New frontiers in the synthesis and structures of rare earth metal-organic complexes

This thesis develops three new synthetic routes for highly reactive lanthanoid metal-organic complexes, including synthesis of lanthanoid metal-organic complexes I) by redox transmetallation protolysis (RTP) reactions of Ln metals utilising pentafluorophenylsilver; II) by RTP reactions of Ln metals utilising trispentafluorophenylbismuth; III) by the direct reaction of Ln metals with iodine and a proligand. Below is an overview of each chapter of original research (chapter 2 to 5). A number of lanthanoid pyrazolates and formamidinates were obtained by the new methods and their structures were determined

Selective Oxidation of a Single Metal Site of Divalent Calix[4]pyrrolide Compounds [Ln₂(N₄Et₈)(thf)₄] (Ln = Sm or Eu), Giving Mixed Valent Lanthanoid(II/III) Complexes

The samarium(II) calix[4]pyrrolide complex [Sm2(N4Et8)(thf)4] (N4Et8 = meso-octaethylcalix[4]pyrrolide) undergoes selective oxidation of one SmII site on reaction with a range of metal carbonyls giving mixed valence Sm(II/III) complexes. Thus, reactions with TM(CO)6 (TM = Mo or Cr) entrap M2(CO)102– ions between two mixed valence hosts in [{(thf)2SmII(N4Et8)SmIII(thf)(μ–OC)TM(CO)4}2]·PhMe (TM = Mo, 1; Cr, 2), while W(CO)6 on a different stoichiometry traps W(CO)52– in [{(thf)2SmII(N4Et8)SmIII}2{(μ–OC)W(CO)4}]·PhMe 3 in which the isocarbonyl group is disordered over two sites. In contrast, [Sm2(N4Et8)(thf)4] reacts with dicobalt octacarbonyl, bis(cyclopentadienyl)tetracarbonyl diiron, and dimanganese decacarbonyl to give the mixed valence species [(thf)2SmII(N4Et8)SmIII(thf)(μ–OC)TM(CO)3]·2PhMe (TM = Co, 4; Fe, 5) and [(thf)2SmII(N4Et8)SmIII(thf)(μ–OC)Mn(CO)4]·1.5PhMe 6. However, both SmII sites of [Sm2(N4Et8)(thf)4] can be oxidized as its reaction with cyclooctatetraene (COT) yields the SmIII species [(thf)SmIII(N4Et8)SmIII(COT)] 7. The analogous EuII reagent, [Eu2(N4Et8)(thf)4] induces C–halogen activation of perfluorodecalin, hexachloroethane, and bromoethane to form the mixed oxidation state species [(thf)2EuII(N4Et8)EuIII(μ–X)]2 (X = F, 8; Cl, 9; Br, 10) despite the use of a sufficient reagent to oxidize both EuII sites. The synthetic potential of the halogenido complexes was illustrated by the reaction of 10 with sodium bis(trimethylsilyl)amide to give the mixed oxidation state [(thf)2EuII(N4Et8)EuIII(N(SiMe3)2)] 11

Selective Oxidation of a Single Metal Site of Divalent Calix[4]pyrrolide Compounds [Ln₂(N₄Et₈)(thf)₄] (Ln = Sm or Eu), Giving Mixed Valent Lanthanoid(II/III) Complexes

