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PubMed2004

Compounds of 6Li and natural Li for EPR dosimetry in photon/neutron mixed radiation fields.

Formates and dithionates of 6Li, enriched and 7Li in natural composition of Li offer a possibility to measure the absorbed dose from photons and thermal neutrons in a mixed radiation field for instance at a boron neutron capture therapy (BNCT) facility. Tests with formates and dithionates of enriched 6Li and lithium compounds with natural composition have been performed at the BNCT facility at Studsvik, Sweden. Irradiations have been performed at 3 cm depth in a Perspex phantom in a fluence rate of thermal neutrons 1.8 x 10(9) n cm(-2) s(-1). The compounds were also irradiated in a pure X-ray field from a 4MV linear accelerator at 5 cm depth in a phantom with accurately determined absorbed doses. The signal intensity and shape was investigated within 3 h after the irradiation. A single line spectrum attributed to the CO2- radical was observed after irradiation of lithium formate. An increase in line width occurring after neutron irradiation in comparison with photon irradiation of the 6Li sample was attributed to dipolar broadening between CO2- radicals trapped in the tracks of the alpha particles. A spectrum due to the SO3- radical anion was observed after irradiation of lithium dithionate. The signal amplitude increased using the 6Li in place of the Li with natural composition of isotopes, in studies with low energy X-ray irradiation. Due to the decreased line width, caused by the difference in g(N) and I between the isotopes, the sensitivity with 6Li dithionate may be enhanced by an order of magnitude compared to alanine dosimetry. After comprehensive examination of the different combinations of compounds with different amounts of 6Li and 7Li regarding dosimetry, radiation chemistry and EPR properties these dosimeter material might be used for dose determinations at BNCT treatments and for biomedical experiments. Interesting properties of the radical formation might be visible due to the large difference in ionization density of neutrons compared to photons.

Alanine↗
PubMed2004

Electrocardiographic abnormalities as predictors for over-range lithium levels.

BACKGROUND: Lithium compounds have been widely used in the treatment of manic-depressive illness. Several electrocardiogram (ECG) abnormalities, including ventricular arrhythmias, atrioventricular conduction abnormalities, T wave changes and QT interval prolongation, have been reported to be associated with lithium. However, the correlation between serum lithium levels and ECG changes has never been characterized in a systematic way. METHODS: This retrospective study included 76 patients undergoing lithium treatment with available records of lithium levels. Eleven patients (4 men) had serum lithium levels >1.2 mEq/l and were diagnosed as lithium over range. Clinical characteristics and various ECG changes were analyzed in patients with and without lithium over range. RESULTS: Patients with lithium over range had a slower heart rate and longer PR, QT and corrected QT (QTc) intervals. QTc interval >440 ms was more commonly found in patients with lithium over range (55 vs. 8%, p < 0.001). Similarly, diffuse T wave inversion was more commonly associated with lithium over range (73 vs. 17%, p < 0.001). The daily dosage of lithium was similar between patients with and without over-range lithium levels. When these two ECG changes were combined, the sensitivity and specificity in predicting lithium over range were 64 and 97%, respectively. These findings were independent of the concomitant use of beta-blockers. CONCLUSIONS: QTc interval >440 ms and diffuse T wave inversion were significantly more common in patients with lithium over range, and were good predictors of lithium over range. More liberal checkup of the ECG in patients undergoing lithium treatment may be of help in the early detection of lithium over range.

Adult↗
PubMed1992

[Saluresis in hypothermia and posthypothermia under the influence of LiCl].

Lithium compounds administered into rats' organisms in euthermia elicited accelerated urinary excretion of physiological cations, especially the Na and K ones. Homeothermic organisms in hypothermia, returnig from hypothermia and in posthypothermia showed considerable caliuresis with delayed excretion of Na during the following days. By way of gastric filling lithium load (in a form of water LiCl solution, with concentration of 0.2 n and the amount of 3.0 ml/100 cm2 ger body surface) administered to rats in deep hypothermia (17 degrees C - 19 degrees C measured high in the sigma), recovering of hypothermia (4 h) and in posthypothermia (20 h) did not elicit delayed natriuresis but efficiency of lithium and hypothermia had been summarised (clearly enhanced natriuresis and extremely enhanced caliuresis as a summarised efficiency).

