Synthesis, Reactivity, and Structural Characterization of Sodium and Ytterbium Complexes Containing New Imidazolidine-Bridged Bis(phenolato) Ligands

A new imidazolidine-bridged bis(phenol) [ONNO]H2 ([ONNO]H2 = 1,4-bis(2-hydroxy-3,5-di-tert-butyl-benzyl)imidazolidine) was prepared in relatively high yield by Mannish reaction of 2,4-di-tert-butylphenol, formaldehyde, and ethylenediamine in a 2:3:1 molar ratio. Reaction of the bis(phenol) with NaH in THF, after workup, afforded the sodium bis(phenolate) {[ONNO]Na2(THF)2}2·2THF (1) as a dimeric tetranuclear complex in an almost quantitative yield. Reaction of YbCl3 with complex 1 in a 2:1 molar ratio in THF, in the presence of HMPA, produced the desired bis(phenolate) ytterbium dichloride as bimetallic complex [ONNO]{YbCl2(HMPA)}2·2.5C7H8 (2). Complex 2 can be used as a precursor for the synthesis of ytterbium derivatives by salt metathesis reactions. Reaction of complex 2 with NaOiPr in a 1:2 molar ratio in THF led to the formation of bimetallic alkoxide [ONNO]{Yb(μ-OiPr)Cl(HMPA)}2·THF (3). However, the residual chlorine atoms in complex 3 are inactive for the further substituted reaction. Further study revealed that the bulkiness of the reagent has profound effect on the outcome of the reaction. Complex 2 reacted with bulky NaOAr (ArO = 2,6-di-tert-butyl-4-methylphenoxo) or NaNPh2 in a 1:2 molar ratio under the same reaction conditions, after workup, to give the ligand redistributed products, (ArO)2YbCl(HMPA)2 (4) and [ONNO]YbCl(HMPA)2 (5) for the former and complexes 5 and (Ph2N)2YbCl(HMPA)2 (6) for the latter. If the molar ratio of complex 2 to NaNPh2 decreased to 1:4, the expected ligand redistributed products [ONNO]YbNPh2(HMPA) (7) and (Ph2N)3Yb(HMPA)2·C7H8 (8) can be isolated in high yields. All of the complexes were well characterized, and the definitive molecular structures of complexes 1−4, 7, and 8 were provided by single-crystal X-ray analysis

Synthesis, Reactivity, and Structural Characterization of Sodium and Ytterbium Complexes Containing New Imidazolidine-Bridged Bis(phenolato) Ligands

A new imidazolidine-bridged bis(phenol) [ONNO]H2 ([ONNO]H2 = 1,4-bis(2-hydroxy-3,5-di-tert-butyl-benzyl)imidazolidine) was prepared in relatively high yield by Mannish reaction of 2,4-di-tert-butylphenol, formaldehyde, and ethylenediamine in a 2:3:1 molar ratio. Reaction of the bis(phenol) with NaH in THF, after workup, afforded the sodium bis(phenolate) {[ONNO]Na2(THF)2}2·2THF (1) as a dimeric tetranuclear complex in an almost quantitative yield. Reaction of YbCl3 with complex 1 in a 2:1 molar ratio in THF, in the presence of HMPA, produced the desired bis(phenolate) ytterbium dichloride as bimetallic complex [ONNO]{YbCl2(HMPA)}2·2.5C7H8 (2). Complex 2 can be used as a precursor for the synthesis of ytterbium derivatives by salt metathesis reactions. Reaction of complex 2 with NaOiPr in a 1:2 molar ratio in THF led to the formation of bimetallic alkoxide [ONNO]{Yb(μ-OiPr)Cl(HMPA)}2·THF (3). However, the residual chlorine atoms in complex 3 are inactive for the further substituted reaction. Further study revealed that the bulkiness of the reagent has profound effect on the outcome of the reaction. Complex 2 reacted with bulky NaOAr (ArO = 2,6-di-tert-butyl-4-methylphenoxo) or NaNPh2 in a 1:2 molar ratio under the same reaction conditions, after workup, to give the ligand redistributed products, (ArO)2YbCl(HMPA)2 (4) and [ONNO]YbCl(HMPA)2 (5) for the former and complexes 5 and (Ph2N)2YbCl(HMPA)2 (6) for the latter. If the molar ratio of complex 2 to NaNPh2 decreased to 1:4, the expected ligand redistributed products [ONNO]YbNPh2(HMPA) (7) and (Ph2N)3Yb(HMPA)2·C7H8 (8) can be isolated in high yields. All of the complexes were well characterized, and the definitive molecular structures of complexes 1−4, 7, and 8 were provided by single-crystal X-ray analysis

Controlled Syntheses, Characterization, and Reactivity of Neutral and Anionic Lanthanide Amides Supported by Methylene-Linked Bis(phenolate) Ligands