The samarium(II) calix[4]pyrrolide complex [Sm2(N4Et8)(thf)4] (N4Et8 = meso-octaethylcalix[4]pyrrolide) undergoes selective oxidation of one SmII site on reaction with a range of metal carbonyls giving mixed valence Sm(II/III) complexes. Thus, reactions with TM(CO)6 (TM = Mo or Cr) entrap M2(CO)102– ions between two mixed valence hosts in [{(thf)2SmII(N4Et8)SmIII(thf)(μ–OC)TM(CO)4}2]·PhMe (TM = Mo, 1; Cr, 2), while W(CO)6 on a different stoichiometry traps W(CO)52– in [{(thf)2SmII(N4Et8)SmIII}2{(μ–OC)W(CO)4}]·PhMe 3 in which the isocarbonyl group is disordered over two sites. In contrast, [Sm2(N4Et8)(thf)4] reacts with dicobalt octacarbonyl, bis(cyclopentadienyl)tetracarbonyl diiron, and dimanganese decacarbonyl to give the mixed valence species [(thf)2SmII(N4Et8)SmIII(thf)(μ–OC)TM(CO)3]·2PhMe (TM = Co, 4; Fe, 5) and [(thf)2SmII(N4Et8)SmIII(thf)(μ–OC)Mn(CO)4]·1.5PhMe 6. However, both SmII sites of [Sm2(N4Et8)(thf)4] can be oxidized as its reaction with cyclooctatetraene (COT) yields the SmIII species [(thf)SmIII(N4Et8)SmIII(COT)] 7. The analogous EuII reagent, [Eu2(N4Et8)(thf)4] induces C–halogen activation of perfluorodecalin, hexachloroethane, and bromoethane to form the mixed oxidation state species [(thf)2EuII(N4Et8)EuIII(μ–X)]2 (X = F, 8; Cl, 9; Br, 10) despite the use of a sufficient reagent to oxidize both EuII sites. The synthetic potential of the halogenido complexes was illustrated by the reaction of 10 with sodium bis(trimethylsilyl)amide to give the mixed oxidation state [(thf)2EuII(N4Et8)EuIII(N(SiMe3)2)] 11

Rare Earth 4‐Hydroxyphenylacetate Complexes: Synthesis, Structural Characterization, and Corrosion Inhibition Properties#

Four different structural types of rare earth aqua 4‐hydroxyphenylacetate complexes {[Ce(L)3(H2O)2]⋅H2O}n (a), {[RE2(L)6(H2O)]⋅4H2O]}n (RE = Nd (b), Gd (c)), {[RE2(L)6(H2O)]⋅3H2O]}n (RE = Dy (d), Y (e)), {[RE2(L)6(H2O)]⋅5H2O]}n (RE = Er (f), Yb (g)), (L = 4‐hydroxyphenylacetate) have been synthesized by the metathesis reactions of corresponding rare earth metals chlorides or nitrates and sodium 4‐hydroxyphenylacetate (NaL). All compounds were obtained as 1‐D polymeric structures, with a common carboxylate coordination mode of chelating bridging. The structure of a differs in being a monometallic repeating unit and having two coordinated waters whilst the others have binuclear repeating units that resulted from the alternating coordination of one water molecule along the chain. Corrosion tests by the weight loss method and potentiodynamic polarisation tests revealed that {[Gd2(L)6(H2O)]⋅4H2O}n has the best corrosion inhibition properties for mild steel in 0.01 M NaCl. Furthermore, all a‐g complexes are more effective corrosion inhibitors than both the aqua and 2,2’‐bipyridine (bpy) complexes of unsubstituted phenylacetate indicating that 4‐OH substitution of phenylacetate enhances anti‐corrosion properties

Effective Dual-Functional Metal–Organic Framework (DF-MOF) as a Catalyst for the Solvent-Free Cycloaddition Reaction

A new porous metal–organic framework, [Co (oba) (bpdh)]·(DMF) (TMU-63), containing accessible nitrogen-rich diazahexadiene groups was successfully prepared with the solvothermal assembly of 5-bis­(4-pyridyl)-3,4-diaza-2,4-hexadiene (4-bpdh), 4,4′-oxybis­(benzoic) acid (oba), and Co­(II) ions. The combination of Lewis basic functional groups and porosity leads to high performance in CO2 adsorption and conversion in the cycloaddition reaction of epoxides under solvent-free conditions. To further enhance the catalytic efficiency of TMU-63, we introduced a highly acidic malonamide ligand into the structure via solvent-assisted ligand exchange (SALE) as a postsynthesis method. Incorporating different percentages of N1,N3-di­(pyridine-4-yl) malonamide linker (4-dpm) into TMU-63 created a new porous structure. Powder X-ray diffraction (PXRD) and NMR spectroscopy confirmed that 4-bpdh was successfully replaced with 4-dpm in the daughter MOF, TMU-63S. The catalytic activity of both MOFs was confirmed by significant amounts of CO2 cycloaddition of epoxides under solvent-free conditions. The catalytic cycloaddition activities were found to be well-correlated with the Lewis base/Brønsted acid distributions of the materials examined in the TMU-63S series, showing that the concurrent presence of both acid and base sites was desirable for high catalytic activity. Furthermore, the heterogeneous catalysts could easily be separated out from the reaction mixtures and reused four times without loss of catalytic activity and with no structural deterioration

Additional file 1 of Water channel protein AQP1 in cytoplasm is a critical factor in breast cancer local invasion

