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Photodegradation of haloacetic acids in water.

The global distribution and high stability of some haloacetic acids (HAAs) has prompted concern that they will tend to accumulate in surface waters and pose threats to humans and the ecosystem. It is important to study the degradation pathways of HAAs in aqueous systems to understand their ecotoxicological effects. Previous studies involving thermal degradation reactions show relatively long lifetimes for HAAs in the natural environment. Photolysis and photocatalytic dissociation are potentially efficient routes for the degradation of HAAs such as trichloroacetic acid to hydrochloric acid, carbon dioxide and chloroform, although such processes are poorly understood in surface waters. In our present study, we have used light to degrade the HAAs in the presence of titanium dioxide suspensions. All chloro and bromo HAAs degrade in photocatalysis experiments and the rate of degradation is directly proportional to the number of halogen atoms in the acid molecule. The half-lives of the HAAs from the photodegradation at 15 degrees C in the presence of suspended titanium dioxide photocatalyst are 8, 14, 83 days for the tri-, di- and mono-bromoacetic acids. Tri-, di- and mono-chloroacectic acids have half-lives of 6, 10 and 42 days respectively. The mixed bromochloro and chlorodifluoroacetic acids degrade with half-lives of 18 and 42 days respectively. Our results therefore suggest that the photocatalytic process can provide an additional degradation pathway for the HAAs in natural waters.

Acetates↗

Lysozyme purification from tobacco extract by polyelectrolyte precipitation.

Tobacco is widely used as a model plant for feasibility studies of recombinant protein production from transgenic plants. However, dealing with large quantities of biomass to recover recombinant proteins is a challenge for down-stream processing. In this study, the effect of isoelectric precipitation on native tobacco protein was first studied. Among the three acids studied, hydrochloric acid is shown to be more effective than acetic or citric acid, and at pH 4, 60% of native tobacco protein was precipitated by HCl. Egg white lysozyme was used as the model protein to test the feasibility of polyelectrolyte precipitation in protein recovery from tobacco extract. Precipitation of lysozyme at pH 7 was shown ineffective probably because of the interference of polyphenolic acids. However, after isoelectric precipitation at pH 5 poly(acrylic) acid (PAA) was shown to precipitate 85% of the soluble lysozyme when the polymer dosage was increased to 1.5 mg polymer/mg lysozyme, while negligible amounts of native tobacco protein was co-precipitated. Lysozyme precipitation by PAA in tobacco extract obtained at pH 5 was also studied, and lysozyme yield was significant improved.

Chemical Precipitation↗

Investigation of the formation of N-nitrosodiethanolamine in B6C3F1 mice following topical administration of triethanolamine.

To determine potential nitrosation of triethanolamine (TEA) to N-nitrosodiethanolamine (NDELA) at different physiological conditions of the GI tract, in vitro NDELA formation was examined in aqueous reaction mixtures at several pHs (2-10) adjusted with acetic, sulphuric or hydrochloric acids or in cultures of mouse cecal microflora incubated. In vivo NDELA formation was also determined in blood, ingesta, and urine of female B6C3F1 mice after repeated dermal, most relevant human route, or single oral exposure to 1000 mg/kg TEA in the presence of high oral dosages of NaNO(2). Appropriate diethanolamine (DEA) controls were included to account for this impurity in the TEA used. Samples were analyzed for NDELA using GC/MS. The highest degree of nitrosation of TEA to NDELA ( approximately 3%) was observed in the in vitro cultures at pH 4 and acetic acid with lower amounts obtained using sulphuric acid ( approximately 1.3%) and hydrochloric acid ( approximately 1.2%). At pH 7, <1% of the TEA was nitrosated to NDELA and at pH 2 (HCl) or pH 10 (NaOH) no NDELA was found above the limit of detection. In incubated cultures containing cecal microflora and nutrient broth, only 0.68% of TEA was nitrosated to NDELA. No NDELA was formed in rats repeatedly dermally dosed with TEA at the limits of detection in blood (0.001 microg/ml, ppm), ingesta (0.006 microg/ml, ppm), and urine (0.47 microg/ml, ppm). Levels of NDELA measured in blood and ingesta after a single oral dose of TEA and NaNO(2) were less than those in DEA controls. These findings in toto confirm the lack of any significant formation of NDELA from TEA in vivo.

