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PubMed1993

Effects of various salts on the steady-state enzymatic activity of E. coli alkaline phosphatase.

Seventeen salts were tested at various concentrations for their effects on E. coli alkaline phosphatase steady-state activity. Three effects were distinguished: a general ionic strength effect, and weaker cation and anion effects. 1. All salts tested, including those with "noninteracting" cations and anions, stimulate alkaline phosphatase activity usually ca. 100% at moderate (0.05-0.3 M) concentrations. 2. Cations such as Na+ and Li+ produce further increases in activity at concentrations up to 1 M. The noninteracting cations tetramethylammonium and tetrapropylammonium produce lower activities at these concentrations. These do not provide the secondary stimulatory effect of cations such as Na+ or Li+. 3. Anions associated with greater "salting in" effectiveness such as thiocyanate also reduce activity at ca. 1 M concentrations. These latter effects are not dependent on protein concentration so they probably do not involve subunit dissociation. There is little effect on the fluorescence or fluorescence-polarization spectrum of the enzyme so there is no general effect of 1 M salts on the conformation of the protein. The Michaelis constant for the substrate, p-nitrophenylphosphate, and inhibition constant for inorganic phosphate are increased to some extent by salts, but the increase in activity is due to an increase in Vmax. Our working hypothesis is that increased ionic strength weakens electrostatic interactions, enabling noncovalently bound phosphate to dissociate more rapidly.

Alkaline Phosphatase↗
PubMed1996

Several roles of CCKA and CCKB receptor subtypes in CCK-8-induced and LiCl-induced taste aversion conditioning.

Administration of a relatively large IP dose of sulfated cholecystokinin (26-33) (CCK-8; 1.0 mumol/kg) consistently induced moderate taste aversion conditioning (TAC) using a 20-min, one-bottle test in Long-Evans rats. Because CCK-8 has affinity for both CCKA and CCKB receptor subtypes, we wanted to determine the subtype involved in CCK-8-induced TAC. Pretreatment with the selective CCKA antagonist MK-329 (L-364, 718 or devazepide), at doses of 0.1, 1.0, or 10.0 mumol/kg, markedly antagonized (> 70%) CCK-8-induced TAC. Pretreatment with the selective CCKB antagonist L-365,260, at doses of 0.1 or 1.0 mumol/kg, partially antagonized (approximately 50%) CCK-8-induced TAC, although the highest dose of L-365,260. 10.0 mumol/kg, did not. These partial antagonistic effects of L-365,260 on CCK-8-induced TAC were replicated in our second study. In our third study, we observed that another CCKB antagonist, the dipeptoid CI-988, also partially antagonized CCK-8-induced TAC at a dose of 0.1, but not 1.0 or 10.0, mumol/kg. In our final study, pretreatments with a single dose (i.e., 10.0, but not 0.1 or 1.0, mumol/kg) of either MK-329 or L-365,260 were also shown to partially antagonize the formation of moderate TAC induced by treatment with LiCl at 708 mumol/kg. Marked antagonism of LiCl-induced TAC was also observed following pretreatment with the known anxiolytic chlordiazepoxide HCl at 7.4 mumol/kg. Considering the existing data on the induction of TAC by various CCK analogues, we consider an action of CCK-8 on peripheral CCKA, but not CCKB, receptors necessary for the induction of TAC. Our results of partial antagonism of CCK-8- and LiCl-induced TAC by L-365,260, CI-988, or MK-329 suggest, but do not prove, that both CCKA and CCKB mechanisms may be operative during TAC. Because the CCK antagonists affected TAC like chlordiazepoxide, blockade of CCKA and CCKB mechanisms may produce a mild anxiolytic effect.

Animals↗
PubMed1992

Dual effect of monovalent cations on the glucose-induced transient increase in the rate of DMP influx into Saccharomyces cerevisiae.

The transient increase in the rate of 2-(4-di-methyl-aminostyryl)-1-ethylpyridinium (DMP) influx in Saccharomyces cerevisiae caused by addition of glucose to a suspension of non-metabolizing cells at relatively high pH can be prevented by monovalent cations. Their concentrations for half-maximum inhibition of DMP uptake are of the same order of magnitude as the corresponding Km values for their uptake into yeast cells. It is argued that the inhibition of DMP uptake by monovalent cations is caused by a fast depolarization of the cell membrane and a second further decrease in the rate of DMP uptake. The latter effect develops slowly with time and depends upon the extent of accumulation of the monovalent cations in the cells.

Cations, Monovalent↗
PubMed2006

Synthesis and antitubercular activity of substituted phenylmethyl- and pyridylmethyl amines.

