PubMed Health⌕ Search

SEARCH · PubMed Health

Results for “Halogenation”

Explore indexed PubMed citations for clinical trials, systematic reviews and public health research. Read source abstracts and follow each citation to its original PubMed record.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 415 records · Page 23Linked to original sources
PubMedDate not supplied

DOTA-D-Tyr(1)-octreotate: a somatostatin analogue for labeling with metal and halogen radionuclides for cancer imaging and therapy.

The goal of this study was to evaluate a somatostatin receptor ligand, DOTA-D-Tyr(1)-octreotate (DOTA-DY1-TATE), that has the chelator 1,4,7,10-tetraazacyclotetradecane-N,N',N'',N'"-tetraacetic acid (DOTA) attached to the D-Tyr(1) residue, allowing radiolabeling with both radiohalogens and radiometals. A potential advantage of having a chelator attached to the Tyr(1) residue is that halogen radiolabels may residualize or remain trapped in tumor cells rather than clear from the tumor. DOTA-DY1-TATE was synthesized by solid-phase methods and radiolabeled with (61)Cu, (64)Cu, and (125)I in high radiochemical purity and specific activity. A competitive binding assay demonstrated that (nat)Cu-DOTA-DY1-TATE and DOTA-(nat)I-DY1-TATE had comparable affinity to (nat)In-DTPA-OC in AR42J rat pancreatic tumor cells membranes. (61)Cu-DOTA-DY1-TATE had a dissociation constant (K(d)) of 176.4 pM and a receptor concentration (B(max)) of 244.4 fmol/mg. A tumor uptake of 1.515 %ID/g was determined for (64)Cu-DOTA-DY1-TATE and 0.814 %ID/g for DOTA-(125)I-DY1-TATE in AR42J tumor bearing Lewis rats at 1 h postinjection. DOTA-(125)I-DY1-TATE remained in the tumor at a higher concentration out to 4 h postinjection, suggesting that the iodine may have residualized in the tumor cells. MicroPET imaging of (64)Cu-DOTA-DY1-TATE in AR42J tumor bearing rats and SCID mice at 2 h postinjection showed significant uptake and good contrast in the thigh tumors in the rat model and in the neck and thigh tumors of the mouse. This study demonstrates that DOTA-DY1-TATE is a somatostatin analogue that can be labeled with both metal and halogen radionuclides, and its (64)Cu- and (125)I-radiolabeled compounds showed somatostatin receptor-mediated uptake in normal and tumor tissues.

Animals↗
PubMed2001

Photoreductive dehalogenation of halogenated benzene derivatives using ZnS or CdS nanocrystallites as photocatalysts.

ZnS nanocrystallites (nc-ZnS) prepared in N,N-dimethylformamide (DMF) photocatalyze dehalogenation of halogenated benzenes to benzene as the final product from chlorinated benzenes and to difluorobenzenes from fluorinated benzenes in the presence of triethylamine (TEA) as an electron donor under UV light irradiation (lambda > 300 nm). When CdS nanocrystallites (nc-CdS) are used as a photocatalyst (lambda > 400 nm), halogenated benzenes are photoreductively dehalogenated, yielding trichlorobenzene from hexachlorobenzene and tetrafluorobenzene isomers from hexafluorobenzene as the final products. Photoformed electrons on nc-ZnS and nc-CdS have such negative reduction potentials that these electrons reduce polyhalogenated benzenes, leading to the successive dehalogenation. nc-ZnS exhibits higher photocatalytic activitythan nc-CdS due to the more negative potential of the electrons on nc-ZnS than that on nc-CdS. The higher activities of nc-ZnS and nc-CdS compared to their bulk forms are explained as being due to their quantum size effects and the adsorptive interaction between the substrates and the nanosized photocatalysts.

Benzene Derivatives↗
PubMed2001

Halogenated organic contaminants in sediments of the Havel and Spree rivers (Germany). Part 5 of organic compounds as contaminants of the Elbe river and its tributaries.

