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PubMed2005

First evaluation of the thermodynamic properties for spheres to elongated micelles transition of some propanediyl-alpha,omega-bis(dimethylalkylammonium bromide) surfactants in aqueous solution.

The apparent and partial molar enthalpies, apparent molar volumes, and adiabatic compressibilities at 298 K of the aqueous solutions of the cationic gemini surfactants propanediyl-alpha,omega-bis(octyldimethylammonium bromide) (8-3-8) and propanediyl-alpha,omega-bis(dodecyldimethylammonium bromide) (12-3-12) have been measured as a function of concentration. The trends of the partial molar enthalpies versus concentration are the first well documented thermodynamic evidence of sphere to rod transition in the micellar phase, involving a detectable quantity of heat, and allow the determination of the change in enthalpy associated with this transition. The changes in enthalpies upon micellization and for the sphere to elongated micelles transition, DeltaH(s)(-->)(r), have been obtained from the experimental data by using a pseudo-phase transition approach: -1.5 kJ mol(-1) for 8-3-8 and -3.9 kJ mol(-1) for 12-3-12. No evidence of the above transition is found in the trends of volumetric properties versus m. The apparent adiabatic molar compressibilities for the compounds under investigation are also reported here for the first time: a negative group contribution for the methylene group is evaluated, when the surfactants are present in solution as a single molecule, reflecting its solvation structure. In the micellar phase, the -CH(2)- group contribution becomes positive. A value of 1.17 x 10(-3) cm(3) bar(-1) mol(-1) for the change in adiabatic molar compressibility upon micellization is obtained. The lower values of the methylene group contributions to the volumetric properties for the monomers support the hypothesis of partial association of the chains before the cmc.

Bromides↗
PubMed2004

Palladium-catalyzed cross-coupling of aryl triethylammonium bis(catechol) silicates with aryl bromides using microwave irradiation.

The scope of the palladium-catalyzed cross-coupling reaction of aryl bis(catechol) silicates has been extended to include the coupling of aryl bromides by employing microwave irradiation. This new set of coupling conditions is tolerant of electron-rich and -deficient aryl bromides. In addition, a variety of substituted aryl bis(catechol) silicates have been successfully cross-coupled.

Bromides↗
PubMed1997

Derivatization and template-guided ligation of oligodeoxyribonucleotides using cyanogen bromide and N-substituted morpholines.

Cyanogen bromide has been found to induce the template-guided condensation of oligonucleotides only in the presence of N-substituted morpholines. Based on 31P, 1H and 13C NMR spectroscopy data, the mechanism of the phosphomonoester group activation by cyanogen bromide in N-substituted morpholine buffers is suggested. It has also been shown that BrCN can be used for the synthesis of oligonucleotide derivatives in aqueous solution.

Buffers↗
PubMed2002

Peroxo-bridged divanadate as selective bromide oxidant in bromoperoxidation.

Diperoxovanadate is effective only in presence of free vanadate in vanadium-dependent bromoperoxidation at physiological pH. Peroxide in the form of bridged divanadate complex (VOOV-type), but not the bidentate form as in diperoxovanadate, is proposed to be the oxidant of bromide. In order to obtain direct evidence, peroxo-divanadate complexes with glycyl-glycine, glycyl-alanine and glycyl-asparagine as heteroligands were synthesized. By elemental analysis and spectral studies they were characterized to be triperoxo-divanadates, [V2O,(O2)3(peptide)3] x H2O, with the two vanadium atoms bridged by a peroxide and a heteroligand. The dipeptide seems to stabilize the peroxo-bridge by inter-ligand interaction, possibly hydrogen bonding. This is indicated by rapid degradation of these compounds on dissolving in water with partial loss of peroxide accompanied by release of bubbles of oxygen. The 51V-NMR spectra of such solutions showed diperoxovanadate and decavanadate (oligomerized from vanadate) as the products. Additional oxygen was released on treating these solutions with catalase as expected of residual diperoxovanadate. The solid compounds when added to the reaction mixtures showed transient, rapid bromoperoxidation reaction, but not oxidation of NADH or inactivation of glucose oxidase, the other two activities shown by a mixture of diperoxovanadate and vanadyl. This demonstration of peroxide-bridged divanadate as a powerful, selective oxidant of bromide, active at physiological pH, should make it a possible candidate of mimic in the action of vanadium in bromoperoxidase proteins.