Animals↗
PubMed2005

The synthesis, characterisation and reactivity of 2-phosphanylethylcyclopentadienyl complexes of cobalt, rhodium and iridium.

2-Phosphanylethylcyclopentadienyl lithium compounds, Li[C(5)R'(4)(CH(2))(2)PR(2)] (R = Et, R' = H or Me, R = Ph, R' = Me), have been prepared from the reaction of spirohydrocarbons C(5)R'(4)(C(2)H(4)) with LiPR(2). C(5)Et(4)HSiMe(2)CH(2)PMe(2), was prepared from reaction of Li[C(5)Et(4)] with Me(2)SiCl(2) followed by Me(2)PCH(2)Li. The lithium salts were reacted with [RhCl(CO)(2)](2), [IrCl(CO)(3)] or [Co(2)(CO)(8)] to give [M(C(5)R'(4)(CH(2))(2)PR(2))(CO)] (M = Rh, R = Et, R' = H or Me, R = Ph, R' = Me; M = Ir or Co, R = Et, R' = Me), which have been fully characterised, in many cases crystallographically as monomers with coordination of the phosphorus atom and the cyclopentadienyl ring. The values of nu(CO) for these complexes are usually lower than those for the analogous complexes without the bridge between the cyclopentadienyl ring and the phosphine, the exception being [Rh(Cp'(CH(2))(2)PEt(2))(CO)] (Cp' = C(5)Me(4)), the most electron rich of the complexes. [Rh(C(5)Et(4)SiMe(2)CH(2)PMe(2))(CO)] may be a dimer. [Co(2)(CO)(8)] reacts with C(5)H(5)(CH(2))(2)PEt(2) or C(5)Et(4)HSiMe(2)CH(2)PMe(2) (L) to give binuclear complexes of the form [Co(2)(CO)(6)L(2)] with almost linear PCoCoP skeletons. [Rh(Cp'(CH(2))(2)PEt(2))(CO)] and [Rh(Cp'(CH(2))(2)PPh(2))(CO)] are active for methanol carbonylation at 150 degrees C and 27 bar CO, with the rate using [Rh(Cp'(CH(2))(2)PPh(2))(CO)] (0.81 mol dm(-3) h(-1)) being higher than that for [RhI(2)(CO)(2)](-) (0.64 mol dm(-3) h(-1)). The most electron rich complex, [Rh(Cp'(CH(2))(2)PEt(2))(CO)] (0.38 mol dm(-3) h(-1)) gave a comparable rate to [Cp*Rh(PEt(3))(CO)] (0.30 mol dm(-3) h(-1)), which was unstable towards oxidation of the phosphine. [Rh(Cp'(CH(2))(2)PEt(2))I(2)], which is inactive for methanol carbonylation, was isolated after the methanol carbonylation reaction using [Rh(Cp'(CH(2))(2)PEt(2))(CO)]. Neither of [M(Cp'(CH(2))(2)PEt(2))(CO)] (M = Co or Ir) was active for methanol carbonylation under these conditions, nor under many other conditions investigated, except that [Ir(Cp'(CH(2))(2)PEt(2))(CO)] showed some activity at higher temperature (190 degrees C), probably as a result of degradation to [IrI(2)(CO)(2)](-). [M(Cp'(CH(2))(2)PEt(2))(CO)] react with MeI to give [M(Cp'(CH(2))(2)PEt(2))(C(O)Me)I] (M = Co or Rh) or [Ir(Cp'(CH(2))(2)PEt(2))Me(CO)]I. The rates of oxidative addition of MeI to [Rh(C(5)H(4)(CH(2))(2)PEt(2))(CO)] and [Rh(Cp'(CH(2))(2)PPh(2))(CO)] are 62 and 1770 times faster than to [Cp*Rh(CO)(2)]. Methyl migration is slower, however. High pressure NMR studies show that [Co(Cp'(CH(2))(2)PEt(2))(CO)] and [Cp*Rh(PEt(3))(CO)] are unstable towards phosphine oxidation and/or quaternisation under methanol carbonylation conditions, but that [Rh(Cp'(CH(2))(2)PEt(2))(CO)] does not exhibit phosphine degradation, eventually producing inactive [Rh(Cp'(CH(2))(2)PEt(2))I(2)] at least under conditions of poor gas mixing. The observation of [Rh(Cp'(CH(2))(2)PEt(2))(C(O)Me)I] under methanol carbonylation conditions suggests that the rhodium centre has become so electron rich that reductive elimination of ethanoyl iodide has become rate determining for methanol carbonylation. In addition to the high electron density at rhodium.

