Human urine certified reference material CZ 6010: creatinine and toluene metabolites (hippuric acid and o-cresol) and a benzene metabolite (phenol)

A reference material for the biological monitoring of occupational exposure to toluene, benzene and phenol was prepared. O-cresol and hippuric acid (metabolites of toluene) are used for the biological monitoring of occupational exposure to toluene. Phenol, a metabolite of benzene, is used for the biological monitoring of exposure to benzene, but phenol can of course also be used as an indicator of exposure to phenol as well. The reference material (RM) used for the determination of these metabolites was prepared by freeze-drying pooled urine samples obtained from healthy persons occupationally exposed to toluene and those taking part in an inhalation experiment. Tests for homogeneity and stability were performed by determining urine concentrations of o-cresol, hippuric acid, creatinine and phenol. To investigate the stability of the RM, the urinary concentrations of o-cresol and phenol were monitored for eighteen months using GC and HPLC, while those of hippuric acid and creatinine were followed for five and six years, respectively, using HPLC. Analysis of variance showed that the concentrations did not change. The certified concentration values (and their uncertainties) of the substances in this reference material (phenol concentration c=6.46+/-0.58 mg l(-1); o-cresol concentration c=1.17+/-0.15 mg l(-1); hippuric acid concentration c=1328+/-30 mg l(-1); creatinine concentration c=0.82+/-0.10 g l(-1)) were evaluated via the interactive statistical programme IPECA.

Electrochemical and In Situ FTIR Study of o-Cresol on Platinum Electrode in Acid Medium

The electrochemical behaviour of o-cresol in acidic medium on platinum electrode has been studied by cyclic voltammetry and in situ Fourier transform infrared spectroscopy. The o-cresol suffers hydrolysis during oxidation giving rise to the formation of methyl-p-benzoquinone. In situ FTIR spectroscopic studies also reveal the presence of CO2, formed as a consequence of the rupture of the aromatic ring. Moreover, the oxidation of o-cresol in acidic medium produces a polymeric film on the platinum surface that precludes further oxidation of o-cresol. The reduction of o-cresol at potentials below 0 V produces in the first step the partial reduction of the aromatic ring and when the potential goes to values below 0 V, methyl-cyclohexanone.

Hierarchical mesoporous Pd/ZSM-5 for the selective catalytic hydrodeoxygenation of m-cresol to methylcyclohexane

Mesopore incorporation into ZSM-5 enhances the dispersion of Pd nanoparticles throughout the hierarchical framework, significantly accelerating m-cresol conversion relative to a conventional microporous ZSM-5, and dramatically increasing selectivity towards the desired methylcyclohexane deoxygenated product. Increasing the acid site density further promotes m-cresol conversion and methylcyclohexane selectivity through efficient dehydration of the intermediate methylcyclohexanol.

Interaction of Phenol, o-Cresol, and p-Cresol with a Clay-Rich Soil Sample.

2010

Metabolic fate of menthofuran in rats. Novel oxidative pathways

Metabolic fate of menthofuran (II) in rats was investigated. Menthofuran (II) was administered orally (200 mg/kg of the body weight/day) to rats for 3 days. The following metabolites were isolated from the urine of these animals: p-cresol (VI), 5-methyl-2-cyclohexen-1- one (VII), 3-methylcyclohexanone (VIII), 3-methylcyclohexanol (IX), 4- hydroxy-4-methyl-2-cyclohexen-1-one (V), geranic acid (XI), neronic acid (XII), benzoic acid (XIII), and 2-[2'-keto-4'- methylcyclohexyl]propionic acid (X). Incubation of menthofuran (II) with phenobarbital-induced rat liver microsomes in the presence of NADPH and oxygen resulted in the formation of a metabolite tentatively identified as 2-Z-(2'-keto-4'-methylcyclohexylidene)propanal (III; alpha,beta-unsaturated-gamma-keto-aldehyde). The structure assigned was further supported by trapping this metabolite (III) as a cinnoline derivative. Phenobarbital-induced rat liver microsomes also converted 4- methyl-2-cyclohexenone (IV) to 4-hydroxy-4-methyl-2-cyclohexenone (V) and p-cresol (VI) in the presence of NADPH and oxygen. On the basis of both in vivo and in vitro studies, a possible mechanism for the formation of p-cresol from menthofuran has been proposed.