Bromides↗
PubMed1989

Determination of nitrite, sulphate, bromide and nitrate in human serum by ion chromatography.

An ion chromatographic method has been developed for the determination of trace amounts of nitrite, sulphate, bromide and nitrate in human serum, using an ODS column dynamically coated with cetylpyridinium chloride. The anions studied were eluted with 1 mM citrate - 2.5% methanol (pH 6.5) as the mobile phase and detected by an ultraviolet detector. The interfering proteins in human serum were removed by an initial filtration through an ultrafilter-paper. The many inorganic and organic anions commonly found in serum had little effect on the determination of the four anions. Recoveries of nitrite, sulphate, bromide and nitrate in serum were 107-110, 94-106, 106-110 and 92-100%, respectively. The proposed method was also applied to human saliva and urine.

Bromides↗
PubMed2002

Role of halogen(I) cation-transfer mechanisms in water chlorination in the presence of bromide ion.

Bromide ion is rapidly converted to HOBr via BrCl by reaction with HOCl. The subsequent slow reactions of (HOCl, OCl-)/(HOBr, OBr-) mixtures are monitored directly by multiwavelength UV-vis absorbance methods and simultaneously by ion chromatographic measurement of ClO2-, ClO3-, and BrO3- (p[H+] 5.6-7.6). A first-order loss of HOCl is observed which is catalyzed by trace concentrations of Br- and BrCl. Chlorite ion forms first and is subsequently oxidized to ClO3-. The loss of HOBr is slower and is second-order in HOBr, so that BrO3- formation takes longer than ClO3- formation. Under the conditions of this work, the relative yield of BrO3- increases with increase in pH. The decomposition of HOCI by bromide proceeds primarily by a series of halogen(I) cation-transfer reactions with subsequent halide release. The presence of HOCI increases the BrO3- yield three-fold from HOBr decay alone.

Bromides↗
PubMed1967

Cyanogen bromide cleavage and partial sequence of the heavy chain of a pathological immunoglobulin G.

The heavy chain of a pathological immunoglobulin G (Daw) of type L, subclass gamma(2b) (We) and Gm(a+)(f-), has been cleaved with cyanogen bromide. The five fragments resulting from the cleavage have been isolated and analysed. The papain-digest fragments, Fab and Fc, have also been cleaved with cyanogen bromide and the products analysed and compared with those from the heavy chain. The order of the five fragments in the heavy chain has been established and the location of some of the inter-chain and inter-fragment disulphide bonds has been determined. The sequence of the N-terminal fragment consisting of 34 residues is reported.

Amino Acid Sequence↗
PubMed1967

The metabolism of phenethyl bromide, styrene and styrene oxide in the rabbit and rat.

1. The chief sulphur-containing metabolite of styrene and sytrene oxide in the rabbit and rat is chromatographically identical with N-acetyl-S-(beta-hydroxyphenethyl)-l-cysteine and this compound is also formed, together with N-acetyl-S-phenethyl-l-cysteine, as a metabolite of phenethyl bromide. 2. The amounts of the phenethylmercapturic acid and its hydroxy derivative excreted in the urine of animals dosed with phenethyl bromide, styrene, styrene oxide, phenyl glycol, S-phenylethylcysteine and phenethylmercapturic acid have been determined. 3. Liver slices convert phenethylcysteine and phenethylmercapturic acid into N-acetyl-S-(beta-hydroxyphenethyl)-l-cysteine. 4. Methods for the determination by gas-liquid chromatography of mandelic acid and hippuric acid, which are metabolites of some of the compounds studied, are described.

Animals↗
PubMed1974

Purification and characterization of the seven cyanogen bromide fragments of human serum transferrin.

1. Procedures are described for the isolation of seven distinct cyanogen bromide fragments in high yield from human serum transferrin. 2. Cyanogen bromide-cleaved transferrin is separated into three fragments (CN-A, CN-B and CN-C) by gel filtration with Sephadex G-100. 3. Four peptides are obtained from CN-A (the largest fragment) after reduction and carboxamidomethylation, by gel filtration in acidic solvents. Two peptides are similarly obtained from fragment CN-B, whereas fragment CN-C is a single cystine-free peptide. 4. The molecular weights of the seven peptides, as determined by polyacrylamide-gel electrophoresis in the presence of sodium dodecyl sulphate, by sedimentation-equilibrium ultracentrifugation and by sequence studies, range from 3100 to 27000. Together they account for a molecular weight of 76200 for transferrin. 5. The two largest fragments contain the carbohydrate attachment sites of the protein, and the smallest fragment is derived from the N-terminus. 6. The amino acid compositions and N-terminal groups of the fragments are reported and the results compared with those of previous investigations.

