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PubMed2004

Structural study of the T#2-LixCoO2 (0.52 < x < or = 0.72) phase.

The metastable O2-LiCoO(2) phase undergoes several reversible phase transitions upon lithium deintercalation. The first transition leads to an unusual oxygen stacking in such layered compounds. This stacking is found to be stable for 0.52 < x < or = 0.72 in Li(x)()CoO(2) and is called T(#)2. We studied this phase from a structural viewpoint using X-ray and neutron diffraction (ab initio method). The new stacking derives from the O2 one by gliding every second CoO(2) slab by (1/3, 1/6, 0). The lithium ions are found to occupy very distorted tetrahedral sites in this structure. We also discuss the possibility of this T(#)2 phase to exhibit stacking faults, whose amount depends on the method used to prepare this deintercalated phase.

Journal Article↗
PubMedDate not supplied

Mesoporous SnO2 synthesized with non-ionic surfactants as an anode material for lithium batteries.

Mesoporous tin oxides were successfully prepared with the use of non-ionic surfactants, Pluronic 123 (P-123) and Tetronic 908 (T-908). Surface analysis of SnO2 synthesized with P123 showed an average pore size of approximately 15 nm. The high-resolution transmission electron microscopy and low-angle X-ray diffraction (XRD) measurements also confirmed their mesoporous nature. The X-ray photoelectron spectroscopy and wide-angle XRD studies revealed that these compounds have a casserite-type SnO2 structure. The electrochemical properties of these materials as anodes in lithium batteries showed excellent performance with good reversibility. The first-cycle reversible capacity was 1026 mAh/g for the material synthesized with P123. There was a high first-cycle irreversible capacity for SnO2 synthesized with the use of both non-ionic surfactants. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were employed to study the electrode kinetics during the lithium insertion process in the first cycle. There was a decrease in the charge-transfer resistance with respect to the discharge potential. The synthesis and structural and electrochemical properties of the mesoporous tin oxides are correlated and discussed in detail.

Crystallization↗
PubMed2000

New Insights into the Chemistry of Lithium Carbamoyls: Characterization of an Adduct (R(2)NC(O)CLi(OLi)NR(2)).

Studies of the reaction of lithium dicyclohexylamide with N,N-dibutylformamide, 1-formylpiperidine, and 4-formylmorpholine indicate that the equilibria resulting from these compounds are shifted toward the formation of an adduct, which quickly collapses to dicyclohexylamine and the lithiated carbamoyl anion derived from the initial disubstituted formamide. Further reactions of the lithium carbamoyl lead to a new adduct where a lithiated carbon is bounded to N, O, and a carbonyl functionality. The (13)C NMR analysis of the reaction mixtures showed the presence of similar intermediates in all cases: adducts of this type have not been reported before. These dilithiated intermediates were trapped with methyl iodide giving the corresponding doubly methylated derivatives. Isolation of substituted glyoxylamides and quantitative determination of the products yields constitute further evidence of the whole reaction scheme proposed.

Journal Article↗
PubMed2000

Relationship of crystal structure to interionic interactions in the lithium-manganese spinel oxides

Lithium manganese oxides in the form of cubic spinel phases (space group Fd3m) are formed in a LixMn3-xO4 system for rather limited values of x. Structural investigations by X-ray powder diffraction, applied to the Li-Mn-O compounds, indicate the formation of a second crystalline phase, Li2MnO3 (space group C2/m), with the increasing lithium content. Total Li+ content per unit cell and the cation distribution over a spinel lattice in LixMn3-xO4 have been studied by measurements of integrated intensities of X-ray reflections, and by structure refinement using Rietveld profile analysis. In an attempt to understand the factors affecting cation distribution in the spinel lattice, we applied the computer modelling techniques and investigated the Li+, Mn3+ and Mn4+ ion distribution by calculating the lattice energy, combined with energy minimisation procedures, using the General Utility Lattice Program (GULP), a program designed for simulation of ionic and semi-ionic solids, based on interatomic potential models.

