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PubMed2002

[Raman spectroscopic study of silicon-oxygen tetrahedrons microstructure in x CaSiO3.LiBO2 solid solutions].

Raman spectra of xCaSiO3.LiBO2 (by weight ratio, x = 0, 0.25, 0.33, 0.50) crystals were measured. The microstructure of different silicon-oxygen tetrahedrons and their abundant variations with silica contents were studied. It shows that all the silicon-oxygen tetrahedrons are isolated by Si-Ob-B bondings or free SiO4(4-). No evidence suggests that there exist considerable Si-Ob-Si bondings. The abundance of Q2, Q4 species increases with the increasing silica content, there exists barely Q3 species even at high silica content. And the sum of integrated Raman peaks for all Qi species are linearly correlated with silica concentration in crystal, which offers the possibility to analysis silica in minerals, slags, glasses and soil samples directly.

Borates↗
PubMed2001

Caspase-3 activation induced by inhibition of mitochondrial complex I is facilitated by glycogen synthase kinase-3beta and attenuated by lithium.

The compound 1-methyl-4-phenylpyridinium (MPP) is a selective inhibitor of mitochondrial complex I, and is widely used in model systems to elicit neurochemical alterations that may be associated with Parkinson's disease. In the present study treatment of human neuroblastoma SH-SY5Y cells with MPP resulted in a time- and concentration-dependent activation of the apoptosis-associated cysteine protease caspase-3, and caused morphological changes characteristic of apoptosis. To test if the activation state of the cell survival-promoting phosphatidylinositol 3-kinase (PI3K)/Akt signaling pathway affects MPP-induced caspase-3 activation, PI3K was inhibited with LY294002, or activated with insulin-like growth factor-1. MPP-induced caspase-3 activation was increased by inhibition of PI3K, and decreased by stimulation of PI3K, indicative of anti-apoptotic signaling by the PI3K/Akt pathway. To test if glycogen synthase kinase-3beta (GSK3beta), a pro-apoptotic kinase that is inhibited by Akt, is involved in regulating MPP-induced apoptosis, overexpression of GSK3beta and lithium, a selective inhibitor of GSK3beta, were used to directly alter GSK3beta activity. MPP-induced caspase-3 activity was increased by overexpression of GSK3beta. Conversely, the GSK3beta inhibitor lithium attenuated MPP-induced caspase-3 activation. To test if these regulatory interactions applied to other mitochondrial complex I inhibitors, cells were treated with rotenone. Rotenone-induced activation of caspase-3 was enhanced by inhibition of PI3K or increased GSK3beta activity, and was attenuated by inhibiting GSK3beta with lithium. Overall, these results indicate that inhibition of GSK3beta provides protection against the toxic effects of agents, such as MPP and rotenone, that impair mitochondrial function.

1-Methyl-4-phenylpyridinium↗
PubMed2005

Lithium-nitrogen and lithium-boron-nitrogen cage compounds formed using the phenylhydrazido backbone.

Two rare examples of the crystal structures of large molecular clusters formed from the lithium salts of multianions are reported; the first is the dilithium salt of phenylhydrazine, which forms a tetrameric cage with a core of eight Li and eight N centres; the second is a 32-membered cage which forms from the aggregation of two [B(NNPh)3]6- hexaanions, two [NH-NPh]2- dianions and 16 Li+ cations.

Journal Article↗
PubMed1994

Influence of colorants on crystallization and mechanical properties of lithia-based glass-ceramics.

