Decarboxylate Amino Acids Research Articles

Influence of plants and spices on the formation of biogenic amines in meat

Biogenic amines (BAs) consist of organic nitrogenous compounds produced by the amino acid’s decarboxylation. They are present in various foods, such as meat products, and are associated with several health hazards. In meat, BAs are produced by the action of microorganisms that can decarboxylate amino acids. BAs can also be produced in meat naturally by enzymatic pathways. Tyramine, histamine, cadaverine, and putrescine are BAs frequently found in meat products. BAs are frequently found in fish depending on the species and time-temperature control, but can also be present in meat, particularly in canned, cured and fermented meat products. BAs are associated with various health disorders and toxicological effects including cardiovascular, respiratory and gastrointestinal system problems. Numerous factors influence the BAs generation in meat products. Factors such a handling, storage temperature, and processing procedures are essential for minimizing the risk of BAs formation to ensure food safety. Plant extracts and spices, play a multifaceted role in regulating BAs developments in diverse food items. Plant extracts containing phenolic/polyphenols, terpenoids and alkaloids have exhibited antimicrobial properties that can hinder the growth of microorganisms responsible for producing amines, consequently reducing BAs formation. Also, spices frequently contain compounds that impede the enzymatic conversion of precursor amino acids into biogenic amines.

Are there profiles of cheeses with a high GABA and safe histamine content?

Some bacteria decarboxylate amino acids as a means of resisting acid stress. It is a mechanism commonly used by bacteria in fermented dairy products. The decarboxylation of histidine to histamine occurs frequently in some types of cheese, but high concentrations of histamine can be harmful to consumers. Not all amino acid decarboxylation products are, however, undesirable. GABA, the decarboxylation product of glutamate, has positive effects on human health. Although histamine and GABA accumulate in large quantities in many types of cheese, there is little information regarding their relationship, and that which is available is restricted to a few cheese varieties. The present work examines whether cheeses exist with high concentrations of GABA but safe concentrations of histamine. The GABA and histamine contents of 250 cheeses representing 143 European varieties were examined, and the technological, environmental and metabolic (TEM) traits governing their accumulation identified. Two TEM profiles were associated with high GABA contents and safe histamine concentrations. These findings could help the dairy industry select the best technological conditions for making GABA-rich, histamine-safe cheeses. • GABA and histamine were determined in 250 cheeses of 143 different varieties. • GABA (healthy) and histamine (toxic) can accumulate at high concentrations. • A positive correlation exists between GABA and histamine concentration. • Cheeses with high GABA and low histamine contents were identified. • The technological/environmental/metabolic profiles of these cheeses were recorded.

Preliminary Characterization of Yeasts from Bombino Bianco, a Grape Variety of Apulian Region, and Selection of an Isolate as a Potential Starter

Eighty-seven yeasts were isolated from Bombino bianco, a white grape variety from Apulian Region (Southern Italy). The isolates were characterized for the splitting of arbutin, the hydrolysis of pectins, sulphite production, the resistance to acetic acid, SO2, and ethanol. An enhanced arbutin splitting (β-glucosidase) and a moderate pectolytic activity were found. Concerning ethanol resistance, the most of yeast population showed a low-to-moderate resistance, but some isolates, identified as Saccharomyces cerevisiae, were able to grow in presence of 15% v/v of ethanol. Four isolates were selected (coded as 43D, 44D, 45D, and 46D), studied for their ability to decarboxylate amino acids and used in small-scale fermentation trial; for this last experiment a reference strain was used (S. cerevisiae EC1118). This experiment suggested the existence of an isolate (S. cerevisiae 46D) with interesting traits and performances, which could be potentially proposed as a starter for Bombino bianco.

