Redox Activity of IrIII Complexes with Multidentate Ligands Based on Dipyrido-Annulated N-Heterocyclic Carbenes: Access to High Valent and High Spin State with Carbon Donors.

Synthetic strategies to access high-valent iridium complexes usually require use of π donating ligands bearing electronegative atoms (e. g. amide or oxide) or σ donating electropositive atoms (e. g. boryl or hydride). Besides the η5 -(methyl)cyclopentadienyl derivatives, high-valent η1 carbon-ligated iridium complexes are challenging to synthesize. To meet this challenge, this work reports the oxidation behavior of an all-carbon-ligated anionic bis(CCC-pincer) IrIII complex. Being both σ and π donating, the diaryl dipyrido-annulated N-heterocyclic carbene (dpa-NHC) IrIII complex allowed a stepwise 4e- oxidation sequence. The first 2e- oxidation led to an oxidative coupling of two adjacent aryl groups, resulting in formation of a cationic chiral IrIII complex bearing a CCCC-tetradentate ligand. A further 2e- oxidation allowed isolation of a high-valent tricationic complex with a triplet ground state. These results close a synthetic gap for carbon-ligated iridium complexes and demonstrate the electronic tuning potential of organic π ligands for unusual electronic properties.

Complication analysis of complete versus partial coverage of tissue expanders using serratus anterior musculofascial flaps in immediate breast reconstruction.

PURPOSE: To prevent tissue expander (TE) exposure following mastectomy flap necrosis in immediate breast reconstruction, the TE is usually covered completely or partially with a musculofascial (MF) flap. This study compares the complications of the two coverage methods. METHODS: We reviewed, retrospectively, 106 cases of immediate TE-based breast reconstruction. The patients were divided into two groups according to whether complete or partial TE coverage was done. In the complete coverage group, the serratus anterior MF flap was dissected and sutured to the pectoralis major muscle to cover the TE completely. In the partial coverage group, the serratus anterior MF flap was not dissected, and the lateral border of the pectoralis major muscle was sutured to the mastectomy skin flaps. RESULTS: The TEs were covered completely in 60 breasts and partially in 46 breasts. The mastectomy flap necrosis rate was significantly higher in the complete coverage group (p < 0.01), but there was no incidence of TE exposure in either groups. The lateral migration rate was significantly higher in the partial coverage group (p = 0.033). There were no significant differences in the cranial migration rate (p = 0.133). CONCLUSIONS: The complete coverage method is a better option if there is a high risk of mastectomy flap necrosis; however, surgeons should monitor carefully for cranial migration.

Sentinel lymph node biopsy after neoadjuvant chemotherapy predicts pathological axillary lymph node status in breast cancer patients with clinically positive axillary lymph nodes at presentation.

BACKGROUND: It is still controversial whether axillary lymph node (ALN) dissection (ALND) can be omitted after negative sentinel lymph node (SLN) biopsy (SLNB) in breast cancer (BC) patients with clinically positive ALNs at presentation treated with neoadjuvant chemotherapy (NAC). The study aim was to analyze whether SLNB could be useful in these patients. METHODS: In a retrospective study, eligible patients were women with invasive BC with clinically positive ALNs at presentation, treated with NAC then a total or partial mastectomy, with an intraoperative histological examination of SLNs and non-SLNs suspicious for metastasis followed by ALND. Non-SLNs suspicious for metastasis were defined as hard or large nodes located in the same level of the axilla where clinically positive ALNs had been initially identified. The results of SLNB and clinicopathological characteristics were analyzed for correlation with pathological ALN status. RESULTS: In a consecutive series of 105 women with 107 BC cases, 81 (75.7 %) had at least 1 SLN, and the remaining 26 (24.3 %) had at least 1 non-SLN suspicious for metastasis. The intraoperative (or final) histological examination of these nodes revealed that the false-negative (FN) rate and accuracy were 8.2 (or 6.3) % and 95.1 (or 96.3) %, respectively. Estrogen receptor status at presentation, pathological tumor response, lymphovascular invasion after NAC, and NAC regimen were correlated with pathological ALN status. CONCLUSION: The histological examination of SLNs and that of non-SLNs suspicious for metastasis are useful for predicting pathological ALN status in BC patients with clinically positive ALNs at presentation who are treated with NAC.

[Efficacy and tolerability of controlled-release oxycodone against nab-paclitaxel-induced musculoskeletal pain in breast cancer patients].

Paclitaxel therapy often causes musculoskeletal pain, and some clinical studies have indicated that this pain is due to nerve injury, rather than muscle or joint lesion. We report four clinical cases in which controlled-release oxycodone improved pain intensity in breast cancer patients with severe musculoskeletal pain caused by nab-paclitaxel therapy. In each case, oxycodone was well-tolerated and the symptoms of peripheral neuropathy were quite mild, indicating that oxycodone exhibited a preventive or therapeutic effect on peripheral neuropathy. Therefore, oxycodone may have favorable efficacy and tolerability against cancer therapy-related pain with a neuropathic element in breast cancer patients.

Continuous local intravenous heparin infusion after re-exploration for venous congestion in free-flap breast reconstruction: A case series.

We demonstrated local intravenous heparin infusion to salvage flaps after re-exploration for postoperative venous congestion after free-flap breast reconstruction. All flaps were salvaged using local intravenous heparin infusion without major complications. Local intravenous heparin infusion is an effective and safe procedure.

Usefulness of Harmonic Focus during anterolateral thigh flap elevation.