Absorption↗

Simple relationship between acid dissociation constant and minimal pH for microbial growth in laboratory medium.

A simple relationship was observed in growth medium, between the dissociation constant (via the pKa) of the acid used to control pH and the minimum pH at which Salmonellae and Escherichia coli initiate growth. From this new relationship, a simple method was proposed to predict the minimum growth pH for a given strain and different acid types. This method, illustrated on Listeria monocytogenes, would merely require the knowledge of two minimum pH values, one for a strong acid (e.g. hydrochloric acid) and one for a weak acid (e.g. acetic or propionic acid). From these two values, it seems possible to estimate for a given growth medium, the minimum pH value for any other acid within the defined pKa range.

Bacteria↗

Improvement of ethyl glucuronide determination in human urine and serum samples by solid-phase extraction.

An improved method for the determination of ethyl glucuronide (EtG) in human serum and urine was developed using solid-phase extraction (SPE) and gas chromatography (GC) with mass spectrometric detection (MS). EtG was isolated from serum and urine using aminopropyl SPE columns after deproteination with perchloric acid and hydrochloric acid, respectively. The chromatographic separation was performed on a DB 1701 fused-silica column. At a signal-to-noise ratio of 3:1, a quantification limit of 173 and 560 ng/ml and a detection limit of 37 and 168 ng/ml could be determined for serum and urine, respectively. This indicates high specificity and sensitivity of the described method. The mean absolute recovery was approximately 85%, while intra- and inter-day precision of the assay were all less than 7.5%. The linearity of the calibration curves was satisfying as indicated by correlation coefficients of >0.993. The presented method provides the basis for determination and identification of EtG in human serum and urine samples in a low-concentration range for monitoring alcohol consumption during treatment for alcohol dependence and comorbid alcohol abuse of psychotherapy patients.

Calibration↗

Sensitive determination of methomyl in blood using gas chromatography-mass spectrometry as its oxime tert.-butyldimethylsilyl derivative.

A sensitive, selective and reliable method was developed to determine methomyl ¿methyl-N-[(methylcarbamoyl)oxy]-thioacetimidate¿, a carbamate insecticide in human blood, using gas chromatography-mass spectrometry. Dimethylglyoxime served as an internal standard (I.S.). Methomyl in the blood was converted to its oxime form by sodium hydroxide. The solution made acidic with hydrochloric acid was poured into a column packed with Extrelut. Methomyloxime and I.S. were eluted from the column with a mixture of dichloromethane-ethyl acetate-chloroform (65:25:10), transformed to tert.-butyldimethylsilyl derivatives, and analyzed by gas chromatography-mass spectrometry in the electron impact mode. The calibration curves were linear in the concentration range from 1 ng/g to 100 ng/g and 100 ng/g to at least 5000 ng/g. The lower limit of detection was 0.5 ng/g. The absolute recoveries were 72-93% and within-day coefficients of variation were 3.1-5.6% at blood concentrations of 10 and 1000 ng/g. Two practical forensic applications are described.

Acetamides↗

A layered tungstic acid H2W2O7 x nH2O with a double-octahedral sheet structure: conversion process from an aurivillius phase Bi2W2O9 and structural characterization.

