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An in vivo study to compare a plasma arc light and a conventional quartz halogen curing light in orthodontic bonding.

The purpose of this study was to compare the effectiveness of a plasma arc lamp with a conventional tungsten quartz halogen lamp in orthodontic bonding. Twenty consecutive patients had their brackets bonded either with Transbond XT (n = 10) or Fuji Ortho LC (n = 10). In total, 352 teeth were bonded, 176 in each group. Using a randomized cross-mouth control study design, where diagonally opposite quadrants were assigned a particular treatment, the bonds were then either cured with the control light, namely a halogen lamp, or a plasma arc lamp. The halogen light was used for 20 seconds per tooth and the plasma arc lamp for 3 seconds per tooth. The measurement parameter used was bond failure and the patients were monitored for a period of 6 months following initial bond placement. In the Transbond XT group, the proportion of bond failures was 3.41 per cent for both the halogen and the plasma arc lamp. For the Fuji Ortho LC group, the proportions were 11.4 and 10.2 per cent, respectively. No difference was observed with respect to in-service bond failure proportions between bonds cured with the plasma arc or the conventional halogen lamp, irrespective of the bonding agent. Use of the plasma arc lamp could therefore lead to considerable savings in clinical time. However, this must be weighed against the increased purchase price of the plasma arc lamp.

Adhesives↗

Mutagenic and lethal effects of halogenated methanes in the Ara test of Salmonella typhimurium: quantitative relationship with chemical reactivity.

The mutagenic and lethal effects of nine halogenated methanes (CCl4, carbon tetrachloride; CHCl3, chloroform; CH2Cl2, dichloromethane; CBr4, carbon tetrachloride; CHBr3, bromoform; CH2Br2, dibromomethane; CI4, carbon tetraiodide; CHI3, iodoform; and CH2I2, diiodomethane) have been investigated with the Ara forward-mutation assay of Salmonella typhimurium. Five substances (CH2Cl2, CBr4, CH2Br2, CHI3 and CH2I2) gave clear mutagenic responses. In all these cases the mutagenicity diminished in the presence of mammalian metabolic activation (S9 mixture). Two halomethanes (CCl4 and CHBr3) were classified as 'questionable' mutagens since they did not double the spontaneous value although a dose-response curve was obtained. All halomethanes tested exerted a lethal effect. A high concordance was found between lethality and chemical reactivity, as expected from the type and number of halogenated substituents. Compounds with equal numbers of substituents were lethal in the order I > Br > Cl. Additionally, the lethality of compounds with identical halogen substituents increased by successive halogenations. No such concordances were observed with respect to mutagenic activity. Structure-activity quantitative relationships were investigated by using the previously reported values of the polarographic half-wave reduction potential (-E1/2), a physicochemical parameter related to the energy required to put an electron into the lowest unoccupied molecular orbital. The lethality, quantified as LD37, correlated highly with the -E1/2 values for the nine halogenated compounds (r = -0.955 P < 0.001). These data suggest that halomethanes which are reduced easily will induce higher lethality than those with low reduction potential, in agreement with the predicted effects on lipid peroxidation and hepatotoxicity.(ABSTRACT TRUNCATED AT 250 WORDS)

Dose-Response Relationship, Drug↗

Synthesis and properties of artificial base pairs by use of halogen bonds.

Artificial base pairs by use of halogen bonding were designed and their interaction energies were estimated by ab initio calculations. The optimized structures of the artificial base pairs were almost consistent with those of the canonical base pairs, and the interaction energies were ca. 5-11 kcal/mol. To investigate the thermal stability of the base pairs containing halogen bonds in oligodeoxynucleotide duplexes, deoxynucleoside 3'-phosphoramidite building blocks as halogen bonding acceptors and donors were synthesized and used for incorporation into oligodeoxynucleotides. UV-melting experiments suggest that these halogen bonding base pairs have low stability compared with the A-T base pair. Furthermore, the effect of the halogen bonding on stabilization of duplexes was studied in detail by comparison with the hybridization ability of oligodeoxynucleotides containing a modified base having a iodo group with that of the complementary DNA strands lacking the donor site.

Base Pairing↗

The actions of halogenated ethers on the ionic currents of the squid giant axon.

