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Gauge symmetry, chirality and parity effects in four-particle systems: Coulomb's law as a universal function for diatomic molecules.

Following recent work in search for a universal function (Van Hooydonk, Eur. J. Inorg. Chem., (1999), 1617), we test four symmetric +/- a(n)Rn potentials for reproducing molecular potential energy curves (PECs). Classical gauge symmetry for 1/R-potentials results in generic left right asymmetric PECs. A pair of symmetric perturbed Coulomb potentials is quantitatively in accordance with observed PECs. For a bond, a four-particle system, charge inversion (a parity effect, atom chirality) is the key to explain this shape generically. A parity adapted Hamiltonian reduces from ten to two terms and to a soluble Bohr-like formula, a Kratzer (1 - Re/R)2 potential. The result is similar to the combined action of spin and wave function symmetry upon the Hamiltonian in Heitler-London theory. Analytical perturbed Coulomb functions varying with (1 - Re/R) scale attractive and repulsive branches of PECs for 13 bonds H2, HF, LiH, KH, AuH, Li2, LiF, KLi, NaCs, Rb2, RbCs, Cs2 and I2 in a single straight line. The 400 turning points for 13 bonds are reproduced with a deviation of 0.007 A at both branches. For 230 points at the repulsive side, the deviation is 0.003 A. The perturbed electrostatic Coulomb law is a universal molecular function. Ab initio zero molecular parameter functions give PECs of acceptable quality, just using atomic ionisation energies. The function can be used as a model potential for inverting levels and gives a first principle's comparison of short- and long-range interactions, important for the study of cold atoms. Wave-packet dynamics, femto-chemistry applied to the crossing of covalent and ionic curves, can provide evidence for this theory. We anticipate this scale/shape invariant scheme applies to smaller scales in nuclear and high-energy particle physics. For larger gravitational scales (Newton 1/R potentials), problems with super-unification are discussed. Reactions between hydrogen and antihydrogen, feasible in the near future, will probably produce normal H2.

Cesium↗

Ion solvation and association in LiClO4/sulfolane solution: a vibrational spectroscopic and molecular orbital study.

Solvation interaction and ion association in solutions of lithium perchlorate/sulfolane have been studied by using infrared and Raman spectra as a function of concentration of lithium perchlorate. The band changes of antisymmetric OSO stretch, antisymmetric CSC stretch, -SO2 wag and twist suggest that there is an interaction between Li+ and sulfolane molecules, and the site of solvation is the oxygen atom of -SO2 group. The molecular orbital calculation supports this suggestion. On the other hand, the apparent solvation number was calculated, and the band fitting for the ClO4- band reveals the presence of contact ion pair, solvent separated ion pair and free ClO4- anion in the concentrated solutions.

Electrolytes↗

Spectroscopic study of the interactions of alkali fluorides with D-xylose.

The interactions of alkali fluorides with D-xylose have been studied by X-ray diffraction (XRD), infrared spectroscopy (IR), nuclear magnetic resonance (NMR, 1H and 13C) and atomic absorption spectrophotometry. KF and CsF form complexes with D-xylose in a 1:1 molar ratio. These complexes can be obtained by solid state milling the reactants in an agate mortar or from methanolic solutions of the sugar and the salt. LiF and NaF do not form complex with D-xylose. IR and XRD prove the identical nature of the complexes obtained by milling and from solution. IR spectra indicate strong perturbation of the OH stretching vibrations with considerable shifts to lower frequencies, which must be caused by strong hydrogen bond formation to the fluorine anion. The perturbations of C-O bond are weak, indicating that cation binding to the oxygen atoms is not the main interaction responsible for the complex formation. 1H NMR spectra of the D-xylose-KF complex dissolved in deuterium oxide is equal to that of pure D-xylose, indicating the destruction of the complex in solution. The complex is stable in DMSO, and 13C spectra of the complex in DMSO-d6 and in solid state (CPMAS) spectra are in accordance with the observed interactions in the IR spectra. As far as we know, this is the first report of a sugar-halide salt complex in which the anion instead of the cation provides the binding forces.