Journal Article↗
PubMed1965

GRAMICIDIN AND ION TRANSPORT IN ISOLATED LIVER MITOCHONDRIA.

1. Gramicidin caused H(+) production by liver mitochondria; this process was dependent on the presence of Na(+), Li(+), Rb(+) or Cs(+). In the presence of one of these alkali-metal ions and phosphate, gramicidin caused mitochondrial swelling and increased oxygen consumption. 2. Uncoupling agents, anaerobic conditions or respiratory inhibitors both inhibited and reversed H(+) production and swelling. Both these processes could be supported by coupled electron transport through even a restricted portion of the respiratory chain. 3. NH(4) (+) also caused stimulation of respiration in the presence of gramicidin. In this case phosphate was not required. NH(4) (+), in the presence of gramicidin, caused contraction of the mitochondria and a reversal of K(+)-induced swelling and H(+) production. 4. Uncoupling agents or NH(4) (+) together with gramicidin caused the release of Sr(2+) that had been accumulated by mitochondria in the presence of phosphate. 5. These results are discussed in relation to a postulated respiration-dependent H(+) pump located in the mitochondrial membrane. It is suggested that gramicidin allows alkali-metal ions to pass through the mitochondrial membrane.

Ammonium Compounds↗
PubMed1995

Ramipril-induced decrease in renal lithium excretion in the rat.

1. The interaction of ramipril, an inhibitor of angiotensin I converting enzyme, with renal lithium handling was analysed in conscious normotensive Wistar rats and compared with the known increase in renal tubular lithium reabsorption induced by the non-steroidal anti-inflammatory drug, indomethacin. 2. The rats were treated for five days with ramipril (1 mg kg-1 day-1 orally), indomethacin (2.5 mg kg-1 day-1 intramuscularly) or their solvents. Lithium chloride (16.7 mg kg-1 intraperitonealy) was given as a single dose on the fifth day and renal functions were measured. 3. Ramipril induced a decrease in renal lithium clearance which was correlated with the decrease in the quantity of filtered lithium and the increase in the tubular fractional reabsorption of the metal. Ramipril also reduced the systolic blood pressure of the rats by about 15 mmHg. 4. In the absence of any effect on creatinine clearance or systolic blood pressure, indomethacin increased renal fractional lithium reabsorption and led to an increase in plasma lithium levels, as previously reported by our group. 5. In conclusions, our results indicate that ramipril decreases renal lithium excretion in Wistar rats, when given orally at a dose of 1 mg kg-1 day-1 over five days.

Angiotensin I↗
PubMed1964

NEUTRAL SALTS: THE GENERALITY OF THEIR EFFECTS ON THE STABILITY OF MACROMOLECULAR CONFORMATIONS.

The effects of various neutral salts on the temperature of the thermally-induced denaturation of the globular protein ribonuclease are described and compared with the effects of these salts on helix-coil transition temperatures in other macromolecules. These agents affect the stability of the native form of macromolecules as diverse as ribonuclease, collagen, DNA, and myosin in very similar ways; salts such as KSCN and CaCl(2) serve as very potent general structural destabilizers or denaturants, while salts such as (NH(4))(2)SO(4) and K(2)HPO(4) strongly stabilize the native conformation. The effectiveness of the neutral salts as ribonuclease destabilizers is compared with that of urea and the guanidinium salts.

Acetates↗
PubMed1992

Cisplatin-induced conditioned taste aversion: attenuation by dexamethasone but not zacopride or GR38032F.