Studies on the metabolism of a monoterpene ketone, R-(+)-pulegone-a hepatotoxin in rat: isolation and characterization of new metabolites

1. The metabolic disposition of R-(+)-pulegone (1) was examined in rats following four daily oral doses (250 mg/kg). 2. Six metabolites, namely pulegol (II), 2-hydroxy-2-(1-hydroxy-1-methylethyl)-5-methylcyclohexanone (III), 3,6-dimethyl-7a-hydroxy-5,6,7,7a-tetrahydro-2(4H)-benzofuranone (IV), menthofuran (V), 5-methyl-2-(1-methyl-1-carboxyethylidene)cyclohexanone (VI), and 5-methyl-5-hydroxy-2-(1-hydroxy-1-carboxyethyl)cyclohexanone (VII) have previously been isolated from rat urine, and identified (Moorthy et al. (1989a). Eight new metabolites have now been isolated from rat urine, namely, 5-hydroxy-pulegone (VIII), piperitone (IX), piperitenone (X), 7-hydroxy-piperitone (XI), 8-hydroxy piperitone (XII), p-cresol (XIII), geranic acid (XIV) and neronic acid (XV). These were identified by n.m.r., i.r. and mass spectrometry. 3. Based on these results, metabolic pathways for the biotransformation of R-(+)-pulegone in rat have been proposed.

Planar triazinium cations from vanadyl-mediated ring cyclizations: the thiazole species for efficient nuclear staining and photocytotoxicity

Planar triazinium cationic species from vanadyl-assisted cyclization of 1-(2-thiazolylazo)-2-naphthol (H-TAN, 1), 1-(2-pyridylazo)-2-naphthol (H-PAN, 2), 2-(2'-thiazolylazo)-p-cresol (H-TAC, 3) and 6-(2'-thiazolylazo)- resorcinol (H-TAR, 5) were prepared and characterized. A dioxovanadium(V) species VO2(TAR)] (4) was also isolated. Compounds 1, 2 and 4 were structurally characterized. Both 1 and 2 have planar structures. Complex 4 has (VO3N2)-O-V coordination geometry. The cyclised triazinium compound forms a radical species within -0.06 to -0.29 V vs. SCE in DMF-0.1 M tetrabutylammonium perchlorate with a second response due to formation of an anionic species. A confocal microscopic study showed higher nuclear uptake for 1 having a fused thiazole moiety than 2 with a fused pyridine ring. The compounds showed a partial intercalative mode of binding to calf thymus DNA. Compound 1 showed plasmid DNA photo-cleavage activity under argon and photocytotoxicity in HeLa and MCF-7 cells with IC50 values of 15.1 and 3.4 mu M respectively in visible light of 400-700 nm, while being essentially non-toxic in the dark with IC50 values of 90.4 and 21.9 mu M. ATDDFT study was done to rationalize the experimental data.

Selective and Sensitive Turn-on Chemosensor for Arsenite Ion at the ppb Level in Aqueous Media Applicable in Cell Staining

A newly designed and structurally characterized cell permeable diformyl-p-cresol based receptor (HL) selectively senses the AsO33- ion up to ca. 4.1 ppb in aqueous media over the other competitive ions at biological pH through an intermolecular H-bonding induced CHEF (chelationenhanced fluorescence) process, established by detailed experimental and theoretical studies. This biofriendly probe is highly competent in recognizing the existence of AsO33- ions in a living organism by developing an image under a fluorescence microscope and useful to estimate the amount of arsenite ions in various water samples.