To give a detailed and comprehensive view on the state of pollution of the Havel and Spree rivers nontarget screening as well as quantitative (target) analyses were applied to anoxic sedimentsamples. Based on nontarget GC/MS analysis a significant contribution to the anthropogenic contamination could be attributed to halogenated compounds. Three groups of contaminants corresponding either to diffuse or local contamination could be distinguished. Several commonly observable compounds including pentachloroanisol, polychlorinated biphenyles, 2,4-dichlorobenzoic acid, and chlorinated benzenes were detected with a distribution reflecting the contribution of nonpoint source emissions. A second group of chlorinated as well as brominated compounds was attributed to a strong point source emission at the Teltow Canal. At the sampling locations influenced by this point source the amount of mono- and dibrominated naphthalenes, chlorinated naphthalenes, and hexachlorocyclohexanes as well as DDT- and methoxychlor-related compounds increased significantly as compared to the background concentrations. A third group of halogen compounds emitted at this site consisted of the pesticides bromopropylate, methoxychlor, and chlorfensone as well as specific brominated aromatics including 2,4,6-tribromoaniline, 4,4'-dibromobenzophenone, and brominated benzenes. In addition, tetrabromochlorotoluenes, tribromodichlorotoluenes, dibromotrichlorotoluenes, and 2,2-bis(4-bromophenyl)acetic acid isopropyl ester were identified and are reported for the first time as environmental contaminants. The amounts of brominated compounds detected in Teltow Canal sediments occurred at a similar concentration level as their chlorinated analogues. Therefore, investigations on the occurrence of such a broad spectrum of brominated compounds as established in this work are presumably required more frequently to assess the environmental impact of this type of emissions.

DDT↗
PubMed2005

Halogen substitution patterns among disinfection byproducts in the information collection rule database.

Disinfection byproduct halogen substitution patterns were examined using Information Collection Rule data. A new metric was developed to quantify and compare extents of specific halogen substitution in different byproduct classes. Bromine substitution in four byproduct classes ranged widely across 6565 samples but strong interdependencies existed between classes on an individual sample basis. Bromine substitution in dihaloacetic acids and trihalomethanes was comparable whereas bromine substitution in trihaloacetic acids and dihaloacetonitriles tended to be 10% lower and 60% higher than in trihalomethanes, respectively. However, these bromine substitution measurements were significantly impacted by censored data handling because reporting limit left-censoring increased with the number of bromine substituents in each class and minimum reporting levels varied between and within classes. Correlation among extents of bromine substitution in the four byproduct classes examined motivated their treatment as a multivariate response with application of a test for multivariate outliers. The test was effective at exposing inconsistencies indicative of data entry or analytical error. This work shows that disinfection byproduct data with full homologue series for multiple compound classes contain redundant information in the form of expected interdependencies among species. Application to quality assurance is demonstrated in this paper. Further applications to modeling and monitoring design are anticipated.

Acetates↗
PubMed2004

Rhodium-catalyzed cycloisomerization of 1,6-enynes with an intramolecular halogen shift: reaction scope and mechanism.

The rhodium(I)-species-catalyzed cycloisomerization reaction of a wide spectrum of 1,6-enynes with an unusual intramolecular halogen shift was investigated. This Rh-catalyzed enyne cyclization reaction represents a new process for the synthesis of stereodefined alpha-halomethylene-gamma-butyrolactones, lactams, tetrahydrofurans, pyrrolidines, and cyclopentanes. Coordinatively unsaturated rhodium species ([Rh(COD)Cl](2) + dppb + AgSbF(6)) only catalyzes the reaction with enyne substrates bearing a Z-form double bond, while neutral rhodium species (RhCl(PPh(3))(3)) could catalyze enyne substrates bearing a Z- or E-form double bond to form the desired products and has a wider substrate scopes. The mechanism of the reaction was studied by the employment of control experiments with different enyne isomers, and a pi-allyl rhodium intermediate was suggested to explain the formation of the cyclic products with an intramolecular halogen shift.

Alkynes↗
PubMed2004

Use of thiazoles in the halogen dance reaction: application to the total synthesis of WS75624 B.

