Elucidation of Design Criteria for V-based Redox Mediators: Structure-Function Relationships that Dictate Rates of Heterogeneous Electron Transfer.

Redox mediators are attractive solutions for addressing the stringent kinetic stipulations required for efficient energy conversion processes. In this work, we compare the electrochemical properties of four vanadium complexes, namely [V(acac)3], [V6O7(OMe)12], [nBu4N]3[V6O13(TRISNO2)2], and [nBu4N]5[V18O46(NO3)] in non-aqueous solutions on glassy carbon electrodes. The goal of this study is to investigate the electron transfer kinetics and diffusivity of these compounds under identical experimental conditions to develop an understanding of structure-function relationships that dictate the physicochemical properties of vanadium oxide assemblies. Complex selection was dictated by two criteria - (1) nuclearity of the transition metal complexes (2) distribution of electron density in the native electronic configuration. Our analyses establish that electronic communication between metal centers significantly impacts charge transfer kinetics of these vanadium-based compounds.

Improved solubility of titanium-doped polyoxovanadate charge carriers for symmetric non-aqueous redox flow batteries.

Non-aqueous redox flow batteries constitute a promising solution for grid-scale energy storage due to the ability to achieve larger cell voltages than can be readily accessed in water. However, their widespread application is limited by low solubility of the electroactive species in organic solvents. In this work, we demonstrate that organic functionalization of titanium-substituted polyoxovanadate-alkoxide clusters increases the solubility of these assemblies over that of their homoleptic congeners by a factor of >10 in acetonitrile. Cyclic voltammetry, chronoamperometry, and charge-discharge cycling experiments are reported, assessing the electrochemical properties of these clusters relevant to their ability to serve as multielectron charge carriers for energy storage. The kinetic implications of ligand variation are assessed, demonstrating the role of ligand structure on the diffusivity and heterogeneous rates of electron transfer in mixed-metal charge carriers. Our results offer new insights into the impact of structural modifications on the physicochemical properties of these assemblies.

A Ru(II)-arene-ferrocene complex with promising antibacterial activity.

The evolution of high virulence bacterial strains has necessitated the development of novel therapeutic agents to treat resistant infections. Metal-based therapeutics represent a promising avenue for advancement, given their structural variability and unique modes of action relative to classical organic molecules. One strategy that has seen marked success is the incorporation of ferrocene into the framework of established antibacterial agents, while ruthenium-based complexes have also shown promise as bioactive compounds. This work focused on the preparation of novel ruthenium(II)-arene complexes containing Schiff base ligands with an attached ferrocene, and evaluation of their antibacterial activity. Structure-activity relationships identified the importance of having a phenyl group between the Schiff base imine and the appended ferrocene. This complex, C2, showed prominent activity against several clinically relevant bacterial strains, including a minimum inhibitory concentration of 16 µg mL-1 for methicillin-resistant Staphylococcus aureus (MSRA). Overall, the results of this study represent a promising new lead for future development of novel antibacterial agents.

Comparative Analysis of Peri-Operative Outcomes Following Total Laparoscopic Hysterectomy with Conventional Bipolar-Electrosurgery versus High-Pressure Pulsed LigaSure Use.

Objectives: Quick and effective hemostasis is essential for a successful laparoscopic surgery. Hence, it is of utmost importance for laparoscopic surgeons to understand the various available and emerging energy sources to tailor their use according to their properties and surgical requirement. The aim of this study was to compare LigaSure, an advanced bipolar versus conventional bipolar in total laparoscopic hysterectomy, with respect to operating time, mean blood loss, mean reduction in hemoglobin, intraoperative, and postoperative complications, and duration of prospective hospital stay. Materials and Methods: It was a randomized controlled study. One hundred and twenty patients scheduled for elective hysterectomy for any benign indication were randomly allocated to two groups namely, conventional bipolar group and LigaSure group. Patients with a history of ≥3 laparotomies, uterine size >20 weeks were excluded. Total laparoscopic hysterectomy with bilateral salpingectomy/salpingo oophorectomy was done in all the patients and endpoints were evaluated. Results: All the recruited participants (n = 120) achieved study endpoints. There was statistically significant difference in the meantime to dissect adnexal ligaments, primary and total operating time (for adnexal ligaments: Conventional bipolar-9.44 min vs. LigaSure-7.05 min; P = 0.000) (Primary: Conventional bipolar-97.03 min vs. LigaSure 74.39 min; P = 0.000) (Total: 142.5 min vs. 136.37 min P = 0.002). Mean blood loss (145 ml vs. 141.67 ml; P = 0.846), mean reduction in hemoglobin (0.802 versus 0.752; P = 0.484) and duration of postoperative stay (2.54 days vs. 2.32 days; P = 0.128) were comparable (P > 0.05). None of the participants suffered from any major complication during the surgery or in the postoperative recovery period. Conclusion: With an ability to effectively reduce operating time, LigaSure is a safe and efficient instrument for laparoscopic hysterectomy.

Interstitial and Cornual Ectopic Pregnancy: Conservative Surgical and Medical Management.

BACKGROUND: Interstitial and cornual ectopic pregnancy is rare, accounting for 2-4% of ectopic pregnancies and remains the most difficult type of ectopic pregnancy to diagnose due to low sensitivity and specificity of symptoms and imaging. The classic triad of ectopic pregnancy-abdominal pain, amenorrhea and vaginal bleeding-occurs in less than 40% of patients. The site of implantation in the intrauterine portion of fallopian tube and invasion through the uterine wall make this pregnancy difficult to differentiate from an intrauterine pregnancy on ultrasound. The high mortality in this type of pregnancy is partially due to delay in diagnosis as well as the speed of hemorrhage. METHODS: Three cases of interstitial pregnancy were retrospectively analyzed. RESULT: Successful laparoscopic cornuostomy and removal of products of conception were performed in two cases, while one case was successfully managed by local injection with KCL and methotrexate followed by systemic methotrexate. CONCLUSION: Early diagnosis and timely management are key to the management of interstitial and cornual ectopic pregnancy. With expertise in ultrasound imaging and advances in laparoscopic skills progressively, conservative medical and surgical measures are being used to treat interstitial and cornual ectopic pregnancy successfully.