Journal Article↗
PubMed2001

The configurational stability of an enantioenriched alpha-thiobenzyllithium derivative and the stereochemical course of its electrophilic substitution reactions; synthesis of enantiomerically pure, tertiary benzylic thiols.

The lithium compound (S)-7, formed by deprotonation of the (S)-S-1-phenylethyl thiocarbamate (S)-10, is configurationally stable at -70 degrees C. Even at elevated temperatures it racemizes only very slowly. It represents the first essentially enantiopure alpha-thiocarbanion derivative and can be utilized in asymmetric synthesis. Most electrophiles (except proton acids) add to (S)-7 with complete stereoinversion. Cleavage of the substitution products leads to practically enantiopure, tertiary 1-phenylalkanethiols.

Journal Article↗
PubMed2001

C3-chiral tripodal amido complexes.

A comprehensive study into the coordination chemistry of two C3-chiral tripodal amido ligands has been carried out. The amido ligands contain a trisilylmethane backbone and chiral peripheral substituents. The amine precursors. HC(SiMe2NH[(S)-1-phenylethyl]]3 (1) and HC[SiMe2NH[(R)-1-indanyl]]3 (2) were found to be in equilibrium in solution with the cyclic diamines HC[SiMe2N[(S)-1-phenylethyl]2](SiMe2NH-[(S)-1-phenylethyl]] (3) and HC[SiMe2NH[(R)-1-indanyl]][SiMe2NH[(R)-1-indanyl]) (4), which are generated upon ejection of one molecule of the chiral primary amine. Reaction of these equilibrium mixtures with three molar equivalents of butyllithium instantaneously gave the trilithium triamides HC[SiMe2N(Li)[(S)-1-phenylethyl]]3 (5) and HC[SiMe2N(Li)[(R)-1-indanyl]]3 (6), both of which were characterised by an X-ray diffraction study. Both lithium compounds possess a central heteroadamantane core, in which the two-coordinate Li atoms are additionally weakly solvated by the three aryl groups of the chiral peripheral substituents, the Li-C contacts being in the range of 2.65-2.73 A. Reaction of 5 and 6 with [TiCl4(thf)2] and ZrCl4 gave the corresponding amido complexes [TiCl-[HC[SiMe2N[(S)-1-phenylethyl]]3]] (7), [TiCl(HC[SiMe2N[(R)-1-indanyl]]3]] (8), [ZrCl[HC[SiMe2N[(S)-1-phenylethyl]]3]] (9) and [ZrCl[HC[SiMe2N[(R)-1-indanyl]]3]] (10), respectively. Of these, compound 7 was structurally characterised by X-ray structure analysis and was shown to possess a C3-symmetrical arrangement of the tripod ligand. The chiral anionic dinuclear complex [Li-(OEt2)4][Zr2Cl3[HC[SiMe2N[(S)-1-phenylethyl]]3]2] (11) was isolated from reaction mixtures leading to 9. An X-ray diffraction study established its dimeric structure, in which the chiral amido ligands cap the two metal centres, which are linked through three symmetrically arranged, bridging chloro ligands. Reaction of 9 and 10 with a series of alkyl Grignard and alkyllithium reagents yielded the corresponding alkylzirconium complexes. X-ray structure analyses of [Zr(CH3)[HC[SiMe2N[(S)-1-phenylethyl]]3]] (12) and [Zr(CH3)-[HC[SiMe2N)[(R)-1-indanyl]]3]] (20) established their detailed molecular arrangements. While the reaction of 12 with the aryl ketones PhC(O)R (R = CH = CHPh, iPr, Et) gave the corresponding C-O insertion products, which contain an additional chiral centre in the alkoxy group, with low stereoselectivity (0-40% de). The corresponding conversions with several aryl aldehydes yielded the alkoxo complexes with high stereoselectivity. Upon hydrolysis, the chiral alcohols were isolated and shown to have enantiomeric excesses between 68 and 82%. High stereodiscrimination was also observed in the insertion reactions of several chiral ketones and aldehydes. However, this was shown to originate primarily from the chirality of the substrate. In analogous experiments with carbonyl compounds, the ethyl- and butyl-zirconium analogues of 12 did not undergo CO insertion into the metal-alkyl bond. Instead, beta-elimination and formal insertion into the metal-hydride bond occurred. It was found that the elimination of the alkene was induced by

Journal Article↗
PubMed1999

Examples of Hartmann-Hahn match conditions for CP/MAS between two half-integer quadrupolar nuclei.

