Cassidyrindom9665

The control of the redox reactivity, magnetic and optical properties of the different redox states of complexes with redox-active ligands permits their rational use in catalysis and materials science. The redox-chemistry of octahedrally coordinated high-spin CoII complexes (three unpaired electrons) with one redox-active bisguanidine ligand and two acetylacetonato (acac) co-ligands is completely changed by replacing the acac by hexafluoro-acetylacetonato (hfacac) co-ligands. The first one-electron oxidation is metal-centered in the case of the complexes with acac co-ligands, giving diamagnetic CoIII complexes. By contrast, in the case of the less Lewis-basic hfacac co-ligands, the first one-electron oxidation becomes ligand-centered, leading to high-spin CoII complexes with a radical monocationic guanidine ligand unit (four unpaired electrons). Ferromagnetic coupling between the spins on the metal and the organic radical in solution is evidenced by temperature-dependent paramagnetic NMR studies, allowing to estimate the isotropic exchange coupling constant in solution. Second one-electron oxidation leads to high-spin CoII complexes with dicationic guanidine ligand units (three unpaired electrons) in the presence of hfacac co-ligands, but to low-spin CoIII complexes with radical monocationic, peralkylated guanidine ligand (one unpaired electron) in the presence of acac co-ligands. The analysis of the electronic structures is complemented by quantum-chemical calculations on the spin density distributions and relative energies of the possible redox isomers.Left ventricular free wall rupture (LVFWR) is a rarest but often lethal mechanical complication of acute myocardial infarction (AMI). The mortality rate for LVFWR is described from 75% to 90% and it is the cause for 20% of in-hospital deaths after AMI. Death results essentially from the limited time available for emergent intervention after onset of symptoms. Emergency surgery is indicated and normally the rupture site is easily identified, but it may not be apparent macroscopically, corresponding to transmyocardial or subepicardial dissection with an external rupture far from the infarction site, or already thrombosed and contained. Repair of the ventricular wall is usually achieved either by suturing the edges of the tear or closing it with patches of artificial material or biological tissues, usually using some kind of biological glue. However, several cases of successful conservative management have been described. In this Editorial, I comment on the metanalysis conducted by Matteucci et al, published in this issue of the Journal, including 11 nonrandomized studies and enrolling a total of 363 patients, which brings a great deal of new knowledge that can help not only in the prevention but also in the management of this dreadful complication of AMI.

The cost-effectiveness of endoscopic submucosal dissection (ESD) and piecemeal endoscopic mucosal resection (pEMR) for colorectal laterally spreading tumors (LSTs) remains unclear. C75 trans clinical trial We examined the cost-effectiveness of these procedures for cases of colon/rectal LST-non-granular-type ≥2cm and LST-granular-mixed-type ≥3cm.

We performed a simulation model analysis using parameters based on clinical data from the National Cancer Center Hospital, Tokyo, and previous literature. The number of recurrences and surgeries and the required costs for 5years following ESD and pEMR were assessed. Japanese cost data were used in the base-case analysis, and probabilistic sensitivity analysis (PSA) was performed. The Swedish cost data were used in the scenario analysis.

Endoscopic submucosal dissection yielded a considerably lower number of recurrences and surgeries but required a higher cost than pEMR. The recurrence rates following ESD and pEMR were 0.9-1.3% and 21.1-25.9%, respectively. The incremental cost-effectiveness ratios for an avoided recurrence and surgery for ESD against pEMR were 376,796-476,496 JPY (3575-4521 USD) and 7,335,436-8,187,476 JPY (69,604-77,689 USD), respectively. PSA demonstrated that the probability of ESD being chosen as a more cost-effective option than pEMR was >50% at willingness-to-pay values of ≥400,000-500,000 JPY (3795-4744 USD) for avoiding a recurrence and ≥9,500,000-10,500,000 JPY (90,143-99,631 USD) for avoiding a surgery. In the scenario analysis, the required cost was also lower for ESD.

Our findings suggest potentially favorable cost-effectiveness of ESD, depending on cost settings and the willingness-to-pay value for avoiding recurrence/surgery.

Our findings suggest potentially favorable cost-effectiveness of ESD, depending on cost settings and the willingness-to-pay value for avoiding recurrence/surgery.The silylated hexatriynyl complex trans-(C6 F5 )(p-tol3 P)2 Pt(C≡C)3 SiEt3 (PtC6 TES) is converted in situ to PtC6 H (wet n-Bu4 N+ F- , THF) and cross coupled with the diyne H(C≡C)2 SiEt3 (HC4 TES; CuCl/TMEDA, O2 ) to give PtC10 TES (71 %). This sequence is repeated twice to afford PtC14 TES (65 %) and then PtC18 TES (27 %). An analogous series of reactions starting with PtC8 TES gives PtC12 TES (60 %), then PtC16 TES (43 %), and then PtC20 TES (17 %). Similar cross couplings with H(C≡C)2 Si(i-Pr)3 (HC4 TIPS) give PtC12 TIPS (68 %), PtC14 TIPS (68 %), and PtC16 TIPS (34 %). The trialkylsilyl species (up to PtC18 TES) are converted to 3+2 "click" cycloadducts or 1,4-disubstituted 1,2,3-triazoles trans-(C6 F5 )(p-tol3 P)2 Pt(C≡C)n-1 C=CHN(CH2 C6 H5 )N=N (29-92 % after workups). The most general procedure involves generating the terminal polyynes PtCx H (wet n-Bu4 N+ F- , THF) in the presence of benzyl azide in DMF and aqueous CuSO4 /ascorbic acid. All of the preceding complexes are crystallographically characterized and the structural and spectroscopic properties analyzed as a function of chain length. Two pseudopolymorphs of PtC20 TES are obtained, both of which feature molecules with parallel sp carbon chains in a pairwise head/tail packing motif with extensive sp/sp van der Waals contacts.

CD30 is variably expressed in diffuse large B-cell lymphoma (DLBCL), but its prognostic potential for the affected patients remains debatable and unclear. Therefore, we aimed to determine the frequency of CD30 expression in DLBCL and its potential for prognostic determination.

An electronic systematic review was performed using multiple databases, followed by a quantitative meta-analysis to assess the frequency of CD30 expression with positivity cut-off values of >0% and >20%, and to determine its association with clinicopathological features and patients' survival.

Using a cut-off value >0%, we observed that 3.5%-59.1% of the cases were considered positive for CD30. There was a significant association of the protein expression with a lower number of extra-nodal sites affected by the neoplasm, with Ann Arbor advanced stage, the absence of B-symptoms, the lack of MYC and BCL2 translocations, and a lower ECOG performance. Using a cut-off value >20%, we observed that 2.5%-36.7% of the cases were considered positive for CD30, being significantly associated with a lower number of extra-nodal sites affected by the neoplasm, Ann Arbor stages III/IV, non-GCB tumours, the lack of MYC and BCL2 translocations, and a lower ECOG value.