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PubMed2004

Effect of sonication on the electroless Ni-B deposited powder from acid bath.

The electroless deposition rate of Ni-B powder increased with sonication (ultrasonic agitation). The boron content in deposited amorphous powder was about 2.2% with and without sonication. When Ni(II) ion was 20.0 mol/dm(3), deposition efficiency was 65% in 14 mmol/dm(3) dimethylamine boran (DMAB) and 90.2% of Ni(II) ion deposited over 33.9 mmol/dm(3) DMAB adding 100 mg/dm(3) powder. When DMAB ion was 1.7 times of Ni(II) ion, deposition efficiency was 90.2% over 20.0 mmol/dm(3) Ni(II) ion adding 100 mg/dm(3) powder. The optimum ratio of Ni(II) ion and DMAB concentration was 1:1.7. Deposition efficiency was larger about two times compared with that of the stationary state. The powder was amorphous. The particle form was spherical. Particle size of 0.75-1.25 microm was about 40%, and that of 1.25-1.75 microm was about 25%. Crystals of amorphous powder formed by heating from 573 to 773 K.

Journal Article↗
PubMed1981

Amines in the subretinal fluid and aqueous.

We examined 49 samples of subretinal fluid and nine samples of aqueous from patients with retinal detachments. Seven amines (histamine, dopamine, methylamine, ethanolamine, dimethylamine, pyridoxamine, and piperidine) were positively identified and quantitated. The amines in the subretinal fluid were similar to those present in the aqueous. The presence of histamine in the subretinal fluid, observed only in fresh retinal detachment, suggested an inflammatory process, at least in the early stages of some cases of retinal detachment. This is consistent with the clinical observations that mild uveitis frequently accompanies a rhegmatogenous retinal detachment.

Aqueous Humor↗
PubMed1997

Laurdan properties in glycosphingolipid-phospholipid mixtures: a comparative fluorescence and calorimetric study.

Laurdan (6-dodecanoyl-2-dimethylamine-naphthalene) is a fluorescent membrane probe of recent characterization. It was shown that this probe discriminates between phase transitions, phase fluctuations and the coexistence of phase domains in phospholipid multilamellar aggregates. We measured the excitation and emission generalized polarization (GP(ex) and GP(em)) of Laurdan in aggregates of complex glycosphingolipids in their pure form and in mixtures with dipalmitoylphosphatidylcholine (DPPC). Our results show that Laurdan detects the broad main phase transition temperature of the neutral ceramide-tetrasaccharide Gg(4)Cer (asialo-G(M1)) and shows a value of GP(ex) in between that of DPPC and that of ganglioside G(M1). In contrast, Laurdan was unable to detect the thermotropic phase transition of G(M1). The probe also appears to be unable to detect phase coexistence in both types of pure glycolipid aggregates. Deconvolution of the excess heat capacity vs. temperature curves of pure Gg(4)Cer and DPPC/Gg(4)Cer mixtures indicates that the thermograms are composed by different transition components. For these cases, Laurdan detects only the high cooperativity component of the transition of the mixture. The peculiar behaviour of Laurdan in aggregates containing complex glycosphingolipids may result from the inherent topological features of the interface that are conferred by the bulky and highly hydrated polar head group of these lipids.

1,2-Dipalmitoylphosphatidylcholine↗
PubMed2000

Serum-dependent effects of tamoxifen and cannabinoids upon C6 glioma cell viability.