Occurrence of biogenic amines in beers produced with malted organic Emmer wheat (Triticum dicoccum)

Because several groups of microorganisms are able to decarboxylate amino acids, the presence of biogenic amines (BA) can be seen as an index of the microbiological quality of the brewing process. BAs were quantified for the first time in the intermediate products and craft beers produced with malted organic Emmer wheat (Triticum dicoccum) in a small size brewery in order to assess the possible presence of critical control points related to biological hazard in the brewing process. BA levels in beers produced exclusively from malted organic Emmer wheat were between 15.4 and 25.2 mg l–1 in the samples of light beer (Lt) and between 8.9 and 15.3 mg l–1 in double malt beers (DM) ready for consumption (the beers stored for 90 days at 1–2°C). Cadaverine and tyramine were the main BAs in the Lt and DM beers, respectively. Increased concentrations of BAs seemed to be more related to the heat treatment of the processing product during mashing and wort boiling, rather than to the fermentation process. Much lower concentrations were found in finished beers obtained from 50% malted organic Emmer wheat and 50% malted barley (up to 3.2 mg l–1) or from 30% malted Emmer wheat (up to 8.3 mg l–1). Thus, Emmer wheat malt can be a useful alternative to wheat and spelt for the production of beer with a limited content of BA, if the processing technology is kept under control.

Tumor formation and antitumor immunity; the overlooked significance of histamine.

HA is a biogenic amine, widely distributed throughout the body. Given the observations that HA, the decarboxylated amino acid histidine, can be induced and made available in an unstored, diffusible form in tissues undergoing rapid growth (such as tumors and regenerating tissues), it could have a role in antitumor response beyond the well-studied inflammatory and allergic responses.

Mechanistic approach of the difference in hydrolysis rate between the 2‐ and 4‐isomers of no‐carrier‐added [18F]fluoromethyl‐L‐phenylalanine

AbstractNo‐carrier‐added (n.c.a.) 2‐[18F]fluoromethyl‐l‐phenylalanine (2‐[18F]FMP) was found to be very sensitive to hydrolysis in aqueous solutions. In this paper, the defluorination reaction was studied in detail to elucidate its mechanism. Therefore, besides 2‐[18F]FMP and 4‐[18F]FMP, 2‐[18F]fluoromethyl‐phenethylamine (2‐[18F]FMPAM) and 4‐[18F]FMPAM were synthesized, both ‘mimetic’ molecules of the decarboxylated amino acid analogues. Radiosynthesis, using a customized Scintomics automatic synthesis hotboxthree module, resulted in a high overall yield and a radiochemical purity of >99%. The defluorination rates of all compounds were studied by HPLC. The defluorination rate of 2‐[18F]FMLP at 50°C was approximately 300 times faster than that of n.c.a. 4‐[18F]FMLP. The defluorination rate of 2‐[18F]FMPAM is somewhat lower than of 2‐[18F]FMP but still very high in comparison with 4‐[18F]FMPAM, which is virtually stable. It allowed to elucidate the reaction mechanism ruled by two distinct intramolecular interactions. First, the hydrogen bond interaction between the amine and the benzylic fluorine weakening the carbon–fluorine bond. Secondly, the formation of a second hydrogen bond between the carboxyl oxygen atom and one of the benzylic hydrogen atoms rendering the benzyl fluoride group even more susceptible to hydrolysis. Copyright © 2010 John Wiley & Sons, Ltd.

Safety-related properties of staphylococci isolated from food and food environments

To test some safety-related properties within 321 staphylococci strains isolated from food and food environments. The isolates were identified as Staphylococcus aureus, Staphylococcus epidermidis, Staphylococcus saprophyticus, Staphylococcus pasteuri, Staphylococcus sciuri, Staphylococcus warneri and Staphylococcus xylosus. Decarboxylase activity was quite common for the various Staphylococcus spp., and tyrosine was the most frequently decarboxylated amino acid. The frequency of antibiotic resistance was highest in Staph. pasteuri and Staph. xylosus. Several of the isolates were tolerant to QAC compounds, and in some cases, QAC tolerance was present in antibiotic-resistant strains. Most of the strains displayed moderate to high adhesion rates to stainless steel and Teflon(®). The strains that readily formed biofilms belonged to the species Staph. aureus, Staph. epidermidis and Staph. pasteuri. An high incidence of some safety hazards was found within the staphylococcal strains of food origin tested in this study. In particular, amino acid decarboxylase activity and biofilm-forming ability were common within strains, and antibiotic resistance and tolerance to QAC-based compounds occurred frequently as well. These characteristics are an important safety concern for food industry. This work gives a first picture of safety hazards within staphylococcal species isolated from food environments. The presence of disinfectant-resistant staphylococci is a concern because resistance can be genetically transferred between the various Staphylococcus species. This could lead an increase and spread of resistant enterotoxic staphylococci and/or pathogenic staphylococci.

