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PubMed2002

F+ tunable laser activity and interaction of atomic halogens (F, Cl and Br) at the low coordinated surface sites of SrOAb initio and DFT calculations.

The twofold potential of F+ color centers at the low coordinated surfaces of SrO for providing tunable laser activity and adsorption properties for atomic halogens (F, Cl and Br) has been investigated using ab initio electronic structure calculations. SrO clusters of variable sizes were embedded in simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces and the nearest neighbor ions to F+ were allowed to relax to equilibrium. Based on Stokes shifted optical transition bands and horizontal shifts along the configuration coordinate diagrams, the F+ laser activity was found to decrease as the coordination number of the surface ions decreases from 5 (flat) to 4 (edge) to 3 (corner). An attempt has been made to explain this result in terms of Madelung potentials and optical-optical conversion efficiencies. All relaxed excited states are deep below the conduction bands of the perfect ground states, implying that F+ is a laser-suitable defect. The most laser active flat surface is the least probable for relaxed excited state orientational destruction of F+. The excited state at the edge has the highest energy, implying exciton (energy) transfer to the flat and edge sites. F+ relaxation and defect-formation energies increase with increasing surface coordination number. The Glasner-Tompkins relation between the fundamental optical absorption of F+ in solids and the fundamental absorption of the host crystals can be generalized to include the low coordinated surfaces of SrO. The F+ color center changes the nature of halogen-surface interaction (adsorption energies) from physical adsorption to chemical adsorption. The halogen-surface interactions increase with increasing electronegativity of the halogen. The calculated adsorption energies can be explained in terms of surface electrostatic potentials, and the covalent spin pairing mechanism plays a dominant role in determining adsorbate-substrate interactions.

Computer Simulation↗

PubMed1979

The mutagenicity of halogenated alkanols and their phosphoric acid esters for Salmonella typhimurium.

9 halogenated alkanols, 9 corresponding tris (haloalkyl)phosphates, and 2 bis-(2,3-dibromopropyl)phosphate salts were evaluated for mutagenicity against Salmonella typhimurium TA98, TA100, TA1535, TA1537 and TA1538, with and without rat liver in vitro metabolic activation system (S9 mix). Most of the test samples showed mutagenic activity in the strains TA100 and TA1535, but not in the strains TA98, TA1537 and TA1538. In general, the mutagenic activities of the phosphates obtained with S9 mix were greater than the activities obtained without S9 mix. Among the phosphates, several structure--activity relationships were found; i.e., (i) the bromoalkyl derivatives were more mutagenic than the corresponding chloroalkyl derivatives, (ii) the beta-haloethyl derivatives were more mutagenic than the gamma-halopropyl derivatives, (iii) the phosphates having adjacent beta and gamma halogen atoms in the alkyl moiety, e.g., tris-(2,3-dibromopropyl)phosphate, were particularly potent mutagens, (iv) the branched carbon chain reduced the mutagenic activities in spite of the presence of beta-halogen atoms, e.g., tris(1-bromomethyl-2-bromoethyl)phosphate. However, such relations did not necessarily apply to the halogenated alkanols. It is concluded that the metabolic activation pathway via haloalkanols to mutagens must not be in common with all tris-BP-like phosphates.

Alcohols↗

PubMed1996

Electronic structure of bridging halogen atoms in metal halide dimers studied by the AM1 method and NQR spectroscopy.

A nuclear quadrupole resonance (NQR) study of the electronic structure of bridging halogen atoms in dimers of transition and non-transition metal halides has been performed. An explanation of the differences in the NQR frequencies for transition and non-transition metal halides is proposed. The population of the bridging halogen atom orbitals and the metal-halogen bond lengths have been estimated by the AM1 method. The aim of this paper was to obtain a relationship describing the lengths of the metal-halogen bonds.

Chemical Phenomena↗

PubMed2004

Plasma arc versus halogen light-curing of adhesive-precoated orthodontic brackets: a 12-month clinical study of bond failures.