The effects of fourteen halogenated ethers on the sodium and potassium currents of voltage-clamped squid giant axons have been examined. Effects under open-circuit were also studied. In voltage-clamped axons, the ethers tended to reduce potassium currents at least as much, if not more, than sodium currents. This finding distinguishes the halogenated ethers from many other general anaesthetics. Certain, but not all, halogenated ethers induced a pronounced maximum in potassium current traces as a function of time. This property can be formally described if an inactivation term is added to the Hodgkin-Huxley equation for potassium currents. Large shifts in the sodium-current inactivation parameter h infinity were produced in some instances. Two fully halogenated methyl ethyl ethers, known to produce convulsions in mice, depressed both sodium and potassium currents, but with a very slow time course of action. The electrophysiological effects of the halogenated ethers investigated appear to depend on the position and number of hydrogen bonds that can be formed.

Animals↗

Accuracy of LED and halogen radiometers using different light sources.

PURPOSE: To determine the accuracy of commercially available, handheld light-emitting diode (LED) and halogen-based radiometers using LED and quartz-tungsten-halogen (QTH) curing lights with light guides of various diameters. METHODS: The irradiance of an LED curing light (L.E. Demetron 1, SDS/Kerr, Orange, CA, USA) and a QTH curing light (Optilux 501, SDS/Kerr) were measured using multiple units of an LED (Demetron L.E.D. Radiometer, SDS/Kerr) and a halogen radiometer (Demetron 100, SDS/Kerr) and compared with each other and to a laboratory-grade power meter (control). Measurements were made using five light guides with distal light guide diameters of 4, 7, 8, 10, and 12.5 mm. For each light guide, five readings were made with each of three radiometers of each radiometer type. Data were analyzed with two-way analysis of variance/Tukey; alpha = 0.05. RESULTS: In general, both handheld radiometer types exhibited significantly different irradiance readings compared with the control meter. Additionally, readings between radiometer types were found to differ slightly, but were correlated. In general, the LED radiometer provided slightly lower irradiance readings than the halogen radiometer, irrespective of light source. With both types of handheld radiometers, the use of the larger-diameter light guides tended to overestimate the irradiance values as seen in the control, while smaller-diameter light guides tended to underestimate. CLINICAL SIGNIFICANCE: The evaluated LED or halogen handheld radiometers may be used interchangeably to determine the irradiance of both LED and QTH visible-light-curing units. Measured differences between the two radiometer types were small and probably not clinically significant. However, the diameter of light guides may affect the accuracy of the radiometers, with larger-diameter light guides overestimating and smaller-diameter guides underestimating the irradiance value measured by the control instrument.

Analysis of Variance↗

Degradation of halogenated aliphatic compounds by Xanthobacter autotrophicus GJ10.

A bacterium that is able to utilize a number of halogenated short-chain hydrocarbons and halogenated carboxylic acids as sole carbon source for growth was identified as a strain of Xanthobacter autotrophicus. The organism constitutively produces two different dehalogenases. One enzyme is specific for halogenated alkanes, whereas the other, which is more heat stable and has a higher pH optimum, is specific for halogenated carboxylic acids. Haloalkanes were hydrolyzed in cell extracts to produce alcohols and halide ions, and a route for the metabolism of 1,2-dichlorethane is proposed. Both dehalogenases show a broad substrate specificity, allowing the degradation of bromine- and chlorine-substituted organic compounds. The results show that X. autotrophicus may play a role in the degradation of organochlorine compounds and that hydrolytic dehalogenases may be involved in the microbial metabolism of short-chain halogenated hydrocarbons in microorganisms.

Biodegradation, Environmental↗

Biosynthesis of halogenated metabolites by bacteria.

Halogenated metabolites, originally thought to be infrequent in nature, are actually nothing unusual at all, and are produced by many different organisms, including bacteria. Whereas marine bacteria usually produce brominated compounds, terrestrial bacteria preferentially synthesize chlorometabolites, but fluoro- and iodometabolites can also be found. Haloperoxidases, enzymes capable of catalyzing the formation of carbon halogen bonds in the presence of hydrogen peroxide and halide ions (Cl-, Br- and I-) have been isolated and characterized from different bacteria. These enzymes turned out to be very unspecific and are obviously not the type of halogenating enzymes responsible for the formation of halometabolites in bacteria. A yet-unknown type of halogenating enzyme having both substrate and regio-specificity must be involved in the biosynthesis of halogenated compounds.