Biogenic amines in fermented foods

Food-fermenting lactic acid bacteria (LAB) are generally considered to be non-toxic and non-pathogenic. Some species of LAB, however, can produce biogenic amines (BAs). BAs are organic, basic, nitrogenous compounds, mainly formed through decarboxylation of amino acids. BAs are present in a wide range of foods, including dairy products, and can occasionally accumulate in high concentrations. The consumption of food containing large amounts of these amines can have toxicological consequences. Although there is no specific legislation regarding BA content in many fermented products, it is generally assumed that they should not be allowed to accumulate. The ability of microorganisms to decarboxylate amino acids is highly variable, often being strain specific, and therefore the detection of bacteria possessing amino acid decarboxylase activity is important to estimate the likelihood that foods contain BA and to prevent their accumulation in food products. Moreover, improved knowledge of the factors involved in the synthesis and accumulation of BA should lead to a reduction in their incidence in foods.

PCR methods for the detection of biogenic amine-producing bacteria on wine

Biogenic amines are low molecular weight organic bases frequently found in wine. Several toxicological problems resulting from the ingestion of wine containing biogenic amines have been described. In wine, histamine, tyramine, and putrescine are mainly produced by the decarboxylation of the amino acid histidine, tyrosine, and ornithine, respectively, by lactic acid bacteria action. The bacterial ability to decarboxylate amino acids is highly variable, and therefore the detection of bacteria possessing amino acid decarboxylase activity is important to prevent biogenic amine accumulation in wine. Molecular methods for the early and rapid detection of these producer bacteria are becoming an alternative to traditional culture methods. Moreover, quantitative PCR methods are useful to enumerate biogenic amine-producer bacteria on wine. Molecular methods detect potential biogenic amine risk formation in wine before the amine is produced. This review will cover the molecular methods proposed in the literature for the detection of biogenic amine-producing bacteria in wine. These methods could improve winemaking control in order to avoid biogenic amine production.

Cu(II)-Catalyzed Reactions in Ternary [Cu(AA)(AA – H)]+ Complexes (AA = Gly, Ala, Val, Leu, Ile, t-Leu, Phe)

The unimolecular chemistry of [Cu(II)AA(AA - H)](+) complexes, composed of an intact and a deprotonated amino acid (AA) ligand, have been probed in the gas phase by tandem and multistage mass spectrometry in an electrospray ionization quadrupole ion trap mass spectrometer. The amino acids examined include Gly, Ala, Val, Leu, Ile, t-Leu and Phe. Upon collisionally-activated dissociation (CAD), the [Cu(II)AA(AA - H)](+) complexes undergo decarboxylation with simultaneous reduction of Cu(II) to Cu(I); during this process, a radical site is created at the alpha-carbon of the decarboxylated ligand (H(2)N(1) - (*)C(alpha)H - C(beta)H(2) - R; R = side chain substituent). The radical site is able to move along the backbone of the decarboxylated amino acid to form two new radicals (HN(1)(*) - C(alpha)H(2) - C(beta)H(2) - R and H(2)N(1) - C(alpha)H(2) - (*)C(beta)H - R). From the complexes of Gly and t-Leu, only C(alpha) and N(1) radicals can be formed. The whole radical ligand can be lost to form [Cu(I)AA](+) from these three isomeric radicals. Alternatively, further radical induced dissociations can take place along the backbone of the decarboxylated amino acid ligand to yield [Cu(II)AA(AA - 2H - CO(2))](+), [Cu(I)AA((*)NH(2))](+), [Cu(I)AA(HN = C(alpha)H(2))](+), or [Cu(I)AA(H(2)N - C(alpha)H = C(beta)H - R'](+) (R' = partial side chain substituent). The sodiated copper complexes, [Cu(II)(AA - H + Na)(AA - H)](+), show the same fragmentation patterns as their non-sodiated counterparts; sodium ion is retained on the intact amino acid ligand and is not involved in the CAD pathways. The amino groups of both AA units, the carbonyl group of the intact amino acid, and the deprotonated hydroxyl oxygen coordinate Cu(II) in square-planar fashion. Ab initio calculations indicate that the metal ion facilitates hydrogen atom shuttling between the N(1), C(alpha) and C(beta) atoms of the decarboxylated amino acid ligand. The dissociations of the decarboxylated radical ions unveil important insight about the so far largely unknown intrinsic chemistry of alpha-amino acid and peptide radicals, which are implicated as intermediates in numerous pathogenic biological processes.