The purpose of this randomized clinical trial was to evaluate the performance of adhesive-precoated brackets cured with 2 different light-curing units (conventional halogen light and plasma arc light). Thirty patients treated with fixed appliances were included in the investigation. Each patient's mouth was divided by the split-mouth design into 4 quadrants. In 15 randomly selected patients, the maxillary left and mandibular right quadrants were cured with the halogen light, and the remaining quadrants were cured with the plasma arc light. In the other 15 patients, the quadrants were inverted. A total of 600 adhesive precoated stainless steel brackets were examined: 300 were cured with a conventional halogen light for 20 seconds, and the others were cured with the plasma arc light for 5 seconds. The number, cause, and date of bracket failures were recorded for each light-curing unit over 12 months. Statistical analysis was performed with the Fisher exact test, Kaplan-Meier survival estimates, and the log-rank test. No statistically significant differences in bond failure rates were found between the adhesive-precoated brackets cured with the halogen light and those cured with the plasma arc light; neither were any significant differences in performance found with each light-curing unit between the maxillary and mandibular arches. Plasma arc lights can be considered an advantageous alternative to conventional light curing, because they enable the clinician to reduce the curing time of adhesive-precoated orthodontic brackets without significantly affecting their bond failure rate.

Adolescent↗

PubMed2006

Effect of light-tip distance on the shear bond strengths of resin-modified glass ionomer cured with high-intensity halogen, light-emitting diode, and plasma arc lights.

INTRODUCTION: The purpose of this study was to assess the effect of light-tip distance on the shear bond strength and the failure site of brackets cured with 3 light-curing units (high-intensity halogen, light-emitting diode, and plasma arc). METHODS: One hundred thirty-five bovine mandibular permanent incisors were randomly allocated to 9 groups of 15 specimens each. Stainless steel brackets (Victory Series, Unitek/3M, Monrovia, Calif) were bonded with a resin-modified glass-ionomer (Fuji Ortho LC, GC Europe, Leuven, Belgium) to the teeth, and each curing light was tested at 3 distances from the bracket: 0, 3, and 6 mm. After bonding, all samples were stored in distilled water at room temperature for 24 hours and subsequently tested for shear bond strength. RESULTS: When the 3 light-curing units were compared at a light-tip distance of 0mm, they showed no significantly different shear bond strengths. At a light-tip distance of 3 mm, no significant differences were found between the halogen and plasma arc lights, but both lights showed significantly higher shear bond strengths than the light-emitting diode light. At a light-tip distance of 6 mm, no significant differences were found between the halogen and light-emitting diode lights, but both showed significantly lower bond strengths than the plasma arc light. When the effect of the light-tip distance on each light-curing unit was evaluated, the halogen and light-emitting diode lights showed no significant differences among the 3 distances. However, the plasma arc light produced significantly higher shear bond strengths at a greater light-tip distance. No significant differences were found among the adhesive remnant index scores of the various groups, except with the LED light at a distance of 3 mm. CONCLUSIONS: In hard-to-reach areas, the plasma arc curing light is suggested for optimal curing efficiency.

Acrylic Resins↗

PubMed2006

Halogenation of 4-hydroxy-3-methoxybenzyl thiourea TRPV1 agonists showed enhanced antagonism to capsaicin.

Selected potent TRPV1 agonists (1-6) have been modified by 5- or 6-halogenation on the aromatic A-region to analyze their effects on potency and efficacy (agonism versus antagonism). The halogenation caused enhanced functional antagonism at TRPV1 compared to the corresponding prototype agonists. The analysis of SAR indicated that the antagonism was enhanced as the size of the halogen increased (I>Br>Cl) and when the 6-position was halogenated. Compounds 23c and 31b were found to be potent full antagonists with K(i) (as functional antagonist)=23.1 and 30.3 nM in rTRPV1/CHO system, respectively.