Bacteria↗

The role of halogen substitution in classical cannabinoids: a CB1 pharmacophore model.

The presence of halogens within the classical cannabinoid structure leads to large variations in the compounds' potencies and affinities for the CB1 receptors. To explore the structure activity relationships within this class of analogs we have used a series of halogen-substituted (-)-Delta8-tetrahydrocannabinol analogs and compared their affinities for the CB1 cannabinoid receptor. Our results indicate that halogen substitution at the end-carbon of the side chain leads to an enhancement in affinity with the bulkier halogens (Br, I) producing the largest effects. Conversely, 2-iodo substitution on the phenolic ring leads to a 2-fold reduction in affinity while iodo-substitution in the C1'-position of the side chain lowers the compound's affinity for CB1 by more than 8-fold. The pharmacophoric requirements resulting from halogen-substitution are explored using computer modeling methods.

Animals↗

Effectiveness of composite resin polymerization using light-emitting diodes (LEDs) or halogen-based light-curing units.

The clinical performance of composite resins is greatly influenced by the quality of the light-curing unit used. The aim of this study was to compare the efficiency of a commercial light-emitting diode (LED) with that of a halogen-based light-curing unit by means of dye penetration of a micro hybrid composite resin. The composite resin evaluated was Filtek Z250 (3M Dental). The composite was filled into acrylic moulds that were randomly polymerized for 40 seconds by each of the light-emitting systems: light-emitting diode Ultraled (Dabi Atlante) or halogen light Degulux (Degussa Hülls) curing units. Immediately after polymerization, each specimen was individually immersed in 1 ml of 2% methylene blue solution at 37 degrees C +/- 2 degrees C. After 24 hours, the specimens were rinsed under running distilled water for 1 minute and stored at 37 degrees C +/- 2 degrees C at relative humidity for 24 hours. The composite resins were removed from the moulds and individually triturated before being immersed in new test tubes containing 1 ml of absolute alcohol for 24 hours. The solutions were filtered and centrifuged for 3 minutes at 4,000 rpm and the supernatant was used to determine absorbance in a spectrophotometer at 590 nm. To verify the differences between groups polymerized by LED or halogen light t-test was applied. No significant differences were found between composite resins light-cured by LED or halogen light-curing unit (p > 0.05). The commercially LED-based light-curing unit is as effective to polymerize hybrid composite resins as the halogen-based unit.

Composite Resins↗

A perspective on the environmental risk of halogenated by-products from uses of hypochlorite using a whole effluent toxicity based approach.

An assessment has been made of the potential for toxic effects to aquatic life that may arise from halogenated organic by-products formed by reaction of hypochlorite with organic matter in various use scenarios as a contribution to the risk assessment of sodium hypochlorite under the European Union Existing Chemicals legislation. In the study, samples that would represent worst-case models for effluents containing halogenated by-products from a range of uses of hypochlorite were prepared by chlorinating and then dechlorinating (removing residual chlorine) raw settled sewage (C/D-RSS). This sample was then compared to raw settled sewage that had not been treated (RSS) to assess whether halogenated by-products formed in the chlorination process were toxic or bioaccumulable and persistent. The relative toxicity of the samples was assessed using a series of tests with representatives of different taxonomic groups (bacteria, algae, and invertebrates). The persistence and potential for bioaccumulation of chlorinated by-products was assessed by exposing solid-phase microextraction fibers to samples of RSS and C/D-RSS before and after degradation in a Zahn-Wellens test. For all the taxa tested in the study, the mixture of by-products formed in the C/D-RSS sample did not increase toxicity relative to that measured in the RSS sample. Chlorination of the raw settled sewage did produce additional potentially bioaccumulable halogenated substances compared to the raw settled sewage. However, after degradation, the amount of potentially bioaccumulable halogenated substances in the RSS and C/D-RSS samples was comparable, indicating that these substances were degradable. The results are discussed in the context of the overall risk assessment for sodium hypochlorite.