The conversion process of an Aurivillius phase, Bi(2)W(2)O(9), into a layered tungstic acid by hydrochloric acid treatment has been investigated, and resultant H(2)W(2)O(7) x nH(2)O has been fully characterized. The c parameter of Bi(2)W(2)O(9) [2.37063(5) nm] decreases to 2.21(1) nm in an acid-treated product dried at ambient temperature. The a and b parameters of Bi(2)W(2)O(9) [a = 0.54377(1) nm and b = 0.54166(1) nm] also decrease slightly to a = 0.524(1) nm and b = 0.513(1) nm in the acid-treated product dried at ambient temperature, indicating structural changes in the ReO(3)-like slabs in Bi(2)W(2)O(9) upon acid treatment. Drying at 120 degrees C leads to a further decrease in the c parameter [1.86(1) nm] with no notable change in the a and b parameters [a = 0.5249(2) nm and b = 0.513(2) nm]. The formation of an expandable layered structure is demonstrated by the successful intercalation of n-octylamine [interlayer distance 2.597(9) nm] and n-dodecylamine [interlayer distance 3.56(2) nm]. The compositions of the acid-treated products are determined to be H(2)W(2)O(7) x nH(2)O typically with n = 0.58 for the air-dried product and n = 0 for the product dried at 120 degrees C. As a consequence, the composition of the layer is H(2)W(2)O(7), and the decrease in the c parameter upon drying is ascribable to the loss of interlayer water. Scanning electron microscopy reveals no morphological change during acid treatment, which strongly suggests a selective leaching of the bismuth oxide sheets as a reaction mechanism. High-resolution transmission electron microscopy (HREM) observation of the acid-treated product shows consistency with a structural model for H(2)W(2)O(7), derived from Bi(2)W(2)O(9) through removal of the bismuth oxide sheets and contraction along the c axis. HREM observation also reveals that the WO(6) octahedra arrangement changes slightly with acid treatment. A one-dimensional electron density map projected on the c axis for the product dried at 120 degrees C, H(2)W(2)O(7), shows good consistency with that calculated for the structural model.

Journal Article↗

Protonation and subsequent intramolecular hydrogen bonding as a method to control chain structure and tune luminescence in heteroatomic conjugated polymers.

We report the effects of protonation on the structural and spectroscopic properties of 1,4-dimethoxy-2,5-bis(2-pyridyl)benzene (9) and the related AB coploymer poly(2,5-pyridylene-co-1,4-[2,5-bis(2-ethylhexyloxy)]phenylene) (7). X-ray crystallographic analysis of 9, 1,4-dimethoxy-2,5-bis(2-pyridyl)benzene bis(formic acid) complex 10, and 1,4-dimethoxy-2,5-bis(2-pyridinium)benzene bis(tetrafluoroborate salt) (11) establishes that reaction of formic acid with 9 does not form an ionic pyridinium salt in the solid state, rather, the product 10 is a molecular complex with strong hydrogen bonds between each nitrogen atom and the hydroxyl hydrogen in formic acid. In contrast, reaction of 9 with tetrafluoroboric acid leads to the dication salt 11 with significant intramolecular hydrogen bonding (N-H.O-Me) causing planarization of the molecule. The pyridinium and benzene rings in 11 form a dihedral angle of only 3.9 degrees (cf. pyridine-benzene dihedral angles of 35.4 degrees and 31.4 degrees in 9, and 43.8 degrees in 10). Accordingly, there are large red shifts in the optical absorption and emission spectra of 11, compared to 9 and 10. Polymer 7 displays a similar red shift in its absorption and photoluminescence spectra upon treatment with strong acids in neutral solution (e.g. methanesulfonic acid, camphorsulfonic acid, and hydrochloric acid). This is also observed in films of polymer 7 doped with strong acids. Excitation profiles show that emission arises from both protonated and nonprotonated sites in the polymer backbone. The protonation of the pyridine rings in polymer 7, accompanied by intramolecular hydrogen bonding to the oxygen of the adjacent solubilizing alkoxy substituent, provides a novel mechanism for driving the polymer into a near-planar conformation, thereby extending the pi-conjugation, and tuning the absorption and emission profiles. The electroluminescence of a device of configuration ITO/PEDOT/polymer 7/Ca/Al is similarly red-shifted by protonation of the polymer.

Journal Article↗

Application of ionic liquid halide nucleophilicity for the cleavage of ethers: a green protocol for the regeneration of phenols from ethers.