A total of 42 benzyl- and pyridylmethyl amines were synthesized either by reductive amination of aromatic/heteroaromatic aldehydes with amines or by conjugate addition of amines to the cinnamates followed by reduction of the ester group with lithium aluminium hydride to the respective propanolamines. All the synthesized compounds were evaluated against both avirulent and virulent strains of Mycobacterium tuberculosis. Many of the compounds exhibited MIC as low as 1.56microg/mL. Few of potent compounds were also evaluated against clinical isolates of MDR TB and found to be active at one or other concentrations with MIC as low as 3.12microg/mL.

Amines↗
PubMed2004

Mercury and methylmercury concentrations and loads in the Cache Creek watershed, California.

Concentrations and loads of total mercury and methylmercury were measured in streams draining abandoned mercury mines and in the proximity of geothermal discharge in the Cache Creek watershed of California during a 17-month period from January 2000 through May 2001. Rainfall and runoff were lower than long-term averages during the study period. The greatest loading of mercury and methylmercury from upstream sources to downstream receiving waters, such as San Francisco Bay, generally occurred during or after winter rainfall events. During the study period, loads of mercury and methylmercury from geothermal sources tended to be greater than those from abandoned mining areas, a pattern attributable to the lack of large precipitation events capable of mobilizing significant amounts of either mercury-laden sediment or dissolved mercury and methylmercury from mine waste. Streambed sediments of Cache Creek are a significant source of mercury and methylmercury to downstream receiving bodies of water. Much of the mercury in these sediments is the result of deposition over the last 100-150 years by either storm-water runoff, from abandoned mines, or continuous discharges from geothermal areas. Several geochemical constituents were useful as natural tracers for mining and geothermal areas, including the aqueous concentrations of boron, chloride, lithium and sulfate, and the stable isotopes of hydrogen and oxygen in water. Stable isotopes of water in areas draining geothermal discharges showed a distinct trend toward enrichment of (18)O compared with meteoric waters, whereas much of the runoff from abandoned mines indicated a stable isotopic pattern more consistent with local meteoric water.

Boron↗
PubMed1999

Lithium decreases Cl--ATPase activity and increases intracellular Cl- concentration in cultured rat hippocampal neurons.

Under the conditions of stimulated phosphatidylinositol turnover (0. 1 mM carbachol plus 20 mM KCl), LiCl (0.1-10 mM) reduced the activity of Cl--ATPase in cultured rat hippocampal neurons without affecting Na+/K+- or anion-insensitive Mg2+-ATPase. This inhibition of Cl--ATPase was attenuated by the addition of 0.5 mM inositol to culture media. The intracellular Cl- concentrations of the LiCl-treated neurons increased in an inositol-sensitive manner.

Adenosine Triphosphatases↗
PubMed2000

Ion chromatography detector based on solid-state ion-selective electrode array.

A variety of neutral carrier type ionophores for monovalent cations were employed to prepare solid-state cation-selective electrodes (SSEs) for use as a detector in single-column ion chromatography (IC). The polyurethane-based pseudoreference electrode made it possible to assemble an array type SSE detector for IC. An SSE-based detector provides not only the overall chromatogram for the separated ion species (monensin methyl ester-nonactin-based membrane), but also the enhanced chromatogram for specified ions of interest (valinomycin as K+ and nonactin for NH4+). This feature makes it possible to perform highly quantitative analysis with low detection limits even if the separation efficiency of the ion-exchange is not sufficient. Since SSE-based IC detectors are easily miniaturized and replaceable at low cost, they are an ideal component of a portable IC system.

Cations, Monovalent↗
PubMed2003

High-speed ion chromatographic separation of cations at elevated temperature.

The application of temperatures up to 90 degrees C for high-speed cation separations by ion chromatography is investigated. A Dionex CS12A column (150 x 3 mm I.D.) and suppressed conductivity detection are used for the separation of Li+, Na+, NH4+, K+, Rb+, Cs+, Mg2+, Ca2+, and Sr2+. Elevated temperatures reduce the viscosity of the eluent, which allows the use of flow-rates up to 1.3 ml/min, which are significantly higher than that typically used (0.5 ml/min). Further, separation efficiencies improved with temperature, even at high flow-rates. However, elevated temperatures decrease the retention of all cations, with the decrease being most pronounced for the strongly retained cations. This limits the optimal column temperature to 60 degrees C. Nevertheless at 60 degrees C, the separation of nine cations is accomplished in under 5 min, compared to 12 min under conventional conditions, i.e., 60% reduction in analysis time.

Calcium↗
PubMed2003

Production of radioactive particles for use in environmental studies.

This paper presents an aerosol generation technique developed to produce dry aerosol particles of various sizes from aqueous solutions of salt. The technique was tested with sodium chloride, lithium carbonate and uranyl acetate at various aqueous concentrations which produced particles in the size range of 0.13-1.37 microm Mass Median Diameter (MMD). The generated aerosols were acceptably monodisperse with a geometric standard deviation of 1.4-2. Both MMD and Mass Median Aerodynamic Diameter (MMAD) increased significantly (p<0.001) with increased concentration of the salt in solution. The technique can also be used to generate aerosols of different chemical species. The results obtained indicate that the system is convenient for use with various aerosol-forming materials, with a stable particle size distribution being maintained for a long period of steady operation. The technique was successfully applied in wind tunnel studies to simulate the release of submicron radioactive particles and their interception by crops, grass and tree canopies. The relevance and application of the technique in other areas of environmental assessment studies is discussed.

