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PubMed2000

[Identification of synthetic adhesives by simultaneous pyrolysis methylation gas chromatography].

At present, pyrolysis gas chromatography (Py-GC) is an effective analytical method for trace synthetic adhesives. Synthetic adhesives are usually composed of polar components. Thus, the polar pyrolysis products are normally difficult to measure by Py-GC due to their partial or complete adsorption in the pyrolysis zone, injection system or capillary column and the accuracy of results is seriously affected. Simultaneous pyrolysis methylation gas chromatography (Py-Me-GC) is a fast analytical method which was developed in recent years for polar compounds. The five synthetic adhesives have been identified by using Py-Me-GC in our study. Analytical conditions were: filament pyrolysis apparatus, flame ionization detector (FID), gas chromatograph, FFAP capillary column (30 m x 0.25 mm i.d.) and a quaternary ammonium salt as methylating agent. Major peaks of the products of pyrolysis were analysed qualitatively by GC/MS and comparisons were also made between the results by Py-Me-GC and those by Py-GC. The information gained from the components of substances by Py-Me-GC is more than that by Py-GC. The method is suitable for identifying synthetic adhesives of trace evidence in forensic science.

Adhesives↗
PubMed1975

Acrylonitrile biotransformation in rats, mice, and chinese hamsters as influenced by the route of administration and by phenobarbital, SKF 525-A, cysteine, dimercaprol, or thiosulfate.

Female wistar rats, conventional albino mice, and Chinese hamsters were given a single dose of acrylonitrile, 0.5 or 0.75 mM/kg body weight. The elimination in the urine of thiocyanate, which is the main metabolite of acrylonitrile, indicated a decreasing proportion of biotransformation after oral (over 20%), intraperitoneal, or subcutaneous (2 to 5%), and intravenous (1%) administration in rats. Oral administration of acrylonitrile in hamsters and mice was also followed by higher biotransformation than intraperitoneal administration. Pretreatment of rats with phenobarbital, SKF 525 A, cysteine, or dimercaprol did not significantly influence elimination of thiocyanate in the urine after the administration of acrylonitrile, but simultaneous administration of thiosulfate significantly increased the metabolized portion of acrylonitrile given intraperitoneally in rats (almost twice) and mice (more than three times). Acrylonitrile was found to be strongly bound in blood. The study confirmed the marked effect of distribution (first-pass metabolic phenomenon) on the metabolic fate of foreign compounds. The strong acrylonitrile binding and cyanoethylation are apparently responsible for the unusually high influence of the different routes of administration on the metabolic fate of acrylonitrile. Acrylonitrile was more effectively metabolized to thiocyanate in mice than in rats after oral, intraperitoneal, and intravenous administration. A greater response of acrylonitrile to thiocyanate metabolism and a larger decrease in its acute toxicity after thiosulfate in mice than in rats indicate possible differences in the mechanism of acrylonitrile toxicity in these animals. Cyanide apparently plays a minor role in the acrylonitrile toxicity in rats, but may play quite an important one in mice.

Administration, Oral↗
PubMed1973

Stereospecific enzymes in the degradation of aromatic compounds by pseudomonas putida.

Two reactions in the catabolism of catechol by meta-fission, namely, hydration of 2-oxopent-4-enoate (vinylpyruvate) and aldol fission of the product, are catalyzed by stereospecific enzymes. The absolute configuration of this hydration product was shown to be l(S)-4-hydroxy-2-oxopentanoate. Vinylpyruvate hydratase, purified almost to homogeneity, had a molecular weight of about 287,000 and was dissociated in sodium dodecyl sulfate, without prior treatment with mercaptoethanol, into a species with an approximate molecular weight of 28,000. The hydratase was highly specific for its substrates; thus, although 2-oxo-cis-hex-4-enoate was also hydrated, structurally similar compounds such as the trans isomer, vinylacetic and crotonic acids, and the ring-fission products of catechol and methylcatechols were not attacked. Vinylpyruvate hydratase was activated by Mn(2+) ions. On the basis of these observations, a mechanism is proposed which closely resembles that for 4-hydroxy-2-oxopentanoate aldolase. A possible evolutionary connection between functionally related, divalent cation-activated hydro-lyases and aldolases is discussed. It was also demonstrated that l-(S)-4-hydroxy-2-oxohexanoate is the biologically active enantiomer of this hydroxy acid.