Amino Acid Sequence↗
PubMed1980

Identification of cyanogen bromide peptides involved in intermolecular cross-linking of bovine type III collagen.

Cyanogn bromide peptides derived from bovine type III collagen and containing reducible cross-links were isolated and identified. Two peptides, alpha 1 (III)CB7 and alpha 1 (III)CB9B, from within the helical portion of the molecule were shown to contain the 'amino donor' residues cross-linked to non-helical 'aldehyde donor' residues in the formation of cross-links. This information, in conjunction with previously published data for the order of the cyanogen bromide peptides [Fietzek, Allman, Rauterberg & Wachter (1977) Proc. Natl. Acad. Sci. U.S.A. 74, 84-86], suggests that in type III collagen intermolecular cross-links are located in the end-overlap regions, so as to stabilize a quarter-stagger arrangement of molecules within the fibre in a similar manner to that proposed for type I and type II collagens.

Amino Acids↗
PubMed2002

Vecuronium bromide, phenylephrine and atropine combinations as mydriatics in juvenile double-crested cormorants (Phalacrocorax auritus).

Topical vecuronium bromide (Norcuron) and combinations with atropine and phenylephrine, were evaluated as mydriatics in juvenile double-crested cormorants (Phalacrocorax auritus). Nine cormorants were treated with each of four protocols: 1% atropine; 4 mg/mL vecuronium bromide (total 0.16 mg/eye); atropine with vecuronium; and atropine, 2.5% phenylephrine, followed by vecuronium. Drugs were applied topically at 15-min intervals (0.01 mL/drop). Pupil diameter was measured manually every 15 min with a pupil gauge calibrated to the nearest 0.5 mm. No effect was observed with atropine alone. Average +/- SD peak pupil diameter for vecuronium, atropine/vecuronium, and atropine/phenylephrine/vecuronium were 5.4 +/- 1.1 mm, 5.7 +/- 0.8 mm and 6.2 +/- 0.4 mm, respectively; and duration of peak diameters were 38 +/- 28 min, 79 +/- 71 min and 103 +/- 58 min, respectively. The combined atropine, phenylephrine and vecuronium provided the most consistent dilation with larger average pupil size and longer average duration. No side-effects from vecuronium were observed in these birds.

Animals↗
PubMed1996

Neurotoxicity resulting from coexposure to pyridostigmine bromide, deet, and permethrin: implications of Gulf War chemical exposures.

Of the three-quarters of a million service personnel involved in the Persian Gulf War, approximately 30,000 have complained of neurological symptoms of unknown etiology. One contributing factor to the emergence of such symptoms may be the simultaneous exposure to multiple agents used to protect the health of service personnel, in particular, the anti-nerve agent pyridostigmine bromide (PB; 3-dimethylaminocarbonyloxy-N-methylpyridinium bromide), the insect repellent DEET (N,N-diethyl-m-toluamide), and the insecticide permethrin (3-(2,2-dichloro-ethenyl)-2,2-dimethylcyclopropanecarboxylic acid (3-phenoxyphenyl)methyl ester). This study investigated neurotoxicity produced in hens by individual or simultaneous exposure to these agents (5 d/wk for 2 months to 5 mg/kg/d PB in water, po; 500 mg/kg/d DEET, neat, sc; and 500 mg/kg/d permethrin in corn oil, sc). At these dosages, exposure to single compounds resulted in minimal toxicity. Combinations of two agents produced greater neurotoxicity than that caused by individual agents. Neurotoxicity was further enhanced following concurrent administration of all three agents. We hypothesize that competition for liver and plasma esterases by these compounds leads to their decreased breakdown and increased transport of the parent compound to nervous tissues. Thus, carbamylation of peripheral esterases by PB reduces the hydrolysis of DEET and permethrin and increases their availability to the nervous system. In effect, PB "pumps" more DEET and permethrin into the central nervous system. Consistent with this hypothesis, hens exposed to the combination of the three agents exhibited neuropathological lesions with several characteristics similar to those previously reported in studies of near-lethal doses of DEET and permethrin. If this hypothesis is correct, then blood and liver esterases play an important "buffering" role in protecting against neurotoxicity in the population at large. It also suggests that individuals with low plasma esterase activity may be predisposed to neurologic deficits produced by exposure to certain chemical mixtures.