Additional file 1: Supplementary Fig. 1. Cytoplasmic expression of AQP1 was positively correlated with breast cancer progression. (a) Patients who had a recurrence or metastasis had a higher AQP1 cytoplasmic expression (62.2% vs 38.9%, P = 0.009). Cyto-AQP1: cytoplasmic AQP1 expression. (b) Patients who had a lymph node metastasis (n > 4) had a higher AQP1 cytoplasmic expression (50.0% vs 38.1%, P = 0.038). Cyto-AQP1: cytoplasmic AQP1 expression. (c-d) The relationship between pT stage and AQP1 cytoplasmic expression. Cyto-AQP1: cytoplasmic AQP1 expression. (e) The tumor volume in Flag-vector/MDA-MB-231 and Flag-AQP1/MDA-MB-231 mice group. Values were expressed as mean ± SD (two-tailed Student’s t test and two-way ANOVA, **P 60 cells per group, two-tailed Student’s t test). Scale bar=20 μm. All experiments were independently repeated for three times. Supplementary Fig. 9. The effect of the expression of AQP1/ANXA2/Rab1b/CTSS/ICAM1 on the prognosis of breast cancer patients. (a) Kaplan–Meier analysis showed the association between AQP1 expression and overall survival of breast cancer patients in GEPIA database (log-rank test). (b) Kaplan–Meier analysis showed the association between ANXA2 expression and overall survival of breast cancer patients in Kaplan-Meier plotter database (log-rank test). (c) Kaplan–Meier analysis showed the association between Rab1b expression and overall survival of breast cancer patients in Kaplan-Meier plotter database (log-rank test). (d) Kaplan–Meier analysis showed the association between CTSS expression and overall survival of breast cancer patients in Kaplan-Meier plotter database (log-rank test). (e) Kaplan–Meier analysis showed the association between ICAM1 expression and overall survival of breast cancer patients in Kaplan-Meier plotter database (log-rank test). Supplementary Fig. 10. Relationship of AQP1 with ANXA2, Rab1b, CTSS and ICAM1. (a) In 194 IDC patients, AQP1 had a positive correlation with ANXA2. (b-d) Correlation analysis using GEPIA (http://gepia.cancer-pku.cn) indicated that AQP1 was positively correlated with Rab1b, CTSS and ICAM1 in breast cancer patients

Additional file 2 of Water channel protein AQP1 in cytoplasm is a critical factor in breast cancer local invasion

Additional file 2: Supplementary Table S1. List of plasmids and RNA interference sequences used in this study. Supplementary Table S2. List of antibodies used in this study. Supplementary Table S3. Cytoplasmic AQP1 expression in IDC patients. Supplementary Table S4. Relationship between AQP1 cytoplasmic expression and pathological tumor size (pT). Supplementary Table S5. Univariate and multivariate analysis for overall survival (OS) and progression-free survival (PFS). Supplementary Table S6. List of proteins in the supernant of Flag-vector/MDA-MB-231 cells by mass spectrometry. Supplementary Table S7. List of proteins in the supernant of Flag-AQP1/MDA-MB-231 cells by mass spectrometry. Supplementary Table S8. Correlations among the expression of AQP1, ANXA2 and CTSS in 194 IDC patients. Supplementary Table S9. Relationship between AQP1 cytoplasmic expression and ANXA2 membrane expression in IDC patients (n=194). Supplementary Table S10. List of 23 genes of Rab family associated with AQP1 and ANXA2 by analysis of TCGA database

Table2_Breast Cancer Patients With Positive Apical or Infraclavicular/Ipsilateral Supraclavicular Lymph Nodes Should Be Excluded in the Application of the Lymph Node Ratio System.DOCX

