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.

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.

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.

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.

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.

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.

Protonation and electrochemical properties of a bisphosphide diiron hexacarbonyl complex bearing amino groups on the phosphide bridge.

A bisphosphide-bridged diiron hexacarbonyl complex 3 with NEt2 groups on the phosphide bridge was synthesized to examine a new proton relay system from the NEt2 group to the bridging hydride between the two iron centers. As a precursor of the bridging moiety, peri-Et2NP-PNEt2-bridged naphthylene 5 was synthesized by the reaction of 1,8-dilithionaphthylene with two equivalents of Cl2PNEt2 followed by reductive P-P bond formation by magnesium. The reaction of the diphosphine ligand 5 with Fe2(CO)9 gave the diiron hexacarbonyl complex 3, in which the P-P bond of the ligand was cleaved to form the bisphosphide-bridge. The molecular structure of 3 indicated that the trigonal plane of the NEt2 group was forced to face the Fe-Fe bond to avoid steric congestion with the naphthylene group linking the two phosphide groups. The NEt2 group could be protonated by p-toluenesulfonic acid. Density functional theory (DFT) calculations confirmed that the proton of the N(H)Et2 group adopted a position close to the bridging hydride. The DFT results for the ferrocene analogue 1, in which the 1,8-naphthylene group of 3 was replaced with the 1,1'-ferrocenylene group, also revealed that the most stable orientation of the protonated NHEt2 group was that in the protonated 3. As a result, electrochemical proton reduction reactions using complexes 1 and 3 proceeded with similar catalytic efficiencies. Unfortunately, the catalytic efficiencies (CEs) of these complexes were much lower than those of the complexes with a proton relay system of the terminal hydrogen, indicating that the reactive properties of the bridging hydride in the present proton relay system cannot exceed those of the terminal hydride.

On-Surface Modification of Copper Cathodes by Copper(I)-Catalyzed Azide Alkyne Cycloaddition and CO2 Reduction in Organic Environments.

In this study, organic structures were introduced onto copper cathodes to induce changes in their electrocatalytic CO2 reduction activity. Poorly soluble organic polymers were distributed onto the copper surface as a thin layer by polymerizing monomeric precursors via a copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) activated by anodization of the copper substrate. The resulting structure possesses copper surface atoms that are available to participate in the CO2 reduction reaction-comparable to close-contact organic structures-and stabilize the adsorption of organic layers through the CO2 reduction process. The CO2 reduction performance of the on-surface modified copper cathode exhibited improved CO2 reduction over H2 evolution compared with traditional cast modification systems. Preventing organic moieties from forming densely packed assemblies on the metal surface appears to be important to promote the CO2 reduction process on the copper atoms. The suppression of H2 evolution, a high methane/ethylene ratio, and the influence of stirring demonstrate that the improved CO2 reduction activity is not only a result of the copper atom reorganization accompanied by repeating anodization for modification; the organic layer also apparently plays an important role in proton transfer and CO2 accumulation onto the copper surface.

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.

Novel chloride-centered Ag18 clusters featuring a cuboctahedral Ag12 skeleton.

Two novel chloride-centered Ag18 clusters with the same framework but different supporting phosphines are synthesized by the reaction of PhC[triple bond, length as m-dash]CAg, AgSbF6, PPh3 (or P(p-Tol)3), and NaBH4 in CH2Cl2, followed by the addition of PhC[triple bond, length as m-dash]CH and NEt3. The inner twelve Ag atoms of these two clusters are arranged in a rare cuboctahedral structure, which can be rationalized by considering a ligand effect. Through careful analysis, we find that the central chloride arises from a generally ignored but nonetheless existing reaction between CH2Cl2 and NEt3, which is well recognized as the Menshutkin reaction. This research provides insights into the dependence of the cluster structure on the nature of the ligand and into the cluster formation mechanism of the Menshutkin reaction.

Deltopectoral and Pectoralis Musculocutaneous Flap Technique for Cervical Esophageal Reconstruction after Free-Jejunal-Flap Necrosis.

BACKGROUND: Free jejunal transfer has a high success rate, but if vascular thrombosis occurs, the salvage of failing flap with reanastomosis is difficult. This study described a combined deltopectoral (DP) and pectoralis major musculocutaneous (PMMC) flap 2-step technique for cervical esophageal reconstruction after free-jejunal-flap necrosis. METHODS: In step 1, the detection of free jejunal flap with the subsequent debridement of necrotic and infected tissue was followed by the construction of external fistula on the pharyngeal side with the hole in cervical skin and the construction of another external fistula on the esophageal side and tracheal stoma with a single or double DP flap. In step 2, after the primary healing of all wounds was confirmed, a wide hinge flap was elevated for reconstructing the posterior wall or full circumferential defect of cervical esophagus. PMMC flap harvested from either the left or right anterior chest wall was used for reconstructing the cervical surface defect or anterior pharyngeal wall. RESULTS: This technique was used for cervical esophageal reconstruction after free-jejunal-flap necrosis in 5 patients. Step 1 surgery was performed at an average of 10 days after primary-free-jejunal flap transfer. Oral intake was resumed in all cases at an average of 117 days after step 2 surgery. No complications including esophageal stricture were found during a 6-month follow-up period. CONCLUSIONS: Combined DP and PMMC flap technique was useful for cervical esophageal reconstruction after free-jejunal-flap necrosis and applicable to patients with the late detection of jejunal necrosis and surgical-site infection.

Application of a rhomboid flap for the coverage of defects after malignant breast tumor resection: A case report.

