Di(hydroperoxy)alkane Adducts of Phosphine Oxides: Safe, Solid, Stoichiometric and Soluble Oxidizing Agents

Despite its importance and wide use as oxidizing agent, aqueous H₂O₂ has disadvantages. It easily decomposes, and when the substrates are not water-soluble, biphasic reaction mixtures are required. Thus, oxidizing agents that are anhydrous and soluble in organic solvents are desired. To this purpose, several H₂O₂ adducts of phosphine oxides, for example [tBu₃PO• H₂O₂]2₂and [Ph₃PO• H₂O₂]₂ H₂O₂, have been synthesized and characterized. These adducts represent an extension to the adducts previously reported by the Bluemel group, and display comparable physical properties. Furthermore, di(hydroperoxy)alkane adducts, R₃PO•(HOO)₂CR'R" (R, R', R" = alkyl, aryl), were synthesized and fully characterized. These adducts can be constructed using a wide variety of alkanes and phosphine oxides. All di(hydroperoxy)alkane adducts are structurally well defined as proven by single crystal X-ray analysis, and they contain two active oxygen atoms per assembly. These adducts of the type R₃PO•(HOO)₂CR'R" are highly soluble in organic solvents, allowing for oxidation reactions to occur in one phase. Moreover, there are many beneficial features to be harvested from their well-defined molecular structure and relatively anhydrous character. For example, selective and fast oxidation of dialkylsulfides to corresponding sulfoxides can be accomplished, without overoxidation to sulfones, because the solid oxidizing agents can easily be administered stoichiometrically. The adducts can also successfully oxidize substrates sensitive to hydrolysis, such as Ph₂P-PPh₂, without cleaving the P-P bond. The R₃PO•(HOO)₂CR'R" adducts are robust and practically no decomposition is found after storing the solids for 100 days at 4 °C. At room temperature, the adducts slowly decompose over time, via the release of oxygen gas. When exposed to higher temperatures or mechanical stress such as hammering or grinding, no sudden release of energy and/or oxygen was observed, attesting to the stability of the adducts. In the presence of catalytic amounts of acid, adducts with di(hydroperoxy)cycloalkane moieties decompose by undergoing a Baeyer-Villiger oxidation, and the di(hydroperoxy)cycloalkanes are transformed into the corresponding lactones. The R₃PO•(HOO)₂CR'R" adducts are stable, solid, stoichiometric and soluble materials, and can serve as an excellent complement to aqueous H₂O₂ as oxidizing agents

Di(hydroperoxy)alkane Adducts of Phosphine Oxides: Safe, Solid, Stoichiometric and Soluble Oxidizing Agents

Despite its importance and wide use as oxidizing agent, aqueous H₂O₂ has disadvantages. It easily decomposes, and when the substrates are not water-soluble, biphasic reaction mixtures are required. Thus, oxidizing agents that are anhydrous and soluble in organic solvents are desired. To this purpose, several H₂O₂ adducts of phosphine oxides, for example [tBu₃PO• H₂O₂]2₂and [Ph₃PO• H₂O₂]₂ H₂O₂, have been synthesized and characterized. These adducts represent an extension to the adducts previously reported by the Bluemel group, and display comparable physical properties. Furthermore, di(hydroperoxy)alkane adducts, R₃PO•(HOO)₂CR'R" (R, R', R" = alkyl, aryl), were synthesized and fully characterized. These adducts can be constructed using a wide variety of alkanes and phosphine oxides. All di(hydroperoxy)alkane adducts are structurally well defined as proven by single crystal X-ray analysis, and they contain two active oxygen atoms per assembly. These adducts of the type R₃PO•(HOO)₂CR'R" are highly soluble in organic solvents, allowing for oxidation reactions to occur in one phase. Moreover, there are many beneficial features to be harvested from their well-defined molecular structure and relatively anhydrous character. For example, selective and fast oxidation of dialkylsulfides to corresponding sulfoxides can be accomplished, without overoxidation to sulfones, because the solid oxidizing agents can easily be administered stoichiometrically. The adducts can also successfully oxidize substrates sensitive to hydrolysis, such as Ph₂P-PPh₂, without cleaving the P-P bond. The R₃PO•(HOO)₂CR'R" adducts are robust and practically no decomposition is found after storing the solids for 100 days at 4 °C. At room temperature, the adducts slowly decompose over time, via the release of oxygen gas. When exposed to higher temperatures or mechanical stress such as hammering or grinding, no sudden release of energy and/or oxygen was observed, attesting to the stability of the adducts. In the presence of catalytic amounts of acid, adducts with di(hydroperoxy)cycloalkane moieties decompose by undergoing a Baeyer-Villiger oxidation, and the di(hydroperoxy)cycloalkanes are transformed into the corresponding lactones. The R₃PO•(HOO)₂CR'R" adducts are stable, solid, stoichiometric and soluble materials, and can serve as an excellent complement to aqueous H₂O₂ as oxidizing agents

Effects of uncertainty and spousal support on infertility-related quality of life in women undergoing assisted reproductive technologies