In the present study, the effects of the combination of tamoxifen ((Z)-2[p-(1,2-diphenyl-1-butenyl)phenoxy]-N,N-dimethylamine citrate) and three cannabinoids (Delta(9)-tetrahydrocannabinol [Delta(9)-THC], cannabidiol, and anandamide [AEA]) upon the viability of C6 rat glioma cells was assessed at different incubation times and using different culturing concentrations of foetal bovine serum (FBS). Consistent with previous data for human glioblastoma cells, the tamoxifen sensitivity of the cells was increased as the FBS content of the culture medium was reduced from 10 to 0.4 and 0%. The cells expressed protein kinase C alpha and calmodulin (the concentration of which did not change significantly as the FBS concentration was reduced), but did not express estrogen receptors. Delta(9)-THC and cannabidiol, but not AEA, produced a modest reduction in cell viability after 6 days of incubation in serum-free medium, whereas no effects were seen in 10% FBS-containing medium. There was no observed synergy between the effects of tamoxifen and the cannabinoids upon cell viability.

Animals↗
PubMed2001

Inhibitory effect of alpha-lipoic acid and its positively charged amide analogue on nitric oxide production in RAW 264.7 macrophages.

The aim of this study was to investigate the effect of the mitochondrial cofactor alpha-lipoic acid [R (+) LA] or its lipoamide analogue, 2-(N,N-dimethylamine) ethylamido lipoate [R (+) LA-plus], on nitric oxide (NO) production in RAW 264.7 macrophages. NO production from RAW 264.7 cells stimulated with 10 microg/mL of lipopolysaccharide and 50 U/mL of interferon-gamma was measured directly by electron spin resonance using spin-trapping techniques. R (+) LA or R (+) LA-plus was found to inhibit NO production at pharmacologically relevant concentrations. However, in a cell-free chemical system, neither R (+) LA nor R (+) LA-plus was able to directly scavenge NO. Furthermore, in the presence of 2.5 or 25 mM glucose, the inhibitory effects of R (+) LA and R (+) LA-plus on NO production were decreased markedly, while they showed more potent inhibitory effects in the presence of 2 microM rotenone or 5 microg/mL of antimycin A, inhibitors of mitochondrial complex I and complex III, respectively. Glucose, rotenone, or antimycin A alone resulted in an increase of NO production. These results suggest that NO production in macrophages can be regulated by glucose and mitochondrial respiration, and that modulation of NO production by lipoic acid or lipoamide analogues in inflammatory situations is attributed not to their radical scavenging activity but to their redox properties.

Amides↗
PubMed1972

Photochemical electron transport in photosynthetic reaction centers from Rhodopseudomonas spheroides. II. Interaction with external electron donors and acceptors and a reevaluation of some spectroscopic data.

Photochemical reaction centers prepared from Rhodopseudomonas spheroides were treated with reduced cytochrome c (cyt c), and in some cases with ubiquinone (UQ), and illuminated. The light-induced oxidation of cy and reduction of UQ were observed, and also the variations in fluorescence of P870. These observations indicated that each reaction center contains a primary photochemical electron acceptor capable of holding just one electron. Depending on the method of preparation, the reaction centers may also contain secondary electron acceptor pools consisting mainly of UQ. The role of native UQ as an electron acceptor could be duplicated by added UQ. The yield of P870 fluorescence increased by a factor of 3-4, at most, during illumination of reaction centers in the presence of an electron donor such as reduced cyt. This suggests that the quantum efficiency for the primary photoact is about 0.7, rather than 0.9-1.0 as concluded in the past from optical absorption measurements. The apparent quantum efficiency for the oxidation of cyt by illuminated reaction centers can be increased by the addition of UQ and is decreased at higher concentrations of the detergent lauryl dimethylamine oxide (LDAO). These treatments do not affect the quantum efficiency of P870 oxidation, measured in the absence of cyt.

Cytochromes↗
PubMed1972

Photochemical electron transport in photosynthetic reaction centers from Rhodopseudomonas spheroides. I. Kinetics of the oxidation and reduction of P-870 as affected by external factors.