The 5-HT3 receptor antagonists zacopride and GR38032F are highly effective inhibitors of emesis induced by ionizing radiation and chemotherapeutic drugs such as cisplatin. The present study evaluated zacopride and GR38032F for efficacy in inhibiting the formation of the conditioned taste aversion (CTA) induced by cisplatin or lithium chloride in rats. The glucocorticoid dexamethasone, which has been reported to be effective against both the emetic and CTA-inducing effects of cisplatin, was included as a reference compound. When administered alone by i.p. injection, zacopride (0.1-10 mg/kg), GR38032F (10 mg/kg) and cisplatin (0.32-1.8 mg/kg) induced a CTA to an 0.1% saccharin solution; lower doses of each compound were ineffective. When administered as a pretreatment, neither zacopride (0.001-0.1 mg/kg) nor GR38032F (0.01-10 mg/kg) attenuated the CTA induced by cisplatin (0.32 and 0.56 mg/kg) or lithium chloride (10 mg/kg). In contrast, dexamethasone (0.32 and 1.0 mg/kg) attenuated the CTA induced by 0.32 but not 0.56 mg/kg of cisplatin. In an attempt to evaluate higher doses of zacopride against cisplatin without the potentially confounding factor that these doses by themselves induce a CTA, rats were injected with zacopride on three separate days prior to the aversion conditioning session. This pre-exposure treatment blocked the formation of the zacopride-induced CTA, but did not improve the efficacy of zacopride in attenuating the cisplatin-induced CTA. These results suggest that neither the cisplatin- nor the lithium-induced CTA in rats are due to effects that are sensitive to 5-HT3 receptor blockade.

Analysis of Variance↗
PubMed2003

Effect of cannabinoids on lithium-induced vomiting in the Suncus murinus (house musk shrew).

RATIONALE: Marijuana has been reported to interfere with nausea and vomiting in chemotherapy patients. The principal cannabinoids found in marijuana include the psychoactive compound Delta-9-tetrahydrocannabinol (THC) and the non-psychoactive compound cannabidiol (CBD). The experiments reported here evaluated the potential of THC and CBD to interfere with vomiting in the Suncus murinus (house musk shrew) produced by lithium chloride (LiCl), which is the most commonly employed unconditioned stimulus for taste avoidance. OBJECTIVES: To evaluate the potential of the principal components of marijuana, THC and CBD, to suppress Li-induced vomiting in the house musk shrew. METHODS: Shrews were injected with vehicle or one of two cannabinoids [Delta-9-THC (1-20 mg/kg), or CBD (2.5-40 mg/kg)] 10 min prior to an injection of LiCl (390 mg/kg of 0.15 M) and were then observed for 45 min. The frequency of vomiting episodes and the latency to the first episode were measured. The role of the CB1 receptor in these effects was also evaluated by pretreatment with SR-141716. RESULTS: Delta-9-THC produced a dose-dependent suppression of Li-induced vomiting, with higher doses producing greater suppression than lower doses. CBD produced a biphasic effect with lower doses producing suppression and higher doses producing enhancement of Li-induced vomiting. The suppression of Li-induced vomiting by THC, but not by CBD, was reversed by SR-141716. CONCLUSIONS: These results indicate that two major cannabinoid compounds found in marijuana, THC and CBD, are effective treatments for Li-induced vomiting; however, only THC acts by the CB1 receptor. The effects of THC and CBD on vomiting were dose dependent; with THC the effect was linear, but with CBD the effect was biphasic.

Animals↗
PubMed2003

Tetra-microchloro-1:2kappa(4)Cl;1:3kappa(4)Cl-bis(4,4'-dimethyl-2,2'-bipyridine)-2kappa(2)N,3kappa(2)N-lithium(I)dipalladium(II) tetrakis(pentafluorophenyl)borate dichloromethane 1.196-solvate.

In the crystal structure of the title compound, [LiPd(2)Cl(4)(C(12)H(12)N(2))(2)](C(24)F(20)B).1.196CD(2)Cl(2) or [[(Me(2)bipy)PdCl(2)](2)(micro-Li)](+).B(C(6)F(5))(4)(-).1.196CD(2)Cl(2) (Me(2)bipy is 4,4'-dimethyl-2,2'-bipyridine), an Li(+) cation is stabilized by complexation with two (Me(2)bipy)PdCl(2) units through weak Li-Cl interactions. This compound is thus a rare example of a complex that exhibits an arrested Cl(-) abstraction.

Journal Article↗
PubMed2004

Effects of phosphoinositide cycle modifiers on apoptosis of peritoneal macrophages.