Alcohols↗

Solvation of LiClO4 and NaClO4 in deuterated acetonitrile studied by means of infrared and Raman spectroscopy.

Vibrational characteristics of CD3CN solutions of LiClO4 and NaClO4 have been studied by means of infrared and Raman spectroscopy. Blue shifts of 22 and 11 cm(-1) of the v2 C[triple bond]N stretch are observed resulting from interaction of CD3CN with Li+ and Na+, respectively. The number of primary solvation sites of both Li+ and Na+ in acetonitrile is believed to be four from the comparison of the Raman intensities of the C[triple bond]N stretch for free CD3CN and those coordinated to Li+ and Na+. Evidently formation of contact ion pairs of the cation (Li+ or Na+) and anion (ClO4-) is more probable at a higher concentration of the salt. The characteristics of the v2 C[triple bond]N stretch, v4 C-C stretch, and v8 CCN deformation bands vary substantially upon coordination, while other vibrational bands are relatively immune to the donor-acceptor interaction. DFT calculations have also been performed at the BLYP/6-31 + G(2d,p) level to examine the structures and vibrational characteristics of CD3CN coordinated to Li+ and Na+. The calculated results are in good agreement with the observed vibrational characteristics.

Acetonitriles↗

Structural and vibrational characterization of the mono and dilithiated species derived from phenylacetonitrile in THF by infrared and Raman spectroscopy and density functional theory calculations.

The structures and spectra of mono and dianionic species derived from PhCH2CN under the action of an organic base LHMDS or n-BuLi in THF solution have been investigated by vibrational spectroscopy and DFT calculations. The assignments previously proposed for the monoanion, the bridged, linear and dimeric monoanionic ion pairs compare well with the calculated ones. The addition of HMPA to a THF solution of PhCHCNLi leads to the formation of an HMPA solvated linear ion pair, distinguishable from the bridged ion pair by the wave number of the 8a v(CC) phenyl ring mode. The calculated structure of the phenylacetonitrile anion in the (PhCHCNLi, CH3Li) mixed dimer or 'Quadac' is very similar to that in the linear ion pair or in the dimer and to that observed by X-ray in (PhCHCNLi, [CH(CH9)2]2NLi) 'Quadac'. The structure of the anion is planar, indicating a charge delocalization from the benzene ring to the -CHCN group. The calculated spectra of the free, mono and dilithiated dianionic species compare well with the experimental ones of the species formed under addition of more than one equivalent of n-BuLi. The structure of the >C-C-CN2- group is very close to that of an imine. The v(CN) bands of the free, mono and dilithiated dianionic species are located at 1912, 1930 and 1890 cm(-1), respectively. The large wave number shift observed between the free monoanion and dianion (approximately 176 cm(-1)), in good accordance with the calculated one (170 cm(-1)) allows differentiating mono and dianionic species. The shifts observed for the 8a and 19a v(CC) phenyl ring modes, although much smaller, also allows discriminating the different species. These small shifts indicate a small variation of the electronic delocalization in the benzene ring in agreement with the calculations.

Acetonitriles↗

Ion-molecule interactions in solutions of lithium perchlorate in propylene carbonate + diethyl carbonate mixtures: an IR and molecular orbital study.

FTIR spectra have been recorded and analyzed for solutions of lithium perchlorate in propylene carbonate (PC), diethyl carbonate (DEC), and PC + DEC mixtures. It has been shown that the carbonyl stretch bands for PC and DEC are very sensitive to the interaction between Li+ and the solvent molecules. They split with addition of LiClO4, indicating a strong interaction of Li+ with PC and DEC through the oxygen group of PC and both oxygen and ether oxygen atoms of DEC. In conjunction with molecular orbital calculation, the optimized geometries of solvation are given. In addition, solvent separated ion pairs and contact ion pairs were observed in LiClO4/DEC solutions, and no preferential solvation of Li+ in LiClO4/PC + DEC solutions were detected.

Carbonates↗

Electrochemical properties and Fourier transform-infrared spectroscopic investigations of the redox behaviour of poly(indole-5-carboxylic acid) in LiClO4-acetonitrile solutions.

