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Breakdown products on metabolic pathway of degradation of benz[a]anthracene by a ligninolytic fungus.

Cultures of the ligninolytic fungus Irpex lacteus incubated in a nutrient liquid medium degraded more than 70% of the initially applied benz[a]anthracene within 14 days. At the first step of metabolization, benz[a]anthracene was transformed via a typical pathway of ligninolytic fungi to benz[a]anthracene-7,12-dione (BaAQ). The product was further transformed by at least two ways, whereas one is complied with the anthracene metabolic pathway of I. lacteus. Benz[a]anthracene-7,12-dione was degraded to 1,2-naphthalenedicarboxylic acid and phthalic acid that was followed with production of 2-hydroxymethyl benzoic acid or monomethyl and dimethylesters of phthalic acid. Another degradation product of BaAQ was identified as 1-tetralone. Its transformation via 1,4-naphthalenedione, 1,4-naphthalenediol and 1,2,3,4-tetrahydro-1-hydroxynaphthalene resulted again in phthalic acid. None of the intermediates were identified as dead-end metabolites. Metabolites produced by ring cleavage of benz[a]anthracene using the ligninolytic fungus are firstly presented in this work.

Basidiomycota↗

Competitive adsorption of organic matter with phosphate on aluminum hydroxide.

The effects of orthophosphate on the adsorption of natural organic matter (NOM) on aluminum hydroxide were investigated using three organic compounds as surrogates, including humic acid (HA), phthalic acid, and 2,3-dihydroxybenzoic acid (2,3-DHBA). The adsorption of phthalic acid and 2,3-DHBA was very limited compared to that of HA, whereas their adsorption was reduced much more significantly than that of HA by phosphate. The efficiency of phosphate in reducing HA adsorption increased with increasing phosphate concentration. Phosphate adsorption was slightly reduced by phthalic acid and 2,3-DHBA but moderately suppressed by HA. The adjacent carboxylic groups mainly contributed to the adsorption of humic acid at low pH, while the adjacent phenol groups were responsible for the adsorption of humic acid at high pH. HPLC-SEC and SUVA analysis revealed that HA molecules with high molecular weight were adsorbed preferentially but were easily displaced by the specifically adsorbed phosphate. TM-AFM images revealed that the aggregation of HA molecules and the protonation of carboxylic groups at low pH facilitated the adsorption under acidic conditions. The presence of phosphate increases the coagulant dosage for NOM removal as some sites on the coagulant precipitates become utilized by phosphate.

Journal Article↗

Comparative study of the uterotrophic potency of 14 chemicals in a uterotrophic assay and their receptor-binding affinity.

We performed an immature rat uterotrophic assay of 14 chemicals having various receptor-binding affinities in order to assess the relationship between their uterotrophic potency and receptor-binding affinity. The chemicals tested were phthalic acid di-n-hexyl ester, phthalic acid di-n-amyl ester, phthalic acid di-n-propyl ester, 2-ethylhexyl-p-hydroxybenzoate, 4,4'-biphenol, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenylmethane, 2,4-dihydroxybenzophenone, 4,4'-cyclohexylidenebisphenol, 4-t-butylpyrocatechol, clomiphene citrate, 4,4'-(1,3-phenylenediisopropylidene)bisphenol, p-t-butylphenol, and diallylterephthlate. Two of the 14 chemicals, phthalic acid di-n-propyl ester and diallylterephthlate, exhibited no receptor-binding affinity, and the receptor-binding affinity of phthalic acid di-n-hexyl ester and phthalic acid di-n-amyl ester was lower than that of the other chemicals. Ten of the chemicals showed uterotrophic potency, the exceptions being phthalic acid di-n-propyl ester, diallylterephthlate, phthalic acid di-n-hexyl ester, and phthalic acid di-n-amyl ester. The results of the present study demonstrate that the affinity of the chemicals in the receptor-binding assay correlated well with their potency in the uterotrophic assay except for a few chemicals with very low receptor-binding affinity.

Animals↗

Comparison of the Hershberger assay and androgen receptor binding assay of twelve chemicals.