The total synthesis of the pyridine-thiazole-containing natural product WS75624 B (1) is described. This synthesis proceeds via the Stille coupling of appropriately functionalized pyridine and thiazole components, and this paper details our studies on the use of the halogen dance reaction to prepare the desired thiazole. Various halogen dance reactions on thizoles are described, including a novel one-pot multistep reaction in which 2-bromothiazole is treated with LDA in the presence of a silyl chloride at -78 degrees C and quenched with an electrophile to provide the highly functionalized thiazole derivatives 27.

Biological Factors↗
PubMed2006

Effects of halogenated WNA derivatives on sequence dependency for expansion of recognition sequences in non-natural-type triplexes.

Triplex-forming oligonucleotides (TFOs) are sequence-specific DNA-binding agents, but their target duplexes are limited to homopurine/homopyrimidine sequences because of interruption of the pyrimidines bases in the purine region. This problem has not been fully solved despite a wide variety of studies. Recently, we have developed a bicyclic system as a novel scaffold for nucleoside analogues (WNA, W-shaped nucleoside analogues) and determined two useful compounds, WNA-betaT (2) and WNA-betaC (5), for highly stable and selective triplex formation at a TA and a CG interrupting site, respectively. However, subsequent investigations have shown that the triplex formation using WNA is dependent on the neighboring bases of the TFOs. In this study, we have synthesized new WNA derivatives having halogenated recognition bases or benzene rings and evaluated the effects of the modifications on the triplex stability as well as selectivity. It has been found that the WNA-betaT analogues holding 5-halogenated pyrimidine bases (WNA-beta(Br)U (3) and WNA-beta(F)U (4)) exhibit high CG-selectivity. On the other hand, the WNA-betaT derivatives having the bromo-substituted benzene ring (mBr-WNA-betaT (10) and oBr-WNA-betaT (11)) have shown high selectivity to a TA interrupting site with high stability in the sequences to which the original WNA-betaT do not bind. Thus, sequence-dependency has been overcome by the sequence-dependent use of WNA-betaT, mBr-WNA-betaT, and oBr-WNA-betaT.

Base Sequence↗
PubMed2005

The effect of halogen substitution in self-assembled monolayers of 4-mercaptobiphenyls on noble metal substrates.

Self-assembled monolayers (SAMs) formed from 4'-substituted 4-mercaptobiphenyls X-(C6H4)2SH (X-BPT, with X = I, Cl, and F) on polycrystalline (111) gold and silver substrates have been characterized by synchrotron-based high-resolution X-ray photoelectron spectroscopy and angle-resolved near-edge X-ray absorption fine structure spectroscopy. The X-BPT molecules were found to form highly oriented and densely packed SAMs on both substrates, with a smaller molecular inclination in the case of Ag. The experimental data show clear evidence for the charge transfer between the 4'-substituent and biphenyl moieties with the direction and extent of the transfer depending on the electronegativity of the halogen substituent. At the same time, no direct evidence of the charge transfer between the 4'-substituent and the thiolate group was observed. However, the substitution of the 4'-hydrogen by a halogen atom seems to affect the detailed packing arrangements of the SAM constituents.

Halogens↗
PubMed2006

Computational studies on stable triplet states of heteroacetylenes and the effects of halogen substituents.

This paper describes theoretical studies of halogen-substituted heteroacetylenes (XCMY, M = Si and Ge; X, Y = H, Cl and F) performed at the QCISD(T)/6-311G//QCISD/6-31G level of theory. The electronegative halogen substituents destabilize the singlet state such that the triplet state tends to become favorable. The triplet state has the bifunctional electronic structure of a triplet carbene joined to a heavy singlet carbene. We found that the substituents effectively reduce the energy of the donor-acceptor interactions (E(D-A)) between the two in-plane lone pairs of electrons of the singlet state; therefore, the remaining pi bond is less favorable energetically than the triplet state with a sigma bond. A related phenomenon occurs for the homonuclear heavy acetylenes in singlets in which the lead compound RPbPbR switches to a Pb-Pb sigma bond from the pi bonds observed for the lighter acetylenes.

Alkynes↗
PubMed2003

Halogenating enzymes in the biosynthesis of antibiotics.

