Bazi Bushen ameliorates age-related energy metabolism dysregulation by targeting the IL-17/TNF inflammatory pathway associated with SASP.

BACKGROUND: Chronic inflammation and metabolic dysfunction are key features of systemic aging, closely associated with the development and progression of age-related metabolic diseases. Bazi Bushen (BZBS), a traditional Chinese medicine used to alleviate frailty, delays biological aging by modulating DNA methylation levels. However, the precise mechanism of its anti-aging effect remains unclear. In this study, we developed the Energy Expenditure Aging Index (EEAI) to estimate biological age. By integrating the EEAI with transcriptome analysis, we aimed to explore the impact of BZBS on age-related metabolic dysregulation and inflammation in naturally aging mice. METHODS: We conducted indirect calorimetry analysis on five groups of mice with different ages and utilized the data to construct EEAI. 12 -month-old C57BL/6 J mice were treated with BZBS or ß-Nicotinamide Mononucleotide (NMN) for 8 months. Micro-CT, Oil Red O staining, indirect calorimetry, RNA sequencing, bioinformatics analysis, and qRT-PCR were performed to investigate the regulatory effects of BZBS on energy metabolism, glycolipid metabolism, and inflammaging. RESULTS: The results revealed that BZBS treatment effectively reversed the age-related decline in energy expenditure and enhanced overall metabolism, as indicated by the aging index of energy expenditure derived from energy metabolism parameters across various ages. Subsequent investigations showed that BZBS reduced age-induced visceral fat accumulation and hepatic lipid droplet aggregation. Transcriptomic analysis of perirenal fat and liver indicated that BZBS effectively enhanced lipid metabolism pathways, such as the PPAR signaling pathway, fatty acid oxidation, and cholesterol metabolism, and improved glycolysis and mitochondrial respiration. Additionally, there was a significant improvement in inhibiting the inflammation-related arachidonic acid-linoleic acid metabolism pathway and restraining the IL-17 and TNF inflammatory pathways activated via senescence associated secretory phenotype (SASP). CONCLUSIONS: BZBS has the potential to alleviate inflammation in metabolic organs of naturally aged mice and maintain metabolic homeostasis. This study presents novel clinical therapeutic approaches for the prevention and treatment of age-related metabolic diseases.

The Protective Effects of Curcumin against Renal Toxicity.

Curcumin is a naturally polyphenolic compound used for hepatoprotective, thrombosuppressive, neuroprotective, cardioprotective, antineoplastic, antiproliferative, hypoglycemic, and antiarthritic effects. Kidney disease is a major public health problem associated with severe clinical complications worldwide. The protective effects of curcumin against nephrotoxicity have been evaluated in several experimental models. In this review, we discussed how curcumin exerts its protective effect against renal toxicity and also illustrated the mechanisms of action such as anti-inflammatory, antioxidant, regulating cell death, and anti-fibrotic. This provides new perspectives and directions for the clinical guidance and molecular mechanisms for the treatment of renal diseases by curcumin.

Angelica keiskei water extract Mitigates Age-Associated Physiological Decline in Mice.

OBJECTIVE: Angelica keiskei is a medicinal and edible plant that has been reported to possess potent antioxidant properties in several in vitro models, but its effectiveness on naturally aging organisms is still lacking. This study explores the antioxidant and health-promoting effects of Angelica keiskei in naturally aging mice. METHODS: We treated 48-week-old mice with Angelica keiskei water extract (AKWE) 30 days, and measured indicators related to aging and antioxidants. In addition, we conducted network pharmacology analysis, component-target molecular docking, real-time PCR, and MTS assays to investigate relevant factors. RESULTS: The results indicated that administration of AKWE to mice led to decrease blood glucose levels, improve muscle fiber structure, muscle strength, gait stability, and increase levels of glutathione and superoxide dismutase in serum. Additionally, it decreased pigmentation of the heart tissues. Angelica keiskei combats oxidative stress by regulating multiple redox signaling pathways, and its ingredients Coumarin and Flavonoids have the potential to bind to SIRT3 and SIRT5. CONCLUSIONS: Our findings indicated the potential of Angelica keiskei as a safe and effective dietary supplement to combat aging and revealed the broad prospects of medicinal and edible plants for addressing aging and age-related chronic diseases.

Identification of central symptoms of children depression and development of two short version of Children's Depression Inventory: Based on network analysis and machine learning.