We performed the Hershberger assay of 12 chemicals based on the OECD draft protocol. The chemicals tested by the Hershberger assay were phthalic acid di-n-hexyl ester, phthalic acid di-n-amyl ester, phthalic acid di-n-propyl ester, diethylstilbestrol, 17beta-estradiol, tamoxifen, 5alpha-dihydrotestosterone, dichlorodiphenyldichloroethane, cyproterone acetate, 6alpha-methyl-17alpha-hydroxy-progesterone, atrazine, and spironolactone. Phthalic acid di-n-hexyl ester, phthalic acid di-n-amyl ester, and phthalic acid di-n-propyl ester are phthalates; diethylstilbestrol and 17beta-estradiol are estrogenic chemicals; tamoxifen is partial estrogen receptor antagonist with mainly estrogenic properties; 5alpha-dihydrotestosterone is an androgen derivatives; dichlorodiphenyldichloroethane is a reference androgen antagonistic chemical; cyproterone acetate, 6alpha-methyl-17alpha-hydroxy-progesterone, and spironolactone have an androgenic steroid structure and are known as androgen antagonistic chemicals; and atrazine is a reference endocrine disruptor. We also subjected these chemicals to the receptor binding assay for androgen. A clear androgen agonistic effect was detected in 5alpha-dihydrotestosterone, and an androgen antagonistic effect was observed in five chemicals: cyproterone acetate, spironolactone, 6alpha-methyl-17alpha-hydroxy-progesterone, phthalic acid di-n-amyl ester, and dichlorodiphenyldichloroethane. By contrast, diethylstilbestrol, 17beta-estradiol, tamoxifen, 5alpha-dihydrotestosterone, dichlorodiphenyldichloroethane, cyproterone acetate, 6alpha-methyl-17alpha-hydroxy-progesterone, and spironolactone were positive in the receptor binding assay for androgen. Three estrogenic chemicals, diethylstilbestrol, 17beta-estradiol, and tamoxifen, were negative in the Hershberger assay with receptor binding affinity. On the other hand, the Hershberger assays of three phthalates were performed at the same dosages, and the results showed androgen antagonistic affinity only in the assay of phthalic acid di-n-amyl ester without receptor binding affinity.

Administration, Oral↗

Toxicity of mono- and diesters of o-phthalic esters to a crustacean, a green alga, and a bacterium.

The degradation of phthalic acid diesters may lead to formation of o-phthalic acid and phthalic acid monoesters. The ecotoxic properties of the monoesters have never been systematically investigated, and concern has been raised that these degradation products may be more toxic than the diesters. Therefore, the aquatic toxicity of phthalic acid, six monoesters, and five diesters of o-phthalic acid was tested in three standardized toxicity tests using the bacteria Vibrio fischeri, the green algae Pseudokirchneriella subcapitata, and the crustacean Daphnia magna. The monoesters tested were monomethyl, monoethyl, monobutyl, monobenzyl, mono(2-ethylhexyl), and monodecyl phthalate, while the diesters tested were dimethyl, diethyl, dibutyl, butylbentyl, and di(2-ethylhexyl)phthalate, which were assumed to be below their water solubility. The median effective concentration (EC50) values for the three organisms ranged from 103 mg/L to >4.710 mg/L for phthalic acid, and corresponding values for the monoesters ranged from 2.3 mg/L (monodecyl phthalate in bacteria test) to 4,130 mg/L (monomethyl phthalate in bacteria test). Dimethyl and diethyl phthalate were found to be the least toxic of the diesters (EC50 26.2-377 mg/L), and the toxicity of the other diesters (butylbenzyl and dibutyl phthalate) ranged from 0.96 to 7.74 mg/L. In general, the phthalate monoesters (degradation products) were less toxic than the corresponding diesters (mother compounds).

Animals↗

Fluorescence and FT-IR spectroscopic studies of Suwannee River fulvic acid complexation with aluminum, terbium and calcium.