Using blot hybridization, it has been shown that microorganisms producing halogen-containing antibiotics--Pseudomonas pyrrocinia, P. aureofaciens ACN, P. aureofaciens Pa1, P. fluorescens CHA0, Actinoplanes sp., Kitasatasporia sp., Sacharothrix aerocolonigenes, Actinomadura melliaura, and Streptomyces albogriseolus--contain the genes of the halogenating enzymes related to tryptophan-7-halogenase and monodechloroaminopyrrolnitrin halogenase from P. fluorescens BL 915.

Anti-Bacterial Agents↗
PubMed2003

Flame retardants in the indoor environment -- Part II: release of VOCs (triethylphosphate and halogenated degradation products) from polyurethane.

Organophosphate esters, halogenated and non-halogenated, are frequently used for fire protection of building materials. With regard to toxicological profiles it is desired to avoid human exposure in the indoor environment. Moreover, some hazardous volatile organic compounds detected in indoor air are directly linked to the utilization of flame retardants. In this study, different polyurethane (PUR) products for building and indoor use treated with organophosphate flame retardants were tested in 1 m(3) emission test chambers. Emissions of flame retardants and degradation products were measured under living conditions. A PUR hard foam sample showed area-specific emission rates >100 microg/m(2) h for the compound triethylphosphate. During the tests several chlorinated degradation products of organophophorous flame retardants could be identified in the chamber air.

Air Pollution, Indoor↗
PubMed2003

Allylic halogenation of unsaturated amino acids.

A range of dehydro amino acid derivatives has been prepared and subjected to halogenation using either molecular bromine or chlorine, or NBS. Allylic halogenation of the unsaturated amino acid side chains occurs through radical bromination with NBS. The procedure is complementary to treatment with chlorine, which also affords allyl halides. This latter and unusual reaction is shown through a deuterium labelling study to proceed via an ionic mechanism. The choice of NBS or chlorine for allyl halide synthesis is shown to depend on the potential to avoid competing reactions, such as halolactonization of leucine derivatives with chlorine, and hydrogen abstraction and bromine incorporation at multiple sites on treatment of isoleucine derivatives with NBS. The synthetic utility of the allyl halides prepared in this study is indicated through the synthesis of a cyclopropyl amino acid derivative and the extension of the carbon skeleton of an amino acid side chain.

Allyl Compounds↗
PubMed1978

Chemical structure and biodegradability of halogenated aromatic compounds. Substituent effects on 1,2-dioxygenation of catechol.

1. The influence of halogen substituents on the 1,2-dioxygenation of catechols was investigated. The results obtained with the two isoenzymes pyrocatechase I and pyrocatechase II from the haloarene-utilizing Pseudomonas sp. B 13 and the pyrocatechase from benzoate-induced cells of Alcaligenes eutrophus B.9 were compared. 2. Substituents on catechol were found to interfere with O2 binding by the two isoenzymes from Pseudomonas sp. B 13, whereas the Km value for catechol kept constant at different O2 concentrations. 3. Electron-attracting substituents decreased the Km values for catechols. 4. Results from binding studies with substituted catechols demonstrated narrow stereospecificities of pyrocatechase I from pseudomonas sp. B 13 and the pyrocatechase from alcaligenes eutrophus B.9. In contrast, a low steric hindrance by substituents in the binding of catechols with pyrocatechase II was observed. 5. Low pK'1 values of substituted catechols resulted in low Michaelis constants. 6. Electron-attracting substituents such as halogen decreased the reaction rates of catechol 1,2-dioxygenation. The correlation of the Vmax. values observed with pyrocatechase II from Pseudomonas sp. B 13 with the substituent constant sigma+ (Okamoto--Brown equation) was distinctly greater than with Hammett's sigma values. The corresponding logVmax. against sigma+ correlation for pyrocatechase I was considerably disturbed by steric influences of the substituents.

Alcaligenes↗
PubMed2006

The origin of stable halogenated compounds in volcanic gases.