Administration, Oral↗
PubMed2004

Role of thiocyanate, bromide and hypobromous acid in hydrogen peroxide-induced apoptosis.

We have previously reported that H2O2-induced apoptosis in HL-60 human leukemia cells takes place in the presence of chloride, requires myeloperoxidase (MPO), and occurs through oxidative reactions involving hypochlorous acid and chloramines. We now report that when chloride is replaced by the pseudohalide thiocyanate, there is little or no H2O2-induced apoptosis. Furthermore, thiocyanate inhibits H2O2-induced apoptosis when chloride is present at physiological concentrations, and this occurs at thiocyanate concentrations that are present in human serum and saliva. In contrast, bromide can substitute for chloride in H2O2-induced apoptosis, but results in a lower percent of the cells induced into apoptosis. Hypobromous acid is likely a short-lived intermediate in this H2O2/MPO/bromide apoptosis, and reagent hypobromous acid and bromamines induce apoptosis in HL-60 cells. We conclude that the physiologic concentrations of thiocyanate found in human plasma could modulate the cytototoxicity of H2O2 and its resulting highly toxic MPO-generated hypochlorous acid by competing with chloride for MPO. Furthermore, the oxidative products of the reaction of thiocyanate with MPO are relatively innocuous for human leukemic cells in culture. In contrast, bromide can support H2O2/MPO/halide apoptosis, but is less potent than chloride and it has no effect in the presence of physiological levels of chloride.

Amines↗
PubMed1987

Antigenic and immunogenic properties of cyanogen bromide peptides from gonococcal outer membrane protein IB. Evidence for the existence of a surface-exposed conserved epitope.

Two distinct species of gonococcal porin proteins exist that differ with regard to surface exposure. Protein IB, expressed by strains of the WII/III serogroup, has both termini buried in the outer membrane, leaving a central region of the molecule exposed at the cell surface. We have attempted to define this region of protein IB in detail by studying the antigenic and immunogenic properties of peptides derived from protein IB. Treatment of gonococcal protein IB (serotype 5) with cyanogen bromide resulted in cleavage of protein IB into three major fragments of Mr of 15,000, 13,000, and 8,000. The location of these peptides in the intact protein was determined by analysis of partial cleavage products. The 8,000 Mr peptide (CB2) was found to be located in the central region of the protein. Chymotrypsin cleavage of protein IB revealed a cleavage site near one of the cyanogen bromide cleavage sites. Trypsin was found to cleave the protein, either in outer membranes complexes (OMC) or in detergent micelles, in the central CB2 fragment. These results suggest that CB2 is a part of the surface-exposed region of protein IB. Immunization of mice with purified protein IB (serotype 5) induced antibodies against all three CB-peptides. Absorption of the sera with homologous OMC resulted in a complete removal of antibodies against CB2, supplying further evidence for its surface-exposed nature. Antibodies against the 13,000 Mr peptide (CB1) could not be absorbed with intact OMC, suggesting that this peptide is buried within the outer membrane. Antisera raised against CB2 of serotype 5 demonstrated a considerable cross-reactivity with heterologous outer membranes. On the contrary, intact OMC induced mainly type-specific antibodies. These data demonstrate the presence of conserved epitopes on the surface-exposed CB2 peptide. These conserved epitopes are generally not very immunogenic when present in intact OMC.

Animals↗
PubMed1976

The role of tryptophanyl residues in heavy meromyosin as studied by chemical modification with 2-hydroxy-5-nitrobenzyl bromide.