In this study fluorescence emission and IR spectroscopy have been used to investigate the interaction of the class A (oxygen seeking "hard acid") metal Al(3+), with Suwannee River fulvic acid. Addition of Al(3+) ion results in a significant enhancement in fulvic acid fluorescence emission (at lambda(em)=424 nm) and significant red shift of the excitation wavelength (from lambda(ex)=324 nm to lambda(ex)=344 nm) at low pH values (pH approximately 4.0-5.0). At pH 4.0 (0.1 M ionic strength), where the predominant aluminum ion species is the "free" (aquo) ion, the fulvic acid fluorescence reaches 142% of the value in the absence of added metal ion. Analysis of the pH 4.0 and pH 5.0 fluorescence enhancement data with the nonlinear (single site) model of Ryan and Weber indicated binding constants in the range of 4.67.10(4)-2.87.10(6) M(-1) and concentrations of ligand sites in the range of 18.6.10(-6)-24.0.10(-6) M, both consistent with previous studies performed on both aquatic and soil fulvic acids. Companion fluorescence experiments performed on two other class A metal ions, Ca(2+) and Tb(3+), indicated no significant enhancement or quenching with Ca(2+) and only slight quenching with Tb(3+). Comparison of FT-IR spectra collected on fulvic acid alone and fulvic acid in the presence of the three class A metals (Al(3+), Ca(2+) and Tb(3+)) provides strong evidence for the involvement of carboxyl carbonyl functions in the binding of all three metal ions, which is not unexpected. The spectra also reveal, however, a very pronounced difference in the 4000-2000 cm(-1) IR spectral region between the Al(3+) spectrum and the Ca(2+) and Tb(3+) spectra. The -OH stretch spectral region in the Al(3+) spectrum has a major component shifted to higher energy (compared to fulvic acid alone or to fulvic acid in the presence of Ca(2+) or Tb(3+)). Even more striking is the emergence of a pronounced IR band at 2407 cm(-1), which is present only in the Al(3+) spectrum. The results of fluorescence and IR experiments with the model compounds salicylic acid and phthalic acid further confirm that both salicylic acid-like sites and phthalic acid-like sites are likely complexation sites for Al(3+) in fulvic acid and are major contributors to the observed spectroscopic changes associated with Al(3+) ion complexation. From a comparison of both the fluorescence and IR spectral results for all three class A metals, differing most strongly in the value of their ionic index, it seems clear that major sources of the deviation in spectral properties between Al(3+) and Ca(2+)/Tb(3+) is the unusually high value of its charge density and relatively low propensity for involvement in covalent bonding interactions (very high ionic index and relatively low covalent index in the Nieboer and Richardson classification of environmental metals), as well as affinity for certain functional groups.

Aluminum↗

NTP Toxicology and Carcinogenesis Studies of Diethylphthalate (CAS No. 84-66-2) in F344/N Rats and B6C3F1 Mice (Dermal Studies) with Dermal Initiation/ Promotion Study of Diethylphthalate and Dimethylphthalate (CAS No. 131-11-3) in Male Swiss (CD-1(R)) Mice.

