower than those in the analogue [Ru(bpy)3]2+. This structural relaxation upon localization of the charge on S-Sbpy is found to be the reason for the formation of a single long-lived species independent of the excitation wavelength.

Serum high-density lipoprotein level and prognosis of ovarian cancer.

This study aimed to investigate the prognostic value of serum high-density lipoprotein (HDL) level in patients with ovarian cancer. This study enrolled 152 patients diagnosed with ovarian cancer and 119 patients with benign ovarian tumors. The associations of patient characteristics and disease with survival were determined using Cox regression analysis, t tests, analysis of variance for multiple-group comparisons, and chi-square tests. The potential association between HDL levels and the clinical characteristics of the disease was also analyzed. The diagnostic value of HDL was estimated using receiver operating characteristic curve analysis and calculation of the area under the curve. Progression-free survival and overall survival were determined using the Kaplan-Meier method, and their associations with patient and pathological variables, including HDL, were determined using the log-rank test. The median serum HDL was 1.15 mm measured in 152 patients with ovarian cancer and 1.30 mm in 119 patients with benign ovarian tumors (P = .000054). The receiver operating characteristic curve analysis yielded an area under the curve of 0.735 for serum HDL levels. Serum HDL levels were significantly associated with tumor pathological types (non-serous vs serous, P < .05). No association was observed between serum HDL levels and patient age, age at menarche or marriage, number of children, tumor grade, or clinical stage (P > .05). Patients with high serum HDL levels had a longer progression-free survival and overall survival than those with low serum HDL levels. Serum HDL levels are an independent prognostic factor for ovarian cancer.

Efficacy and influencing factors of the four-step approach combining the situational simulation teaching method in the clinical practice of standardized training for residents.

Background and Aims: Clinical skills practice is an essential component in standardized residency training. However, traditionally skill training methods are dogmatic and not all residents are exposed to such prescribed situations during their residency. The aims of this study were to evaluate the effectiveness and influence factors of a four-step approach combining situational simulation teaching methods in clinical practice for residents. Methods: Enrolled all second-year residents from the internal medicine base between May 2017 and May 2018 (n = 94), randomly divided into two groups. Forty-eight residents were selected as experimental group, while the others 46 as the control group. Adopted traditional clinical practice method in the teaching and assessment of the control group, while used four-step approach combining situational simulation teaching method in experimental group. We compared the theoretical and skill assessment scores in preclass and postclass. Conducted a satisfaction survey after class and analyzed the influencing factors of the teaching effect evaluation. Results: There were no significant differences in the theoretical and skill assessment scores between experimental group and control group at the beginning. After the class, both the average skill assessment and Direct Observation of Procedural Skills scores of the experimental group were higher than those of the control. Satisfaction survey findings identified that the experimental group expressed higher satisfaction. Logistic regression showed that educational background, "situational simulation mode helps to improve clinical skills training," "helps to maintain attention during learning," and "helps improve the ability to exercise analysis and solve problems" were the influencing factors of learners' satisfaction. Conclusion: The application of four-step approach combining situational simulation teaching methods in the clinical practice of residents can significantly improve skills, thinking ability, decision-making ability, and teaching satisfaction. Therefore, four-step approach combining situational simulation teaching methods is worth promoting in teaching clinical skills for internal medicine residency training.