Acetaldehyde↗
PubMed2005

Synthesis of enamines, enol ethers and related compounds by cross-coupling reactions.

For several decades, enamines and related compounds have been used as intermediates in organic synthesis and many methods are known for their preparation. Most of the synthetic protocols, however, require harsh reaction conditions. Recently, a new approach has emerged, inspired by the analogous arylation of amines catalysed by palladium or copper complexes (Buchwald-Hartwig reaction). Simultaneous and independent work from several research groups has led to the development of very powerful protocols for the preparation of enamines and their derivatives that require only readily available starting materials and proceed under very mild reaction conditions. Noteworthy is the fact that in less than five years an almost unknown reaction has reached such a high level of scope and generality that it is now very frequently applied in total syntheses of natural products.

Alcohols↗
PubMed2006

Potent anti-inflammatory activity of 3-aminovinylphosphonates as inhibitors of reactive oxygen intermediates, nitric oxides generation, and tumor necrosis factor-alpha release.

Two 3-aminoalkenylphosphonate compounds 1, 2, and a hydroxyl derivative, 2-(3-hydroxy-3-phenylpropyl)hex-1-enylphosphonate 3, recently synthesized in our lab, have been evaluated for their ability to modulate the production of reactive oxygen intermediates, nitric oxide (NO) and tumor necrosis factor (TNF-alpha) by murine macrophages. We found that all three molecules suppressed generation of reactive oxygen intermediates, NO, and TNF-alpha. However, although 2-(3-hydroxy-3-phenylpropyl)hex-1-enylphosphonate 3 possessed higher activity in suppression of reactive oxygen intermediates and nitric oxide compared to 3-aminoalkenylphosphonates 1 and 2, it showed less activity in the inhibition of tumor necrosis factor release.

Animals↗
PubMed1992

Synthesis, chemical, and biological properties of vinylogous hydroxamic acids: dual inhibitors of 5-lipoxygenase and IL-1 biosynthesis.

Vinylogous hydroxamic acids (3-(N-hydroxy-N-alkylamino)-2-propen-1-ones, VHA) were prepared as antiinflammatory agents. The synthesis, chemical properties, and in vitro biological activities of these relatively unexplored compounds are described. The VHAs were prepared by condensation of the appropriate N-substituted hydroxylamine with any of the three reagents: a 1,3-dicarbonyl compound (method A); a vinylogous amide (method B); or an alkynone (method C). The VHAs exist as one or more tautomers in solution with the relative proportions of each being dependent upon the structure of the VHA, solvent, and pH. VHAs undergo some of the typical reactions of hydroxamic acids as well as those of vinylogous amides. VHAs are active as inhibitors of 5-lipoxygenase and of IL-1 biosynthesis in vitro, which do not inhibit other enzymes of the arachidonic acid cascade. They have been shown by ESR studies to bring about inhibition of soybean type 1 15-lipoxygenase by reduction of the active site iron.

Animals↗
PubMed1998

Comparison of the properties of polymeric and C8 based materials for solid phase extraction.