Electropolymerisation of indole-5-carboxylic-acid leads to the formation of electroactive polymer films. Potentiostatic deposition of the related polymer, poly(indole-5-carboxylic-acid), was carried out at a constant potential at 1.35 V versus SCE. The cyclic voltammogram of the resulting polymer in LiClO4 (0.15 mol dm(-3))/acetonitrile solution is characterized by two poorly resolved anodic and cathodic set peaks. FTIR spectroscopy was used to characterize both reduced and oxidized forms of poly(indole-5-carboxylic-acid). Assignments of the vibrational modes were proposed by comparison of the vibrational spectra of polyindole and polycyanoindole. The polymerization sites correspond to the 2 and 3 carbon positions of the pyrrole cycle. In the oxidized form of the polymer, the NH group is deprotonated while the quinoid form is present between the pyrrole rings.

Acetonitriles↗

Investigations of the EPR parameters for Sm3+ ions in KY3F10 and LiYF4 crystals.

In this paper, we calculate the EPR parameters (g factors g parallel, g perpendicular and hyperfine structure constants A parallel, A perpendicular) of rare earth ion Sm3+ in fluoride crystals KY3F10 and LiYF4 from the perturbation formulas of EPR parameters for a 4f5 ion in tetragonal symmetry. In these formulas, the crystal-field J-mixing of the first and second excited-state multiplets 6H(7/2) and 6H(9/2) into the ground state multiplet 6H(5/2), the mixtures among the states with the same J value via spin-orbit coupling interaction and the interactions between the ground Kramers doublet Gammagamma and the same irreducible representation as Gammagamma in other 11 Kramers doublets Gammax within 6HJ (J=5/2, 7/2, 9/2) states via crystal-field and orbital angular momentum (or hyperfine structure) are considered. The calculated results (which are in agreement with the observed values) are discussed.

Electron Spin Resonance Spectroscopy↗

Lamotrigine combined with divalproex or lithium for bipolar disorder: a case series.

OBJECTIVE: To assess the efficacy of lamotrigine combined with either divalproex or lithium for the treatment of bipolar disorder. INTRODUCTION: Lithium and divalproex seem to be predominantly effective for manic and mixed symptoms of bipolar disorder, whereas lamotrigine may be more effective for bipolar depression than for mania. Combination therapy may provide more efficacious treatment for many patients with bipolar disorder. METHODS: Data from charts of adult outpatients with bipolar disorder treated with lamotrigine plus divalproex or lithium during a 3-year period were retrospectively analyzed. The Clinical Global Impressions for Bipolar Disorder scale was used to assess severity of illness at baseline (adjunct-therapy initiation) and improvement after 3 months of treatment. The safety and tolerability of the medication combinations were assessed. RESULTS: After 3 months of treatment, 26 of 39 patients (67%) receiving lamotrigine plus divalproex had a depression rating of 1 (very much improved) or 2 (much improved) compared with seven of 16 (44%) taking lamotrigine plus lithium. The mania rating was 1 or 2 for 13 of 39 (39%) patients treated with lamotrigine plus divalproex and 7 of 16 (44%) patients receiving lamotrigine plus lithium. For overall illness severity, 26 of 39 (67%) patients given lamotrigine plus divalproex had scores of 1 or 2 compared with 10 of 16 (62%) patients taking lamotrigine plus lithium. Five of 39 patients (13%) taking lamotrigine plus divalproex and 5 of 16 (31%) receiving lamotrigine plus lithium discontinued at least one part of the combination in <3 months due to adverse events. CONCLUSION: Combination therapy with lamotrigine plus divalproex or lithium may be a valuable option for managing symptoms of bipolar disorder. The combinations were generally well tolerated and apparently effective in improving depression as well as mania. The percentage of patients showing improvement in depression was somewhat larger. Tolerability was somewhat better for lamotrigine plus divalproex in combination than for lamotrigine plus lithium. Differences in tolerability are consistent with studies indicating poorer tolerability of lithium compared with divalproex.

