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At least 19 recordsLinked to original sources

Inhibitory and excitatory effects of iodobenzene on the antennal benzoic acid receptor cells of the female silk moth Bombyx mori L.

As shown in single-sensillum recordings, iodobenzene has a bimodal effect on the receptor cell tuned to benzoic acid (BA) of the female silk moth Bombyx mori. Exposure to iodobenzene causes an inhibition of the response to BA. With stimulation by iodobenzene alone, a reduction of basic nerve impulse firing during exposure is followed by a transient post-stimulus excitation (rebound). We suggest that inhibition suppresses excitation during exposure but fades afterwards more rapidly than excitation. Due to the spatial equivalence of the iodine and the acid residue, these effects might indicate opposing interactions of iodobenzene with the specific site for the key compound BA. This is supported by the fact that substitutions by smaller halogens are less effective in both inhibition and rebound. The inhibitory effect but not the rebound with iodobenzene alone was also observed in receptor cells tuned to key compounds other than benzoic acid, e.g. in the cell most sensitive to 2,6-dimethyl-5-heptene-2-ol (DMH-cell) occurring in the same sensillum as the BA-cell, or in the bombykol- and bombykal-cells of the male. At least in these cells the inhibitory effect might reflect the action of iodobenzene on a general site, e.g. the lipid matrix of the plasma membrane of the receptor cells.

Aniline Compounds↗

Assembly of linear clusters of iodobenzene dimers on Cu(110).

Low-temperature STM observations of the low-coverage chemisorption behavior of iodobenzene on Cu(110) are presented at two annealing temperatures. When a random distribution of isolated iodobenzene molecules deposited at T < 100 K is annealed to approximately 170 K, the undissociated molecules assemble into chainlike clusters composed of identical subunits. An STM tip-induced dissociation reaction is used to determine that the individual units in the chains are composed of pairs of iodobenzene molecules. A model is proposed in which iodine atoms on each member of the pair are directed toward one another. The driving force for the formation of such clusters is suggested to be the dispersion interactions between the polarizable iodobenzene molecules.

Letter↗

Iodobenzene-catalyzed alpha-acetoxylation of ketones. in situ generation of hypervalent (diacyloxyiodo)benzenes using m-chloroperbenzoic acid.

Reported here for the first time is the iodobenzene-catalyzed alpha-oxidation of ketones, in which diacyloxy(phenyl)-lambda3-iodanes generated in situ act as real oxidants of ketones and m-chloroperbenzoic acid serves as a terminal oxidant. Oxidation of a ketone with m-chloroperbenzoic acid in acetic acid in the presence of a catalytic amount of iodobenzene, BF3.Et2O, and water at room temperature under argon affords an alpha-acetoxy ketone in good yield. p-Methyl- and p-chloroiodobenzene also serve as efficient catalysts in this direct oxidation. We found that when the reaction was carried out in the absence of a catalytic amount of iodobenzene, Baeyer-Villiger oxidation of a ketone took place. It is noted that use of water and BF3.Et2O is crucial to the success of this alpha-acetoxylation.

Journal Article↗

Glutathione depletion, lipid peroxidation, and liver necrosis following bromobenzene and iodobenzene intoxication.

NMRI Albino mice, in which the hepatic glutathione (GSH) content was decreased by nearly 50% by either the administration of a pure glucose diet or by starvation, were intoxicated with aryl halides, bromobenzene, and iodobenzene (13 and 9 mmol/kg body weight, respectively, p.o.). After both intoxications, the hepatic glutathione content decreased rapidly to very low values, and liver necrosis, as assessed by serum transaminase levels, occurred in about 45 or 60% of the animals (in the case of bromobenzene or iodobenzene, respectively) after a lag phase of 9 or 6 hr. In both instances liver necrosis was evident only when the hepatic GSH depletion reached a threshold value (3.5-2.5 nmols/mg protein). The same threshold value was evident for the occurrence of lipid peroxidation (measured as both carbonyl functions and conjugated dienes in liver phospholipids). The possibility that the depletion in hepatic GSH level is capable of inducing lipid peroxidation and necrosis could be supported by the fact that similar results were obtained after the administration of inethylmaleate (12 mmol/kg, p.o.), a drug which is expected to conjugate directly with GSH without previous metabolism. The covalent binding of reactive metabolites to cellular macromolecules was determined in the case of bromobenzene poisoning. A dissociation between liver necrosis and covalent binding was observed in experiments in which Trolox C, a lower homolog of vitamin E, was administered (270 mumol/kg) 9 and 13 hr after bromobenzene poisoning. The treatment with Trolox C, in fact, almost completely prevented both liver necrosis and lipid peroxidation, while the extent of the covalent binding of bromobenzene metabolites to liver proteins was not altered.