The extraction properties of two polymeric solid phase extraction materials, styryldivinyl benzene (SDB) and 'Oasis' have been compared with those of a base deactivated C8 bonded silica gel using a range of acidic and basic test analytes. In the case of the two polymer phases good extraction of all the test compounds from aqueous buffer was obtained over the pH range 2-10. On the C8 material, efficient extraction of the most polar acidic analyte, anisic acid, was only obtained between pH 2 and 6. The use of methanol water mixtures, or methanol water mixtures modified with either trifluoroacetic acid (TFA) or triethylamine (TEA) as eluents was investigated for the recovery of the analytes following extraction. The use of TFA or TEA as ionic modifiers strongly influenced the efficiency of the elution step. The effect of a plasma matrix on extraction efficiency was also investigated, with the result depending upon the analyte. An approach to assessing the performance of the three phases has been developed based on the percentages of methanol in the eluent resulting in the recovery of 50% of the analyte, and in determining the difference between eluents giving recoveries of 10 and 90%.

Chemistry Techniques, Analytical↗
PubMed2001

Integrated plastic microfluidic devices with ESI-MS for drug screening and residue analysis.

For this work, two different plastic microfluidic devices are designed and fabricated for applications in high-throughput residue analysis of food contaminants and drug screening of small-molecule libraries. Microfluidic networks on copolyester and poly(dimethylsiloxane) substrates are fabricated by silicon template imprinting and capillary molding techniques. The first device is developed to perform affinity capture, concentration, and direct identification of targeted compounds using electrospray ionization mass spectrometry. Poly(vinylidene fluoride) membranes sandwiched between the imprinted copolyester microchannels in an integrated platform provide continuous affinity dialysis and concentration of a reaction mixture containing aflatoxin B1 antibody and aflatoxins. The second microfluidic device is composed of microchannels on the poly(dimethylsiloxane) substrates. The device is designed to perform miniaturized ultrafiltration of affinity complexes of phenobarbital antibody and barbiturates, including the sequential loading, washing, and dissociation steps. These microfabricated devices not only significantly reduce dead volume and sample consumption but also increase the detection sensitivity by at least 1-2 orders of magnitude over those reported previously. Improvements in detection sensitivity are attributed to analyte preconcentration during the affinity purification step, limited analyte dilution in the microdialysis junction, minimal sample loss, and the amenability of ESI-MS to nanoscale sample flow rates.

Aflatoxin B1↗
PubMed1997

Mechanism-based inhibitors for the inactivation of the bacterial phosphotriesterase.

1-Bromovinyl (I), Z-2-bromovinyl (II), 1,2-dibromoethyl (III), and a series of 4-(halomethyl)-2-nitrophenyl (IVa-c) diethyl phosphate esters were examined as substrates and mechanism-based inhibitors for the bacterial phosphotriesterase. All of these compounds were found to act as substrates for the enzyme. Inhibitor I rapidly inactivated the enzyme within 1 min, giving a partition ratio of 230. The newly formed covalent adduct with inhibitor I was susceptible to hydrolysis at elevated values of pH and dissociation by NH2OH. Azide was not able to protect the enzyme from inactivation with inhibitor I, implying that the reactive species was not released into solution prior to the inactivation event. The reactive species was proposed to be either an acyl bromide or a ketene intermediate formed by the enzymatic hydrolysis of inhibitor I. Compounds II and III were shown to be relatively poor substrates of phosphotriesterase and they did not induce any significant inactivation of the enzyme. The inhibitor, 4-(bromomethyl)-2-nitrophenyl diethyl phosphate (IVa), was found to irreversibly inactivate the enzyme with a KI = 7.9 mM and kinact = 1. 2 min-1 at pH 9.0. There was no effect on the rate of inactivation upon the addition of the exogenous nucleophiles, azide, and NH2OH. The species responsible for the covalent modification of the enzyme by IVa was most likely a quinone methide formed by the elimination of bromide from the phenolic intermediate. NMR experiments demonstrated that the quinone methide did not accumulate in solution. The chloro (IVb) and fluoro (IVc) analogues did not inactivate the enzyme. These results suggest that the elimination of the halide ion from the phenolic intermediate largely determines the partition ratio for inactivation.

Aryldialkylphosphatase↗
PubMedDate not supplied

Metabolism of 1-chloro-2-methylpropene. Evidence for reactive chloroaldehyde intermediates.