Animals↗

PubMed2001

Halogenated metabolites with antibacterial activity from the Okinawan Laurencia species.

The chemical compositions of five species of the red algal genus Laurencia from coastal waters of Okinawa Prefecture, Japan, have been investigated. A halogenated C(15) acetogenin, (12E)-lembyne-A, was isolated from L. mariannensis, and a halogenated sesquiterpene, (6R,9R,10S)-10-bromo-9-hydroxy-chamigra-2,7(14)-diene, was first found from L. majuscula as a naturally occurring compound. Laurencia nidifica yielded previously known laurinterol and isolaurinterol. Samples of L. cartilaginea and L. concreta afforded no halogenated metabolites. The structures of these halogenated metabolites as well as their antibacterial activity against some marine bacteria are reported.

Anti-Bacterial Agents↗

PubMed2001

Boiling points of halogenated organic compounds.

The normal boiling points of a number of halogenated organic compounds have been compiled from experimental measurements over three decades. Some of these chemicals have not been reported in the literature. The substances listed are halogenated aliphatic hydrocarbons, halogenated aliphatic ethers, halogenated ring (cyclic) hydrocarbons and other related compounds.

Halogens↗

PubMed2001

Quantitative structure-property relationship study on reductive dehalogenation of selected halogenated aliphatic hydrocarbons in sediment slurries.

In this study, by the use of partial least squares (PLS) method and 26 quantum chemical descriptors computed by PM3 Hamiltonian, a quantitative structure-property relationship (QSPR) model was developed for reductive dehalogenation rate constants of 13 halogenated aliphatic compounds in sediment slurry under anaerobic conditions. The model can be used to explain the dehalogenation mechanism. Halogenated aliphatic compounds with great energy of the lowest unoccupied molecular orbital (Elumo), total energy (TE), electronic energy (EE), the smallest bond order of the carbon-halogen bonds (BO) and the most positive net atomic charges on an atom of the molecule (q+) values tend to be reductively dehalogenated slow, whereas halogenated aliphatic compounds with high values of molecular weight (Mw), average molecular polarizability (alpha) and core-core repulsion energy (CCR) values tend to be reductively dehalogenated fastest.

Electrons↗

PubMed1998

Evaluation of forcefields for molecular mechanics/dynamics calculations involving halogenated anesthetics.

(1) Successful application of molecular mechanics and molecular dynamics calculations to the binding of halogenated anesthetics requires forcefields with correct parameters for halocarbons. (2) Unfortunately, our survey of six popular forcefields revealed that some of them provide a very poor representation of electrostatic interactions for the halogens. (3) This problem is due to poor or missing assignments of partial atomic charges to the halogen atoms. (4) We describe the forcefields most appropriate for use with halogenated anesthetics and suggest a general method for editing the assignment of partial atomic charges by performing an initial quantum mechanics calculation.

Anesthetics↗

PubMed2003

Metabolic flux analysis of halogenated monoterpene biosynthesis in microplantlets of the macrophytic red alga Ochtodes secundiramea.

The bioprocess engineering of marine macroalgae (i.e. seaweeds) for the production of secondary metabolites is an emerging area of marine biotechnology. One novel system is the biosynthesis of halogenated monoterpenes by "microplantlet" suspension cultures derived from the red alga Ochtodes secundiramea. This biosynthetic platform has three principal components: elaboration of myrcene from geranyl diphosphate (GPP); bromonium-ion promoted halogenation of myrcene to 10E-bromomyrcene, 3-chloro-10E-bromo-alpha-myrcene, and 3,10E-dibromomyrcene; bromonium-ion promoted cyclization of myrcene to Apakaochtodene B. In this study, a metabolic flux analysis on halogenated monoterpene biosynthesis was performed. To facilitate this effort, a "bromine free" cell line of O. secundiramea microplantlets was developed where biohalogenation was temporarily disabled but myrcene biosynthesis was still enabled. This cell line was cultivated within an airlift photobioreactor under nutrient medium perfusion. Halogenated monoterpene biosynthesis was "turned on" by coordinated addition of bromide and vanadate (a co-factor for vanadium bromoperoxidase) to the perfusion medium. From these experiments, the effects of bromide and vanadate delivery on the metabolic flux of each metabolite were determined. Bromination of myrcene at its Delta(6-10) olefinic bond was the dominant branch of the bioreaction network, whereas chlorination steps in the pathway were "weakly rigid". This study represents the first application of metabolic engineering principles to the analysis and manipulation of secondary metabolism in macrophytic marine organisms.