1. Two moles of 2-hydroxy-5-nitrobenzyl group bound selectively to one mole of heavy meromyosin when it was treated with 2-hydroxy-5-nitrobenzyl bromide, a specific reagent for tryptophanyl residues. The binding with ADP, the size of the initial burst of Pi liberation and the difference absorption spectrum with and without ADP of the bound 2-hydroxy-5-nitrobenzyl groups were measured with heavy meromyosin modified with various amounts of reagent. The properties of the modified heavy meromyosin did not change until the molar binding ratio of the reagent, rH, was about 1, but the properties changed remarkably when rH increased from 1 to 2. 2. Subfragment-1 was prepared from the modified heavy meromyosin by trypsin [EC 3.4.21.4] digestion. The molar binding ratio of the reagent in subfragment-1, rS, was found to be less than 0.1 when rH of the starting heavy meromyosin was less than 0.8. However, rS was about 0.5 in subfragment-1 prepared from heavy meromyosin of rH about 2. The results indicate that only one mole of 2-hydroxy-5-nitrobenzyl group, which was bound with lower reactivity than the other, was bound to a head part of heavy meromyosin. 3. Subfragment-1 fraction prepared from the modified heavy meromyosin could be separated into two fractions by DE-32 cellulose column chromatography; the subfragment-1 portion which eluted later showed a higher rS than that eluted in front. The binding with ADP, the size of the initial burst of Pi liberation and the difference absorption spectrum induced by ATP were measured with the modified subfragment-1 separated by DE-32 cellulose column chromatography. The ADP-binding ability and the size of the initial burst were not dependent on rS, and coincided with those of subfragment-1 prepared from unmodified heavy meromyosin. 4. The results of ADP binding studies suggest that heavy meromyosin is constituted from nonidentical subunits, and that there is an interaction between them which controls the ADP binding. Two tryptophanyl residues having specific reactivity toward 2-hydroxy-5-nitrobenzyl bromide are assumed to be involved in the interaction.

2-Hydroxy-5-nitrobenzyl Bromide↗
PubMed1984

CT demonstration of hyperdense cerebral vasculature due to bromide therapy.

An increase in the effective atomic number of blood is among the factors allowing or influencing the visualization of the major cerebral vessels on noncontrast CT. Bromine (atomic number, 50) attenuates 70 keV X-rays significantly and was responsible for a striking enhancement of the major cerebral vessels on the noncontrast CT in a child being treated for epilepsy. Although oral bromides are only occasionally used in the treatment of epilepsy, their use causes an increase in blood density and thus bromides need to be considered along with other etiologies (reviewed) that allow visualization of the major cerebral vessels on noncontrast CT.

Brain↗
PubMed2006

Plethysmography and impulse oscillometry assessment of tiotropium and ipratropium bromide; a randomized, double-blind, placebo-controlled, cross-over study in healthy subjects.

AIMS: Spirometry, plethysmography and impulse oscillometry (IOS) measure different aspects of lung function. These methods have not been compared for their ability to assess long- and short-acting anticholinergic agents. We therefore performed a double-blind, placebo-controlled, four-way cross-over study in 30 healthy subjects. METHODS: Single doses of tiotropium bromide (Tio) 54 and 18 mcg, ipratropium bromide (IB) 40 mcg and placebo were administered. Specific conductance (sGaw), total lung capacity (TLC), inspiratory capacity (IC) and residual volume (RV) were measured using plethysmography, while IOS measured resistance (R5-25) and reactance (RF and X5). Pulmonary function was measured for 26 h post dose. RESULTS: Tio caused significant improvements in sGaw, forced expiratory voume in 1 s (FEV(1)), maximum mid-expiratory flow (MMEF) and R5-R25 at time points up to 26 h, with no clear differences between doses. IB improved the same parameters, but only up to 8 h. The weighted mean change (0-24 h) caused by Tio 54 mcg compared with placebo for FEV(1) was 240 ml (95% confidence interval 180, 300), while for sGaw the ratio of geometric means (Tio compared with placebo) was 1.35 (1.28, 1.41). Neither drug caused consistent statistically significant changes in RF, forced vital capacity, TLC or IC over 26 h. RV was significantly improved from 8 to 24 h by Tio 54 mcg only. CONCLUSIONS: In addition to spirometry, IOS resistance measurements and sGaw can distinguish between the effects of long- and shortacting anticholinergic effects in healthy subjects.

Adult↗
PubMed1985

Plasma fluoride and bromide concentrations during occupational exposure to enflurane or halothane.

The plasma fluoride and bromide concentrations were studied in operating theatre personnel. When enflurane was used, the increase in plasma fluoride concentration could not be distinguished from normal individual variations, but the plasma bromide concentration increased significantly when halothane was used. Seven patients were exposed to enflurane in a concentration of 200 parts per million for 4 h. A significant increase in the plasma concentration of fluoride was observed. The peak concentrations of fluoride occurred during exposure and the increase lasted less than 12 h. The increase in fluoride concentration was larger at this trace concentration than reported after anaesthetic concentrations. Cerebrospinal fluid (CSF) fluoride concentration was also studied; a smaller and delayed increase was found in CSF compared to plasma.

Air Pollutants, Occupational↗