We have used the high nucleophilicity of bromide ion in the form of the ionic liquid, 1-n-butyl-3-methylimidazolium bromide ([bmim][Br]), for the nucleophilic displacement of an alkyl group to regenerate a phenol from the corresponding aryl alkyl ether. Using 2-methoxynaphthalene (1) as a model compound, we found that the combination of ionic liquid [bmim][Br] and p-toluenesulfonic acid with warming effected demethylation in 14 h, affording the desired product 2-naphthol (2) in good yield (97%). Various other protic acids (MsOH, hydrochloric acid (35%), dilute sulfuric acid (50%)) could be used as a proton source in this demethylation reaction. Under the same conditions, cleavage of alkyl alkyl ether 2-(3-methoxypropyl)naphthalene yielded mixture of corresponding 2-(3-bromopropyl)naphthalene and 2-(3-hydroxypropyl)naphthalene. Dealkylation of various aryl alkyl ethers could also be achieved using significantly reduced (i.e., stoichiometric) amounts of concentrated hydrobromic acid (47%) in the ionic liquid. Both procedures afforded the desired products in moderate to good yield; however, cleavage of aryl alkyl cyclic ether, 2,3-dihydrobenzofuran, resulted in low yield of the desired product o-2-bromoethylphenol. The convenience of this method for ether cleavage and its effectiveness using only a moderate excess of hydrobromic acid make it attractive as a green chemical method.

Journal Article↗

Micropore to macropore structure-designed silicas with regulated condensation of silicic acid nanoparticles.

A new preparation method for porous silica particles was developed using activated silica sols which are called nano-silica solutions in this paper. Several kinds of organic and inorganic acids are employed to neutralize diluted sodium silicate solutions to form the nano-silica solutions: formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, dl-malic acid, citric acid, and tricarballylic acid as carboxylic acids, and sulfuric acid and hydrochloric acid as inorganic acids. The effect of salts in the nano-silica solution is also studied. The products were investigated using a field emission scanning electron microscope, an X-ray diffractometer, the nitrogen adsorption technique, and a mercury porosimeter. Microporous silicas were produced when carboxylic acids were applied; the formation of micropores was influenced by the pH of the nano-silica solutions and molecular sizes of the carboxylic acids. Addition of a salt in a citric acid solution increased the mesopore volume. Macropores were formed when inorganic acids including salts were applied; the salt nanoparticles which were crystallized in silica spheres acted as templates. The anion types and salt concentrations in the nano-silica solutions affected the aggregation condition of silica nanoparticles, following the Schulze-Hardy rule.

Journal Article↗

A rapid and direct method for the quantitative determination of tryptophan in the intact protein.

1. A method is given for the quantitative determination of free tryptophan or tryptophan in the intact protein by treating with ninhydrin in a mixture of formic acid and hydrochloric acid (reagent b), for 10min at 100 degrees C. Glycyltryptophan was used as a standard for the determination of tryptophan in the intact protein. The extinction at 390nm was linear in the range 0.05-0.5mumol for free tryptophan (in7120) and 0.05-0.30mumol for glycyltryptophan (in15400). 2. Free tryptophan in the presence of protein may be determined by treating with ninhydrin in a mixture of acetic acid and 0.6m-phosphoric acid (reagent a) for 10min at 100 degrees C, the extinction being linear for tryptophan in the range 0.05-0.9mumol. N-Terminal tryptophan peptides also give the typical yellow product on treatment with reagent a. 3. Tryptophan content of several pure intact proteins when treated with the above method gave values in good agreement with those reported by others. A mean tryptophan content of 11.25 (s.e.m. +/-0.08) mumol/100mg of protein was found in rat brain during development from 1 to 82 days after birth.

Animals↗

Preferential alkylation of mitochondrial deoxyribonucleic acid by N-methyl-N-nitrosourea.

The reaction of the carcinogen N-methyl-N-nitrosourea with mitochondrial DNA from various rat tissues was examined in vivo and in vitro. After incubation of isolated mitochondria or cell nuclei with N[(14)C]-methyl-N-nitrosourea in vitro and subsequent isolation and purification of the DNA the specific radioactivity of the mitochondrial DNA was 3-7 times that of the nuclear DNA. The incorporation of (14)C into embryonic mitochondrial DNA in vitro was about twice that into the liver mitochondrial DNA. Identical incorporation rates, however, were found for the reaction of isolated mitochondrial DNA or nuclear DNA respectively with N[(14)C]-methyl-N-nitrosourea. After intraperitoneal injection of 43.3-58.5mg of N[(14)C]-methyl-N-nitrosourea/kg body wt. to adult rats the labelling of the mitochondrial DNA was on average 5 times that of the nuclear DNA. A smaller specific labelling was observed for the ribosomal RNA, transfer RNA, and mitochondrial RNA as well as for the mitochondrial protein as compared with the mitochondrial DNA. After hydrolysis of the alkylated nucleic acids with hydrochloric acid, fractionation was carried out on Dowex 50 cation-exchange columns. In most experiments 70-80% of the input (14)C radioactivity was eluted in the 7-methylguanine fraction. The preferential alkylation of the mitochondrial DNA by N-methyl-N-nitrosourea in situ is discussed in connexion with the cytoplasmic-mutation hypothesis of carcinogenesis.