BACKGROUND: Halogenated compounds in the atmosphere are of great environmental concern due to their demonstrated negative effect on atmospheric chemistry and climate. Detailed knowledge of the emission budgets of halogenated compounds has to be gained to understand better their specific impact on ozone chemistry and the climate. Such data are also highly relevant to guide policy decisions in connexion with international agreements about protection of the ozone layer. In selected cases, the relevance of specific emission sources for certain compounds were unclear. In this study we present new and comprehensive evidence regarding the existence and relevance of a volcanic contribution of chlorofluorocarbons (CFCs), hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), halons (bromine containing halo(hydro)carbons), and fully fluorinated compounds (e.g. CF4 and SF6) to the atmospheric budget. METHODS: In order to obtain new evidence of a volcanic origin of these compounds, we collected repeatedly, during four field campaigns covering a period of two years, gases from fumaroles discharging over a wide range of temperatures at the Nicaraguan subduction zone volcanoes Momotombo, Cerro Negro and Mombacho, and analysed them with very sensitive GC/MS systems. RESULTS AND DISCUSSION: In most fumarolic samples certain CFCs, HFCs, HCFCs, halons, and the fully fluorinated compounds CF4 and SF6 were present above detection limits. However, these compounds occur in the fumarole gases in relative proportions characteristic for ambient air. CONCLUSION: This atmospheric fingerprint can be explained by variable amounts of air entering the porous volcanic edifices and successively being incorporated into the fumarolic gas discharges. Recommendation and Outlook. Our results suggest that the investigated volcanoes do not constitute a significant natural source for CFCs, HFCs, HCFCs, halons, CF4, SF6 and NF3.

Air Pollutants↗
PubMed1978

The detection and identification of unknown halogenated compounds in environmental samples.

A new method is described in which the mass spectrometer is an element specific detector for a gas chromatograph. The elements investigated in this study are F, Cl, Br, J, S and N, but the method might be applied to other elements as well. The molecules coming from the gas chromatograph are atomized in a microwave induced discharge, located in the interface between the gaschromatograph and the mass spectrometer. Unknown compounds containing specific elements can be detected and their retention times can be determined. The method is applied to samples of surface water, fat of a grebe and human adipose tissue for halogenated compounds. Unknown halogenated compounds were found. A number of them were identified in samples of surface water.

Adipose Tissue↗
PubMed1981

Experiences in human milk analysis for halogenated hydrocarbon residues.

Factors affecting the different stages of human milk analysis for halogenated hydrocarbon residues are explored. The variation in milk fat during breast feeding and its consequences for sampling are outlined. Extraction efficiency is discussed in terms of fat content, residue recovery and sample size. The importance of clean-up procedures is illustrated by the removal of fat from the extract and unknown contaminants from adsorbents. Polychlorinated biphenyls (PCBs) are partially separated from other halogenated hydrocarbon residues on a Florisil-silicic acid column. Both packed and capillary gas chromatographic columns can be used for identification and quantification of residues in human milk. Confirmation by chemical derivation and mass spectrometry is illustrated by the perchlorination of PCBs and PCB isomer distribution respectively. Fortification of samples and the use of a collaborative study are described as a means for method evaluation.

Chromatography, Gas↗
PubMed2006

Adsorbable organic halogens (AOXs) in solid residues from hazardous and clinical waste incineration.

Trace concentrations of a variety of chemicals remain in solid residues following combustion even in properly designed and operated incinerators. In the present study, the adsorbable organic halogen (AOX) levels of the solid residues, i.e., bottom ash, fly ash, and filter cake, were investigated during a 82-day of continuous operation of a Hazardous and Clinical Waste Incinerator. The distribution of halogens in the waste input prior to the incineration was also determined. The AOX levels measured in bottom ash, fly ash and filter cake were in the range of 0.014-1.879, 0.012-0.263, and 0.004-0.062 mg-Cl(-)/kg, respectively. The AOX levels are significantly low in the fly ash and filter cake due to the post-combustion process in the incinerator. At the end of the 82 days, the total AOX output in the bottom ash, fly ash, and filter cake were 571, 3.71, and 6.26 g, respectively. The partitioning of the total AOX in solid residues was 98.28, 0.64, and 1.08% for the bottom ash, fly ash and filter cake, respectively. This shows that the bottom ash is more contaminated with AOX than the other two residues.

Adsorption↗