Adsorption↗

Barcoll hardness of different resin-based composites cured by halogen or light emitting diode (LED).

The clinical performance of light curing resin composites is greatly influenced by the quality of the light-curing unit (LCU). Halogen LCUs are commonly used for curing composite materials. However, they have some drawbacks. The development of new, blue, super bright light emitting diodes (LED LCU) of 470-nm wavelength with high light irradiance comes as an alternative to standard halogen LCUs of 450-470-nm wavelengths. This study evaluated the surface hardness of the different resin-based composites (flowable, hybrid and packable resin composites) cured by LED LCU or halogen LCU. A Teflon mold 10-mm in diameter and 2-mm in depth was made to obtain five disk-shaped specimens for each experimental group. Then, the specimens were cured by an LED LCU or halogen LCU for 40 seconds. The hardness of the upper and lower surfaces was measured with a Barcoll hardness-measuring instrument. The statistical analysis was performed using one-way analysis of variance (ANOVA) and Duncan test at a p=0.05 significance level. The results of the hardness test indicated that the hardness of resin composites cured by an LED LCU were greater than those cured by a halogen LCU. Additionally, for all resin-based composites, the hardness values for the upper surfaces were higher than the lower surfaces. However, for both results no statistically significant differences were observed (p>0.05).

Analysis of Variance↗

[Effect of alpha-halogen-alpha-nitroalkanes on methemoglobin formation and activity of antioxidant enzymes in mouse erythrocytes].

It is shown that 1-chlorine, 1-bromine and 1-iodine-nitroethanes intensify methemoglobin formation in vivo. Such an effect was not revealed for 1-fluorine-1-nitroethane. Change of biochemical parameters of erythrocytes under intoxication by alpha-halogen nitroalkanes in a dose LD50 with the exception for 1-fluorine-1-nitroethane is rather identical with that under the intoxication by soda nitrite which is connected with the generality of reaction mechanism of soda nitrite and alpha-halogen-alpha-nitroalkanes with hemoglobin. Thus the administration of alpha-halogen-alpha-nitroalkanes to laboratory animals leads to the increase of the total activity of dehydrogenases of pentose phosphate way and glutathione reductase of erythrocytes (on the example of 1-iodine-1-nitroethane), the increase of lipoperoxidation (on the example of 1-bromine-1-nitroethane), the decrease of catalase activity. Absence of the inhibition of superoxide dismutase activity was found under the intoxication by all the mentioned drugs. The increase of activity of glutathione reductase of erythrocytes (on the example of (1-iodine-1-nitroethane) under intoxication with alpha-halogen-alpha-alkanes in contrast to intoxication by soda nitrite is explained by some differences of mechanisms of hemoglobin interaction with soda nitrite and alpha-halogen-alpha-nitroalkanes.

Alkanes↗

[On the mechanism of the biological persistence of halogenated and sulfonated aromatic hydrocarbons (author's transl)].

Aromatic compounds with unphysiological substituents like halogen or SO2H-groups are mainly degraded by cometabolism. Investigations with model compounds show, that the negative inductive effect (-I-effect) of the halogen substituents impede the electrophilic attack of the oxygenases, particularly the pyrocatechases. Although the "affinity" of the enzyme for the substrate increases with the number of halogen substituents, the rate of ring cleavage decreases by the presence of halogen substituents. Benzoate oxygenation shows that in certain positions of substitution the -I-effect can be weakened by the + M-effect of the halogen. As soon as aromaticity is lost by the action of dioxygenases, halide can be eliminated with greater ease and total mineralization is possible. When naphthalene-2-sulfonic acid is degraded by a naphthalene utilizing Pseudomonas strain the sulfonic acid group appears to be eliminated oxygenolytically and the carbon skeleton is channelled into the naphthalene pathway.

Alcaligenes↗

N.Br halogen bonding: one-dimensional infinite chains through the self-assembly of dibromotetrafluorobenzenes with dipyridyl derivatives.