Adolescent↗

Sodium-myo-inositol co-transporter (SMIT-1) mRNA is increased in neutrophils of patients with bipolar 1 disorder and down-regulated under treatment with mood stabilizers.

Recent in-vitro data indicate that depletion of neural cells of myo-inositol by virtue of down-regulation of the high-affinity sodium-myo-inositol co-transporter (SMIT) may be a common mechanism of action of the mood stabilizers lithium, valproate and carbamazepine. The authors sought to investigate whether or not down-regulation of SMIT also occurs in vivo in bipolar patients. Expression of SMIT mRNA was measured in neutrophils of bipolar patients either unmedicated or treated with lithium salts or valproate and in neutrophils of unmedicated, matched healthy controls using quantitative real-time PCR. The content of SMIT mRNA was significantly reduced in neutrophils of lithium-treated bipolar patients compared to controls and to untreated bipolar patients. Untreated bipolar I patients but not bipolar II patients exhibited a significantly higher expression of SMIT mRNA than controls. Neutrophils of bipolar I patients treated with valproate exhibited a significantly lower expression of SMIT mRNA than untreated bipolar I patients but did not differ from controls. These results suggest that lithium and valproate down-regulate SMIT mRNA in vivo in patients. In addition the data provide first evidence that up-regulation of SMIT might be associated with an increased risk for bipolar I disorder.

Adult↗

Restraint stress influences AP-1 and CREB DNA-binding activity induced by chronic lithium treatment in the rat frontal cortex and hippocampus.

The therapeutic efficacy of mood stabilizers may involve the regulation of gene expression mediated by transcription factor activation. In this study, we investigated AP-1 and cAMP response element-binding protein (CREB) DNA-binding activity in the rat frontal cortex and hippocampus of rats fed a control diet, a lithium diet for 7 wk, or 6 wk of lithium, followed by withdrawal for 7 d. Subsequently, animals were exposed to restraint stress or no stress and the DNA-binding activities assessed at 2, 8 and 24 h post-stress. AP-1 activity was increased in both brain regions by lithium, an effect that persisted with lithium discontinuation. Restraint stress induced AP-1 activity in the frontal cortex of the control group. This stress-induced effect on AP-1 activity was attenuated in lithium-treated and lithium-withdrawn animals. AP-1 DNA binding was also induced by stress in the hippocampus of control animals and the activity diminished over time in the lithium and lithium-withdrawn groups. CREB activity also increased in the frontal cortex and hippocampus of the lithium-treated group. Stress increased CREB activity in the frontal cortex of the controls, and was slightly attenuated with lithium treatment. CREB activity in the hippocampus was insensitive to stress. The proteins involved in the AP-1 and CREB transcription complexes were also characterized. Our findings of increased AP-1 and CREB binding after lithium are consistent with lithium's inhibitory effect on glycogen synthase kinase-3beta, which has been show to negatively regulate AP-1 and CREB transcriptional activity.

Analysis of Variance↗

Radiochemical determination of 241Am and Pu(alpha) in environmental materials.

Americium-241 and plutonium determinations will become of greater importance over the coming decades as 137Cs and 241Pu decay. The impact of 137Cs on environmental chronology has been great, but its potency is waning as it decays and diffuses. Having 241Am and Pu as unequivocal markers for the 1963 weapon fallout maximum is important for short time scale environmental work, but a fast and reliable procedure is required for their separation. The developed method described here begins by digesting samples using a lithium borate fusion although an aqua regia leachate is also effective in many instances. Isolation of the Am and Pu is then achieved using a combination of extraction chromatography and conventional anion exchange chromatography. The whole procedure has been optimized, validated, and assessed for safety. The straightforwardness of this technique permits the analysis of large numbers of samples and makes 241Am-based techniques for high-resolution sediment accumulation rate studies attractive. In addition, the technique can be employed for the sequential measurement of Pu and Am in environmental surveillance programs, potentially reducing analytical costs and turnround times.

Americium↗

Nucleophilic substitution as a tool for the synthesis of unsymmetrical porphyrins.