Hartmann-Hahn match conditions for n2 --> M2 CP/MAS between two quadrupolar nuclei, spin-lock signal as a function of effective nutation frequency, and the correlation of effective nutation frequency and radiofrequency field strength are reported for three samples: sodium diborate (Na2B4O7), aluminum boride (AlB2), and lithiump aluminate (LiAlO2). Radiofrequency field strengths used for CP/MAS are both greater and less than the sample spinning speed of 10 kHz, resulting in the observation of both zero-quantum and double-quantum matches, which have signals of opposite sign. The match conditions for Na2B4O7 are as expected from published theory and CP/MAS experiments on spins 12 and n2 (n = 3 or 5) with quadrupole frequencies (omegaQ) large compared to the radiofrequency field strength of the CP contact pulse, consisting mainly of sideband matches at one and two times the sample spinning frequency, and the correlation of effective nutation frequency and radiofrequency field strength supports the conclusion that omegaQ is large for both 11B and 23Na. Aluminum-27 in AlB2 may have either small or intermediate omegaQ, and 7Li in LiAlO2 is proposed to have intermediate omegaQ in relation to the radiofrequency field strength, and both have curves of the spin-lock signal as a function of effective nutation frequency with central minima, differing from those of the nuclei with large omegaQ. The sign of the CP/MAS signal for AlB2 and LiAlO2 appears to vary with the CP field strengths for the two nuclei so that positive or negative signals cannot be consistently correlated with zero- or double-quantum matches. However, it is possible to assign at least some of the matches as close to integral multiples of the sample spinning frequency, and some of these are matches at greater than two times the sample spinning frequency.

Aluminum Compounds↗
PubMed1994

Influence of P205, AgNO3, and FeCl3 on color and translucency of lithia-based glass-ceramics.

OBJECTIVES: The objective of this study was to characterize the influence of various metals, metal compounds, and P2O5 as a nucleating agent on the color and translucency of a Li2O-Al2O3-CaO-SiO2 glass-ceramic. METHODS: Glass frits of Li2O-Al2O3-CaO-SiO2 (LACS), LACS with 1 mol% P2O5 (LACSP), and/or LACS with one of 16 colorants were melted, poured into a cylindrical graphite mold, cut into disks, annealed, nucleated, crystallized, and annealed again. Ten translucency measurements of each of five disks were made using a tristimulus colorimeter and a D65 standard CIE illuminant. The color of each disk was analyzed using the CIE L*a*b* color space system (1976) as a function of colorant, colorant concentration, and P2O5. RESULTS: Mean L* values of glass-ceramic disks ranged from 63.5 for LACS containing 6.2 mmol% FeCl3 (LACSP-6.2Fe) to 84.1 for LACS. No significant difference (p > 0.05) was found between the mean L* values for LACS, LACSP, and LACS with 0.19 mmol% AgNO3 (LACS-0.19Ag). The mean contrast ratio of glass-ceramic specimens ranged from 0.42 (LACS and LACS-1.0Fe) to 0.98 (LACS-0.78Ag). Mean color difference values varied from 5.8 (LACSP-1.0Fe vs. LACS) to 36.3 (LACSP-0.78Ag vs. LACSP). SIGNIFICANCE: The results of this study indicate that, because certain colorants in glass-ceramics affect opacity as well as hue and chroma, the development of glass-ceramics should be simplified by: 1) employing a nucleating agent that does not affect hue or chroma significantly, 2) controlling fixed levels of translucency consistent with mechanical and physical property requirements, and 3) varying the hue and chroma by means of colorants that do not affect the crystallization process. This implies that the volume fraction and mean size of crystals must be controlled, since the translucency or opacity of glass-ceramics is associated with scattering of light at the interfaces between adjacent crystals, and between crystals and the glass phase because of differences in refractive indices (McMillan, 1979a).