The N.Br halogen bonding drives the self-assembly of 1,4-dibromotetrafluorobenzene (1 a) and its 1,3 or 1,2 analogues (1 b,c, respectively) with dipyridyl derivatives 2 a,b. The isomeric supramolecular architectures 3 a-f are obtained as cocrystals that are stable in the air at room temperature. The solid-state features of these 1D infinite chains 3 have been fully characterized by single-crystal X-ray, Raman, and IR analyses. The occurrence of N.Br halogen bonding in solution has been detected with (19)F NMR spectroscopy. The N.Br halogen bonding is highly selective and directional and the geometry of the single strands of noncovalent copolymers 3 is programmed by the geometry of halogen-bonding donor and acceptor sites on the starting modules. The composition and topology of the instructed networks can be predicted with great accuracy. Experiments of competitive cocrystal formation established the strength of the N.Br interaction relative to other halogen bondings and the ability of different modules 1 to be involved in site-selective supramolecular syntheses.

Journal Article↗

Novel halogenated dihydropyridine derivatives with high vascular selectivity.

Calcium channel antagonists of the dihydropyridine type exhibit preferential vasodilator properties. To study whether this vascular selectivity is due to distinct steric modifications or may be influenced by the physicochemical nature of these drugs, contractility in guinea pig heart isolated papillary muscles, vasodilator properties in isolated rabbit femoral arteries and the lipophilicity of some novel halogenated dihydropyridines have been examined. All newly synthesized derivatives exhibited dose-dependent negative inotropic and vasodilator effects. The negative inotropic potency of all the halogenated derivatives was weaker than that of the parent compound nitrendipine. In contrast, compared to nitrendipine the vasodilator potency of the ester substituted derivatives was slightly increased, while halogen substitution in position 2 and 6 of the dihydropyridine nucleus decreased the vasodilator potency. As a result of the different influence on cardiac and vascular smooth muscle an improved vascular selectivity of the drugs was attained. The ester-substituted dihydropyridine derivatives showed a 9 times (3-bromoethyl-nitrendipine) or 11 times (3-chloroethyl-nitrendipine) higher vascular selectivity with respect to nitrendipine. Correlation of the lipophilicity with the physiological properties showed an increase in biological activity with decreasing lipophilicity. Within the ester-halogenated dihydropyridine derivatives an inverse trend was observed (increasing vasodilation with increasing lipophilicity), indicating a different influence of lipophilicity with the ester-substituted compounds on the different tissues examined. The improved vascular selectivity of the novel halogenated dihydropyridines may be at least in part a consequence of the different lipophilicity of the drugs. In addition, differences in the binding affinities of the dihydropyridines subordinate to distinct voltage dependent conformation states of the calcium channel may contribute.

Animals↗

Adaptation of Pseudomonas sp. GJ1 to 2-bromoethanol caused by overexpression of an NAD-dependent aldehyde dehydrogenase with low affinity for halogenated aldehydes.

Pseudomonas sp. GJ1 is able to grow with 2-chloroethanol as the sole carbon and energy source, but not with 2-bromoethanol, which is toxic at low concentrations (1 mM). A mutant that could grow on 2-bromoethanol with a growth rate of 0.034 h-1 at concentrations up to 5 mM was isolated and designated strain GJ1M9. Measurement of enzyme activities showed that mutant and wild-type strains contained a PMS-linked alcohol dehydrogenase that was active with halogenated alcohols and that was threefold overexpressed in the mutant when grown on 2-chloroethanol, but only slightly overproduced when grown on 2-bromoethanol. Both strains also contained an NAD-dependent alcohol dehydrogenase that had no activity with halogenated alcohols. Haloacetate dehalogenase levels were similar in the wild-type and the mutant. Activities of NAD-dependent aldehyde dehydrogenase were only slightly higher in extracts of the mutant grown with 2-bromoethanol than in those of the wild-type grown with 2-chloroethanol. SDS-PAGE, however, showed that this enzyme amounted to more than 50% of the total cellular protein in extracts of the mutant from 2-bromoethanol-grown cells, which was fourfold higher than in extracts of the wild-type strain grown on 2-chloroethanol. The enzyme was purified and shown to be a tetrameric protein consisting of subunits of 55 kDa. The enzyme had low Km values for acetaldehyde and other non-halogenated aldehydes (0.8-4 microM), but much higher Km values for chloroacetaldehyde (1.7 mM) and bromoacetaldehyde (10.5 mM), while V(max) values were similar for halogenated and non-halogenated aldehydes. Cultures that were pregrown on 2-chloroethanol rapidly lost aldehyde dehydrogenase activity after addition of 2-bromoethanol and chloroamphenicol, which indicates that bromoacetaldehyde inactivates the enzyme. To achieve growth with 2-bromoethanol, the high expression of the enzyme thus appears to be necessary in order to compensate for the high Km for bromoacetaldehyde and for inactivation of the enzyme of bromoacetaldehyde.