Porphyrins readily undergo S(N)Ar reactions with organolithium reagents, preferentially at the meso-positions. The reaction is highly versatile as it is accomplished with both metal complexes and free-base porphyrins in good yields and high regioselectivity. It can be used in sequence for the introduction of up to four different meso-substituents and is the first general method for the direct introduction of functional groups into unactivated porphyrins, including porphine. Depending on the porphyrin, the structure of the anionic intermediate, or the reaction conditions, this method also allows trapping of the intermediary anion with electrophiles, transformation into meso-meso-linked bisporphyrins, synthesis of phlorins or porphodimethenes, and beta-addition to yield hydroporphyrins.

Alkylation↗

Perchlorate-induced denaturation of ribonuclease A: investigation of possible folding intermediates.

Perchlorate-denatured ribonuclease A (PDR) is known to show a circular dichroism (CD) spectrum suggestive of substantial secondary structure. Thus, PDR may be a molten globule form of ribonuclease A. We find that any secondary structure present in PDR does not provide measurable protection against amide proton exchange, and PDR does not belong to the class of structured molten globules. CD spectra of short peptides show that the perchlorate anion affects these spectra in a way that could be mistaken for secondary structure formation; thus, caution must be used in interpreting CD spectra of peptides and proteins taken in perchlorate solutions.

Amino Acid Sequence↗

Platination of the (T2G4)4 telomeric sequence: a structural and cross-linking study.

The telomeric sequence (T(2)G(4))(4) was platinated in aqueous solutions containing 50 mM LiClO(4), NaClO(4), or KClO(4). The identification of the guanines which reacted with [Pt(NH(3))(3)(H(2)O)](2+) revealed that the same type of folding exists in the presence of the three cations and that the latter determine the relative stabilities of the G-quadruplex structures in the order K(+) > Na(+) >> Li(+). The tri-ammine complex yielded ca. 40--90% of adducts, mono- and poly-platinated, bound to 4 guanines out of the 16 guanines in the sequence, in the decreasing amounts G9 > G15 >> G3 > G21. The formation of these adducts was interpreted with a G-quadruplex structure obtained by restrained molecular dynamics (rMD) simulations which confirms the schematic model proposed by Williamson et al. [(1989) Cell 59, 871--880]. The bifunctional complexes cis- and trans-[Pt(NH(3))(2)(H(2)O)(2)](2+) also first reacted with G9 and G15 and gave cross-linked adducts between two guanines, which did not exceed 5% each of the products formed. Both the cis and trans isomers formed a G3-G15 platinum chelate, and the second also formed bis-chelates at both ends of the G-quadruplex structure: G3-G15/G9-G21 and G3-G15/G9-G24. The rMD simulations showed that the cross-linking reactions by the trans complex can occur without disturbing the stacking of the three G-quartets.

Base Sequence↗

A unique molten globule state occurs during unfolding of cytochrome c by LiClO4 near physiological pH and temperature: structural and thermodynamic characterization.

We have carried out denaturation studies of bovine cytochrome c (cyt c) by LiClO4 at pH 6.0 and 25 degrees C by observing changes in difference molar absorbance at 400 nm (Deltaepsilon400), mean residue ellipticities at 222 nm ([theta]222) and difference mean residue ellipticity at 409 nm (Delta[theta]409). The denaturation is a three-step process when measured by Deltaepsilon400 and Delta[theta]409, and it is a two-step process when monitored by [theta]222. The stable folding intermediate state has been characterized by near- and far-UV circular dichroism, tryptophan fluorescence, 8-anilino-1-naphthalene sulfonic acid (ANS) binding, and intrinsic viscosity measurements. A comparison of the conformational and thermodynamic properties of the LiClO4-induced molten globule (MG) state with those induced by other solvent conditions (e.g., low pH, LiCl, and CaCl2) suggests that LiClO4 induces a unique MG state, i.e., (i) the core in the LiClO4-induced state retains less secondary and tertiary structure than that in the MG states obtained in other solvent conditions, and (ii) the thermodynamic stability associated with the LiClO4-induced process, native state <--> MG state, is the same as that observed for each transition between native and MG states induced by other solvent conditions.

Animals↗