Photosynthetic reaction centers from Rhodopseudomonas spheroides were prepared with the detergent lauryl dimethylamine oxide (LDAO). In contrast to reaction centers made with Triton X-100, these contained no cytochromes and little or no ubiquinone (UQ). The reduction of P-870, after its photochemical oxidation, was studied in these materials with the following results. In reaction centers made with Triton X-100, slow kinetic components (seconds to minutes) could be attributed to secondary electron acceptors or traps. In reaction centers made with LDAO the kinetics were predominantly fast (half-times, 100 msec or less); slower components could be introduced by adding UQ. Added UQ appeared to become bound to reaction centers made with LDAO, but the binding might have meant only that both components were trapped within detergent micelles. Ferricyanide could retard the reduction of oxidized P-870, apparently by capturing electrons from the reducing side of the photochemical system. Under conditions in which the participation of secondary electron acceptors seemed to have been eliminated, the recovery of P-870 was mainly by a first-order process with a half-time of about 60 msec at room temperature and 20-30 msec at about -80 degrees C and below. The transition with decreasing temperature suggested the presence of a mixed population, exhibiting both the 60 and 20 msec components, but variations in the absorption spectra with temperature did not suggest the presence of a mixed population. Absorption difference spectra in the ultraviolet were compatible with the idea that UQ added to reaction centers became reduced in the light.

Detergents↗
PubMed1998

Water dynamics in glycosphingolipid aggregates studied by LAURDAN fluorescence.

We have characterized the fluorescence properties of 6-dodecanoyl-2-dimethylamine-naphthalene (LAURDAN) in pure interfaces formed by sphingomyelin and 10 chemically related glycosphingolipids (GSLs).1 The GSLs contain neutral and anionic carbohydrate residues in their oligosaccharide chain. These systems were studied at temperatures below, at, or above the main phase transition temperature of the pure lipid aggregates. The extent of solvent dipolar relaxation around the excited fluorescence probe in the GSLs series increases with the magnitude of the glycosphingolipid polar headgroup below the transition temperature. This conclusion is based on LAURDAN's excitation generalized polarization (GPex) and fluorescence lifetime values found in the different interfaces. A linear dependence between the LAURDAN GPex and the intermolecular spacing among the lipid molecules was found for both neutral and anionic lipids in the GSLs series. This relationship was also followed by phospholipids. We conclude that LAURDAN in these lipid aggregates resides in sites containing different amounts of water. The dimension of these sites increases with the size of the GSLs polar headgroup. The GP function reports on the concentration and dynamics of water molecules in these sites. Upon addition of cholesterol to Gg4Cer, the fluorescence behavior of LAURDAN was similar to that of pure cerebrosides and sphingomyelin vesicles. This observation was attributed to a change in the interfacial hydration as well as changes in the shape and size of the Gg4Cer aggregates in the presence of cholesterol. After the addition of cholesterol to gangliosides, the changes in the LAURDAN's spectral parameters decrease progressively as the polar headgroup of these lipids becomes more complex. This finding suggests that the dehydration effect of cholesterol depends strongly on the curvature radius and the extent of hydration of these lipid aggregates. In the gel phase of phrenosine, GalCer, Gg3Cer, sulfatide, and sphingomyelin, the excitation red band (410 nm) of LAURDAN was reduced with respect to that of LAURDAN in the gel phase of pure phospholipids. This observation indicates a local environment that interacts differently with the ground state of LAURDAN in GSLs when compared with LAURDAN in phospholipids.

2-Naphthylamine↗
PubMed1999

Two-photon fluorescence microscopy observation of shape changes at the phase transition in phospholipid giant unilamellar vesicles.