Recent metabolism and disposition studies of 1-chloro-2-methylpropene (dimethylvinyl chloride) revealed cysteine and N-acetylcysteine conjugates of 3-chloro-2-methylpropenoic acid as the major metabolites. In the present studies we have investigated various steps in the metabolic pathway to determine which step was responsible for the observed trans (E)-stereochemistry of these metabolites. In vitro incubation studies of dimethylvinyl chloride with rat liver microsomes indicated cytochrome P-450-catalyzed aliphatic hydroxylation to be only stereoselective. Both (E)- and (Z)-3-chloro-2-methylpropenols formed in an identical ratio of 2:1 in incubations with microsomes from untreated male and female rats and phenobarbital-treated male rats. No alcohol formation was observed in incubations using microsomes from beta-naphthoflavone-treated male rats. Investigation of the subsequent conjugation reactions of sulfur nucleophiles with haloenoic carbonyl compounds showed that both (E)- and (Z)-3-chloro-2-methylpropenals reacted rapidly with N-acetylcysteine, the E-adduct being the sole product in either case. In contrast, the Michael reaction of the corresponding acids with N-acetylcysteine was very sluggish. Also, whereas the E-acid yielded exclusively the corresponding E-adduct, the Z-isomer afforded both Z- and E-conjugates in the ratio of 3:4. Glutathione S-transferases had poor activity towards conjugation of glutathione with these acids. Formation of only an E-glutathione conjugate could be observed from either the E- or Z-acid in these enzymatic reactions. Direct Michael reaction of glutathione with (E)-3-bromo-2-methylpropenoic acid, used in chemical synthesis of the conjugates, yielded both the E- and Z-adducts in the ratio of 95:5.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗
PubMed2001

Passive monitoring method for 3-ethenylpyridine: a marker for environmental tobacco smoke.

A new method was developed to assess environmental tobacco smoke in air. The method is based on passive sampling and subsequent measurement of the concentration of 3-ethenylpyridine, a vapor-phase compound specific to tobacco smoke. Air samples were collected using a 3M organic vapor monitor. Tests were carried out in a dynamic chamber to determine the sampling rate (25.7 cm3/min). 3-Ethenylpyridine was desorbed from the sampler with 1 mL of pyridine/toluene mixture. 3-Ethenylpyridine was quantified by gas chromatography/mass spectrometry. The limit of detection was 0.01 microgram/sample, corresponding to a concentration of 0.27 microgram/m3 air calculated for a sampling period of 24 h. Field measurements were carried out to test the performance of the method. Mean concentrations ranging from 1.3 to 5.3 micrograms/m3 were measured for 3-ethenylpyridine in smoking environments, but no 3-ethenylpyridine was detected in nonsmoking environments. Active sampling using charcoal tubes was used as a reference method in the chamber tests and field measurements. Individual exposures can be easily and accurately measured by means of the passive sampler. Because of simple sample treatment, the method is also well-suited for large-scale monitoring of environmental tobacco smoke.

Air Pollutants↗
PubMed1995

Synthesis and biological activity of 7-alkylidenecephems.