Analysis of Variance↗
PubMed2000

Effect of lithium co-dopant on the thermoluminescence response of some phosphors.

The effect of lithium co-dopant on the thermoluminescence of some TL phosphors has been studied. These results show that lithium co-dopant when present in CaSO4:Dy, CaSO4,Tm, CaF2:Mn, MgB4O7:Dy, MgB4O7:Tm, MgB4O7:Tb, MgB4O7:Mn, CaB4O7:Dy and CaB4O7:Tm thermoluminescent phosphors induces higher luminescence efficiency either due to better incorporation of activator ions or due to improvement in energy transfer processes. Co-doping with Li of the above given phosphors resulted in increasing the TL sensitivity from 1.2 to 3.4 times, when compared with that of the TL phosphors without lithium co-dopant. The effect of co-doping with lithium impurities on the thermoluminescence of various TL phosphors is also studied in dependence of Li concentration, of the chemical form of added lithium compounds and of the method of addition of Li co-dopant during the TL phosphor preparation. It is observed that the addition of Li co-dopant induces in some TL phosphors enhancement of the lower temperature peak which is correlated with the increase of TL sensitivity. The high TL output of these TL phosphors could be used in dosimetric practice for special short-term measurements.

Journal Article↗
PubMed2005

First complexes of scandium and yttrium with NNO and NNS heteroscorpionate ligands.

The reaction of ScCl(3)(THF)(3) or YCl(3) in a 1:1 molar ratio under reflux for 8 h with [{Li(bdmpza)(H(2)O)}(4)] [bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate], [{Li(bdmpzdta)(H(2)O)}(4)] [bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate], and (Hbdmpze) [bdmpze = 2,2-bis(3,5-dimethylpyrazol-1-yl)ethoxide] affords the corresponding complexes [MCl(2)(kappa(3)-bdmpzx)(THF)] (x = a, M = Sc (1), Y (2); x = dta, M = Sc (3), Y (4); x = e, M = Sc (5), Y (6)). However, when the reaction was carried out for 1 h under reflux between ScCl(3)(THF)(3) and [{Li(bdmpzdta)(H(2)O)}(4)], a new anionic complex [Li(THF)(4)][ScCl(3)(kappa(3)-bdmpzdta)] (7) was obtained. Reaction of [{Li(bdmpza)(H(2)O)}(4)] with YCl(3) in a 2:1 molar ratio under reflux for 8 h gave the complex [YCl(kappa(3)-bdmpza)(2)] (8). The same reaction, but with the lithium compound [{Li(bdmpzdta)(H(2)O)}(4)], led to the formation of an anionic complex [Li(THF)(4)][YCl(3)(kappa(3)-bdmpzdta)] (9). The X-ray crystal structures of 7 and 9 were established. Finally, the addition of 1 equiv of [{Li(bdmpza)(H(2)O)}(4)] or [{Li(bdmpzdta)(H(2)O)}(4)] to a solution of YCl(3) in THF under reflux, followed by the addition of 1 equiv of 1,10-phenanthroline, resulted in the formation of the corresponding complexes [YCl(2)(kappa(3)-bdmpzx)(phen)] (x = a (10), x = dta (11)). These complexes are the first examples of group 3 metals stabilized by heteroscorpionate ligands. In addition, we have explored the reactivity of some of these complexes with alcohols and amides. For example, the direct reaction of [YCl(2)(kappa(3)-bdmpza)(THF)] (2) with several alcohols gave the alkoxide complexes [YCl(kappa(3)-bdmpza)(OR)] (R = Et (12), iPr (13)). Finally, the reaction between [ScCl(2)(kappa(3)-bdmpzdta)(THF)] (3) or [Li(THF)(4)][ScCl(3)(kappa(3)-bdmpzdta)] (7) and LiN(SiMe(3))(2).Et(2)O in 1:1 and 1:2 molar ratios gave rise to the complexes [ScCl(kappa(3)-bdmpzdta){N(SiMe(3))(2)}] (14) and [Sc(kappa(3)-bdmpzdta){N(SiMe(3))(2)}(2)] (15), respectively.

Crystallography, X-Ray↗
PubMed2006

Synthesis of enantiopure (alphaS,betaS)- or (alphaR,betaS)-beta-amino alcohols by complete regioselective opening of aminoepoxides by organolithium reagents LiAlH4 or LiAlD4.