Aim: Increasing studies have demonstrated lymph node ratio (LNR) to be an accurate prognostic indicator in breast cancer and an alternative to pN staging; however, the AJCC-TNM staging system classified apical or infraclavicular/ipsilateral supraclavicular lymph node-positive (APN(+)) patients with a worse prognosis as the pN3 stage. Until now, different reports on LNR in breast cancer have ignored this possibility. Consequently, it is necessary to discuss the role of APN(+) patients in the LNR system to obtain a precise LNR that predicts the prognosis accurately.Materials and Methods: We collected data on 10,120 breast cancer patients, including 3,936 lymph node-positive patients (3,283 APN(−) and 653 APN(+) patients), who visited our hospital from 2007 to 2012. Then we applied X-tile analysis to calculate cut-off values and conduct survival analysis and multivariate analysis to evaluate patients’ prognosis.Results: We confirmed that some APN(+) patients were mis-subgrouped according to previously reported LNR, indicating that APN(+) patients should be excluded in the application of LNR to predict prognosis. Then we applied X-tile analysis to calculate two cut-off values (0.15 and 0.34) for LNR-APN(−) patients and conducted survival analysis and found that LNR-APN(−) staging was superior to pN staging in predicting the prognosis of APN(−) breast cancer patients.Conclusion: From this study, we conclude that excluding APN(+) patients is the most necessary condition for effective implementation of the LNR system. LNR-APN(−) staging could be a more comprehensive approach in predicting prognosis and guiding clinicians to provide accurate and appropriate treatment.</p

Table1_Breast Cancer Patients With Positive Apical or Infraclavicular/Ipsilateral Supraclavicular Lymph Nodes Should Be Excluded in the Application of the Lymph Node Ratio System.DOCX

Aim: Increasing studies have demonstrated lymph node ratio (LNR) to be an accurate prognostic indicator in breast cancer and an alternative to pN staging; however, the AJCC-TNM staging system classified apical or infraclavicular/ipsilateral supraclavicular lymph node-positive (APN(+)) patients with a worse prognosis as the pN3 stage. Until now, different reports on LNR in breast cancer have ignored this possibility. Consequently, it is necessary to discuss the role of APN(+) patients in the LNR system to obtain a precise LNR that predicts the prognosis accurately.Materials and Methods: We collected data on 10,120 breast cancer patients, including 3,936 lymph node-positive patients (3,283 APN(−) and 653 APN(+) patients), who visited our hospital from 2007 to 2012. Then we applied X-tile analysis to calculate cut-off values and conduct survival analysis and multivariate analysis to evaluate patients’ prognosis.Results: We confirmed that some APN(+) patients were mis-subgrouped according to previously reported LNR, indicating that APN(+) patients should be excluded in the application of LNR to predict prognosis. Then we applied X-tile analysis to calculate two cut-off values (0.15 and 0.34) for LNR-APN(−) patients and conducted survival analysis and found that LNR-APN(−) staging was superior to pN staging in predicting the prognosis of APN(−) breast cancer patients.Conclusion: From this study, we conclude that excluding APN(+) patients is the most necessary condition for effective implementation of the LNR system. LNR-APN(−) staging could be a more comprehensive approach in predicting prognosis and guiding clinicians to provide accurate and appropriate treatment.</p

Image1_Breast Cancer Patients With Positive Apical or Infraclavicular/Ipsilateral Supraclavicular Lymph Nodes Should Be Excluded in the Application of the Lymph Node Ratio System.TIF

Aim: Increasing studies have demonstrated lymph node ratio (LNR) to be an accurate prognostic indicator in breast cancer and an alternative to pN staging; however, the AJCC-TNM staging system classified apical or infraclavicular/ipsilateral supraclavicular lymph node-positive (APN(+)) patients with a worse prognosis as the pN3 stage. Until now, different reports on LNR in breast cancer have ignored this possibility. Consequently, it is necessary to discuss the role of APN(+) patients in the LNR system to obtain a precise LNR that predicts the prognosis accurately.Materials and Methods: We collected data on 10,120 breast cancer patients, including 3,936 lymph node-positive patients (3,283 APN(−) and 653 APN(+) patients), who visited our hospital from 2007 to 2012. Then we applied X-tile analysis to calculate cut-off values and conduct survival analysis and multivariate analysis to evaluate patients’ prognosis.Results: We confirmed that some APN(+) patients were mis-subgrouped according to previously reported LNR, indicating that APN(+) patients should be excluded in the application of LNR to predict prognosis. Then we applied X-tile analysis to calculate two cut-off values (0.15 and 0.34) for LNR-APN(−) patients and conducted survival analysis and found that LNR-APN(−) staging was superior to pN staging in predicting the prognosis of APN(−) breast cancer patients.Conclusion: From this study, we conclude that excluding APN(+) patients is the most necessary condition for effective implementation of the LNR system. LNR-APN(−) staging could be a more comprehensive approach in predicting prognosis and guiding clinicians to provide accurate and appropriate treatment.</p