A series of neutral and anionic bis(phenolate) lanthanide amides were synthesized by general metathesis reactions, and their reactivity was explored. Protolytic ligand exchange reactions of MBMPH2 (MBMP = 2,2‘-methylene bis(6-tert-butyl-4-methyl-phenolate)) with [Ln{N(TMS)2}2(μ-Cl)(THF)]2 (TMS = SiMe3) afforded the desired bridged bis(phenolate) lanthanide chlorides [(MBMP)Ln(μ-Cl)(THF)2]2 [Ln = Nd (1), Yb (2)] in high isolated yields. These lanthanide chlorides were found to be useful precursors for the synthesis of the corresponding lanthanide derivatives. Reactions of 1 and 2 with 2 equiv of NaN(TMS)2 in THF produced the expected neutral bis(phenolate) lanthanide amido complexes (MBMP)Ln[N(TMS)2](THF)2 [Ln = Nd (3), Yb (4)] in high yields. Whereas the reactions of 1 and 2 with LiN(TMS)2 in a 1:4 molar ratio gave the anionic bis(phenolate) lanthanide amides as discrete ion-pair complexes [Li(THF)4][(MBMP)Ln{N(TMS)2}2] [Ln = Nd (5), Yb (6)] in high isolated yields. Further study revealed that 5 and 6 can also be conveniently synthesized in high yields by the direct reactions of MBMPH2 with [Ln{N(TMS)2}2(μ-Cl)(THF)]2 in a 2:1 molar ratio, and then with 4 equiv of nBuLi. The reactivity of the neutral and anionic bis(phenolate) lanthanide amides was comparatively investigated. It was found that the insertion reactions of carbodiimide into the Ln−N bond of neutral lanthanide amido complexes 3 and 4 gave the anticipated bis(phenolate) lanthanide guanidinate complexes [(μ-O−MBMP)Nd{(iPrN)2CN(TMS)2}]2 (7) and (MBMP)Yb[(iPrN)2CN(TMS)2] (8), respectively, in high yields, whereas the similar reaction of carbodiimide with anionic amido complex 5 provided the unexpected ligand-redistributed products, and the homoleptic ion-pair bis(phenolate) neodymium complex [Li(DME)2(THF)][(MBMP)2Nd(THF)2] (9) was finally isolated as one of the products. Furthermore, the anionic bis(phenolate) lanthanide amides showed higher catalytic activity for the polymerization of ε-caprolactone than the neutral ones. All of the complexes were characterized with elemental analysis and IR spectra, and the definitive molecular structures of 1−3 and 5−9 were provided by single-crystal X-ray analyses

MOESM4 of Global scale transcriptome analysis reveals differentially expressed genes involve in early somatic embryogenesis in Dimocarpus longan Lour

Additional file 4: Figure S4. Heatmap of the differentially expressed genes in plant hormone signal transduction during longan SE. (a). Abscisic acid signal transduction; (b). Gibberellin signal transduction; (c). Ethylene signal transduction; (d). Salicylic acid signal transduction; (e). Brassinolide signal transduction; (f). Jasmonic acid signal transduction. Heatmaps indicate the gene expression levels by Log2[FPKM + 1] with a rainbow color scale. The IDs and names of selected DEGs are indicated to the right of the histograms

MOESM6 of Global scale transcriptome analysis reveals differentially expressed genes involve in early somatic embryogenesis in Dimocarpus longan Lour

Additional file 6: Table S2. Differentially expressed genes involved in flavonoid biosynthesis. (XLS 50 kb

MOESM3 of Global scale transcriptome analysis reveals differentially expressed genes involve in early somatic embryogenesis in Dimocarpus longan Lour

Additional file 3: Figure S3. Plant hormone signal transduction pathway in the comparison of NEC_vs_EC. Red frame represents a transcript with increased levels of expression and green frame represents transcripts with decreased levels of expression. The image was obtained from http://www.genome.jp/kegg/

Image_1_Defects in mTORC1 Network and mTORC1-STAT3 Pathway Crosstalk Contributes to Non-inflammatory Hepatocellular Carcinoma.tif

Background and AimsMammalian target of rapamycin complex 1 (mTORC1) is frequently hyperactivated in hepatocellular carcinoma (HCC). Cases of HCC without inflammation and cirrhosis are not rarely seen in clinics. However, the molecular basis of non-inflammatory HCC remains unclear.MethodsSpontaneous non-inflammatory HCC in mice was triggered by constitutive elevation of mTORC1 by liver-specific TSC1 knockout (LTsc1KO). A multi-omics approach was utilized on tumor tissues to better understand the molecular basis for the development of HCC in the LTsc1KO model.ResultsWe showed that LTsc1KO in mice triggered spontaneous non-inflammatory HCC, with molecular characteristics similar to those of diethylnitrosamine-mediated non-cirrhotic HCC. Mitochondrial and autophagy defects, as well as hepatic metabolic disorder were manifested in HCC development by LTsc1KO. mTORC1 activation on its own regulated an oncogenic network (DNA-damage-inducible transcript 4, nuclear protein 1, and fibroblast growth factor 21), and mTORC1–signal transducer and activator of transcription pathway crosstalk that altered specific metabolic pathways contributed to the development of non-inflammatory HCC.ConclusionOur findings reveal the mechanisms of mTORC1-driven non-inflammatory HCC and provide insight into further development of a protective strategy against non-inflammatory HCC.</p

MOESM2 of Global scale transcriptome analysis reveals differentially expressed genes involve in early somatic embryogenesis in Dimocarpus longan Lour

Additional file 2: Figure S2. Statistic of KEGG pathway enrichment for the pairwise comparisons of NEC_vs_EC, EC_vs_ICpEC, EC_vs_GE, and ICpEC_vs_GE. (DOC 230 kb

MOESM7 of Global scale transcriptome analysis reveals differentially expressed genes involve in early somatic embryogenesis in Dimocarpus longan Lour

Additional file 7: Table S3. Differentially expressed genes involved in fatty acid biosynthesis during longan SE. (XLS 26 kb

MOESM11 of Global scale transcriptome analysis reveals differentially expressed genes involve in early somatic embryogenesis in Dimocarpus longan Lour

Additional file 11: Table S7. Primers used for real-time quantitative PCR