Using the sectioning effect of the two-photon fluorescence microscope, we studied the behavior of phospholipid giant unilamellar vesicles (GUVs) composed of pure diacylphosphatidylcholine phospholipids during the gel-to-liquid crystalline phase transition. We used the well-characterized excitation generalized polarization function (GP(ex)) of 6-dodecanoyl-2-dimethylamine-naphthalene (LAURDAN), which is sensitive to the changes in water content in the lipid vesicles, to monitor the phase transition in the GUVs. Even though the vesicles do not show temperature hysteresis at the main phase transition, we observed different behaviors of the vesicle shape, depending on how the GUV sample reaches the main phase transition. During the cooling cycles, we observed an increase in the vesicle diameter at the phase transition ( approximately 0.5-1%), followed by a decrease in the diameter when the vesicle reached the gel phase. During the heating cycles and close to the phase transition temperature, a surprising behavior is observed, showing a sequence of different vesicle shapes as follows: spherical-polygonal-ellipsoidal. We attribute these changes to the effect of lipid domain coexistence on the macroscopic structure of the GUVs. The "shape hysteresis" in the GUVs is reversible and largely independent of the temperature scan rate. In the presence of 30 mol% of cholesterol the events observed at the phase transition in the GUVs formed by pure phospholipids were absent.

2-Naphthylamine↗
PubMed1977

Total synthesis of hexuronic acids.

Six stereoisomeric hexuronic acids (tert-butyl esters of methyl pyranosides) having the altro, manno, gluco, gulo, galacto, and talo configurations were obtained from cis,trans-tert-butyl 2-methoxy-5,6-dihydro-2H-pyran-6-carboxylate (5). The synthesis involved the following successive steps: epoxidation of the double bond in 5, opening of the epoxides with dimethylamine, Cope degradation of the dimethyl-amino derivatives, and hydroxylation of the double bond in the tert-butyl hex-3-enuronates. All compounds were obtained as pure diastereoisomers in racemic form.

Hexuronic Acids↗
PubMed2003

The emerging role of asymmetric dimethylarginine as a novel cardiovascular risk factor.

There is abundant evidence that the endothelium plays a crucial role in the maintenance of vascular tone and structure. One of the major endothelium-derived vasoactive mediators is nitric oxide (NO). Asymmetric dimethylarginine (ADMA) is an endogenous inhibitor of NO synthase. ADMA inhibits vascular NO production at concentrations found in pathophysiological conditions (i.e., 3-15 micromol/l); ADMA also causes local vasoconstriction when it is infused intraarterially. The biochemical and physiological pathways related to ADMA are now well understood: dimethylarginines are the result of the degradation of methylated proteins; the methyl group is derived from S-adenosylmethionine. Both ADMA and its regioisomer, SDMA, are eliminated from the body by renal excretion, whereas only ADMA, but not SDMA, is metabolized via hydrolytic degradation to citrulline and dimethylamine by the enzyme dimethylarginine dimethylaminohydrolase (DDAH). DDAH activity and/or expression may therefore contribute to the pathogenesis of endothelial dysfunction in various diseases. ADMA is increased in the plasma of humans with hypercholesterolemia, atherosclerosis, hypertension, chronic renal failure, and chronic heart failure. Increased ADMA levels are associated with reduced NO synthesis as assessed by impaired endothelium-dependent vasodilation. In several prospective and cross-sectional studies, ADMA evolved as a marker of cardiovascular risk. With our increasing knowledge of the role of ADMA in the pathogenesis of cardiovascular disease, ADMA is becoming a goal for pharmacotherapeutic intervention. Among other treatments, the administration of L-arginine has been shown to improve endothelium-dependent vascular function in subjects with high ADMA levels.

Amidohydrolases↗
PubMed1985

Reduced glutathione inhibits the alkylation by N-nitrosodimethylamine of liver DNA in vivo and microsomal fraction in vitro.