BACKGROUND: Using network analysis to study the central symptoms is important for understanding the mechanism of depression symptoms and selecting items for the short version depression screening scale. This study aimed to identify the central symptoms of depression and develop the short and effective depression screening tools for Chinese rural children. METHODS: Firstly, the 2458 individuals (Mage = 10.74; SDage = 1.64; 51.2 % were female) were recruited from the rural children's mental health database. Children's Depression Inventory (CDI) was used to assess depression symptoms. Then, network analysis was used to identify the central symptoms of depression. The accuracy, stability, and gender invariance of the depression symptoms network were tested. Finally, a short version of CDI with central symptoms (CDI-SC) and a new CDI-10 (CDI-10-N) were developed by network analysis and feature selection techniques to optimize the existing CDI-10. Their performances in screening depression symptoms were validated by the cutoff threshold and machine learning. RESULTS: The central symptoms of Chinese rural children's depression were sadness, self-hatred, loneliness and self-deprecation. This result was accurate and stable and depression symptoms network has gender invariance. The AUC values of CDI-10-N and CDI-SC are over 0.9. The CDI-10-N has a higher AUC than CDI-10. The optimal cutoff thresholds for CDI-10-N and CDI-SC are 6 and 1. The performance of machine learning on AUC generally outperforms those of cutoff threshold. CONCLUSIONS: The central symptoms identified in this study should be highlighted in screening depression symptoms, and CDI-10-N and CDI-SC are effective tools for screening depression symptoms in Chinese rural children.

Acupuncture Treatment in a Mouse Model of Chronic Hypoxia-Induced Cognitive Dysfunction.

The treatment of central nervous disorders has consistently posed significant challenges to the medical field. Acupuncture, a non-pharmacological practice rooted in traditional Chinese medicine, entails the insertion of fine needles into precise points on the body and is commonly employed for the management of diverse conditions. Recently, acupuncture has emerged as a promising therapeutic intervention for a range of neurological diseases, including anxiety and respiratory disorders. However, the potential of acupuncture in treating cognitive dysfunction induced by chronic hypoxia has not yet been explored. This paper presents a comprehensive protocol for establishing a mouse model of chronic hypoxia-induced cognitive impairment, administering mild anesthesia, performing acupuncture treatment, and assessing behavioral changes and memory abilities using open field tests and water mazes. The step-by-step protocol provides detailed instructions on accurately locating and positioning acupoints and needles for cognitive improvement. By employing this protocol, researchers can conduct systematic studies to thoroughly evaluate the therapeutic potential of acupuncture for cognitive dysfunction.

Syntheses, Structures, and Corrosion Inhibition of Various Alkali Metal Carboxylate Complexes.

Complexes of the alkali metals Li-Cs with 3-thiophenecarboxylate (3tpc), 2-methyl-3-furoate (2m3fur), 3-furoate (3fur), 4-hydroxycinnamate (4hocin), and 4-hydroxybenzoate (4hob) ions were prepared via neutralisation reactions, and the structures of [Li2(3tpc)2]n (1Li); [K2(3tpc)2]n (1K); [Rb(3tpc)(H2O)]n (1Rb); [Cs{H(3tpc)2}]n (1Cs); [Li2(2m3fur)2(H2O)3] (2Li); [K2(2m3fur)2(H2O)]n (2K); [Li(3fur)]n(3Li); [K(4hocin](H2O)3]n (4K); [Rb{H(4hocin)2}]n.nH2O (4Rb); [Cs(4hocin)(H2O)]n (4Cs); [Li(4hob)]n (5Li); [K(4hob)(H2O)3]n (5K); [Rb(4hob)(H2O)]n (5Rb); and [Cs(4hob)(H2O)]n (5Cs) were determined via X-ray crystallography. Bulk products were also characterised via XPD, IR, and TGA measurements. No sodium derivatives could be obtained as crystallographically suitable single crystals. All were obtained as coordination polymers with a wide variety of carboxylate-binding modes, except for dinuclear 2Li. Under conditions that normally gave coordinated carboxylate ions, the ligation of hydrogen dicarboxylate ions was observed in 1Cs and 4Rb, with short H-bonds and short O…O distances associated with the acidic hydrogen. The alkali-metal carboxylates showed corrosion inhibitor properties inferior to those of the corresponding rare-earth carboxylates.

Family function and anxiety among junior school students during the COVID-19 pandemic: a moderated mediation model.