Animals↗

[Depletion of liver glutathione induced by iodobenzene poisoning and its relation to lipid peroxidation and necrosis].

The mechanisms underlying iodobenzene hepatotoxicity were investigated in Albino mice in which the hepatic glutathione (GSH) content had been decreased by nearly 50% by starvation for 16 h before poisoning. After iodobenzene administration (9 mmol/Kg, p.o.) the hepatic GSH content decreased progressively and liver necrosis, as measured by the plasma transaminase (GPT, GOT) levels, occurred in many animals at 12 and 16 h. A clear cut necrosis was evident only when the hepatic GSH depletion reached a threshold value (3.5-2.5 nmol/mg protein). The same threshold value was evident for the occurrence of lipid peroxidation (measured as both carbonyl functions and conjugated dienes in liver phospholipids). The highly significant correlation found between lipid peroxidation and liver necrosis supports the possibility of a cause-effect relationship between the two phenomena.

Alanine Transaminase↗

Heck reactions of iodobenzene and methyl acrylate with conventional supported palladium catalysts in the presence of organic and/or inorganic bases without ligands

The vinylation of iodobenzene with methyl acrylate has been studied with several supported palladium catalysts in N-methylpyrrolidone in the presence of triethylamine and/or sodium carbonate. The reaction can be performed in air without any solubilizing or activating ligands. It was found that significant amounts of palladium leach out into the solvent and these dissolved Pd species essentially catalyze the reaction. It is interesting, however, that almost all the palladium species in the solution can redeposit onto the surface of the supports after the reaction has been completed (at 100% conversion of iodobenzene). Thus, the catalysts were recyclable without loss of activity. The use of both inorganic and organic bases is very effective in the promotion of the palladium redeposition as well as in the enhancement of the reaction rate. For Heck reactions with bromobenzene and chlorobenzene it was found that the use of triethylamine and sodium carbonate increases the selectivity of the Heck coupling product (benzene is also produced for these two substrates), but the mixed bases do not affect the overall rate of reaction as much.

Journal Article↗

A numerical modelling of voltammetric reduction of substituted iodobenzenes reaction series. A relationship between reductions in the consecutive-mode multistep system and a multicomponent system. Determination of the potential variation of the elementary charge transfer coefficient.

The cyclic voltammetry reduction process of the reaction series of substituted iodobenzenes X-C6H4-I where X = H, p-Cl, p-Br, p-I, p-CH3, m-CF3 was investigated in 0.3 M TBAP in DMF. A numerical model of the process consistent with the ECE mechanism of mono-iodobenzenes reduction and consecutive ECE-ECE reduction of p-diiodobenzene was applied. On the basis of alpha(i) vs. E(p,i) dependence, the value of delta a(i)/delta E was found to be 0.37 +/- 0.07 for first electron transfer (Eq. (10)). The ECE-ECE system seems to be an another example of elementary alpha kinetic discrimination between two identical two-electron processes analogous to that described in a previous paper (Sanecki, P., Kaczmarski, K. (1999). J. Electroanal. Chem. 471, 14 and erratum to it (2001)). A method of simultaneous treatment of the substrate and all electroactive intermediates, i.e. the transformation of any experimental consecutive CV reduction curves (e.g. ECE or ECE-ECE) into curves corresponding to reduction of the multi-component systems is presented and discussed.

Journal Article↗

Palladium-catalyzed coupling of allylboronic acids with iodobenzenes. Selective formation of the branched allylic product in the absence of directing groups.

Palladium-catalyzed coupling reactions of functionalized allylboronic acids with iodobenzenes were achieved under standard Suzuki-Miyaura coupling conditions. The coupling reactions afforded selectively the branched allylic products in high to excellent yields. In contrast to palladium-catalyzed nucleophilic substitution reactions proceeding via (eta3-allyl)palladium intermediates, this process does not require directing groups in the allyl moiety to achieve substitution at the congested allylic terminus. The regioselectivity of the process was largely unaffected by the substituent effects of the iodobenzenes and the allylic substrates.

Journal Article↗

On the evaluation of quadratic response functions at the four-component Hartree-Fock level: nonlinear polarization and two-photon absorption in bromo- and iodobenzene.

The nonlinear polarization and two-photon absorption parameters have been determined for dibromo- and di-iodobenzene in their meta- and ortho-conformations and with relativistic effects accounted for to a varying degree. By exclusion of small component integrals in the calculations of the first-order hyperpolarizability, results within 1% of fully relativistic four-component Hartree-Fock values are obtained at a cost of 8.7 times the corresponding nonrelativistic calculations. It is shown that the nonlinear absorption in bromobenzene (and even more so in iodobenzene) is broad banded due to spin-orbit interactions among the excited states, and nonrelativistic and scalar relativistic calculations are not to be used in this case.