Several 7-alkylidenecephalosporins were synthesized and biologically evaluated as beta-lactamase inhibitors. The three beta-lactamase enzymes used in this study included two type C beta-lactamases, derived from Enterobacter cloacae P99 and E. cloacae SC12368, and one type A beta-lactamase, derived from Escherichia coli WC3310. Of the cephalosporins prepared, compound 7e, the sodium salt of 7-[(Z)-(2'-pyridyl)methylene]cephalosporanic acid sulfone, was found to have excellent inhibitory properties against both type C enzymes. Also, compound 7f, the sodium salt of 7-[(Z)-(tert-butoxycarbonyl)methylene]cephalosporanic acid sulfone showed high activity as an inhibitor of the type A enzyme. The inhibition kinetics of 7e were further explored. The IC50 value of 7e indicated that this compound was approximately 20-fold more active than tazobactam against the enzyme derived from E. cloacae P99 and 167-fold more active than tazobactam against the enzyme derived from E. cloacae SC12368. A plot of enzymatic activity vs incubation time with stoichiometric amounts of inhibitor reveals a rapid deactivation of the enzyme followed by an extremely slow reactivation. 7e exhibited a second-order rate constant of k3' = 5.3 x 10(6) L/mol.min, and a partition ratio of approximately 20:1 inhibitor:enzyme was determined for this inhibitor. After separation of excess inhibitor with Sephadex filtration, a rate constant of enzyme reactivation was measured at kreactiv = 1.0 x 10(-3) s-1. Following 24 h of incubation of enzyme with a large excess of inhibitor and sephadex filtration to remove excess inhibitor, the enzyme was able to recover only 43% of its original activity, indicating an irreversible component to the inhibition. Potential mechanisms of inhibition for both 7e and 7f are suggested.

Anti-Bacterial Agents↗
PubMed1990

Comparison of the disposition and in vitro metabolism of 4-vinylcyclohexene in the female mouse and rat.

4-Vinylcyclohexene (VCH) is a chemical to which humans are exposed in the rubber industry. A chronic carcinogenicity bioassay conducted by the National Toxicology Program showed that oral administration of VCH induced tumors in the ovaries of mice but not in those of rats. The hypothesis tested was that the species and organ specificity of VCH toxicity was due to differences in the disposition of VCH between the female rat and mouse. Therefore, the disposition of a single oral dose of 400 mg/kg [14C]VCH was studied in female B6C3F1 mice and Fischer 344 rats. Mice eliminated greater than 95% of the dose in 24 hr, whereas rats required 48 hr to eliminate greater than 95% of the dose. The major routes of excretion of [14C]VCH-derived radioactivity were in the urine (50-60%) and expired air (30-40%). No evidence was obtained to indicate that the ovaries of either species retained VCH as a parent compound or as radioactive equivalents. A dramatic difference was observed between the rat and mouse in the appearance of a monoepoxide of VCH in blood from 0.5 to 6 hr after VCH administration (800 mg/kg, ip). VCH-1,2-epoxide was present in the blood of mice with the highest concentration at 2 hr (41 nmol/ml). The blood concentration of VCH-1,2-epoxide in rats was less than 2.5 nmol/ml at all times examined. VCH-7,8-epoxide was not present in the blood of either species at the level of detection. These findings were supported by in vitro studies of VCH epoxidation by liver microsomes. The rate of epoxidation of VCH (1 mM) to VCH-1,2-epoxide was 6.5-fold greater in mouse liver microsomes than that in rat liver microsomes. The species difference in the rate of epoxide formation by the liver may be an important factor in the species difference in susceptibility to VCH-induced ovarian tumors.

Administration, Oral↗
PubMed2002

Structural investigation of catalyst deactivation of Pt/SDB for catalytic oxidation of VOC-containing wastewater.

The stability of styrene-divinyl benzene copolymer (SDB)-supported Pt (Pt/SDB) catalysts for destruction of volatile-organic-compound (VOC) in wastewater was examined. The test reaction was wet oxidation of water-containing aliphatic alcohol and formaldehyde at 140 degrees C and 90 psig for 40 h. The catalytic performance tests indicated that activity of the Pt/SDB catalysts could be maintained for VOC concentration of 3 wt.%, whereas the catalysts deactivated rapidly for 10 wt.% VOC containing wastewater. In order to investigate the nature of catalyst deactivation, extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge (XANES) spectroscopy were used to characterize the fresh and used catalysts. After the reaction, there is no oxidation of Pt clusters observed in EXAFS and XANES spectroscopy suggesting that the oxidation reaction takes places via the adsorbed oxygen. The spectroscopy results further indicated that deactivation of the catalysts were mainly caused by the increase of Pd particle size. After the reaction, the Pt-Pt coordination number has no significant change for the 3 wt.% wastewater whereas increase from 5.6 to 6.2 for 10 wt.% wastewater. Combined with the fact that the catalysts fractured during the reactions, we suggested that Pt agglomeration was mainly caused by thermal migration of the metal clusters.