The transfer of radioactivity from N-nitroso-[14C]dimethylamine to trichloroacetic acid precipitable macromolecules in the microsomal fraction of rat liver was investigated. This transfer was found to depend on N-nitrosodimethylamine being metabolized. Cytosolic fraction and cytosol enriched with reduced glutathione inhibited the binding of radioactivity to acid insoluble proteins. Depletion of glutathione in rat liver with diethylmaleate prior to i.v. administration of 10 mg N-nitroso-[14C]dimethylamine/kg led to an increase in O6-methylguanine and N-7-methylguanine in DNA. If rats were fed disulfiram for 6 days (2 g/kg feed), glutathione and glutathione S-transferase were enhanced, and the degree of methylation of guanine by N-nitrosodimethylamine was greatly reduced, as was the metabolism of N-nitrosodimethylamine in the intact animal. Fasting rats for 24 h did not change the N-nitrosodimethylamine-demethylase activity in vitro but greatly enhanced the methylation of guanine in vivo, while the glutathione content and glutathione S-transferase activity were not changed compared to fed animals.

Alkylation↗
PubMed1997

1H NMR spectra of normal urines: reference ranges of the major metabolites.

Serial urine samples from 50 normal subjects were studied by 1H NMR spectroscopy operating at 300 MHz. Analyses of the spectra have shown the presence of the following metabolites in 100% of the normal subjects: Creatinine, lactate, alanine, citrate, dimethylamine, trimethylamine-N-oxide, glycine and hippurate. Other analytes, such as creatine, valine, betaine, leucine and isoleucine, were sometimes found. All metabolites were quantified on the basis of peak heights and were expressed as mmol/mol of creatinine. The study of metabolic profiles in serial samples allowed us to evaluate intra-individual variability and physiological changes due to feeding. The aim of our report is to define standard conditions for this analytical technique and to calculate confidence intervals for the major metabolites in normal urine samples, such as preliminary and mandatory stages for clinical diagnostic 1H NMR utilization.

Adult↗
PubMed1987

N-nitrosamines and nitrosatable amines, potential precursors of N-nitramines, in children's pacifiers and baby-bottle nipples.

Sixteen types of children's pacifiers and baby-bottle nipples, bought in shops in Israel but produced both there and elsewhere in the world, were analyzed for their contents of N-nitrosamines, which have been shown to be potent carcinogens in animals, and of nitrosatable amines. Two methods were used: one, originating in the United States, involved dichloromethane extraction of total volatile N-nitrosamines from the nipples and pacifiers, and the other, from the Federal Republic of Germany, consisted of analysis of N-nitrosamines and their amine precursors that migrated into artificial saliva. N-Nitrosodibutylamine (NDBA). N-nitrosodiethylamine (NDEA), N-nitrosodimethylamine (NDMA). N-nitrosopiperidine (NPIP), and N-nitrosopyrrolidine (NPYR) were detected by the first method, at individual levels as high as 369 ppb. Using the second method, NDBA, NDEA, NDMA, and N-nitrosomorpholine (NMOR) were detected at concentrations up to 41 ppb, in addition to the three nitrosatable amines dibutylamine, diethylamine, and dimethylamine. Upon nitrosation in the artificial saliva, these amines produced not only the related N-nitrosamines but also relatively high levels of the corresponding N-nitramines (N-nitrodibutylamine, N-nitrodiethylamine, and N-nitrodimethylamine), probably formed by oxidation of the N-nitrosamines by peroxides used for vulcanization of elastomers. Thus, if N-nitramines are not measured in addition to N-nitrosamines after nitrosation, the second method may underestimate the quantities of nitrosatable amines present in artificial saliva extracts. Whether N-nitramines, some of which have been shown to be both mutagenic and carcinogenic, also occur in the saliva of babies exposed to these products remains to be confirmed. Of the samples tested, 50% failed to meet both the U.S. and the FRG regulations. A larger percentage, 60%, would not conform to the new standard suggested in the United States, and more than 80% failed to comply with the even stricter Dutch standard.

Amines↗
PubMed2004

Multivariable optimization of a multiproduct continuous chemicals facility.