Hydrogen peroxide stimulates apoptosis of zymosan-activated rat peritoneal macrophages. Phosphoinositide cycle modifiers enhance the proapoptotic effect of H(2)O(2) in a concentration of 1 mM and necrosis-stimulating effect of H(2)O(2) in a concentration of 10 mM. Disorders in phosphoinositide metabolism and impaired reaction of the cell to proinflammatory agents are the cause of programmed cell death. Rejection of defective cells can be realized via variation of H(2)O(2) concentration.

Aluminum Compounds↗
PubMed2006

Vibrational spectroscopic investigation of structurally-related LiFePO4, NaFePO4, and FePO4 compounds.

Vibrational spectroscopy was utilized to investigate the local structure of LiFePO(4), NaFePO(4), and FePO(4). The factor group splitting of the intramolecular PO(4)(3-) vibrations is between 10 and 20 cm(-1) less for NaFePO(4) than for LiFePO(4). This is because Li(+) ions have a higher charge density than Na(+) ions and can form stronger coordinative bonds with the PO(4)(3-) anions. Thus, the internal modes are more perturbed in LiFePO(4) and exhibit larger factor group splitting effects. The similarity of the factor group multiplets for both LiFePO(4) and NaFePO(4), particularly the PO(4)(3-) bending modes, strongly suggests that the 506 and 470 cm(-1) bands of LiFePO(4) consist almost entirely of lithium translatory motion. There are marked differences between the vibrational spectrum of FePO(4) and those of LiMPO(4) (M=Mn, Fe, Co, or Ni) or NaFePO(4). The monovalent cations interact with the oxygen atoms of the phosphate groups, affecting the frequencies and intensities of the intramolecular PO(4)(3-) modes, in a manner that is absent in FePO(4).

Electrochemistry↗
PubMed1975

Insertion Compounds of 2H-TaS(2).NH(3).

A new method of intercalating metals into layer compounds has been developed using electrolytic generation from the salt solution in ammonia. The results suggest that metals that are soluble in ammonia will form a homogeneous metal-ammonia intercalate layer, NH(3).M(x), when x is less than the limiting solubility of M in NH(3). The superconducting transition temperature (T(c)) was found to increase as the c-axis expansion [2delta = c(TaS(2).NH(3).M(x)) - c(2H-TaS(2))] decreased when M = lithium, sodium, and potassium. Of all the alkali metals, potassium gave the most stable compounds and the highest T(c), 4.7 degrees K.

Journal Article↗
PubMed1999

Manipulation of separation selectivity for alkali metals and ammonium in ion-exchange capillary electrochromatography using a suspension of cation exchange particles in the electrolyte as a pseudostationary phase.

The viability of using ion-exchange particles as a pseudostationary phase in capillary electrochromatography for the separation of monovalent inorganic cations has been investigated. Using sulfonated polymeric particles (average diameter 225 nm) as the pseudostationary phase, the separation selectivity for alkali metals and ammonium was examined under a range of background electrolyte compositions and employing indirect absorbance detection. Addition of ion-exchange particles to the background electrolyte resulted in a reduction in the observed electrophoretic mobility of the analytes due to the establishment of ion-exchange interaction with the pseudostationary phase, with the decrease in mobilities following the ion-exchange interaction order for these analytes with a sulfonated stationary phase. Increasing the concentration of the particles resulted in a uniform reduction in the electrophoretic mobility of the analytes, similar to that observed in micellar electrokinetic chromatography. Conversely, increasing the concentration of the cationic indirect detection probe (which also acted as an ion-exchange competing cation) resulted in a decrease in the ion-exchange interaction with the particles and a reduction of the relative ion-exchange contribution to the overall separation mechanism. Plots of log[retention factor] versus log[electrolyte concentration] were linear, as is the case for ion-exchange chromatography, but the observed slopes were greater than predicted from ion-exchange theory. Indirect absorbance detection was found to give poor sensitivity due to light scattering effects caused by the particles of pseudostationary phase.

Cations↗