Bioreactors↗

PubMed1992

Para-substituted Phe3 deltorphin analogues: enhanced selectivity of halogenated derivatives for delta opioid receptor sites.

The delta-selective opioid peptide deltorphin C(H-Tyr-D-Ala-Phe-Asp-Val-Val-Gly-NH2) (DEL C) was modified by para-substitution of Phe3 with halogens (F, Cl, Br, I), amino, or nitro groups. The bioactive potencies in peripheral tissues and brain receptor selectivities of these analogues depended upon the particular substituent; peptides containing halogen substituents exhibited the least disruptive effect. In the mouse vas deferens (MVD) bioassay, [p-ClPhe3]DEL C displayed equivalent bioactivities to DEL C; in combination with the guinea pig ileum (GPI) bioassay, [p-ClPhe3]DEL C and [p-BrPhe3]DEL C exhibited marked preference for delta sites (IC50GPI/IC50MVD = 11,250 and 6,363, respectively), which are approximately 4- and 2-fold greater than DEL C. In a receptor binding assay, none of the halogenated analogues had delta affinities (Ki) exceeding that of DEL C; however, in terms of delta selectivity (Ki mu/Ki delta), [p-BrPhe3]DEL C was nearly twice as selective as DEL C, while [p-FPhe3]DEL C was equivalent, and [p-IPhe3]DEL C only 25% less selective. The only correlation evident with the halogenated derivatives occurred between IC50GPI and Ki mu (r = 0.814) rather than between delta receptor studies (MVD or Ki delta); interestingly, IC50GPI also correlated with K' (r = 0.982). The p-amino or p-nitro substituents of Phe3 in DEL C and DEL B (= [Glu4]DEL C) were deleterious for bioactivity (MVD) (losses ranged from 400- to approximately 8,000-fold) and in receptor binding assays, where delta affinities decreased 140- to 840-fold and delta selectivities by 34- to 380-fold. p-Nitro-Phe3 was the most detrimental substitution for all the parameters measured for both deltorphins: the loss in MVD activity, however, was less with DEL B than with DEL C, which was the opposite for delta receptor affinity.

Amino Acid Sequence↗

PubMed2006

Exploring gradients of halogens and zinc in the surface and subsurface of Nereis jaws.

The outstanding mechanical properties of impact-bearing tissues, such as Nereis jaws, make their morphology and chemical composition a subject of particular interest. The complex structure of the jaw was recently reported to exhibit molecular gradients that were closely correlated with stiffness and hardness.(18) Accordingly, we have explored the spatial distribution and bonding chemistries of Zn and the halogens in the surface structure of the jaws. Using secondary ion mass spectrometry (SIMS) and scanning electron microscopy (SEM), we found that Cl, Br, and I distributions are enhanced in surface layers of the basal protected portion of the jaw but are shifted to greater depths toward the exposed jaw tip. There are thus two complementary halogen gradients in the jaw: one on the surface that decreases from the base to the tip, coupled to an increasing one in the subsurface layers. The outer surface coating appeared to have granular morphology, in contrast to the anisotropic, fibrous core that dominates the subarchitecture. Using X-ray photoelectron spectroscopy (XPS), we discovered that Zn, I, and Br in the jaws have single chemical environments whereas chlorine is present in two distinct modes (Cl-Zn and Cl-C). Given the inverse relationship between surface exposure and halogen abundance in the jaws, it is unlikely that the halogens contribute directly to mechanical properties such as wear and hardness.