Guide to best practices for ocean CO2 measurements

CHAP 1 - Introduction to the Guide CHAP 2 - Solution chemistry of carbon dioxide in sea water CHAP 3 - Quality assurance CHAP 4 - Recommended standard operating procedures (SOPs) SOP 1 - Water sampling for the parameters of the oceanic carbon dioxide system SOP 2 - Determination of total dissolved inorganic carbon in sea water SOP 3a - Determination of total alkalinity in sea water using a closed-cell titration SOP 3b - Determination of total alkalinity in sea water using an open-cell titration SOP 4 - Determination of p(CO2) in air that is in equilibrium with a discrete sample of sea water SOP 5 - Determination of p(CO2) in air that is in equilibrium with a continuous stream of sea water SOP 6a - Determination of the pH of sea water using a glass/reference electrode cell SOP 6b - Determination of the pH of sea water using the indicator dye m-cresol purple SOP 7 - Determination of dissolved organic carbon and total dissolved nitrogen in sea water SOP 7 en Español - Determinacion de carbono organico disuelto y nitrogeno total disuelto en agua de mar SOP 11 - Gravimetric calibration of the volume of a gas loop using water SOP 12 - Gravimetric calibration of volume delivered using water SOP 13 - Gravimetric calibration of volume contained using water SOP 14 - Procedure for preparing sodium carbonate solutions for the calibration of coulometric CT measurements SOP 21 - Applying air buoyancy corrections SOP 22 - Preparation of control charts SOP 23 - Statistical techniques used in quality assessment SOP 24 - Calculation of the fugacity of carbon dioxide in the pure gas or in air CHAP 5 - Physical and thermodynamic data Errata - to the hard copy of the Guide to best practices for ocean CO2 measurements

Medição experimental e previsão de velocidade do som de componentes de biocombustíveis

A velocidade do som é uma propriedade que vem sendo cada vez mais utilizada em diferentes áreas tecnológicas. Além disso, a velocidade do som é uma propriedade termodinâmica que está associada a outras propriedades do meio como a compressibilidade isentrópica e isotérmica, entre outras. Neste contexto, muitos estudos foram realizados a fim de obter modelos precisos que possam representar fielmente a velocidade do som, sendo observados desvios absolutos médios entre 0,13 e 24,8%. Neste trabalho, um banco de dados de velocidade do som e massa específica à pressão atmosférica de n-alcanos, alcanos ramificados, n-alcenos, aromáticos, alcoóis, éteres e ésteres, foram compilados da literatura aberta. Utilizando estes dados e baseando-se no modelo de Wada por contribuição de grupo recentemente proposto, foi desenvolvido um novo modelo por contribuição atômica para predizer a velocidade do som de todas as famílias dos compostos investigados neste trabalho. É mostrado que o modelo proposto é capaz de prever a velocidade do som para os compostos destas famílias com desvios próximos da incerteza experimental calculada a partir de diferentes dados da literatura. Este trabalho também discute o efeito da ramificação das cadeias na constante Wada, ressaltando a importância de novas medições para este tipo de compostos. Além disso, observou-se que a literatura necessita de mais dados experimentais de velocidade do som, à pressão atmosférica e diferentes temperaturas para substâncias puras presentes em biodiesel e bio-óleo de pirólise rápida. Neste contexto, o presente trabalho fornece novos dados experimentais de velocidade do som e massa específica de cinco ésteres metílicos de ácidos graxos, também conhecidos como FAMEs, (caprilato de metila, caprato de metila, palmitato de metila, estearato de metila e linoleato de metila), e sete componentes puros presentes em bio-óleo de pirólise à pressão atmosférica, de vários fenóis (fenol, o-, m- e p-cresol), dois éteres fenólicos (2-metoxifenol e eugenol) e um éster fenólico (salicilato de metila), a temperaturas de (288,15-343,15) K. O modelo preditivo de Wada atômico foi utilizado para calcular a velocidade do som dos FAMEs estudados neste trabalho, e os desvios foram comparados com o modelo de Wada por contribuição de grupo. O modelo atômico de Wada foi utilizado para prever a velocidade do som dos componentes puros presentes no bio-óleo de pirólise rápida experimentalmente estudados nesta dissertação. Além disso, os dados de massa específica e velocidade de som foram correlacionados com o modelo de Prigogine-Flory-Patterson (PFP). As propriedades foram bem representadas pelo modelo PFP, no entanto, para a velocidade do som o modelo apresenta desvios sistemáticos na dependência com a temperatura. O desempenho do modelo preditivo de Wada atômico foi considerado satisfatório, devido os desvios observados serem compatíveis ou até menores do que os desvios típicos obtidos na literatura com outros modelos correlativos para o cálculo da velocidade do som de outras substâncias