Alkylation↗

Preferences by northern grasshopper mice for solutions of sugars, acids, and salts in Richter-type drinking tests.

Taste preferences, as measured in 48-hour, Richter-type drinking tests (test solution opposite distilled water), were determined for northern grasshopper mice (Onychomys leucogaster, ssp. breviauritus). The Ss were nine males and nine females which were individually housed within an environmental chamber. The test solutions were prepared from five sugars (fructose, glucose, lactose, maltose, sucrose) three salts (magnesium sulfate, potassium chloride, sodium chloride), and two acids (citric acid and hydrochloric acid). In randomly assigned order, each sugar and each salt solution was presented at five molar concentrations, and each acid was paired with distilled water at six levels of pH. Strong drinking preferences were shown for all concentrations of the sugars above .05-.10 M, and sugars ranked in order of preference as follows: Maltose = sucrose greater than glucose = fructose greater than lactose. Preferences were also shown for hypotonic concentrations of NaCl. The other salts and both acids, however, were indifferently preferred at low concentrations and were rejected at the higher concentrations. Taste preferences by grasshopper mice for these chemicals were similar to those exhibited by Monogolian gerbils tested with the same items. The similar patterns of preference shown by New World cricetid rodents (grasshopper mice) and Old World cricetid rodents (gerbils) suggest that conclusions concerning disparity in taste sensibilities among animal forms may be premature.

Acids↗

Inorganic acid emission factors of semiconductor manufacturing processes.

A huge amount of inorganic acids can be produced and emitted with waste gases from integrated circuit manufacturing processes such as cleaning and etching. Emission of inorganic acids from selected semiconductor factories was measured in this study. The sampling of the inorganic acids was based on the porous metal denuders, and samples were then analyzed by ion chromatography. The amount of chemical usage was adopted from the data that were reported to the Environmental Protection Bureau in Hsin-chu County according to the Taiwan Environmental Protection Agency regulation. The emission factor is defined as the emission rate (kg/month) divided by the amount of chemical usage (L/month). Emission factors of three inorganic acids (i.e., hydrofluoric acid [HF], hydrochloric acid [HCl], and sulfuric acid [H2SO4]) were estimated by the same method. The emission factors of HF and HCl were determined to be 0.0075 kg/L (coefficient of variation [CV] = 60.7%, n = 80) and 0.0096 kg/L (CV = 68.2%, n = 91), respectively. Linear regression equations are proposed to fit the data with correlation coefficient square (R2) = 0.82 and 0.9, respectively. The emission factor of H2SO4, which is in the droplet form, was determined to be 0.0016 kg/L (CV = 99.2%, n = 107), and its R2 was 0.84. The emission profiles of gaseous inorganic acids show that HF is the dominant chemical in most of the fabricators.

Acids↗

The influence of acid on astringency of alum and phenolic compounds.

Astringency of aqueous solutions of phenolic compounds (grape seed tannins, tannic acid, catechin and gallic acid) increased upon addition of citric acid, whereas the astringency of alum was reduced. Astringency of alum was decreased equivalently by addition of equi-sour levels of lactic acid, citric acid or hydrochloric acid. The difference between alum and the phenolic compounds is speculated to result from chemical modifications affecting binding of the astringents with oral proteins rather than cognitive differences. Chelation of the aluminum ion in alum by acids reduces its availability for interacting with salivary proteins or epithelial proteins. In contrast, the increased astringency produced upon acidification of phenolic compounds is speculated to result from the pH driven increase in the affinity of the phenols for binding with proteins. These results suggest that alum cannot be used interchangeably with phenolic astringents in psychophysical studies.