Animal Structures↗

PubMed2003

Halogenation of a capsaicin analogue leads to novel vanilloid TRPV1 receptor antagonists.

1. The C-5 halogenation of the vanillyl moiety of resiniferatoxin, an ultrapotent agonist of vanilloid TRPV1 receptors, results in a potent antagonist for these receptors. Here, we have synthesized a series of halogenated derivatives of 'synthetic capsaicin' (nonanoyl vanillamide=nordihydrocapsaicin) differing for the nature (iodine, bromine-chlorine) and the regiochemistry (C-5, C-6) of the halogenation. 2. The activity of these compounds was investigated on recombinant human TRPV1 receptors overexpressed in HEK-293 cells. None of the six compounds exerted any significant agonist activity, as assessed by measuring their effect on TRPV1-mediated calcium mobilization. Instead, all compounds antagonized, to various extents, the effect of capsaicin in this assay. 3. All 6-halo-nordihydrocapsaicins behaved as competitive antagonists against human TRPV1 according to the corresponding Schild's plots, and were more potent than the corresponding 5-halogenated analogues. The iodo-derivatives were more potent than the bromo- and chloro-derivatives. 4. Using human recombinant TRPV1, 6-iodo-nordihydrocapsaicin (IC(50)=10 nM against 100 nM capsaicin) was about four times more potent than the prototypical TRPV1 antagonist, capsazepine, and was tested against capsaicin also on native TRPV1 in: (i) rat dorsal root ganglion neurons in culture; (ii) guinea-pig urinary bladder; and (iii) guinea-pig bronchi. In all cases, except for the guinea-pig bronchi, the compound was significantly more potent than capsazepine as a TRPV1 antagonist. 5. In conclusion, 6-iodo-nordihydrocapsaicin, a stable and easily prepared compound, is a potent TRPV1 antagonist and a convenient replacement for capsazepine in most of the in vitro preparations currently used to assess the activity of putative vanilloid receptor agonists.

Animals↗

PubMed2006

Molecular mechanisms of enzyme-catalysed halogenation.

Since their discovery, halogenated metabolites have been somewhat of a biological peculiarity and it is only now that we are beginning to realize the full extent of their medicinal value. With the exception of the well characterized haloperoxidases, most of the biosynthetic enzymes and mechanisms responsible for the halogenations have remained elusive. The crystal structures of two functionally diverse halogenases have been recently solved, providing us with new and exciting mechanistic detail. This new insight has the potential to be used both in the development of biomimetic halogenation catalysts and in engineering halogenases, and related enzymes, to halogenate new substrates. Interestingly, these new structures also illustrate how the evolution of these enzymes mirrors that of the monooxygenases, where the cofactor is selected for its ability to generate a powerful oxygenating species. In this highlight article we will examine the proposed catalytic mechanisms of the halogenases and how these relate to their structures. In addition, we will consider how this chemistry might be harnessed and developed to produce novel enzymatic activity.

Animals↗

PubMed1999

Evaluation of 10 aliphatic halogenated hydrocarbons in the mouse bone marrow micronucleus test.

Ten halogenated aliphatic hydrocarbons (carbon tetrachloride, 1-chlorohexane, 2,3-dichlorobutane, 1,2-dichloroethane, 1,2-dichloroethylene, 1,3-dichloropropane, hexachloroethane, 1,1,2-trichloroethane, 1,2,3-trichloropropane and 1,1,3-trichloropropene), previously assayed in genetic assays in fungi, were evaluated in the mouse bone marrow micronucleus test in order to assess their genotoxicity in vivo. All chemicals were administered once i.p. at 40 and 70-80% of their respective LD50 to male and female CD-1 mice, 24 and 48 h before killing. All treatments produced evident clinical symptoms, but no marked depression of bone marrow proliferation. No statistically significant increases in the incidence of micronucleated polychromatic erythrocytes over the control values were observed at any sampling time with any of the 10 halogenated hydrocarbons assayed. The comparison of the results obtained in this study with the findings provided by in vitro micronucleus assays on the same chemicals, reported by other authors, indicate that mouse bone marrow is weakly sensitive to the genotoxic effects induced by halogenated hydrocarbons in other test systems. This suggests that the role of such an assay in carcinogen screening may be questionable for this chemical class. An examination of mouse bone marrow micronucleus test results with the halogenated aliphatic hydrocarbons classified as carcinogens by IARC supports this conclusion.