Catalysis↗
PubMed2002

Quantitative evaluation of adhesive properties and drug-adhesive interactions for transdermal drug delivery formulations using linear solvation energy relationships.

This paper describes the results of the application of linear solvation energy relationships (LSERs) to quantitatively characterize the properties of adhesives and to evaluate the degree of drug-adhesive interaction in transdermal drug delivery formulations. Probe solutions were prepared in acetonitrile (ACN) for a set of probe compounds with different physicochemical properties, and were used to swell the adhesives for subsequent probe molecule-adhesive interactions. The degree of the interactions was measured by the 'sorbed' amount of probe molecules. Based on LSERs, the 'sorbed' amounts were linearly correlated with their properties. The corresponding coefficients reflect the differential interactions of these molecules with the adhesive and ACN, and are quantitative indications of the adhesive properties. Two different transdermal acrylate adhesives (isooctyl acrylate/acrylamide/vinyl acetate in the weight ratios of 75/5/20 and isooctyl acrylate/2-hydroxyethyl acrylate/vinyl acetate in the weight ratios of 58/20/18) were selected for the evaluation of the methodology. It is concluded that the first adhesive is more basic and hydrophobic, which is consistent with the use of acrylamide monomer and significant amount of isooctyl acrylate. The second adhesive is more acidic and polarizable due to a relatively high amount of the 2-hydroxyethyl acrylate. Additionally, the 'sorbed' amount can be regarded as an interaction parameter or index between a drug molecule and the adhesive. Finally, this parameter is expected to correlate with the thermodynamic properties of transdermal formulations such as drug solubility, diffusion coefficient, release rate, and maybe skin permeation rate.

Acrylamide↗
PubMed2003

Formation of vinylogous compounds in model Maillard reaction systems.

The thermal degradation over temperature and time of selected amino acids (Asp, Gln, and Glu) in the presence of reducing sugars was investigated in low moisture model systems. Copyrolysis of glucose-Asp mixtures led to the release of acrylic acid, attaining >5 mmol/mol Asp at 230 degrees C after 5 min. Spurious amounts of 3-butenamide were detected upon heating Gln together with a carbonyl source. Apparently, intramolecular cyclization is favored to procure 2-pyrrolidinone, reaching levels >3 mmol/mol above 230 degrees C. 2-Pyrrolidinone was also formed in comparable amounts in pyrolyzed sugar-Glu mixtures, indicating that the Maillard reaction may be an important contributor to the formation of 2-pyrrolidinone in certain cooked foods. The chemical route to acrylic acid and 3-butenamide is probably analogous to that described for acrylamide recently. Evidence is also presented that acrylic acid may be an intermediate in the formation of acrylamide, and yields could be augmented by coincubation of fructose-Asp with certain amino acids such as Gln, reaching approximately 5% of the yield obtained by the Asn route. A computational study to determine the reactivity of the vinylogous products indicated a reduced ability of 3-butenamide as compared to acrylamide to form stable intermediates by Michael nucleophilic addition. Acrylamide and acrylic acid exhibited a similar theoretical reactivity potential toward nucleophiles. No information is as yet available on the occurrence of acrylic acid in cooked foods. Extensive toxicological evaluation indicates that acrylic acid is of no concern at the amounts to be expected in foods.

Acrylamide↗
PubMed1990

Development of a preformulation lipophilicity screen utilizing a C-18-derivatized polystyrene-divinylbenzene high-performance liquid chromatographic (HPLC) column.