Background: The prevalence of anxiety among adolescents is relatively high during an epidemic. Studies have reported that family function and perceived stress are important factors affecting adolescents' anxiety. However, only few studies have explored the factors influencing the relationship between family function and anxiety. Therefore, this study explored the mediating and moderating mechanisms underlying this relationship among junior school student during the COVID-19 pandemic. Methods: 745 junior school students completed family function, perceived stress, and anxiety questionnaires. Results: (1) The junior school students that were left-behind tended to show lower family function (t = -4.21, p < 0.001), greater perceived stress (t = 2.72, p < 0.01), and higher anxiety (t = 4.24, p < 0.001), (2) Family function in junior school students was negatively associated with anxiety (r = -0.35, p < 0.001); perceived stress mediated the relationship between family function and anxiety (p < 0.001), and (3) Whether the student was left-behind (LB) moderated the link between family function and anxiety (ß = -0.16, t = -3.33, p < 0.001) and between family function and perceived stress (ß = -0.22, t = -2.61, p < 0.001). Conclusion: These findings suggest a negative association between family function and anxiety. Knowledge of the mediating role of perceived stress and moderating role of being left-behind may help prevent and improve anxiety among junior school students during the COVID-19 pandemic.

Divalent ansa-Octaphenyllanthanocenes: Synthesis, Structures, and EuII Luminescence.

Reductive dimerization of fulvenes using low-valent metal precursors is a straightforward one-step approach to access ethylene-bridged metallocenes. This process has so far mainly been employed with fulvenes carrying one or two substituents in the exocyclic position. In this work, a new synthesis of the unsubstituted exocyclic 1,2,3,4-tetraphenylfulvene (1), its full structural characterization by NMR spectroscopy and single-crystal X-ray diffraction, as well as some photophysical properties and its first use in reductive dimerization are described. This fulvene reacted with different lanthanoid metals in thf to provide the divalent ansa-octaphenylmetallocenes [Ln(C5Ph4CH2)2(thf)n] (Ln = Sm, n = 2 (2); Ln = Eu, n = 2 (3); and Ln = Yb, n = 1 (4)). These complexes were characterized by X-ray diffraction, laser desorption/ionization time of flight mass spectrometry, and, in the case of Sm and Yb, multinuclear NMR spectroscopy, showing the influence of the ansa-bridge on solution and solid-state structures compared to previously reported unbridged metallocenes. Furthermore, the luminescence properties of the Eu ansa complex 3 were studied in solution and the solid state, revealing significant differences with the known octa- and deca-phenyleuropocenes, [Eu(C5Ph4H)2(dme)] and [Eu(C5Ph5)2].

Mechanism of testicular injury induced by Di-ethylhexyl phthalate and its protective agents.

Di-ethylhexyl phthalate (DEHP) is used as an important plasticizer in a wide range of products such as paints, food packaging, medical devices and children's toys. In recent years, there has been increasing interest in the toxic effects of DEHP on the male reproductive organs, the testicles. Here, we reviewed the basic pathways of testicular damage caused by DEHP. The mechanism involves oxidative stress, ferroptosis, interfering with hypothalamic-pituitary-gonadal axis (HPGA) and testosterone level. We summarized the protective agents that have been shown to be effective in repairing this type of testicular damage in recent years. This provides a new perspective and direction for future research into the health effects and molecular mechanisms of DEHP.

Direct Reaction - One Step Route to Synthesize Lanthanoid-iodide Formamidinates.