Diethylphthalate and dimethylphthalate are used as phthalate plasticizers, in an extensive array of products. The chronic dermal toxicity of diethylphthalate was evaluated in male and female F344/N rats and B6C3F1 mice in 2-year studies. In a series of special studies, the tumor initiation or promotion potential of diethylphthalate or dimethylphthalate was evaluated in male Swiss (CD-1(R)) mice by an initiation/promotion model of skin carcinogenesis. The genetic toxicity of diethylphthalate and dimethylphthalate in Salmonella typhimurium and cultured Chinese hamster ovary cells was also evaluated. 4-WEEK STUDY IN F344/N RATS: Groups of 10 male and 10 female rats were dermally administered diethylphthalate at volumes of 0, 37.5, 75, 150, or 300 &mgr;L (0, 46, 92, 184, or 369 &mgr;g) applied neat, 5 days per week for 4 weeks. All male and female rats survived to the end of the study. No evidence of dermatotoxicity was observed, with no adverse clinical signs observed and no effects on weight gain or feed consumption. Relative liver weights of 300 &mgr;L males and females and 150 &mgr;L females were greater than those of controls. Relative kidney weights of 150 and 300 &mgr;L males and 150 &mgr;L females were greater than those of controls. No other adverse effects were observed in this study. 4-WEEK STUDY IN B6C3F1 MICE: Groups of 10 male and 10 female mice were dermally administered diethylphthalate at volumes of 0, 12.5, 25, 50, or 100 &mgr;L (0, 15, 31, 62, or 123 &mgr;) applied neat, five days per week for 4 weeks. One control female died before the end of the study; all other mice survived. No evidence of dermatotoxicity or other adverse clinical signs were observed, and no clear adverse effects on weight gain or feed consumption were seen. Absolute and relative liver weights of 25 and 100 &mgr;L females were greater than those of the controls. Based on these 4-week study results, doses of 0, 35, and 100 &mgr;L diethylphthalate were recommended for the 2-year mouse studies. A chronic study in male and female B6C3F1 mice at 0, 35, and 100 &mgr;L (applied neat, once per day, 5 days per week) was started and subsequently stopped after 32 weeks when significant body weight reductions were noted in treated animals (males and females, 100 &mgr;L groups: 19% lower; males, 35 &mgr;L group: 12% lower; females, 35 &mgr;L group: 10% lower than controls). Based on these body weight reductions, doses of 0, 7.5, 15, and 30 &mgr;L in 100 &mgr;L acetone were recommended for the restart of the 2-year mouse study. 2-YEAR STUDY IN F344/N RATS: Based upon the results of the 4-week study, doses of 0, 100, or 300 &mgr;L diethylphthalate (0, 123, or 369 &mgr;) were chosen for the 2-year rat study. Groups of 60 male and 60 female rats received the doses applied neat 5 days per week for 103 weeks and up to 10 animals per group were evaluated after 15 months. Survival, Body Weights, and Clinical Findings: Survival of dosed rats during the first 15 months was similar to that of controls. However, 2-year survival was significantly reduced in all groups of male rats (survival probabilities, males: 0 &mgr;L, 8%; 100 &mgr;L, 12%; and 300 &mgr;L, 12%). The mean body weights of 300 &mgr;L males were slightly less than those of the controls throughout the study. No adverse clinical signs were observed, including no evidence of dermatotoxicity. Pathology Findings: No morphological evidence of dermal or systemic toxicity was observed in male or female rats. Skin neoplasms were not observed in female rats and were only rarely observed in male rats. A high incidence of anterior pituitary adenoma occurred in all groups of male and female rats. The incidence of anterior pituitary adenomas in the 0, 100, and 300 &mgr;L groups were: males, 39/44, 41/49, 41/49; females, 38/50, 33/49, 33/48. The incidence of this benign tumor in control males (84%) exceeded the historical control mean incidence [feed controls, (28.7%)] and range (12% to 60%). Anterior pituitary adenomas were considered a primary contributing factor in the increased mortality observed in all grtor in the increased mortality observed in all groups, regardless of treatment. A dose-related decreasing trend in the incidence of mammary gland fibroadenomas was observed in female rats (21/50, 12/48, 7/50). The incidence of mononuclear cell leukemia in male rats in this study was lower than the historical incidence and may be attributable to the shortened life span of male rats. Similarly, the incidence of interstitial cell tumors of the testes was markedly decreased in all groups of males (4/50, 3/50, 8/50), relative to historical control rates (90.1%; range 74%-98%). The incidence of fatty liver degeneration was notably lower in dosed rats than in controls (males: 26/50, 8/50, 4/51; females: 23/50, 11/50, 3/50). 