Acetaldehyde↗

Relationship between the mutagenic and base-stacking properties of halogenated uracil derivatives. The crystal structures of 5-chloro- and 5-bromouracil.

Three-dimensional X-ray diffraction data were used to determine the crystal structures of 5-chlorouracil and 5-bromouracil, two mutagenic pyrimidine analogs that can substitute for thymine in DNA. Crystals of the two compounds are nearly isostructural. The space group is P21/c, with a equals 8.450(6), b equals 6.842(3), c equals 11.072(16) angstrom, beta equals 123.53(19) degrees for 5-chlorouracil, and a equals 8.598(3), b equals 6.886(1), c equals 11.417(5) angstrom, beta equals 123.93(3) degrees for 5-bromouracil. Intensity data were collected with an automated diffractometer. The structures were refined by full-matrix least-squares to R equals 0.058 for 5-chlorouracil and R equals 0.027 for 5-bromouracil. The analogs from planar, hydrogen-bonded ribbons that are nearly identical to those found in the crystal structure of thymine monohydrate. As in many other structures of 5-halogenated uracil derivatives, the bases assume a stacking pattern that permits intimate contacts between the halogen substituents and the pyrimidine rings of adjacent bases. This stacking pattern involves halogen contacts that are significantly shorter than normal van der Waals interactions. The crystallographic results provide additional evidence that halogen substituents influence the stacking patterns of uracil derivatives, while exerting little direct effect on the hydrogen-bonding properties. The observed stacking patterns are consistent with the hypothesis that altered stacking interactions may account for the mis-pairing between 5-halogenated uracil bases and guanine residues within double-helical nucleic acids.

Bromouracil↗

Mutagenic activity of halogenated propanes and propenes: effect of bromine and chlorine positioning.

A series of halogenated propanes and propenes were studied for mutagenic effects in Salmonella typhimurium TA100 in the absence or presence of NADPH plus liver microsomes from phenobarbital-induced rats as an exogenous metabolism system. The cytotoxic and mutagenic effects of the halogenated propane 1,2-dibromo-3-chloropropane (DBCP) has previously been studied in our laboratories. These studies showed that metabolic activation of DBCP was required to exert its detrimental effects. All of the trihalogenated propane analogues were mutagenic when the microsomal activation system was included. The highest mutagenic activity was obtained with 1,2,3-tribromopropane, with approximately 50-fold higher activity than the least mutagenic trihalogenated propane, 1,2,3-trichloropropane. The order of mutagenicity was as follows: 1,2,3-tribromopropane > or = 1,2-dibromo- 3-chloropropane > 1,3-dibromo-2-chloropropane > or = 1,3-dichloro-2-bromopropane >> 1-bromo-2,3-dichloropropane > 1,2,3-trichloropropane. Compared to DBCP, the dihalogenated propanes were substantially less mutagenic. Only 1,2-dibromopropane was mutagenic and its mutagenic potential was approximately 1/30 of that of DBCP. In contrast to DBCP, 1,2-dibromopropane showed similar mutagenic activity with and without the addition of an activation system. The halogenated propenes 2,3-dibromopropene and 2-bromo-3-chloropropene were mutagenic to the bacteria both in the absence and presence of the activation system, whereas 2,3-dichloropropene did not show any mutagenic effect. The large differences in mutagenic potential between the various halogenated propanes and propenes are proposed to be due to the formation of different possible proximate and ultimate mutagenic metabolites resulting from the microsomal metabolism of the various halogenated propanes and propenes, and to differences in the rate of formation of the metabolites. Pathways are proposed for the formation of genotoxic metabolites of di- and trihalogenated propanes and dihalogenated propenes.

Alkenes↗