This paper describes a novel and simple method - direct reaction of lanthanoid metals with equimolar amounts of iodine and a formamidine under ultrasonication as an effective, metal-based route to lanthanoid(III) diiodide formamidinates, namely I. N,N'-Bis(2,6-diisopropylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(DippForm)I2 (thf)3 ] (Ln=La, 1, Ce, 2, Tb, 3, Ho, 4, Er, 5, Tm, 6); II. N,N'-Bis(2,6-diethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(EtForm)I2 (thf)3 ] (Ln=Ce, 7, Nd, 8, Gd, 9, Tb, 10, Dy, 11, Ho, 12, Er, 13, Lu, 14). III. N,N'-bis(2,6-dimethylphenyl)formamidinatodiiodidolanthanoid(III) complexes [Ln(XylForm)I2 (thf)3 ] (Ln=Ce, 15, Nd, 16, Gd, 17, Tm, 18, Lu 19); IV. N,N'-bis(phenyl)formamidinatodiiodidolanthanoid complexes [Ln(PhForm)I2 (thf)3 ] (Ln=Nd, 20, Gd, 21, Er, 22). Compound [Ce(XylForm)2 I(thf)2 ] (23) was also synthesized by the same method except the ratio of I2 to XylFormH was 1 : 4. Divalent N,N'-bis(2,6-diisopropylphenyl)formamidinato-iodido-lanthanoid(II) complexes [Eu(DippForm)I(thf)4 ] ⋅ thf (24), [Yb(DippForm)I(thf)3 ] ⋅ 2DippFormH (25), [Sm(DippForm)I(thf)4 ] ⋅ thf (26) have also been synthesized by direct reactions of the free metals, iodine and DippFormH. Interestingly, [Sm(DippForm)I2 (thf)3 ] (27) was obtained by the oxidation of [Sm(DippForm)I(thf)4 ] ⋅ thf (26) on exposure to air. N,N'-Bis(2,6-dimethylphenyl)formamidinatoiodidosamarium(II) [Sm(XylForm)I(thf)3 ]n (28) was also prepared by direct reaction of Sm, iodine and XylFormH (mole ratio of I2 : XylFormH=1 : 2). All products have been identified by X-ray crystallography and all the trivalent complexes [Ln(Form)n I3-n ] (n=1 or 2) are stable to rearrangement.

Pushing the Boundary of Covalency in Lanthanoid-Tellurium Bonds: Insights from the Synthesis, Molecular and Electronic Structures of Low-Coordinate, Monomeric Europium(II) and Ytterbium(II) Tellurolates.

Owing to the strict hard/soft dichotomy between the lanthanoids and tellurium atoms, and the strong affinity of lanthanoid ions for high coordination numbers, low-coordinate, monomeric lanthanoid tellurolate complexes have remained elusive as compared to the lanthanoid complexes with lighter group 16 elements (O, S, and Se). This makes the development of suitable ligand systems for low-coordinate, monomeric lanthanoid tellurolate complexes an appealing endeavor. In a first report, a series of low-coordinate, monomeric lanthanoid (Yb, Eu) tellurolate complexes were synthesized by utilizing hybrid organotellurolate ligands containing N-donor pendant arms. The reaction of bis[2-((dimethylamino)methyl)phenyl] ditelluride, 1 and 8,8'diquinolinyl ditelluride, 2 with Ln0 metals (Ln=Eu, Yb) resulted in the formation of monomeric complexes [LnII (TeR)2 (Solv)2 ] [R=C6 H4 -2-CH2 NMe2 ] [3: Ln=Eu, Solv=tetrahydrofuran; 4: Ln=Eu, Solv=acetonitrile; 5: Ln=Yb, Solv=tetrahydrofuran; 6: Ln=Yb, Solv=pyridine] and [EuII (TeNC9 H6 )2 (Solv)n ] (7: Solv=tetrahydrofuran, n=3; 8: Solv=1,2-dimethoxyethane, n=2), respectively. Complexes 3-4 and 7-8 represent the first sets of examples of monomeric europium tellurolate complexes. The molecular structures of complexes 3-8 are validated by single-crystal X-ray diffraction studies. The electronic structures of these complexes were investigated using Density Functional Theory (DFT) calculations, which revealed appreciable covalency between the tellurolate ligands and lanthanoids.

Bromobenzene Transforms Lanthanoid Pseudo-Grignard Chemistry.

Divalent lanthanoid pseudo-Grignard reagents PhLnBr (Ln=Sm, Eu and Yb) can be easily prepared by the oxidative addition of bromobenzene (PhBr) to lanthanoid metals in tetrahydrofuran (THF). PhLnBr reacts with bulky N,N'-bis(2,6-di-isopropylphenyl)formamidine (DippFormH) to generate LnII complexes, namely [Ln(DippForm)Br(thf)3 ]2 ⋅6thf (1; Sm, 2; Eu), and [Yb(DippForm)Br(thf)2 ]2 ⋅2thf (3; Yb). Samarium and europium (in 1 and 2) are seven coordinate, whereas ytterbium (in 3) is six coordinate, and all are bromine-bridged dimers. When PhLnBr reacts with 3,5-diphenylpyrazole (Ph2 pzH), both divalent (5; [Eu(Ph2 pz)2 (thf)4 ]) and trivalent (4 a; [Sm(Ph2 pz)3 (thf)3 ]⋅3thf, 4 b; [Sm(Ph2 pz)3 (dme)2 ]⋅dme) complexes are obtained. In the monomeric compounds 4(a,b), samarium is nine coordinate but europium is eight coordinate in 5. The use of PhLnBr in this work transforms the outcomes from earlier reactions of PhLnI.