Journal Article↗

Optical constants, dielectric constants, molar absorption coefficients, molar polarizability, vibrational assignment and transition moments of liquid iodobenzene between 4000 and 400 cm(-1) at 25 degrees C.

This paper reports the complex refractive index, molar absorption coefficient and imaginary molar polarizability spectra of liquid iodobenzene at 25 degrees C. The imaginary molar polarizability spectrum was fitted with 184 classical damped harmonic bands to determine the integrated intensity of the individual transitions. The standard deviation of the fitted spectrum from the experimental spectrum is 0.024 cm(3) mol(-1), and the R(2) value of the fit is 0.9968 indicating that the fitted spectrum is an accurate representation of the experimental spectrum. The dipole moment derivatives with respect to the normal coordinates and transition moments were determined for 26 of the 30 fundamentals. The total intensities of the in-plane and out-of-plane fundamentals were compared to benzene and other monosubstituted benzene derivatives using the F-sum rule. It was found that the total intensity of the out-of-plane fundamentals is essentially the same for the different compounds while the total intensities for the in-plane fundamentals varies according to the electronegativities of the substituents.

Iodobenzenes↗

Chemoenzymatic synthesis of carbasugars from iodobenzene.

The versatile enantiopure cis-dihydrodiol metabolite 1, formed by bacterial metabolism of iodobenzene, has been used for the synthesis of the pyranose carbasugars (pseudosugars) carba-beta-D-altropyranose 2, carba-alpha-L-galactopyranose 3, carba-beta-D-idopyranose 4 and carba-beta-L-glucopyranose 5. Substitution of the iodine atom by a carbomethoxy group, stereoselective catalytic hydrogenation of an alpha,beta-unsaturated ester, and regioselective inversion of one or two allylic chiral centres are the key steps used in the synthesis of carbasugars 2-5. The relative and absolute configurations of compounds 2-5 were established by a combination of stereochemical correlation, X-ray crystallography and 1H-NMR spectroscopy.

Carbohydrates↗

Liver glutathione depletion induced by bromobenzene, iodobenzene, and diethylmaleate poisoning and its relation to lipid peroxidation and necrosis.

The mechanisms of bromobenzene and iodobenzene hepatotoxicity in vivo were studied in mice. Both the intoxications caused a progressive decrease in hepatic glutathione content. In both instances liver necrosis was evident only when the hepatic glutathione depletion reached a threshold value (3.5-2.5 nmol/mg protein). The same threshold value was evident for the occurrence of lipid peroxidation. Similar results were obtained in a group of mice sacrificed 15-20 hours after the administration of diethylmaleate, a drug which is mainly conjugated with hepatic glutathione without previous metabolism. The correlation between lipid peroxidation and liver necrosis was much more significant than that between covalent binding and liver necrosis. This fact supports the view that lipid peroxidation is the major candidate for the liver cell death produced by bromobenzene intoxication. Moreover, a dissociation of liver necrosis from covalent binding was observed in experiments in which Trolox C (a lower homolog of vitamin E) was administered after bromobenzene poisoning. The treatment with Trolox C, in fact, almost completely prevented both liver necrosis and lipid peroxidation, while not changing at all the extent of the covalent binding of bromobenzene metabolites to liver protein.

Alanine Transaminase↗

Effect of iodobenzene therapy on mitochondrial activity in 2-thiouracil-induced hypothyroidism in weanling rats.

Hypothyroidism was produced in weanling albino rats by the oral administration of 2-thiouracil (TU) for 110 days. These animals recorded nearly 50 per cent reduction in mitochondrial oxidation of succinate, protein content and the activity of inner mitochondrial membrane-bound beta-hydroxybutyrate dehydrogenase. Administration of iodobenzene (IB; 0.1 microgram/rat/day) and L-thyroxine (T4; 0.6 microgram/rat/day) to two sets of hypothyroid rats restored the reduced oxidation rate, enzyme activity and protein content to near normal values. IB was comparable to T4 and may act as a thyroid stimulant.

Animals↗

Internal energy content of n-butylbenzene, bromobenzene, iodobenzene and aniline molecular ions generated by two-photon ionization at 266 nm. A photodissociation study

A technique to investigate photodissociation kinetics on a nanosecond time scale has been devised for molecular ions generated by multiphoton ionization (MPI) using mass-analyzed ion kinetic energy spectrometry. The branching ratio or rate constant has been determined for the photodissociation of the n-butylbenzene, bromobenzene, iodobenzene, and aniline molecular ions generated by MPI at 266 nm. The ion internal energies have been estimated by comparing the measured kinetic data with the previous energy dependence data. The analysis has shown that only those molecular ions generated by two-photon ionization contribute to the photodissociation signals. Around half of the available energy has been found to remain as molecular ion internal energy in the two-photon ionization process. Copyright 1999 John Wiley & Sons, Ltd.