Degradation of asparagine to acrylamide by carbonyl-amine reactions initiated by alkadienals

Abstract The degradation of asparagine to acrylamide produced by 2,4-decadienals was analysed in detail in an attempt to understand the reactions pathways involved in the formation of acrylamide by oxidised lipids. Thus, the effects of aw, pH, oxygen and lipid content, and time and temperature, were studied in different samples of 2,4-decadienal, 2,4-heptadienal, 2,4-hexadienal, 2-octenal, or ethyl 2,4-decadienoate with asparagine, N-acetylasparagine, asparagine t-butyl ester, glutamine or ammonium chloride. Acrylamide was produced to a higher extent in alkadienal/asparagine mixtures, and the reaction yield increased slightly when the chain length of the oxidised lipid decreased. In addition, the reaction yield was very much reduced when the amino acid was esterified or when an alkenal was employed. Furthermore, acrylamide was not produced when ethyl 2,4-decadienoate, N-acetylasparagine, glutamine or ammonium chloride were employed. These results, together with the detection of 3-aminopropionamide and 2-pentylpyridine in 2,4-decadienal/asparagine mixtures, suggested a potential role of the alkadienal in both the decarboxylation of the amino acid and the later conversion of decarboxylated amino acid into acrylamide. This last conclusion was confirmed by studying the effect of the lipid content in the formation of acrylamide in 2,4-decadienal/3-aminopropionamide mixtures.

A Novel Gene Involved in Regulating the Flagellar Gene Cascade inProteus mirabilis

In this study, we identified a transposon insertion in a novel gene, designated disA, that restored swarming motility to a putrescine-deficient speA mutant of Proteus mirabilis. A null allele in disA also increased swarming in a wild-type background. The DisA gene product was homologous to amino acid decarboxylases, and its role in regulating swarming was investigated by examining the expression of genes in the flagellar cascade. In a disA mutant background, we observed a 1.4-fold increase in the expression of flhDC, which encodes FlhD(2)C(2), the master regulator of the flagellar gene cascade. However, the expressions of class 2 (fliA, flgM) and class 3 (flaA) genes were at least 16-fold higher in the disA background during swarmer cell differentiation. Overexpression of DisA on a high-copy-number plasmid did not significantly decrease flhDC mRNA accumulation but resulted in a complete block in mRNA accumulation for both fliA and flaA. DisA overexpression also blocked swarmer cell differentiation. The disA gene was regulated during the swarming cycle, and a single-copy disA::lacZ fusion exhibited a threefold increase in expression in swarmer cells. Given that DisA was similar to amino acid decarboxylases, a panel of decarboxylated amino acids was tested for effects similar to DisA overexpression, and phenethylamine, the product of phenylalanine decarboxylation, was capable of inhibiting both swarming and the expression of class 2 and class 3 genes in the flagellar regulon. A DisA-dependent decarboxylated amino acid may inhibit the formation of active FlhD(2)C(2) heterotetramers or inhibit FlhD(2)C(2) binding to DNA.

Volatile and Biogenic Amines, Microbiological Counts, and Bacterial Amino Acid Decarboxylase Activity throughout the Salt-Ripening Process of Anchovies (Engraulis encrasicholus)

Chemical and microbiological parameters were studied during the industrial production of salt-ripened anchovies (Engraulis encrasicholus). Gradual acidification and increases in the proteolysis index and in total volatile basic nitrogen were observed. At the end of the maturing process, the values reached pH 5.55 ± 0.03, 21.33 ± 5.82%, and 44.06±12.47 mg/100 g, respectively. In the three studied anchovy batches, the biogenic amines tyramine, histamine, putrescine, cadaverine, and agmatine increased during ripening. The highest values were found in the batch where initial microbial load was highest (batch 1), especially for enterobacteria and enterococci. Tyramine was the most abundant amine, reaching values from nondetectable to 90 mg/kg, whereas histamine did not surpass 20 mg/kg. Among the microorganisms isolated, Enterobacter cloacae, Aerococcus viridans, Kocuria varians, and Staphylococcus chromogenes were able to decarboxylate amino acids and produce biogenic amines in vitro. Most (70.59%) of the microorganisms identified were able to produce histamine, 23.53% were able to produce the diamines putrescine and cadaverine, and only 11.76% were able to produce tyramine, although this substance was the major biogenic amine found in anchovy samples.