Experience of chinese counter-marching nurses with COVID-19 patients' death in Wuhan: a qualitative study.

BACKGROUND: The COVID-19 pandemic was occurring worldwide with over a 6.5 million deaths. It's important to explore the instructions for the global nursing community by identifying the personal coping methods of Chinese nurses in Wuhan to deal with patient deaths. METHODOLOGY: The study used a qualitative conventional content analysis with 14 Chinese Counter-marching nurses. Purposive sampling, snowball sampling, and semi-structured interviews were used for participants and data collection. To assess the quality of the findings, Guba and Lincoln's criteria for confidence were fulfilled. RESULTS: The data analysis results in 4 main categories:(1) psychological shocks related to COVID-19 patient's death; (2) personal psychological adjustment and demands; (3) insights on life and values; (4) Needs for relevant knowledge and skills. CONCLUSIONS: During the outbreak of the epidemic or pandemic, adequate psychological care resources need to be provided to nurses when facing the death of infectious patients, to reduce the negative emotions brought by death. Effective coping strategies should also be formulated to enhance their resilience and promote their professional competence.

Never a dull moment with praseodymium metal.

Unexpectedly, a mixture of bismuth N,N'-bis(2,6-diisopropylphenyl)formamidinates in three different oxidation states namely, [BiI2(DippForm)2] (1), [BiII2(DippForm)2(C6F5)2] (2) and [BiIII(DippForm)2(C6F5)] (3), together with [Pr(DippForm)2F(thf)]·PhMe (4), [p-HC6F4DippForm]·0.5thf (5), and a ring-opened tetrahydrofuran [o-HC6F4O(CH2)4DippForm] (6) was obtained by the reaction of an excess of praseodymium metal with tris(pentafluorophenyl)bismuth, [Bi(C6F5)3]·0.5dioxane, and bulky N,N'-bis(2,6-diisopropylphenyl)formamidine (DippFormH) in tetrahydrofuran. Similar reactions between praseodymium metal, [Bi(C6F5)3]·0.5dioxane and 3,5-diphenylpyrazole (Ph2pzH), or 3,5-di-tert-butylpyrazole (tBu2pzH), yielded the paddlewheel dibismuthanes [BiII2(Ph2pz)4]·dioxane (7) and [BiII2(tBu2pz)4] (8) respectively.

Bazi Bushen mitigates epigenetic aging and extends healthspan in naturally aging mice.

Bazi Bushen (BZBS), a traditional Chinese medicine, has been proven effective in the treatment of age-related disease in mouse models. However, whether its therapeutic effects are due to antiaging mechanism has not yet been explored. In the present study, we investigated the antiaging effects of BZBS in naturally aging mice by using behavioral tests, liver DNA methylome sequencing, methylation age estimation, and frailty index assessment. The methylome analysis revealed a decrease of mCpG levels in the aged mouse liver. BZBS treatment tended to restore age-associated methylation decline and prune the methylation pattern toward that of young mice. More importantly, BZBS significantly rejuvenated methylation age of the aged mice, which was computed by an upgraded DNA methylation clock. These results were consistent with enhanced memory and muscular endurance, as well as decreased frailty score and liver pathological changes. KEGG analysis together with aging-related database screening identified methylation-targeted pathways upon BZBS treatment, including oxidative stress, DNA repair, MAPK signaling, and inflammation. Upregulation of key effectors and their downstream effects on elevating Sod2 expression and diminishing DNA damage were further investigated. Finally, in vitro experiments with senescent HUVECs proved a direct effect of BZBS extracts on the regulation of methylation enzymes during cellular aging. In summary, our work has revealed for the first time the antiaging effects of BZBS by slowing the methylation aging. These results suggest that BZBS might have great potential to extend healthspan and also explored the mechanism of BZBS action in the treatment of age-related diseases.

Water channel protein AQP1 in cytoplasm is a critical factor in breast cancer local invasion.