Journal Article↗

Pharmacokinetics and metabolism of the novel synthetic C-nucleoside, 1-(2-deoxy-beta-D-ribofuranosyl)-2,4-difluoro-5-iodobenzene: a potential mimic of 5-iodo-2'-deoxyuridine.

1-(2-Deoxy-beta-D-ribofuranosyl)-2,4-difluoro-5-iodobenzene (5-IDFPdR) is one of the several unnatural 1-(2-deoxy-beta-D-ribofuranosyl)-2,4-difluoro-5-substituted-benzenes recently synthesized for evaluation as anticancer, antiviral and diagnostic imaging agents. This class of C-nucleosides was designed to exploit several potential advantages relative to classical 5-substituted-2'-deoxyuridines, including stability towards phosphorolysis by pyrimidine phosphorylase, increased lipophilicity that may alter their ability to cross the blood-brain-barrier, and a greater resistance towards catabolism and deiodination. The physiochemical evaluation of 5-IDFPdR showed high lipophilicity (log P = 2.8), moderately high protein binding (70-75%), stability towards phosphorolysis (e.g. no evidence of metabolic deglycosylation) by thymidine phosphorylase, and minimal microsomal metabolism in vitro. Pharmacokinetic studies of 5-IDFPdR in rat were characterized by a short elimination half-life (9-12 min), modest urinary elimination in pooled 0-24 h urine specimens (10-14%, including 2% as unconjugated drug) and high oral bioavailability (F = 0.96). Both glucuronide and sulfate metabolites were present in urine. Glucuronidation was the predominant conjugation pathway.

Animals↗

Dose-dependent pharmacokinetics of 1-(2-deoxy-beta-D- ribofuranosyl)-2,4-difluoro-5-iodobenzene: a potential mimic of 5-iodo-2'-deoxyuridine.

The dose-range pharmacokinetics of l-(2-deoxy-beta-D-ribofuranosyl)-2,4-difluoro-5-iodobenzene (5-IDFPdR), a C-aryl nucleoside mimic of IUdR, were studied in male Sprague-Dawley rats following single intravenous (i.v.) and oral doses. After i.v. administration, the blood clearance decreased from approximately 32 ml/min/kg at a dose of 15 mg/kg, to approximately 19 ml/min/kg when dosed at 54 mg/kg, and the elimination half-life increased from 8.4 min to 21.5 min, for the respective doses. While the dose-normalized area under the concentration-time curve (AUCnorm) remained practically unchanged (0.132 kg min ml(-1)) upon increasing the i.v. dose from 5 to 15 mg/kg, it increased by about 44% ( approximately 0.19 kg min ml(-1)) when the i.v. dose was increased from 15 to 54 mg/kg. Similarly, there was a dose-dependent increase in AUCnorm with increasing oral doses: AUCnorm increased by 49% as the oral dose increased from 20 to 40 mg/kg, and further by 55% as the oral dose was increased from 40 mg/kg to 54 mg/kg. For the respective oral doses, the elimination half-life increased from 24.5 min to 176 min, while blood clearance was reduced from approximately 37 ml/min/kg to approximately 17 ml/min/kg. The urinary recoveries of unchanged 5-IDFPdR and its glucuronides (as percent of the dose) were somewhat increased at higher doses. This increase was more pronounced following the highest oral dose. The total biliary recovery of 5-IDFPdR (as percent of the dose) was, however, decreased with increasing doses. The overall kinetic profile of 5-IDFPdR based on these data is suggestive of dose-dependent pharmacokinetics. Decreased elimination of 5-IDFPdR with increasing dose, as supported by longer elimination half-lives at higher doses, is one likely mechanism contributing to the dose-dependent behaviour of this compound. Saturable non-renal metabolism might explain the reduced total body clearance of 5-IDFPdR at higher doses, despite the unchanged or increased urinary clearance. For drugs exhibiting nonlinear kinetics, the dosage regimens may need to be carefully designed to avoid potential unpredictable toxicity and/or lack of pharmacological response associated with the disproportional changes in steady state drug concentrations on changing dose. Manifestation in the rat of nonlinear kinetics at doses of 5-IDFPdR, which may be of therapeutic relevance, warrants extended dose-range evaluations of this compound in future preclinical and clinical studies, to establish safe and efficacious dosage regimens.

Administration, Oral↗