Enterocin AS-48RJ: a variant of enterocin AS-48 chromosomally encoded by Enterococcus faecium RJ16 isolated from food

The bacteriocinogenic strain RJ16 isolated from goat cheese has been identified as Enterococcus faecium by species-specific PCR, DNA–rRNA hybridization and rDNA sequencing. Purified bacteriocin from strain RJ16 is a carboxypeptidase A-resistant peptide with a molecular mass (7125 Da) very close to the cyclic peptide enterocin AS-48. Bacteriocin from strain RJ16 and AS-48 show identical antibacterial spectra, although the former is slightly less active on strains of Listeria monocytogenes and Bacillus cereus. Producer strains show cross-immunity. PCR amplification of total DNA from strain RJ16 with primers for the AS-48 structural gene and sequencing of the amplified fragment revealed an almost identical sequence (99.5%), except for a single mutation that predicts the change of Glu residue at position 20 of AS-48 to Val. Therefore, bacteriocin produced by E. faecium RJ16 should be considered a variant of AS-48, which we call AS-48RJ. PCR amplification revealed that strain RJ16 contains the complete as-48 gene cluster. Hybridization with probes for as-48 gene cluster revealed a chromosomal location of as-48 genes in strain RJ16, being the first example of a chromosomal location of this bacteriocin trait. Strain RJ16 produced enzymes of interest in food processing (esterase, esterase lipase and phytase activities), and did not decarboxylate amino acids precursors for biogenic amines. Strain RJ16 did not exhibit haemolytic or gelatinase activities, and PCR amplification revealed the lack of genes encoding for known virulence determinants (aggregation substance, collagen adhesin, enterococcal surface protein, endocarditis antigens, as well as haemolysin and gelatinase production). Strain RJ16 was resistant to ciprofloxacin ( MIC > 2 mg l - 1 ) and levofloxacin ( MIC > 4 mg l - 1 ) and showed intermediate resistance to nitrofurantoin and erythromycin, but was sensitive to ampicillin, penicillin, streptomycin, gentamicin, rifampicin, chloramphenicol, tetracycline, quinupristin/dalfopristin, vancomycin and teicoplanin. Altogether, results from this study suggest that this broad-spectrum bacteriocin-producing strain may have a potential use in food preservation.

A proteomic approach to studying biogenic amine producing lactic acid bacteria

All fermented foods are subject to the risk of biogenic amine contamination. Histamine and tyramine are among the most toxic amines for consumers' health, exerting undesirable effects on the central nervous and vascular systems, but putrescine and cadaverine can also compromise the organoleptic properties of contaminated foods. These compounds are produced by fermenting microbial flora that decarboxylate amino acids to amines. Little is known of the factors which induce biosynthesis of decarboxylating enzymes and/or which modulate their catalytic activity: the accumulation of amines is generally considered to be a mechanism that contrasts an acidic environment and/or that produces metabolic energy through coupling amino acid decarboxylation with electrogenic amino acid/amine antiporters. Two Lactobacillus strains, Lactobacillus sp. 30a (ATCC 33222), and a Lactobacillus sp. strain (w53) isolated from amine-contaminated wine, carrying genetic determinants for histidine decarboxylase (HDC) and ornithine decarboxylase (ODC), were studied and the influence of some environmental and nutritional parameters on amine production and protein biosynthesis was analyzed through a proteomic approach; this is the first report of a proteomic analysis of amine-producing bacteria. HDC and ODC biosynthesis were shown to be closely dependent on the presence of high concentrations of free amino acids in the growth medium and to be modulated by the growth phase. The stationary phase and high amounts of free amino acids also strongly induced the biosynthesis of an oligopeptide transport protein belonging to the proteolytic system of Lactic Acid Bacteria. At least two isoforms of glyceraldehyde-3-phosphate dehydrogenase, with different M(r), pI and expression profiles, were identified from Lactobacillus sp. w53: the biosynthesis of one isoform, in particular, is apparently repressed by high concentrations of free amino acids. Other proteins were identified from the Lactobacillus proteome, affording a global knowledge of protein biosynthesis modulation during biogenic amine production.