BACKGROUND: Metastasis of breast cancer grows from the local invasion to the distant colonization. Blocking the local invasion step would be promising for breast cancer treatment. Our present study demonstrated AQP1 was a crucial target in breast cancer local invasion. METHODS: Mass spectrometry combined with bioinformatics analysis was used to identify AQP1 associated proteins ANXA2 and Rab1b. Co-immunoprecipitation, immunofluorescence assays and cell functional experiments were carried out to define the relationship among AQP1, ANXA2 and Rab1b and their re-localization in breast cancer cells. The Cox proportional hazards regression model was performed toward the identification of relevant prognostic factors. Survival curves were plotted by the Kaplan-Meier method and compared by the log-rank test. RESULTS: Here, we show that the cytoplasmic water channel protein AQP1, a crucial target in breast cancer local invasion, recruited ANXA2 from the cellular membrane to the Golgi apparatus, promoted Golgi apparatus extension, and induced breast cancer cell migration and invasion. In addition, cytoplasmic AQP1 recruited cytosolic free Rab1b to the Golgi apparatus to form a ternary complex containing AQP1, ANXA2, and Rab1b, which induced cellular secretion of the pro-metastatic proteins ICAM1 and CTSS. Cellular secretion of ICAM1 and CTSS led to the migration and invasion of breast cancer cells. Both in vivo assay and clinical analysis data confirmed above results. CONCLUSIONS: Our findings suggested a novel mechanism for AQP1-induced breast cancer local invasion. Therefore, targeting AQP1 offers promises in breast cancer treatment.

Formation of a cyclooctatetraenylsamarium(III) inverse sandwich that ring-opens tetrahydrofuran.

Reductive trapping of the cyclooctatetraenyl dianion (COT2-) by treatment of [Sm(DippForm)2(thf)2] (DippFormH = N,N'-bis(2,6-diisopropylphenyl)formamidine; thf = tetrahydrofuran) with 1,3,5,7-cyclooctatetraene (C8H8) in toluene yields an inverse sandwich dinuclear complex [Sm2(DippForm)4(COT)] (1), but [Sm(DippForm)(COT)(thf)2] (2) and [Sm(DippForm)2(O-C4H8-DippForm)(thf)] (3) in thf, and 1 yields 2 and 3 on treatment with thf.

RE(III) 3-Furoate Complexes: Synthesis, Structure, and Corrosion Inhibiting Properties.

In this study, two types of Rare Earth (RE) 3-furoate complexes were synthesized by metathesis reactions between RE chlorides or nitrates and preformed sodium 3-furoate. Two different structural motifs were identified as Type 1RE and Type 2RE. The Type 1RE monometallic complexes form 2D polymeric networks with the composition [RE(3fur)3(H2O)2]n (1RE = 1La, 1Ce, 1Pr, 1Nd, 1Gd, 1Dy, 1Ho, 1Y; 3furH = 3-furoic acid) while Type 2RE bimetallic complexes form 3D polymeric systems [NaRE(3fur)4]n (2RE = 2Ho, 2Y, 2Er, 2Yb, 2Lu). The stoichiometric mole ratio used (RE: Na(3fur) = 1:3 or 1:4) in the metathesis reaction determines whether 1RE or 2RE (RE = Ho or Y) is formed, but 2RE (RE = Er, Yb, Lu) were obtained regardless of the ratio. The corrosion inhibition behaviour of the compounds has been examined using immersion studies and electrochemical measurements on AS1020 mild steel surfaces by a 0.01 M NaCl medium. Immersion test results revealed that [Y(3fur)3(H2O)2]n has the highest corrosion inhibition capability with 90% resistance after 168 h of immersion. Potentiodynamic polarisation (PP) measurements also indicate the dominant behaviour of the 1Y compound, and the PP curves show that these rare earth carboxylate compounds act predominantly as anodic inhibitors.

Reinvestigation of Reactions of HgPh2 with Eu and Yb Metal and the Synthesis of a Europium(II) Bis(tetraphenylborate).

Europium bis(tetraphenylborate) [Eu(thf)7][BPh4]2⋅thf containing a fully solvated [Eu(thf)7]2+ cation, was synthesized by protolysis of "EuPh2" (from Eu and HgPh2) with Et3NHBPh4, and the structure was determined by single-crystal X-ray diffraction. Efforts to characterize the putative "Ph2Ln" (Ln = Eu, Yb) reagents led to the synthesis of a mixed-valence complex, [(thf)3YbII(µ-Ph)3YbIII(Ph)2(thf)]⋅2thf, resulting from the reaction of Yb metal with HgPh2 at a low temperature. This mixed-valence YbII/YbIII compound was studied by 171Yb-NMR spectroscopy and single-crystal X-ray diffraction, and the oxidation states of the Yb atoms were assigned.

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.