2-YEAR STUDY IN B6C3F1 MICE: Groups of 60 male and 60 female mice received doses of 0, 7.5, 15, or 30 μL diethylphthalate (0, 9, 18, or 37 μ) in 100 μL acetone 5 days per week for 103 weeks with a 1 week recovery period, and up to 10 animals per group were evaluated after 15 months. Survival, Body Weights, and Clinical Findings: Two-year survival of dosed mice was similar to that of controls: 43/50, 41/48, 46/50, and 43/50 (males), and 41/50, 38/51, 37/49, and 36/49 (females). Mean body weights of dosed male and female mice were similar to those of the controls throughout the study. No adverse clinical signs were observed in mice, including no gross evidence of dermatotoxicity. Feed consumption by male and female mice was similar to or up to 13% greater than that by controls. Pathology Findings: No morphological evidence of dermal toxicity was observed in male or female mice. No skin neoplasms were observed in dosed male mice. In female mice receiving 30 μL, one squamous cell carcinoma and one basal cell carcinoma were seen at the site of application. An increased incidence of liver neoplasms was observed in dosed male and female mice. The incidence of hepatocellular adenoma or carcinoma (combined) in B6C3F1 mice in the 0, 7.5, 15, and 30 μL groups were: (males) 9/50, 14/50, 14/50, and 18/50; (females) 7/50, 16/51, 19/50, and 12/50. The incidence of adenoma or carcinoma (combined) was increased in 30 μL male mice and the incidences of adenoma and of adenoma or carcinoma (combined) were increased in 7.5 and 15 μL females. A positive dose-related trend in the incidence of adenoma or carcinoma (combined) was also observed in male mice. The incidence of basophilic hepatic foci was increased in 15 μL male mice (0/50, 1/50, 9/50, 3/50). The increased incidence of liver neoplasms in this study was considered equivocal because the incidence of hepatocellular neoplasms in control and dosed males was within the historical range and because there was no clear dose-response relationship in females. No other treatment-related findings were observed in this study. 1-YEAR INITIATION/PROMOTION STUDY IN MALE SWISS (CD-1®) MICE: Groups of 50 male mice were dosed dermally with diethylphthalate or dimethylphthalate to study their effect as initiators and promoters. Diethylphthalate and dimethylphthalate were tested as initiators with and without the known skin tumor promoter 12-O-tetradecanoylphorbol-13-acetate (TPA). Diethyl phthalate and dimethylphthalate were tested as promoters with and without the known skin tumor initiator 7,12-dimethylbenzanthrancene (DMBA). Comparative control groups used during the study of diethylphthalate and dimethylphthalate included: vehicle control (acetone/acetone); initiation/promotion control (DMBA/TPA); initiator control (DMBA/acetone); and promoter control (acetone/TPA). Based on the incidence of skin neoplasms diagnosed histologically and the multiplicity of skin neoplasms, there was no suggestion that either diethylphthalate or dimethylphthalate was able to initiate skin carcinogenesis when chronically promoted by TPA. Further, there was no evidence that either diethylphthalate or dimethylphthalate was able to promote skin carcinogenesis in skin previously initiated with DMBA. High incidences of both squamous cell papillomas and squamous cell carcinomas occurred among the initiation/promotion control animals initiated with DMBA and promoted with TPA. All TPA-dosed groups had significantly greater incidences of dermal acanthosis, ulceration, exudation, and hyperkeratosis than controls. GENETIC TOXICOLOGY: Neither diethylphthalate (10-10,000 μ/plate) nor dimethylphthalate (33-6,666 μ/plate) induced gene mutations in Salmonella typhimurium strains TA98, TA100, TA1535, or TA1537, with or without rat and hamster liver S9. In cultured Chinese hamster ovary cells, both diethylphthalate and dimethylphthalate induced sister chromatid exchanges in the presence of S9. Neither induced sister chromatid exchanges in the absence of S9. Neither chemical induced chromosomal aberrations, with or without S9, in cultured Chinese hamster ovary cells. CONCLUSIONS: Under the conditions of these 2-year dermal studies, there was no evidence of carcinogenic activity of diethylphthalate in male or female F344/N rats receiving 100 or 300 μL. The sensitivity of the male rat study was reduced due to low survival in all groups. There was equivocal evidence of carcinogenic activity of diethylphthalate in male and female B6C3F1 mice based on increased incidences of hepatocellular neoplasms, primarily adenomas. In an initiation/promotion model of skin carcinogenesis, there was no evidence of initiating activity of diethylphthalate or dimethylphthalate in male Swiss (CD-1®) mice. Further, there was no evidence of promotion activity of diethylphthalate or dimethylphthalate in male Swiss (CD-1®) mice. The promoting activity of TPA following DMBA initiation was confirmed in these studies. Minor dermal acanthosis was observed following dermal application of diethylphthalate in male and female F344/N rats dosed for 2 years and in male Swiss (CD-1®) mice dosed for 1 year. Synonyms: Diethylphthalate (CAS No. 84-66-2): 1,2-benzenedicarboxylic acid, diethyl ester; DEP; diethyl 1,2-benzenedicarboxylate; diethyl o-phthalate; diethyl phthalate; ethyl phthalate; o-benzenedicarboxylic acid diethyl ester; phthalic acid, diethyl ester; RCRA U088 Dimethylphthalate (CAS No. 131-11-3): 1,2-benzenedicarboxylic acid, dimethyl ester; dimethyl 1,2-benzenedicarboxylate; dimethyl benzene-o-dicarboxylate; dimethyl benzeneorthodicarboxylate; dimethyl o-phthalate; dimethyl phthalate; DMP; FIFRA 028002; methyl phthalate; go-dimethyl phthalate; phthalic acid, dimethyl ester; phthalic acid methyl ester; RCRA U102