Alkane/water partition coefficients have been predicted from the retention times of solutes using a C-18-derivatized polystyrene-divinylbenzene HPLC column (Act-I). Several classes of compounds, with molecular weights from 78 to 379 and partition coefficients ranging over several orders of magnitude, were included in the present study. A high correlation coefficient (0.953) was obtained from log-log plots of alkane/water partition coefficients versus capacity factor. A poor correlation was observed for octanol/water partition coefficient, presumably due to the hydrogen-bonding capability of octanol. The alkane/water correlation suggests that the system is devoid of significant specific solute-stationary phase interactions which are known to impart anomalous retention behavior to traditional reverse phase columns. Deviations of calculated alkane/water partition coefficients (and Hansch II alkane coefficients) from observed values could not be explained in terms of solute (or substituent) polarizability, dipole moment, sigma para, or pKHB values, further suggesting that specific interactions between the stationary phase and the solute are not significant. A molecular weight dependence that was independent of lipophilicity was observed. Thermodynamic and extra-thermodynamic parameters of retention were obtained in order to investigate retention mechanisms for the Act-I column. The molecular weight dependence does not appear to be due to size exclusion or entropic expulsion of the solute from the stationary phase. Hansch II substituent coefficients calculated from retention times were found to be similar for benzene and steroid derivatives. Thus, the Act-I column may be utilized as a rapid lipophilicity screen for drug candidates of similar molecular weight.

Alkanes↗
PubMed1976

Interaction of a 5-trans-vinylcarboxylic acid analogue of pyridoxal 5'-phosphate with apoaspartate aminotransferase. Covalent labeling of the enzyme.

The 5-trans-vinylcarboxylic acid analogue of pyridoxal 5'-phosphate has been prepared. Its pKa values were determined as 3.08, 4.10, and 7.33. The third pKa, that of the pyridinium nitrogen, is considerably lower than that of 8.2 observed for the corresponding saturated compound, 5'-carboxymethyl-5'-deoxypyridoxal. Absorption spectra of individual ionic forms have been resolved into component bands using lognormal distribution curves. The vinylcarboxylic acid analogue inactivates apoaspartate aminotransferase slowly at pH 8.3. An initial product absorbs at 26 kK (385 nm) and is converted slowly to a species with a narrow absorption band at 24.0 kK (417 nm). Meanwhile, the circular dichroism in the same region changes from positive to negative. At pH 5.2 the product abosrbs at 25.2 kK (397 nm). The 24.0-kK (417 nm) form is not reducible with sodium borohydride and the tightly bound chromophore is not released from the protein during denaturation by acid, base, or heat. L-Glutamate and erythro-beta-hydroxyaspartate both facilitate the formation of the 24.0-kK form. The reaction of the analogue with apoenzyme in the presence of erythro-beta-hydroxyaspartate is also accompanied by transient peaks, presumably representing quinonoid forms, at 19.0 kK (526 nm) and 20.3 kK (492 nm). The analogue reacts at basic pH with arginine, alpha-amino-gamma-guanidinobutyric acid, ornithine, cysteine, alpha, gamma-diaminobutyric acid, eh narrow absorption bands centered in the 24.0-24.4-kK (417-410 nm) region and resembling the product formed with the apoenzyme. Nuclear magnetic resonance and absorption spectroscopy indicate that the reaction with alpha- gamma-diaminobutyric acid proceeds via a hexahydropyrimidine derivative to a substituted tetrahydropyrimidine (a cyclic Schiff base) which is the final product. A similar reaction sequence with the apoenzyme is postulated and a structure with an unknown X group from the enzyme replacing the gamma-amino group of alpha, gamma-diaminobutyric acid is proposed for the 24.0-kK (417 nm) chromophore obtained with the apoenzyme. The proposed reactions are closely related to enzymatic and nonenzymatic reactions of pyridoxal 5'-sulfate (Yang, I. -Y., Khomutov, R. M., and Metzler, D. E. (1974), Biochemistry 13, 3877).

Apoenzymes↗