Resection for locally advanced breast cancer (LABC) or malignant phyllodes tumors may cause a large skin defect with bone exposure. Although skin grafts are frequently used to cover such defects, they can result in poor cosmetic outcomes and graft acceptance is dependent upon the condition of the recipient site. To overcome the limitations of skin grafts, various flaps have been developed to cover such defects. The present study used a rhomboid flap for the coverage of skin defects after mastectomy and breast-conservative surgery (BCS). A total of 11 patients with malignant breast cancer underwent reconstructive surgery using the rhomboid flap between September 2011 and December 2013 (mastectomy, 9 patients; BCS, 2 patients). Skin resection size, axillary lymph node dissection, bone exposure, length of surgery, wound complications and whether preoperative/postoperative adjuvant therapy was received were analyzed. The maximum size of skin defect covered with the rhomboid flap in the present study was 20×20 cm. There were no major wound complications and all patients underwent postoperative adjuvant therapy on schedule. During BCS, a portion of the flap was used for augmentation of the breast, in addition to coverage of the skin defect, which resulted in good cosmetic outcomes. The rhomboid flap can be quickly and easily fashioned, and it does not require any special instruments.

Synthesis and coordination chemistry of (PNEt2)2-bridged [2]ferrocenophanes.

The trivalent phosphorus-bridged [2]ferrocenophane complex 2 having NEt2 groups on the respective phosphorus centers was prepared, and its reactions as a diphosphine ligand were examined for iron and chromium carbonyl complexes. Both the phosphorus centers of 2 coordinated to Fe(CO)4 fragments to form (µ-2)-[Fe(CO)4]2, while the bulkier Cr(CO)5 fragment formed only a monochromium complex [Cr(κ1-2)(CO)5]. Dissociation of CO from [Cr(κ1-2)(CO)5] changed the coordination mode of 2 from κ1 to κ2 to form [Cr(κ2-2)(CO)4] having a three-membered ring. A similar approach for the monoiron complex [Fe(κ1-2)(CO)4] did not afford a κ2 complex but instead an Et2NPC(O)PNEt2-bridged [3]ferrocenophane complex in which a CO fragment was inserted into the P-P bond of 2 and both the phosphorus centers coordinated to Fe(CO)3 as a chelate diphosphine. The reaction of this product with an Fe(CO)4 fragment gave µ-{Fe(C5H4PNEt2)2-κP:κP}-[Fe(CO)3]2 (8), in which one terminal CO and the CO group between the two phosphorus atoms were lost to give an [FeFe]hydrogenase mimic having a bis(phosphido)ferrocene chelate as a bridging unit. The two NEt2 groups of the bridging unit were expected to work as protonation sites. The protonated NEt2 groups contributed to an improvement in the reduction potential of the complex to a less negative area, i.e., -2.3 V for the free 8 to -1.0 V for the diprotonated 8. The catalytic reduction of the proton, however, required a more negative potential of -2.0 V, which is almost comparable to that of the phosphido-bridged [FeFe]hydrogenase model complex having no protonation site.

Selection of two optional covalent bonds by electric stimuli: dual catalytic switching of redox-active copper.

Two types of redox functionality were selected for covalent immobilization on a carbon electrode, using an electric potential as the sole stimulus. A redox-active copper catalyst transformed a terminal alkyne in two ways with and without an oxidation process, to form a triazole or butadiyne.

Impact of immediate breast reconstruction on postoperative adjuvant chemotherapy: a single center study.

BACKGROUND: Various studies have indicated a worldwide increase in the number of immediate breast reconstruction surgeries. However, breast reconstruction should not delay or prevent postoperative cancer therapeutics such as adjuvant chemotherapy and radiotherapy. In response to these developments, our team researched the impact of immediate breast reconstruction on postoperative adjuvant chemotherapy. METHODS: From April 2006 to March 2011, 116 patients at Saitama Cancer Center underwent postoperative adjuvant chemotherapy following mastectomy with or without immediate breast reconstruction. Fifty patients received postoperative adjuvant chemotherapy following mastectomy with immediate breast reconstruction (IBR group), and 66 patients received the same treatment but without immediate breast reconstruction (non-IBR group). The outcomes were studied retrospectively by chart review. Patients' average age, body mass index, postoperative complication rate, and days to adjuvant chemotherapy were calculated. RESULTS: Mean age and body mass index of patients were 47.0 ± 9.0 years, 22.2 ± 3.0 kg/m(2) and 55.5 ± 10.1 years, 23.0 ± 3.6 kg/m(2) in IBR group and non-IBR group, respectively. Postoperative complication rate was 10.0 % in IBR group and 6.1 % in non-IBR group. Days to adjuvant chemotherapy was 61.0 ± 10.5 days in IBR group and 58.0 ± 12.3 days in non-IBR group. CONCLUSIONS: Although complication rate and days to adjuvant chemotherapy were slightly increased in IBR group, the delay was not critical to the initiation of adjuvant chemotherapy in these patient groups.

[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.

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.

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.

Synthesis of binuclear complexes bound in an enlarged tetraphosphamacrocycle: two diphosphine metal units linked in front-to-front style.

A large-hole tetraphosphamacrocycle 2, with four phosphorus centers separated at the corners of a 3.7 A wide and 9.7 A long rectangle, was synthesized by a stepwise cyclization reaction between PCl-bridged [1.1]ferrocenophane and bisphenol A in a 2:2 ratio. The macrocycle 2 could incorporate two Ag(+) or Pt(0) fragments in the hole to provide binuclear complexes, which were identified as mu-2-[Ag(NCMe)(2)](2)(BF(4))(2) (3) and mu-2-[Pt(PhCCPh)](2) (5), respectively, using X-ray and spectroscopic analysis. The X-ray structure of 3 demonstrates that the macrocycle 2 serves as a framework in which two diphosphine silver units are aligned in a front-to-front style, while that of 5 indicates that 2 can also bind two bulky Pt(PhCCPh) fragments by the flexible change of its conformation.