Multivariable optimization (MVO) is a powerful nonlinear steady-state flowsheet simulation technique used widely in the chemical process industry to optimize plant performance by increasing plant capacity and/or reducing energy usage. The user supplies the objective function(s), constraints, and variable limits based on operating heuristics, prior experience, and observed process behavior. In this paper we describe how we used MVO in conjunction with improved automation and statistical process monitoring to increase capacity and reduce energy consumption. This project was conducted over a two-year period in a methylamines facility that produces three products: monomethylamine (MMA), dimethylamine (DMA), and trimethylamine (TMA). It led to a 14% improvement in MMA capacity and a 7% improvement in TMA capacity. Energy consumption per pound of main product decreased by approximately 20% for the six-month period (April-September, 2000) when compared to a three-year average (1997-2000). It was accompanied by a 60% improvement in process capability and 31% improvement in product quality. We attribute this improvement to several factors: smoother transition between optimum set points determined by the process optimizer, improved disturbance rejection due to controller installation and tuning, and reduced operator intervention because of controlled operation at or near the optimum set points.

Algorithms↗
PubMed2000

Separation of brompheniramine enantiomers by capillary electrophoresis and study of chiral recognition mechanisms of cyclodextrins using NMR-spectroscopy, UV spectrometry, electrospray ionization mass spectrometry and X-ray crystallography.

Opposite migration order was observed for the enantiomers of brompheniramine [N-[3-(4-bromphenyl)-3-(2-pyridyl)propyl]-N,N-dimethylamine] (BrPh) in capillary electrophoresis (CE) when native beta-cyclodextrin (beta-CD) and heptakis(2,3,6-tri-O-methyl)-beta-CD (TM-beta-CD) were used as chiral selectors. NMR spectrometry was applied in order to obtain information about the stoichiometry, binding constants and structure of the selector-selectand complexes in solution. The data were further confirmed by UV spectrometry and electrospray ionization mass spectrometry. The structure of the complexes in the solid state was determined using X-ray crystallography performed on the co-crystals precipitated from the 1:1 aqueous solution of selector and selectand. This multiple approach allowed an elucidation of the most likely structural reason for a different affinity (binding strength) of BrPh enantiomers towards beta-CD and TM-beta-CD. However, the question about a force responsible for the opposite affinity pattern of BrPh enantiomers towards these CDs could not be answered definitely.

Brompheniramine↗
PubMed2000

Determination of some pesticides and intermediates by ion chromatography.

We explored the possibility of determining some pesticides and process intermediates by ion chromatography. Some applications of this technique, standardized and adopted to meet the requirements of Gharda Chemicals (which is a leading producer of agrochemicals in India), will be presented in this communication. These include analysis of the finished products [(a) dicamba dimethylamine (DMA)/potassium/sodium salt acid and (b) 2,4-dichlorophenoxyacetic acid (2,4-D)], and the process intermediates [(c) tetrachlorobutyric acid and (d) glyoxylic acid/glycollic acid/formic acid]. Ion chromatographic analysis of sub-ppm levels of 2,5-dibromo- and monochlorobromo-phenols, in 2,5-dichlorophenol, after adequate sample preparation steps, is also being presented.

Chromatography, Liquid↗
PubMed2000

Capillary electrophoresis-electrospray ion-trap mass spectrometry for the separation of chlorophenols.

Eighteen positional isomers of chlorophenols were separated by capillary electrophoresis (CE) and detected on-line by electrospray ionization ion-trap mass spectrometry (MS). Conditions for the coupling of CE to MS, e.g., the concentration of carrier electrolyte, the sheath liquid composition and the sheath gas flow-rate were optimized. Diethylmalonic acid (5 mM) at pH 7.25 and isopropanol-250 mM dimethylamine (80:20) as sheath liquid were used. The activation parameters for ion-trap mass spectrometric analysis of chlorophenols were optimized. The mass spectra, obtained for all the analytes, revealed that the [M-H]- ion was the base peak for all chlorophenols. Moreover, conditions for CE-MS-MS detection were established and [M-H-HCl]- ions were detected.

Chlorophenols↗