Meticulous hemostasis and careful ligation of branches are necessary for pedicle dissection during flap elevation. The aim of this study was to evaluate the effectiveness of the Harmonic Focus handpiece (Ethicon Endo-Surgery, Inc., Blue Ash, Cincinnati, OH, USA) in reducing operation time, bleeding volume, and volume of postoperative drainage during anterolateral thigh flap elevation. Ten patients requiring flap elevation were divided into two groups: (1) Harmonic Focus group (three men, two women), and (2) control group (three men, two women). Operating time was found to be lower in the Harmonic Focus group than in the control group. Bleeding volume and postoperative drainage volume were nearly identical in the Harmonic Focus group and the control group, and the number of silk ligatures was significantly lower in the Harmonic Focus group compared with the control group. Although somewhat costly, the Harmonic Scalpel with the Harmonic Focus handpiece is advantageous for flap elevation, and it is likely that Harmonic Scalpel use will increase in plastic surgery.

Uniform wrapping of copper(I) oxide nanocubes by self-controlled copper-catalyzed azide-alkyne cycloaddition toward selective carbon dioxide electrocatalysis.

Copper(I) oxide nanocubes were wrapped with an extremely uniform organic layer grown by self-controlled, Cu-mediated catalysis. This layer aided in retaining the initial cubic structure of the copper nanocubes during their use as a CO2 reduction electrocatalyst, resulting in high CO2 reduction selectivity by strong suppression of hydrogen evolution because of exclusion of water from the surface.

Rhomboid Flap Reconstruction after Mastectomy for Locally Advanced Breast Cancer.

BACKGROUND: In patients undergoing mastectomy for locally advanced breast cancer (LABC), surgical skin flap reconstruction is sometimes required in order to cover large skin defects. This study assessed the efficacy of local, cutaneous (rhomboid) flap reconstruction after mastectomy by comparing data from patients with LABC requiring local flap reconstruction after mastectomy and those that underwent mastectomy alone. METHODS: Data from 68 patients with LABC who underwent mastectomy were reviewed retrospectively; 14 underwent local (rhomboid) flap reconstruction after mastectomy (local flap group) and 54 underwent direct closure after mastectomy (direct closure group). A pinch test was performed to determine the closure method. Data on the operation, postoperative complications, and postoperative quality of life (QOL) were compared between groups. RESULTS: It was possible to close defects in the local flap group that were significantly larger than those in the direct closure group (p=0.0002). There was no significant difference in postoperative complications between groups. Although operative duration was significantly longer in the local flap group than in the direct closure group (p=0.016), the average difference was only 25 minutes. There was no significant difference in variables related to postoperative QOL. CONCLUSIONS: Rhomboid flap reconstruction was effective for covering large defects after mastectomy in patients with LABC.

The [Ag25Cu4H8Br6(CCPh)12(PPh3)12]3+ : Ag13H8 silver hydride core protected by [CuAg3(CCPh)3(PPh3)3]+ motifs.

Copper alkynyl complexes [CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3]+ (Ar = Ph, p-C6H4Me), in which three Ag(PPh3) units are bound among three C[triple bond, length as m-dash]CAr arms of trigonal-planar [Cu(C[triple bond, length as m-dash]CAr)3]2-, were selected as a protecting unit to cover the metal core of an atomically precise core-shell-type cluster. First, the formation of the protecting unit through the reaction of Cu(NCMe)4(PF6) with Ag(C[triple bond, length as m-dash]CAr) and PPh3 in a 1 : 3 : 3 ratio was confirmed. The reaction gave dimeric [CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3]22+, in which the two planar [CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3]+ units were stacked. Next, core-shell-type clusters were synthesized by adding NaBH4 and Et4NX (X = Cl, Br) to a solution similar to that used to prepare the protecting unit. The trigonal-planar protecting units nicely formed core-shell-type Ag nanoclusters formulated as [Ag13H8X6{CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3}4]3+ (X = Cl, Ar = p-C6H4Me; X = Br, Ar = p-C6H4Me; X = Br, Ar = Ph). Their crystal structures revealed that the four [CuAg3(C[triple bond, length as m-dash]CAr)3(PPh3)3]+ units are linked by six halogen ions to form a tetrahedral cage that accommodates a polyhydride-Ag cluster formulated as Ag13H85+. As a concrete proof of the existence of the polyhydride, deuterated analogs Ag13D85+ were synthesized and subsequently characterized by high-resolution electrospray-ionization mass spectrometry measurements.

Deregulation of protein phosphatase 2A inhibitor SET is associated with malignant progression in breast cancer.

To understand the mechanism underlying metastasis, identification of a mechanism-based and common biomarker for circulating tumour cells (CTCs) in heterogenous breast cancer is needed. SET, an endogenous inhibitor of protein phosphatase 2A, was overexpressed in all subtypes of invasive breast carcinoma tissues. Treatment with SET-targeted siRNAs reduced the motility of MCF-7 and MDA-MB-231 cells in transwell assay. SET knockdown reduced the number of mammospheres by 60-70% in MCF-7 and MDA-MB-231 cells, which was associated with the downregulation of OCT4 and SLUG. Hence, we analysed the presence of SET-expressing CTCs (SET-CTCs) in 24 breast cancer patients. CTCs were enriched using a size-based method and then immunocytochemically analysed using an anti-SET antibody. SET-CTCs were detected in 6/6 (100%) patients with recurrent breast cancer with a median value of 12 (12 cells/3 mL blood), and in 13/18 (72.2%) patients with stage I-III breast cancer with a median value of 2.5, while the median value of healthy controls was 0. Importantly, high numbers of SET-CTCs were correlated with lymph node metastasis in patients with stage I-III disease. Our results indicate that SET contributes to breast cancer progression and can act as a potential biomarker of CTCs for the detection of metastasis.