Purpose The purpose of this study was to investigate the effects of uncertainty and spousal support on infertility-related quality of life (QoL) in women undergoing assisted reproductive technologies. Methods In this correlational survey study, 172 infertile women undergoing assisted reproductive technologies for infertility treatment at M hospital in Seoul participated. Data collection took place at the outpatient department of M hospital using a self-report questionnaire from July to August 2019. Data were analyzed using SPSS for Windows version 28.0. Results The mean scores for uncertainty, spousal support, and infertility-related quality of life (QoL) were 28.35 (out of 50), 86.67 (out of 115), and 57.98 (out of 100), respectively. Infertility-related quality of life (QoL) was positively correlated with spousal support and negatively correlated with uncertainty. According to the regression analysis, infertility-related quality of life (QoL) was significantly affected by uncertainty, total number of assisted reproductive technology treatments, marriage duration, subjective health status, the financial burden of infertility testing, and the presence of a burdensome person. These variables had an explanatory power of 35.0% for infertility-related quality of life (QoL). Conclusion Uncertainty was an important factor influencing infertility-related quality of life (QoL) among women undergoing assisted reproductive technologies. It is necessary to develop and implement a nursing intervention program focused on reducing various forms of uncertainty during assisted reproductive procedures and to consider other factors affecting infertility-related quality of life (QoL) in the clinical setting

Enhanced cardiac expression of two isoforms of matrix metalloproteinase-2 in experimental diabetes mellitus.

BackgroundDiabetic cardiomyopathy (DM CMP) is defined as cardiomyocyte damage and ventricular dysfunction directly associated with diabetes independent of concomitant coronary artery disease or hypertension. Matrix metalloproteinases (MMPs), especially MMP-2, have been reported to underlie the pathogenesis of DM CMP by increasing extracellular collagen content.PurposeWe hypothesized that two discrete MMP-2 isoforms (full length MMP-2, FL-MMP-2; N-terminal truncated MMP-2, NTT-MMP-2) are induced by high glucose stimulation in vitro and in an experimental diabetic heart model.MethodsRat cardiomyoblasts (H9C2 cells) were examined to determine whether high glucose can induce the expression of the two isoforms of MMP-2. For the in vivo study, we used the streptozotocin-induced DM mouse heart model and age-matched controls. The changes of each MMP-2 isoform expression in the diabetic mice hearts were determined using quantitative real-time polymerase chain reaction (qRT-PCR). Immunohistochemical stains were conducted to identify the location and patterns of MMP-2 isoform expression. Echocardiography was performed to compare and analyze the changes in cardiac function induced by diabetes.ResultsQuantitative RT-PCR and immunofluorescence staining showed that the two MMP-2 isoforms were strongly induced by high glucose stimulation in H9C2 cells. Although no definite histologic features of diabetic cardiomyopathy were observed in diabetic mice hearts, left ventricular systolic dysfunction was determined by echocardiography. Quantitative RT-PCR and IHC staining showed this abnormal cardiac function was accompanied with the increases in the mRNA levels of the two isoforms of MMP-2 and related to intracellular localization.ConclusionTwo isoforms of MMP-2 were induced by high glucose stimulation in vitro and in a Type 1 DM mouse heart model. Further study is required to examine the role of these isoforms in DM CMP

Stemness Evaluation of Mesenchymal Stem Cells from Placentas According to Developmental Stage: Comparison to Those from Adult Bone Marrow

This study was done to evaluate the stemness of human mesenchymal stem cells (hMSCs) derived from placenta according to the development stage and to compare the results to those from adult bone marrow (BM). Based on the source of hMSCs, three groups were defined: group I included term placentas, group II included first-trimester placentas, and group III included adult BM samples. The stemness was evaluated by the proliferation capacity, immunophenotypic expression, mesoderm differentiation, expression of pluripotency markers including telomerase activity. The cumulative population doubling, indicating the proliferation capacity, was significantly higher in group II (P<0.001, 31.7±5.8 vs. 15.7±6.2 with group I, 9.2±4.9 with group III). The pattern of immunophenotypic expression and mesoderm differentiation into adipocytes and osteocytes were similar in all three groups. The expression of pluripotency markers including ALP, SSEA-4, TRA-1-60, TRA-1-81, Oct-4, and telomerase were strongly positive in group II, but very faint positive in the other groups. In conclusions, hMSCs from placentas have different characteristics according to their developmental stage and express mesenchymal stemness potentials similar to those from adult human BMs

Cryptotanshinone chemosensitivity potentiation by TW-37 in human oral cancer cell lines by targeting STAT3–Mcl-1 signaling

Abstract Background Despite being one of the leading cancer types in the world, the diagnosis of oral cancer and its suitable therapeutic options remain limited. This study aims to investigate the single and chemosensitizing effects of TW-37, a BH3 mimetic in oral cancer, on human oral cancer cell lines. Methods We assessed the single and chemosensitizing effects of TW-37 in vitro using trypan blue exclusion assay, Western blotting, DAPI staining, Annexin V–FITC/PI double staining, and quantitative real-time PCR. Mcl-1 overexpression models were established by transforming vector and transient transfection was performed to test for apoptosis Results TW-37 enhanced the cytotoxicity of human oral cancer cell lines by inducing caspase-dependent apoptosis, which correlates with the reduction of the myeloid cell leukemia-1 (Mcl-1) expression via transcriptional and post-translational regulation. The ectopic expression of Mcl-1 partially attenuated the apoptosis-inducing capacity of TW-37 in human oral cancer cell lines. Besides, TW-37 decreased the phosphorylation of signal transducer and activator of transcription 3 (STAT3) at Tyr705 and nuclear translocation in human oral cancer cell lines at the early time points. Furthermore, TW-37 potentiated chemosusceptibility of cryptotanshinone in human oral cancer cell lines by suppressing STAT3–Mcl-1 signaling compared with either TW-37 or cryptotanshinone alone, resulting in potent apoptosis. Conclusions This study not only unravels the single and chemosensitizing effects of TW-37 for treatment of human oral cancer but also highlights the likelihood of TW-37 as a good therapeutic strategy to enhance the prognosis of patients with oral cancer in the future