Adult↗

Oleandrin distribution in a fatality from rectal and oral Nerium oleander extract administration.

In a fatal (cardiotoxic) case of oleander extract poisoning of a young female, ethanol extracts of blood and tissue homogenates were purified by lead acetate. After removal of excess lead by ammonium sulfate, oleandrin was extracted into chloroform. Oleandrin in the extract concentrates was detected by thin-layer chromatography, with location by fluorescence and chromogenically by means of p-anisaldehyde. Quantitation was performed on dried extracts reconstituted in water/methanol, reacted with hydrogen peroxide, ascorbic acid, and hydrochloric acid, and analyzed by fluorescence spectrophotometry. Excitation was at 355 nm, and fluorescence scanning from 340 to 580 nm. The fluorescence peak at 460 nm was used for the quantitative measurement. The concentrations of oleandrin measured in blood, stomach wall, colon tissue, liver, heart, lung, brain, spleen, and kidney ranged from 10 to 39 micrograms/g, with 200 micrograms/mL in the total gastric content residue submitted for analysis.

Adult↗

Accretion, partitioning and sequestration of calcium and aluminum in red spruce foliage: implications for tree health.

Calcium (Ca) is an essential macronutrient in plants and is an important component of many cellular structures and physiological processes as well as overall forest function. Aluminum (Al) in soil solution can inhibit Ca uptake by plants and disrupt many Ca-dependent metabolic and physiological processes of plants. The ratio of Ca to Al in soil solution can be an important indicator of forest health, especially on acid soils. We used sequential chemical extractions (water, acetic acid and hydrochloric acid) to assess the chemical availability of Ca and Al in foliage from mature red spruce (Picea rubens Sarg.) trees growing under ambient environmental conditions. In plants deficient in Ca and with intermediate total foliar Ca concentration ([Ca]), Ca preferentially accrued in labile and physiologically available forms (water- and acetic acid-extractable). In plants with total foliar [Ca] above a "sufficiency" threshold, Ca also accrued in a chemically sequestered form with low solubility (HCl-extractable), suggesting that Ca sequestration is an inducible process in response to excess foliar Ca. Because it has low solubility, it is likely that sequestered Ca is unavailable for Ca-dependent physiological processes. Immobilization of Al in foliage was related to Ca sequestration, suggesting that Ca sequestration may provide a passive mechanism for Al tolerance in the foliage of these trees. Aluminum immobilization was evident based on the ratio of HCl-extractable Al to the more labile (water- and acetic acid-extractable) forms of Al. Sufficient labile Ca combined with Al sequestration was associated with plant health, including enhanced foliar accretion of Mg and Mn, greater tree growth, enhanced foliar cold hardiness and reduced winter injury. These findings demonstrate that not all chemical forms of foliar Ca and Al are of equal physiological significance and underscore the importance of assessing the biologically significant element forms in biogeochemical research.

Aluminum↗

Studies on the preparation and isomeric composition of 186Re- and 188Re-pentavalent rhenium dimercaptosuccinic acid complex.

The preparative conditions for 186Re(V)DMSA and 188Re(V)DMSA (DMSA = meso-dimercaptosuccinic acid), beta-emitting radiopharmaceuticals that have been shown to localize in medullary thyroid carcinoma, require modification depending on the amount of carrier rhenium and the chemical form and medium in which the rhenium is supplied. Preparative conditions are described for use with carrier-free 188ReO4- in saline, and for use with 186ReO4- in saline, sodium hydroxide or nitric acid. Preparation of 186Re(V)DMSA (carrier present up to 2 mg per 2.5 ml reaction volume) requires a DMSA:SnCl2:Re ratio of 10:5:1 at 100 degrees C for 30 min. Addition of excess nitric acid or hydrochloric acid up to a concentration of 155 mM does not reduce the yield from 100%. A commercial DMSA kit vial (e.g. Amerscan DMSA) can be used for preparation of 188Re(V)DMSA (carrier free) provided the required activity is in a volume of less than 1 ml per vial. A convenient method of concentrating the 188Re generator eluate to the required volume is described.

Isomerism↗