Aerosols↗
PubMedDate not supplied

Determination of lithium cation basicity from molecular structure.

A quantitative structure-property relationship (QSPR) is developed to calculate the Lithium Cationic Basicity (LCB) of a large set of 229 compounds, of very different chemical nature. The proposed models derived from multiple linear regression analysis (MLRA) and computational neural networks (CNN) contain seven descriptors calculated solely from the molecular structure of compounds. The models were validated by an external prediction set. Good results were obtained from both methodologies, being the best those from CNN, that give a rms error of 6.54 (R2 = 0.954) and an average error of 3.57% for the training set; for the prediction set the rms error is 8.61 (R2 = 0.914) and the average error 4.39%. The models derived from the two approaches contain descriptors that belong to the same classes, constitutional and electrostatic. The comparison with the results obtained from high level theoretical methods shows that the values obtained from the QSPR approach are very similar and even better, especially when the sets compared are large and contain compounds of different chemical structure. These good results shows that, despite the complexity of Li+-base interactions, the proposed models contain descriptors which encode properly the characteristics of the molecules directly related to their gas-phase basicity against the Li cations.

Journal Article↗
PubMed2004

pH-triggered assembly of organometallic receptors for lithium ions.

The reaction of half-sandwich complexes of ruthenium, rhodium, and iridium with amino-substituted 3-hydroxy-2-pyridone ligands in aqueous solution gives monomeric O,O'-chelate complexes. Upon addition of base, the complexes assemble to form trimeric metallamacrocycles, as evidenced by NMR spectroscopy and single-crystal X-ray analyses. The macrocycles are able to act as highly selective receptors for lithium ions. The binding constants depend on the nature of the half-sandwich complex, the ligand, and the pH. With a commercially available (cymene)Ru complex, a receptor with a Li+ binding constant of K(a) = 5.8 (+/-1.0) x 10(4) M(-1) and a Li+-Na+ selectivity of 10 000:1 can be obtained. The fact that the assembly process of the receptor is pH-dependent can be used to detect the presence of lithium ions by a pH measurement. Furthermore, it is possible to transduce the binding of Li+ into a change of color by means of a chemical reaction with FeCl(3). This allows the detection of Li+ in the pharmacologically relevant concentration range of 0.5-1.5 mM by the "naked eye".

Cations, Monovalent↗
PubMed2003

Polycyclic aromatic compounds via radical cyclizations of benzannulated enyne-allenes derived from Ireland-Claisen rearrangement.

A new synthetic sequence involving the use of Ireland-Claisen rearrangement of propargylic acetates to form the corresponding benzannulated enyne-allenes followed by Schmittel cyclization to generate benzofulvene biradicals for radical cyclizations leading to polycyclic aromatic compounds was established. Treatment of 9-fluorenone (8) with the lithium acetylide 9 followed by acetic anhydride produced the propargylic acetate 10. A sequence of reactions occurred after 10 was converted to the corresponding silyl ketene acetal 11. An initial Ireland-Claisen rearrangement produced the benzannulated enyne-allene 12, which then underwent a Schmittel cyclization reaction to generate the benzofulvene biradical 13. A subsequent intramolecular radical-radical coupling then produced the formal Diels-Alder adduct 14, which in turn underwent a prototropic rearrangement to give the silyl ester 15 and, after hydrolysis, the carboxylic acid 16 in 57% overall yield from 10 in a single operation. An intramolecular acylation reaction of 16 produced the ketone 17. The carboxylic acids 24-26 were likewise prepared from the diaryl ketones 18-20, respectively. However, the intramolecular [2 + 2] cycloaddition reaction of the benzannulated enyne-allene 33 having a tert-butyl group at the allenic terminus occurred preferentially, producing the 1H-cyclobut[a]indenyl acetic acid 35 as the predominant product.

Journal Article↗
PubMed2004

Palladium(II)-catalyzed intramolecular 1,4-oxyacyloxylation of conjugated dienes. A stereocontrolled route to fused six-membered lactones and pyrans.

Stereocontrolled palladium(II)-catalyzed intramolecular 1,4-oxidations of dienyl acids and alcohols proceed under mild conditions to give fused delta-lactones and pyrans, respectively, in good yields. The stereo- and regioselectivity was affected by the presence of LiCl and solvent composition (HOAc/acetone). The products obtained were used for further functionalizations using copper(I)-mediated reactions. Stoichiometric reactions of preformed dibutylcyanocuprates with pyrans containing an allylic acetate gave cis- and trans-fused ring systems with high gamma-selectivity and in high yields.

Acylation↗