Journal Article↗

Enhancement of the mutagenicity of amino acid pyrolysates by phthalate esters.

The ability of phthalic acid, phthalic acid anhydride, and various phthalate esters to enhance the mutagenicity of many amino acid pyrolysates was observed with the Ames test (Salmonella typhimurium TA98), but not the SOS Chromotest. Phthalate enhancement of the mutagenicity of 4-nitroquinoline-1-oxide, 2-nitrofluorene, and benzo[a]pyrene was not observed with either test. The mutagenicity-enhancing ability may be related to the induction of enzymes such as P450IIB, that metabolize amino acid pyrolysates. By quantitative structure activity relationship (QSAR) analysis, a good correlation was observed between the mutagenicity-enhancing activity of phthalates and their octanol-water partition coefficients.

1-Octanol↗

The endocrine disruptor nonylphenol preferentially blocks cyclooxygenase-1.

The anthropogenic chemicals nonylphenol, bisphenol A, phthalic acid benzyl n-butyl ester, phthalic acid di-n-butyl ester and phthalic acid di(2-ethylhexyl) ester have been shown to possess sex hormone-like activity. To explore the possible actions of these chemicals on the autacoid synthesis in the body, we investigated the effects of nonylphenol, bisphenol A, phthalic acid benzyl n-butyl ester, phthalic acid di-n-butyl ester and phthalic acid di(2-ethylhexyl) ester on the activities of cyclooxygenase-1 and -2. Bisphenol A and all three phthalic acid derivatives had no significant effect on the cyclooxygenase-1 and -2 activities up to 100 microM. On the other hand, nonylphenol exhibited a marked inhibition on the cyclooxygenase-1 activity (10-100 microM nonylphenol, 7-95% inhibition), with no detectable change in the activity of cyclooxygenase-2. The inhibition patterns for the substrate, arachidonic acid, and a cofactor, phenol, were competitive and uncompetitive, respectively. These results suggest that nonylphenol can be a selective inhibitor of cyclooxygenase-1 activity.

Animals↗

[Analysis of low-polarity constituents of Reniochalina sp. by gas chromatography-mass spectrometry].

The sponge of Reniochalina sp. was collected from China Yellow Sea. The specimen (dry weight 100 g) was repeatedly extracted with cyclohexane. The combined crude extract was then evaporated in vacuo, and the dark red residue (5 g) was subjected to a silica gel column for chromatographic separation using gradient mixtures of ethyl acetate and cyclohexane as eluents. The fraction eluted with ethyl acetate-cyclohexane (1:9, v/v) was repeatedly separated by preparative liquid chromatography (HiQ sil C18-10 column, 250 mm x 21.2 mm i.d. ) to afford sample B and sample C as dark red oil. These two low-polarity samples were analyzed by gas chromatography-mass spectrometry (GC-MS) equipped with an HP-5 column (30 m x 0.25 mm i.d.). The oven temperature was raised from 40 degrees C to 250 degrees C at 10 degrees C /min and kept at 250 degrees C for 70 min. Using GC-MS coupled with 1H-nuclear magnetic resonance (1H-NMR), 18 compounds including alkanes, alkenes, fatty acids, fatty acid esters, phthalic acid and phthalic esters, were identified. The results provide to be helpful for in taxonomy of Reniochalina.

Alkanes↗

In situ infrared spectroscopic analysis of the adsorption of aromatic carboxylic acids to TiO2, ZrO2, Al2O3, and Ta2O5 from aqueous solutions.

In situ infrared spectroscopy has been used to investigate the adsorption of a range of simple aromatic carboxylic acids from aqueous solution to metal oxides. Thin films of TiO2, ZrO2, Al2O3 and Ta2O5 were prepared by evaporation of aqueous sols on single reflection ZnSe prisms. Benzoic acid adsorbed very strongly to ZrO2, in a bridging bidentate fashion, but showed only weak adsorption to TiO2 and Ta2O5. Substituted aromatic carboxylic acids; salicylic, phthalic and thiosalicylic, were found to adsorb to each metal oxide. Salicylic and phthalic acids adsorbed to the metal oxides via bidentate interactions, involving coordination through both carboxylate and substituent groups. Thiosalicylic acid adsorbed to the metal oxides as a bridging bidentate carboxylate with no coordination through the thiol substituent group.

Aluminum Oxide↗

Determination of stable carbon isotopic compositions of low molecular weight dicarboxylic acids and ketocarboxylic acids in atmospheric aerosol and snow samples.