Equilíbrio líquido-líquido entre ácido acético, água e fenólicos: experimental e modelagem

Com o passar do tempo, a população mundial vem se conscientizando mais sobre problemas ambientais. Isso fez surgir uma demanda por tecnologias novas que possam se encaixar no cenário de sustentabilidade. Instabilidades frequentes no cenário político-econômico global acabam por elevar o preço do barril do petróleo. Assim a indústria química começa a buscar por alternativas que tenham a mesma versatilidade do petróleo. Dentre as opções de combustíveis renováveis, destaca-se o bio-óleo de pirólise. Seu interesse em estudos científicos vem do fato de poder-se utilizar do rejeito de processos como matéria prima, não necessitando competir por espaço com a plantação de alimentos. Sua composição pode ser representada por ácidos e fenóis. Em especial destacamos o ácido acético e fenóis oxigenados como m-cresol, o-cresol, p-cresol e guaiacol por estarem presentes em grandes quantidades. Sua separação das frações menos polares do bio-óleo pode ser realizada por meio de extração com água que é um reagente abundante e de baixo custo. O conhecimento das propriedades desses componentes puros é amplamente disponível na literatura, porém dados de composições das fases corrosivas, como misturas ternárias de água-ácido acético-m-cresol/o-cresol/p-cresol/guaiacol nas temperaturas de (298,15, 310,65 e 323,15) K são escassos. Devido a isso, o uso de modelos termodinâmicos para simulação do comportamento desses sistemas torna-se interessante. Todavia, quando são testadas as capacidades dos modelos clássicos, como o UNIFAC e NRTL, percebe-se que os mesmos não conseguem reproduzir o comportamento da binodal dos componentes corrosivos. Sendo assim, essa dissertação investigou soluções para melhorar a descrição desses sistemas, assim como obteve dados experimentais para tais sistemas de misturas ternárias de água-ácido acético-m-cresol/o-cresol/p-cresol/guaiacol nas temperaturas de (298,15, 310,65 e 323,15) K; desenvolveu-se uma metodologia para estimar parâmetros do modelo NRTL a partir de dados de composição da binodal e verificou-se a possibilidade de utilizar o modelo UNIFAC para prever o comportamento de equilíbrio de fases. Como resultado foram obtidos 314 novos dados experimentais, obtiveram-se parâmetros para o modelo NRTL que conseguem reproduzir com acurácia a forma da binodal com a metodologia proposta e verificou-se a necessidade de aperfeiçoamento no estudo do modelo UNIFAC para otimizar sua utilização na previsão do comportamento dos sistemas estudados

Novel proton exchange membranes based on water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)]

Novel water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBIs) were synthesized from 6,6'-disulfonic-4,4'-binaphthy]-1,1',8,8'-tetracarboxylic dianhydride (SBTDA) and various aromatic ether tetraamines. The resulting polymers with IEC in the range of 2.17-2.87 mequiv g(-1) have a combination of desired properties such as high solubility in common organic solvents, film-forming ability, and excellent thermal and mechanical properties. Flexible and tough membranes, obtained by casting from m-cresol solution, had tensile strength, elongation at break, and tensile modulus values in the range of 87.6-98.4 MPa, 35.8-52.8%, and 0.94-1.07 GPa. SPBIBI membranes with a high degree of sulfonation displayed high proton conductivity and a good resistance to water swelling as well. SPBIBI-b with IEC of 2.80 mequiv g(-1) displayed the conductivity of 1.74 x 10(-1) S cm(-1) at 100 degrees C, which was comparable to that of Nafion (R) 117 (1.78 x 10(-1) S cm(-1), at 100 degrees C).