Animals↗

PubMed1999

Induction and prevention of micronuclei and chromosomal aberrations in cultured human lymphocytes exposed to the light of halogen tungsten lamps.

Previous studies have shown that the light emitted by halogen tungsten lamps contains UV radiation in the UV-A, UV-B and UV-C regions, induces mutations and irreparable DNA damage in bacteria, enhances the frequency of micronuclei in cultured human lymphocytes and is potently carcinogenic to the skin of hairless mice. The present study showed that the light emitted by an uncovered, traditional halogen lamp induces a significant, dose-related and time-related increase not only in micronuclei but also in chromosome-type aberrations, such as breaks, and even more in chromatid-type aberrations, such as isochromatid breaks, exchanges and isochromatid/chromatid interchanges, all including gaps or not, in cultured human lymphocytes. All these genotoxic effects were completely prevented by shielding the same lamp with a silica glass cover, blocking UV radiation. A new model of halogen lamp, having the quartz bulb treated in order to reduce the output of UV radiation, was considerably less genotoxic than the uncovered halogen lamp, yet induction of chromosomal alterations was observed at high illuminance levels.

Adult↗

PubMed2004

Interaction of halogenated anesthetics with alpha- and beta-adrenoceptor stimulations in diabetic rat myocardium.

BACKGROUND: Halogenated anesthetics potentiate the positive inotropic effects of alpha- and beta-adrenoceptor stimulations. Although diabetes mellitus induces significant myocardial abnormalities, the interaction of halogenated anesthetics and adrenoceptor stimulation in diabetic myocardium remains unknown. METHODS: Left ventricular papillary muscles were provided from healthy and streptozotocin-induced diabetic rats. Effects of 1 minimum alveolar concentration halothane, isoflurane, and sevoflurane on the inotropic and lusitropic responses of alpha (phenylephrine)- and beta (isoproterenol)-adrenoceptor stimulations were studied at 29 degrees C with 12 pulses/min. Data shown are mean percentage of baseline active force +/- SD. RESULTS: Phenylephrine induced comparable positive inotropic effects in healthy and diabetic rats (143 +/- 8 vs. 136 +/- 18%; not significant), but the potentiation by halogenated anesthetics was abolished in the diabetic rats (121 +/- 20, 130 +/- 20, and 123 +/- 20% for halothane, isoflurane, and sevoflurane, respectively; not significant). In diabetic rats, the positive inotropic effect of isoproterenol was markedly diminished (109 +/- 9 vs. 190 +/- 18%; P < 0.05), but its potentiation was preserved with isoflurane (148 +/- 21%; P < 0.05) and sevoflurane (161 +/- 40%; P < 0.05) but not with halothane (126 +/- 16%; not significant). Halothane induced a deleterious effect on the sarcoplasmic reticulum, as shown by its impairment in the lusitropic effect of isoproterenol, compared with isoflurane and sevoflurane. CONCLUSION: Potentiation of the positive inotropic effect of alpha-adrenoceptor stimulation by halogenated anesthetics is abolished in diabetic rats. In contrast, potentiation of beta-adrenoceptor stimulation is preserved with isoflurane and sevoflurane but not with halothane, probably because of its deleterious effects on sarcoplasmic reticulum.

Adrenergic alpha-Agonists↗