We report a new method developed for the determination of stable carbon isotopic composition of homologous alpha,omega-dicarboxylic acids and phthalic acid isolated from environmental samples such as atmospheric aerosols and snow. Dicarboxylic acids are derivatized with BF3/1-butanol to dibutyl esters, which are analyzed for the stable carbon isotopic composition using a capillary GC interfaced to on-line combustion isotope ratio mass spectrometer. The delta13C values for individual dicarboxylic acid are then calculated from delta13C of 1-butanol and butyl ester derivative using a mass balance equation. The accuracy of the delta13C measurement for C2-C10 diacids is within 0.8 per thousand. We report a few examples of the delta13C ratios of saturated C2-C9 alpha,omega-dicarboxylic acids, unsaturated (maleic, phthalic) diacids, and oxocarboxylic acids in the aerosol and snow samples.

Journal Article↗

Transfer of some carboxylic acids in the olfactory system following intranasal administration.

The uptake of [14C]benzoic acid, 4-chloro[14C]benzoic acid, [3H]phthalic acid and [14C]salicylic acid in the nasal passages and brain was determined following a unilateral intranasal instillation in mice. An uptake of radioactivity from the nasal mucosa to the ipsilateral olfactory bulb was observed up to 4 h after administration following intranasal instillation of these carboxylic acids whereas the level was low in the contralateral olfactory bulb. Autoradiography of mice given [14C]benzoic acid and [14C]salicylic acid by intranasal instillation showed a preferential localization of radioactivity in the axonal and glomerular layer of the olfactory bulb 1 h after the administration. Four hours after administration the radioactivity was present as a gradient from the axonal layer towards the center of the olfactory bulb. Pretreatment of mice with a compound known to damage the olfactory neuroepithelium resulted in a decreased uptake of [14C]benzoic acid in the olfactory bulb. Thin layer chromatography of supernatants from the ipsilateral olfactory bulbs of mice given [14C]benzoic acid by nasal instillation indicated that the radioactivity in the bulbs represented unchanged compound. These results suggest that there is a transfer of some aromatic carboxylic acids in the olfactory pathways.

Administration, Intranasal↗

Vacancy ion-exclusion chromatography of aromatic carboxylic acids on a weakly acidic cation-exchange resin.

Determination of aromatic carboxylic acids by conventional ion-exclusion chromatography is relatively difficult and methods generally rely on hydrophobic interaction between the solute and the resin. To overcome the difficulties in determining aromatic carboxylic acids a new approach is presented, termed vacancy ion-exclusion chromatography, which is based on use of the sample as mobile phase and an injection of aqueous 10% methanol onto a weakly acidic cation-exchange column (TSKgel OApak-A). Highly sensitive conductivity detection occurred with sharp and well-shaped peaks, leading to very efficient separations. The effects of sulfuric acid concentration added to the mobile phase, flow-rate, and column temperature on the retention volume of tested aromatic carboxylic acids was investigated. Retention times were found to be affected by the concentration of the analytes in the mobile phase and to some extent also by the addition of an organic modifier such as methanol to the injected water sample. Separation of sulfuric acid (SA), naphthalenetetracarboxylic acid (NTCA), phthalic acid (PA) and benzoic acid (BA) was satisfactory using this new approach. Detection limits were 0.66, 0.67, 0.42 and 0.86 microM and detector responses were linear in the range 1-100, 1-80, 2.5-100 and 10-40 microM, for SA, NTCA, PA and BA, respectively. Precision for retention times was 0.36% and for peak areas was 1.5%.

Benzoic Acid↗

[Effect of organic acids adsorption on catalytic ozonation with metal oxides].

The effectiveness of ozonation, adsorption and catalytic ozonation with ferric hydroxide (FeOOH) and cerium dioxide (CeO2) as catalysts on removal of several organic acids were investigated. The organic acids selected were benzoic acid (BA), phthalic acid (PA), commercial humic acid (CHA), and humic acid of Songhua River water (SHA) concentrated with reverse osmosis (RO). FeOOH was active in catalytic ozonation of the non-adsorbable BA, with 45% of BA removal higher than ozonation alone. It was inactive in case of ozonation of PA, the adsorption of which on FeOOH caused 5% reduction of its concentration. CeO2 enhanced ozonation of PA that was strongly adsorbed, but not for the non-adsorbed BA. Oxalate ions as product of oxidation of PA were also removed by CeO2 catalytic ozonation. As adsorption of humic acids on CeO2 is stronger than that on FeOOH, its catalytic removal by CeO2 was more than by FeOOH. The activity of catalytic ozonation of humic acids was scavenged in case of competition for adsorption sites on the catalysts by inorganic anions.