OBJECTIVES: The objective of the present study was to test the hypothesis that colorants such as AgNO3 and FeCl3 act as conucleating agents with P2O5 in the Li2O-Al2O3-CaO-SiO2 system and that the addition of either colorant and P2O5 produces a greater effect on crystallization and selected mechanical properties than the use of P2O5 alone. METHODS: Microstructural effects were observed by SEM and optical microscopy. Mechanical properties were determined to monitor the effects of structural changes after crystallization. These include controlled-flaw flexure strength, fracture toughness (KIC), and Vickers hardness (VHN). RESULTS: Based on a glass composition of 27.84 mol% Li2O, 2.45 mol% Al2O3, 5.88 mol% CaO, and 63.84 mol% SiO2 (LACS), the mechanical properties of LACS glass-ceramics were influenced by P2O5, the colorant type, and the colorant concentration. The mean strength of the glass-ceramic disks without P2O5 increased with AgNO3 concentration to a peak value of 188 MPa at a concentration of 0.78 mmol%. The maximum value of controlled-flaw flexure strength increased from 120 MPa for one of the FeCl3 groups to 188 MPa for one of the AgNO3 groups. The maximum fracture toughness of glass-ceramic disks without P2O5 (2.45 MPa.m1/2) was associated with a AgNO3 concentration of 0.58 mmol%. This value was significantly greater (p < 0.05) than that of the corresponding group (1.90 MPa.m1/2) which also contained P2O5. There was no significant change in KIC of glass-ceramic specimens containing P2O5 as the AgNO3 concentration increased. The increase in controlled-flaw flexure strength and fracture toughness of specimen groups containing 0.58 to 0.78 mmol% AgNO3 support its use as a colorant and as a nucleating agent in LACS glass-ceramics. SIGNIFICANCE: The development of tougher, higher strength glass-ceramics can be controlled by the use of colorants that are also effective as nucleating agents. Although certain colorants are believed to act synergistically when used in combination with known nucleating agents to enhance the fracture toughness of glass-ceramics, this effect was not observed in this study for the combined use of AgNO3 and the classical nucleating agent, P2O5. In fact, the colorant used in this study (AgNO3) was more effective than P2O5 as a nucleating agent for lithia-based glass-ceramics.

Ceramics↗
PubMed2006

Anion relay chemistry: an effective tactic for diversity oriented synthesis.

An effective one-flask multicomponent linchpin coupling protocol employing the concept of anion relay chemistry (ARC) was developed. This concept calls for addition of an anion (5) to an epoxide (6), bearing on a distal carbon a trialkyl silyl group and an anion stabilizing group (ASG), to furnish upon epoxide ring opening oxyanion 7. Addition of HMPA or other polar solvents to trigger a solvent controlled 1,4-Brook rearrangement then leads to a new distal anion (8), which in turn is available to react with a variety of second electrophiles.

Anions↗
PubMed2005

Hetero-aggregate compounds of aryl and alkyl lithium reagents: a structurally intriguing aspect of organolithium chemistry.

Organolithium compounds are often depicted as mononuclear species. However, such compounds are in fact aggregated species and can form hetero-aggregates containing different organic groups, including heteroatom groups. In reactions involving organolithium reagents, the "pure" homo-aggregate organolithium compound can change into a hetero-aggregate, which has a different structure and reactivity to the homo-aggregate. This fact is often overlooked. When there are chiral centers in the organolithium reagent or the substrate, diastereoselective self-assembly (the preferential formation of a particular diastereoisomeric aggregate) plays a role. The importance of these contributions in understanding the structure and reactivity patterns of organolithium reagents is the focus of this Minireview.

Journal Article↗
PubMed2004

Regio- and stereospecific cleavage of silyl- and disilylepoxides with lithium diphenylphosphide.

Unsubstituted or alpha- and beta-C-substituted silylepoxides react stereospecifically with lithium diphenylphosphide, optionally followed by methylation, to give vinylphosphonium iodides or vinylphosphine oxides resulting from alpha-opening and silyl enol ethers, vinylsilanes or alpha-hydroxysilanes by beta-opening. On the other hand, alpha,beta- or alpha,alpha-disilylepoxides afforded beta-silyl vinylphosphine oxides or alpha-silylated silyl enol ethers by alpha- and beta-cleavage, respectively. All compounds are interesting synthons in organic chemistry.

Epoxy Compounds↗
PubMed2006

FTIR features of lithium-iron phosphates as electrode materials for rechargeable lithium batteries.

The essential structural features of lithium-metal phosphates (LMP) have been studied using FTIR spectroscopy which is a sensitive tool to probe the local environment in the solid materials. Various LMP materials where M is iron have been investigated including phospho-olivine LiFePO(4), diphosphate LiFeP(2)O(7), Nasicon-type phosphate Li(3)Fe(2)(PO(4))(3) and dihydrate FePO(4).2H(2)O. Vitreous and amorphous materials are also considered. Analysis of internal and external modes of vibration allows to distinguish between the different phases and the type of cationic environment in the framework. Results corroborate the contribution of the main factors which are responsible for the complexity of the spectra, i.e. departure from ideal symmetry, interactions between polyhedra, bridging atoms and lattice distortion.

Diphosphates↗