The reaction of chiral (2R,1'S)- or (2S,1'S)-2-(1-aminoalkyl)epoxides, 1 or 2 with a variety of organolithium compounds to obtain the corresponding (alphaS,betaS)- or (alphaR,betaS)- beta-amino alcohols in enantiopure form is reported. In both cases, the opening of the oxirane ring at C-3 proceeded with total regioselectivity. Moreover, the ring opening of aminoepoxides 1 or 2 by hydride (utilizing LiAlH4) to obtain the corresponding (2S,3S)- or (2R,3S)-3-aminoalkan-2-ols is also described. The reaction of 1 or 2 with LiAlD4 in place of LiAlH4 gave the corresponding (2S,3S)- or (2R,3S)-3-amino-1-deuterioalkan-2-ols.

Alkanes↗
PubMed2006

First-principles calculations of migration energy of lithium ions in halides and chalcogenides.

Migration of Li+ ions via the vacancy mechanism in LiX (X = F, Cl, Br, and I) with the rocksalt and hypothetical zinc blende structures and Li2X (X = O, S, Se, and Te) with the antifluorite structure has been investigated using first-principles projector augmented wave calculations with the generalized gradient approximation. The migration paths and energies, determined by the nudged-elastic-band method, are discussed on the basis of two idealized models: the rigid-sphere and charged-sphere models. The trajectories and energy profiles of the migration in these lithium compounds vary between these two models, depending on the anion species and crystal structure. The migration energies in LiX with both the rocksalt and hypothetical zinc blende structures show a tendency to decrease with increasing periodic number of the anion species in the periodic table. This is consistent with the widely accepted view that anion species with large ionic radii and high polarizabilities are favorable for good ionic conduction. In contrast, Li2O exhibits the lowest migration energy among Li2X compounds, although O is the smallest among the chalcogens, indicating that electrostatic attractive interactions play the dominant role in the inter-ion interactions in Li2O and, therefore, in the ion migration.

Journal Article↗
PubMed2006

Asymmetric gamma-deprotonation and homoaldol reaction of 1,3-dien-2-yl carbamates: stereo- and regiochemistry.

[reaction: see text] Lithium compounds 7 are configurationally stable intermediates obtained by deprotonation of 1,3-dien-2-yl carbamates 6 with n-butyllithium/(-)-sparteine with a high degree of enantiotopic differentiation at the gamma-position. They react with electrophiles regioselectively giving highly enantioenriched products. Starting with different isomers or changing the double-bond geometries in 6 leads to either of the enantiomers.

Journal Article↗
PubMed2006

Alkali metal complexes of sterically demanding amino-functionalized secondary phosphanide ligands.

The reaction between {(Me(3)Si)(2)CH}PCl(2) (4) and one equivalent of either [C(6)H(4)-2-NMe(2)]Li or [2-C(5)H(4)N]ZnCl, followed by in situ reduction with LiAlH(4) gives the secondary phosphanes {(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))PH (5) and {(Me(3)Si)(2)CH}(2-C(5)H(4)N)PH (6) in good yields as colourless oils. Metalation of 5 with Bu(n)Li in THF gives the lithium phosphanide [[{(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))P]Li(THF)(2)] (7), which undergoes metathesis with either NaOBu(t) or KOBu(t) to give the heavier alkali metal derivatives [[{(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))P]Na(tmeda)] (8) and [[{(Me(3)Si)(2)CH}(C(6)H(4)-2-NMe(2))P]K(pmdeta)] (9) after recrystallization in the presence of the corresponding amine co-ligand [tmeda = N,N,N',N'-tetramethylethylenediamine, pmdeta = N,N,N',N'',N''-pentamethyldiethylenetriamine]. The pyridyl-functionalized phosphane 6 undergoes deprotonation on treatment with Bu(n)Li to give a red oil corresponding to the lithium compound [{(Me(3)Si)(2)CH}(2-C(5)H(4)N)P]Li (10) which could not be crystallized. Treatment of this oil with NaOBu(t) gives the sodium derivative [{[{(Me(3)Si)(2)CH}(2-C(5)H(4)N)P]Na}(2) x (Et(2)O)](2) (11), whilst treatment of with KOBu(t), followed by recrystallization in the presence of pmdeta gives the complex [[{(Me(3)Si)(2)CH}(2-C(5)H(4)N)P]K(pmdeta)](2) (12). Compounds 5-12 have been characterised by (1)H, (13)C{(1)H} and (31)P{(1)H} NMR spectroscopy and elemental analyses; compounds 7-9, and 12 have additionally been characterised by X-ray crystallography. Compounds 7-9 crystallize as discrete monomers, whereas 11 crystallizes as an unusual dimer of dimers and 12 crystallizes as a dimer with bridging pyridyl-phosphanide ligands.