Adsorption↗

Multiwavelength spectrophotometric determination of acid dissociation constants: Part II. First derivative vs. target factor analysis.

PURPOSE: Acid dissociation constants (pKa values) denote the extent of ionization of drug molecules at different pH values, which is important in understanding their penetration through biological membranes and their interaction with the receptors. However, many drug molecules are sparingly soluble in water or contain ionization centres with overlapping pKa values, making precise pKa determination difficult using conventional spectrophotometric titration. In this work, we investigate a multiwavelength spectrophotometric titration (WApH) method for the determination of pKa values. METHODS: Spectral changes which arise during pH-metric titrations of substances with concentration of about 10(-5) M were captured by means of an optical system developed in this study. All experiments were carried out in 0.15 M KCI solution at 25 +/- 0.5 degrees C. Mathematical treatments based on the first derivative spectrophotometry procedure and the target factor analysis method were applied to calculate the pKa values from the multiwavelength absorption titration data. RESULTS: pKa values were determined by the WApH technique for six ionizable substances, namely, benzoic acid, phenol, phthalic acid, nicotinic acid, p-aminosalicylic acid and phenolphthalein. CONCLUSIONS: The pKa values measured using the WApH technique are in excellent agreement with those measured pH-metrically. We have demonstrated that the first derivative spectrophometry procedure provides a relatively simple way to visualize the pKa values which are consistent with those determined using the target factor analysis method. However, for ionization systems with insufficient spectral data obtained around the sought pKa values or with closely overlapping pKa values, the target factor analysis method outperforms the first derivative procedure in terms of obtaining the results. Using the target factor analysis method, it has been shown that the two-step ionization of phenolphthalein involves a colorless anion intermediate and a red colored di-anion.

Benzoic Acid↗

Metabolism of benzoic acid by bacteria: 3,5-cyclohexadiene-1,2-diol-1-carboxylic acid is an intermediate in the formation of catechol.

3,5-Cyclohexadiene-1,2-diol-1-carboxylic acid (1,2-dihydro-1,2-dihydroxy-benzoic acid) is converted enzymatically to catechol in cell extracts from Acinetobacter, Alcaligenes, Azotobacter, and three Pseudomonas species. This enzymatic activity is present only in cultures which have been grown in the presence of benzoic acid, and which convert benzoic acid to catechol rather than to protocatechuic acid. The reaction is assayed by the concomitant formation of reduced nicotinamide adenine dinucleotide from nicotinamide adenine dinucleotide. The conversion of [(14)C]benzoic acid to [(14)C]dihydrodihydroxybenzoic acid is demonstrated in cell extracts. A scheme for the conversion of benzoic acid to catechol in bacteria is presented, involving the formation of dihydrodihydroxybenzoic acid from benzoic acid by a dioxygenase which is unstable in cell extracts, followed by the dehydrogenation and decarboxylation of dihydrodihydroxybenzoic acid to catechol by a previously undescribed enzyme. Experiments with anthranilic acid and phthalic acid suggest that dihydrodihydroxybenzoic acid is a metabolite unique to benzoic acid metabolism. Two new methods for assaying benzoic acid dioxygenase are suggested.

Acids↗

Determination of 2,4,6-triiodoresorcinol and other side reaction products and intermediates in the colour additive FD&C Red No. 3 (erythrosine) using high-performance liquid chromatography.

An HPLC method was developed for the quantitative determination of 2,4,6-triiodoresorcinol (I3R), 2-(2',4'-dihydroxy-3',5'-diiodobenzoyl)benzoic acid, resorcinol, phthalic acid, and sodium iodide in the colour additive FD&C Red No. 3 (erythrosine) (R3). Due to the fast decomposition of I3R in aqueous solutions, the dye portions analysed were dissolved in methanol and the determinations were performed in the freshly-made solutions. The HPLC method is rapid (50 min total analysis cycle, approximately 16 min to detect I3R and the other intermediates), simple to implement, and generates only small amounts of solvent waste. It was found to be applicable for use in routine batch-certification as shown by the analysis of test portions from 24 lots of R3 submitted for US-certification by domestic and foreign manufacturers during the past three years.

Benzoates↗