Preparation and evaluation of a proton exchange membrane based on oxidation and water stable sulfonated polyimides

A series of novel oxidation and water stable sulfonated polyimides (SPIs) were synthesized from 4,4'-binaphthyl-1,1',8,8'-tetracarboxylic dianhydride (BTDA), and wholly aromatic diamine 2,2'-bis(3-sulfobenzoyl) benzidine (2,2'-BSBB) for proton exchange membrane fuel cells. These polyimides could be cast into flexible and tough membranes from m-cresol solutions. The copolymer membranes exhibited excellent oxidative stability and mechanical properties due to their fully aromatic structure extending through the backbone and pendant groups. Moreover, all BTDA-based SPI membranes exhibited much better water stability than those based on the conventional 1,4,5,8-naphthalenecarboxylic dianhydride. The improved water stability of BTDA-based polyimides was attributed to its unique binaphthalimide structure. The SPI membranes with ion exchange capacity (IEC) of 1.36-1.90 mequiv g(-1) had proton conductivity in the range of 0.41 x 10(-1) to 1. 12 x 10(-1) S cm(-1) at 20 degrees C. The membrane with IEC value of 1.90 mequiv g(-1) displayed reasonably higher proton conductivity than Nafion((R)) 117 (0.9 x 10(-1) S cm(-1)) under the same test condition and the high conductivity of 0.184 S cm(-1) was obtained at 80 degrees C. Microscopic analyses revealed that well-dispersed hydrophilic domains contribute to better proton conducting properties. These results showed that the synthesized materials might have the potential to be applied as the proton exchange membranes for PEMFCs.

Synthesis and properties of novel organosoluble polyimides derived from 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride and various aromatic diamines

A novel triptycene-based dianhydride, 1,4-bis[4-(3,4-dicarboxylphenoxy)]triptycene dianhydride, was prepared from 4-nitro-N-methylphthalimide and potassium phenolate of 1,4-dihydroxytriptycene (1). The aromatic nucleophilic substitution reaction between 4-nitro-N-methylphthalimide and I afforded triptycene-based bis(N-methylphthalimide) (2), which hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). A series of new polyimides containing triptycene moieties were prepared from the dianhydride monomer (3) and various diamines in in-cresol via conventional one-step polycondensation method. Most of the resulting polyimides were soluble in common organic solvents, such as chloroform, THF, DMAc and DMSO. The polyimides exhibited excellent thermal and thermo-oxidative stabilities with the onset decomposition temperature and 10% weight loss temperature ranging from 448 to 486 degrees C and 526 to 565 degrees C in nitrogen atmosphere, respectively. The glass transition temperatures of the polyimides were in the range of 221-296 degrees C. The polyimide films were found to be transparent, flexible, and tough. The films had tensile strengths, elongations at break, and tensile moduli in the ranges 95-118 MPa, 5.3-16.2%, and 1.03-1.38 GPa, respectively. Wide-angle X-ray diffraction measurements revealed that these polyimides were amorphous.

Synthesis and gas transport property of polyimide from 2,2 '-disubstituted biphenyltetracarboxylic dianhydrides (BPDA)

A series of dianhydride monomers, 2,2'-disubstituted-4,4',5,5'-biphenyltetracarboxylic dianhydride (substituents = phenoxy, p-methylphenoxy, p-tert-butylphenoxy, nitro, and methoxy) were synthesized by the nitration of an N-methyl protected 3,3',4,4'-biphenyttetracarboxylic dianhydride (BPDA) and subsequent aromatic nucleophilic substitutions with aroxides (NaOAr) or methoxide. These dianhydrides were polymerized with various aromatic diamines in refluxing m-cresol containing isoquinoline to afford a series of aromatic polyintides. The effects of varying 2,2'-substituents of the dianhydride (BPDA) moiety on the properties of polyimides were investigated. It was found that polyimides from the dianhydrides containing phenoxy, p-methylphenoxy, and p-tert-butylphenoxy side groups possessed excellent solubility and film forming capability whereas polyimides from 2,2'-dinitro-BPDA and 2,2'-dimethoxy-BPDA were less soluble in organic solvent. The soluble polymers formed flexible, tough and transparent films. The films had a tensile strength, elongation at break, and Young's modulus in the ranges 102-168 MPa, 8-21%, 2.02-2.38 GPa, respectively. The polymer gas permeability coefficients (P) and ideal selectivities for N-2, O-2, CO2 and CH4 were determined for the -OAr substituted polyimides. The oxygen permeability coefficient (P-O2) and permselectivity of oxygen to nitrogen (PO2/N-2) of the films were in the ranges 3.4-11.3 barrer and 3.8-4.6, respectively.