Journal Article↗
PubMed2003

(K4Li4)Al8Ge8O32.8H2O: an Li+-exchanged potassium aluminogermanate with the zeolite gismondine (GIS) topology.

The title compound, lithium potassium dialuminium digermanium octaoxide dihydrate, (K,Li)-(Al,Ge)-GIS (GIS is gismondine), is the result of a 50% Li(+) exchange into the K-(Al,Ge)-GIS structure. The (K,Li)-(Al,Ge)-GIS structure was determined from a 4 x 4 x 2 micro m octahedral single crystal at the ESRF synchrotron X-ray source. The ion exchange results in a symmetry transformation from I2/a for K-(Al,Ge)-GIS to C2/c for (K,Li)-(Al,Ge)-GIS. The structural change is due to disordering of K(+) ions with Li(+) ions along the [001] channel and ordering of water molecules in the [101] channels. The distance between sites partially occupied by K(+) ions increases from 2.19 (3) A in K-(Al,Ge)-GIS to 2.94 (3) A in (K,Li)-(Al,Ge)-GIS. The Li(+) ions occupy positions along the twofold axis at the intersection of the eight-membered-ring channels in a twofold coordination with water molecules. For the four closest framework O(2-) anions, the Li.O distances are 3.87 (4) A.

Journal Article↗
PubMedDate not supplied

The effects of lithium gamma-linolenic acid in reversing LPBM5 MuLV induced suppression of hematopoietic progenitor cells in vitro.

Lithium gamma linolenic acid (Li-GLA), was evaluated for its possible role as an antiviral agent. Li-GLA 15 micrograms ml-1 was administered to both normal and LP-BM5 MuLV retroviral infected murine bone marrow cultures. After 2 weeks of treatment, numbers of progenitors being produced by infected/treated cultures were reduced to some 10% that of normal cultures. In the remaining 4 weeks, numbers of CFU-GM and BFU-E hematopoietic progenitors returned within normal range. The efficacy of Li-GLA in relieving retroviral hematopoietic bone marrow suppression correlates to a reduction in interleukin-4 (IL-4) secretion, normally elevated in association with LP-BMP5 infection. These data indicate that this reduction in bone marrow suppression of LP-BMP5 infected cells may be due to a killing of infected cells by the Li-GLA, rather than stimulating hematopoiesis as with other lithium compounds. To conclude this may indicate the possible dual effect of administration of LiGLA to virally infected individuals in reducing viral titre and to lower the toxicities associated with long term drug therapy.

Animals↗
PubMed1990

[Psychoses in epilepsy].

The heterogenous psychoses in epilepsies, caused by well known conditions, are not rare but associated with regularly a few of seizure-types not with the nature and development of attacks. Polar transitional ranks and converging courses of schizophrenic (accentuated) syndromes in epilepsies and idiopathic schizophrenias are rather frequent. Also (sub-)acute schizophrenic psychoses are corresponding to the complete palette of first and second rank symptoms (K. Schneider) of idiopathic schizophrenias. After manifestations of epilepsy these syndromes can appear at any time. It is given a profile of risks. Progressive avoidance of a. phenylaceturea, b. mixtures of antiepileptics did not put an end to psychotic syndromes: Long-term therapies with 1. Polytherapy, 2. Primidone and Phenytoin (dosedependant) as well as 3. Ethosuximide (-monotherapy) cause a disorder of feed back mechanisms, especially a disturbed regulation of vigilance and sleeping-waking-cycle and their psychological correlates. Carbamazepine and Sodium Valproate are, plasma-level-controlled of preventive antipsychotic effect. Selected neuroleptics of rather slight epileptogenic potency are of going down importance. Benzodiazepines are required mostly in prepsychotic syndromes, Lithium compounds in selected cases. There is no more alternative seizures or psychosis.

Anticonvulsants↗