Treatment of calcium or strontium with 2.0 equivalents of N,N-bis(o-methylphenyl)formamidine (o-TolFormH), N,N-bis(2,6-dimethylphenyl)formamidine (XylFormH) or N,N-bis(o-phenylphenyl)formamidine (o-PhPhFormH) in the presence of 1.0 equivalent of Hg(C6F5)2 in tetrahydrofuran (thf) affords the bis(formamidinate) complexes [Ca(o-TolForm)2(thf)2] (1), [Ca(XylForm)2(thf)2] (2), [Ca(o-PhPhForm)2(thf)2].thf (3), [Sr(o-TolForm)2(thf)3] (4), [Sr(XylForm)2(thf)3].3thf (5) and [Sr(o-PhPhForm)2(thf)3].2thf (6). Analogous reactions with barium were generally unsatisfactory but [Ba(o-PhPhForm)2(thf)3].2thf (7) was successfully prepared. Compounds 1-7 have been characterised by various spectroscopic methods (1H, 13C{1H} NMR and IR), elemental analyses and, for 1, 2 and 4-6, X-ray crystallography. The calcium complexes are monomeric and six-coordinate with either transoid octahedral or trigonal prismatic geometry, whilst the larger radius of strontium accommodates an additional thf solvent donor to give seven-coordinate structures with two types of coordination polyhedra. 相似文献
[reaction: see text] The core trioxadispiroketal system representing C26-C40 of spirastrellolide A was assembled using a sequenced double-intramolecular hetero-Michael addition process. 相似文献
Suppressing the mobility of anionic species in polymer electrolytes (PEs) is essential for mitigating the concentration gradient and internal cell polarization, and thereby improving the stability and cycle life of rechargeable alkali metal batteries. Now, an ether‐functionalized anion (EFA) is used as a counter‐charge in a lithium salt. As the salt component in PEs, it achieves low anionic diffusivity but sufficient Li‐ion conductivity. The ethylene oxide unit in EFA endows nanosized self‐agglomeration of anions and trapping interactions between the anions and its structurally homologous matrix, poly(ethylene oxide), thus suppressing the mobility of negative charges. In contrast to previous strategies of using anion traps or tethering anions to a polymer/inorganic backbone, this work offers a facile and elegant methodology on accessing selective and efficient Li‐ion transport in PEs and related electrolyte materials (for example, composites and hybrid electrolytes). 相似文献
A convergent and stereoselective total synthesis of the previously assigned structure of azaspiracid‐3 has been achieved by a late‐stage Nozaki–Hiyama–Kishi coupling to form the C21?C22 bond with the C20 configuration unambiguously established from l ‐(+)‐tartaric acid. Postcoupling steps involved oxidation to an ynone, modified Stryker reduction of the alkyne, global deprotection, and oxidation of the resulting C1 primary alcohol to the carboxylic acid. The synthetic product matched naturally occurring azaspiracid‐3 by mass spectrometry, but differed both chromatographically and spectroscopically. 相似文献
An efficient and readily modifiable synthesis of GEX1A/herboxidiene/TAN-1609 ( 1) was developed. This modular synthesis featured a Suzuki coupling to install the conjugated diene and a Ru-catalyzed lactonization and Roush crotylation to construct the functionalized tetrahydropyran moiety. Myers' alkylation, cross-metathesis, and Keck crotylation were employed for assembly of the biologically essential side-chain domain. 相似文献
This study presents a custom‐made in situ gelling polymeric precursor for cell encapsulation. Composed of poly((2‐hydroxyethyl)methacrylate‐co‐(3‐aminopropyl)methacrylamide) (P(HEMA‐co‐APM) mother backbone and RGD‐mimicking poly(amidoamine) (PAA) moiteis, the comb‐like structured polymeric precursor is tailored to gather the advantages of the two families of synthetic polymers, i.e., the good mechanical integrity of PHEMA‐based polymers and the biocompatibility and biodegradability of PAAs. The role of P(HEMA‐co‐APM) in the regulation of the chemico‐physical properties of P(HEMA‐co‐APM)/PAA hydrogels is thoroughly investigated. On the basis of obtained results, namely the capability of maintaining vital NIH3T3 cell line in vitro for 2 d in a 3D cell culture, the in vivo biocompatibility in murine model for 16 d, and the ability of finely tuning mechanical properties and degradation kinetics, it can be assessed that P(HEMA‐co‐APM)/PAAs offer a cost‐effective valid alternative to the so far studied natural polymer‐based systems for cell encapsulation.
Objectives: The toxicity of chemotherapeutic anticancer drugs is a serious issue in clinics. Drug discovery from edible and medicinal plants represents a promising approach towards finding safer anticancer therapeutics. Justicia insularis T. Anderson (Acanthaceae) is an edible and medicinal plant in Nigeria. This study aims to discover cytotoxic compounds from this rarely explored J. insularis and investigate their underlying mechanism of action. Methods: The cytotoxicity of the plant extract was evaluated in human ovarian cancer cell lines and normal human ovarian surface epithelia (HOE) cells using a sulforhodamine B assay. Bioassay-guided isolation was carried out using column chromatography including HPLC, and the isolated natural products were characterized using GC-MS, LC-HRMS, and 1D/2D NMR techniques. Induction of apoptosis was evaluated using Caspase 3/7, 8, and 9, and Annexin V and PI based flow cytometry assays. SwissADME and SwissTargetPrediction web tools were used to predict the molecular properties and possible protein targets of identified active compounds. Key finding: The two cytotoxic compounds were identified as clerodane diterpenoids: 16(α/β)-hydroxy-cleroda-3,13(14)Z-dien-15,16-olide (1) and 16-oxo-cleroda-3,13(14)E-dien-15-oic acid (2) from the Acanthaceous plant for the first time. Compound 1 was a very abundant compound (0.7% per dry weight of plant material) and was shown to be more potent than compound 2 with IC50 values in the micromolar range against OVCAR-4 and OVCAR-8 cancer cells. Compounds 1 and 2 were less cytotoxic to HOE cell line. Both compounds induced apoptosis by increasing caspase 3/7 activities in a concentration dependent manner. Compound 1 further increased caspase 8 and 9 activities and apoptosis cell populations. Compounds 1 and 2 are both drug like, and compound 1 may target various proteins including a kinase. Conclusions: Clerodane diterpenoids (1 and 2) in J. insularis were identified as cytotoxic to ovarian cancer cells via the induction of apoptosis, providing an abundant and valuable source of hit compounds for the treatment of ovarian cancer. 相似文献
We used Monte Carlo method to generate the configurations of disassembly of hot nucleus Au* based on the Atomic Mass Table and the conservation of mass and charge number.The resulted charge distribution of fragments was then used to calculate the conditional moments.The logarithm correlation between second and third moments of experimental charge distribution is very well reproduced by theory.It seems that no connection to the critical phenomenon of concerned system exists. 相似文献