Histamine, part of the metabolome.

Histamine, a decarboxylated amino acid with a molecular mass of 112 daltons reveals multicoloured functional activities. Its role in allergy and inflammation is abundantly characterized. Moreover histamine is one of the neuotransmitters, has a role in gastric acid production and in maintenance of blood-brain barrier. In the last decade, many data were collected suggesting an important function of histamine in events of immune response and also in both benign and malignant cell proliferation. Our group collected data on the relevance of histamine as an autocrine factor in human melanoma. The outcome of the action seems to be closely related to the local and actual balance of histamine receptors (H1R, H2R, H3R and H4R) on tumor cells. Recently, using a gene targeted mouse strain (lacking an enzyme, histidine decarboxylase, the only one responsible for histamine production) many phenotype of the histamine-free mice were demonstrated. Our data suggest, that histamine, as part of the poorly characterized metabolome of the mammalian cells plays significant role in many physiological and pathological processes.

Influence of Starter and Nonstarter on the Formation of Biogenic Amine in Goat Cheese During Ripening

Two commercial starters were investigated for their potential ability to decarboxylate amino acids during goat cheese ripening. Two batches of goat cheese were produced with identical pasteurized milk but different starter cultures. One of them contained Lactococcus lactis subsp. lactis and Lactococcus lactis subsp. cremoris and the other Lactococcus lactis subsp. lactis. The amine contents, microbial counts, proteolysis-related parameters, pH, total solids and salt content were studied in raw materials and cheeses. In raw materials, polyamines were the prevailing amines, whereas the main amines in cheeses were putrescine, tryptamine and, in particular, tyramine (94.59 mg/kg). Aerobic mesophilic microorganisms and Lactococcus counts increased throughout ripening, while Enterobacteriaceae were no longer detectable in cheese after 30 days of ripening. Amine concentration rose during cheese ripening in both batches. Moreover, the decarboxylase activity of microorganisms isolated from samples during cheese ripening was assayed and discussed.

Biogenic amines in wines: role of lactic acid bacteria

Biogenic amines have undesirable physiological effects when absorbed at too high a concentration. Several kinds of food and beverages contain biogenic amines. Lactic acid bacteria can decarboxylate amino acids. Since winemaking involves the growth of lactic acid bacteria for malolactic fermentation, biogenic amines may occur. However, not all bacterial strains carry these activities. In the same wine-producing area, some wines may contain very low amounts of biogenic amines while others may have relatively large quantities. It is now possible to detect the presence of undesirable histamine-producing strains by PCR test or DNA probe based on the presence of the gene encoding histidine decarboxylase. Other strains have the ornithine and/or tyrosine decarboxylase. When biogenic amine-producing strains are present, the winemaker is encouraged to inoculate selected malolactic starters to replace the indigenous microflora.

Biogenic amines in wines: role of lactic acid bacteria.

Biogenic amines have undesirable physiological effects when absorbed at too high a concentration. Several kinds of food and beverages contain biogenic amines. Lactic acid bacteria can decarboxylate amino acids. Since winemaking involves the growth of lactic acid bacteria for malolactic fermentation, biogenic amines may occur. However, not all bacterial strains carry these activities. In the same wine-producing area, some wines may contain very low amounts of biogenic amines while others may have relatively large quantities. It is now possible to detect the presence of undesirable histamine-producing strains by PCR test or DNA probe based on the presence of the gene encoding histidine decarboxylase. Other strains have the ornithine and/or tyrosine decarboxylase. When biogenic amine-producing strains are present, the winemaker is encouraged to inoculate selected malolactic starters to replace the indigenous microflora.

Synthesis, spectral and structural studies on metal complexes of Schiff bases involving vitamin B6 and histamine

Six metal complexes of Schiff bases involving Vitamin B6 and the decarboxylated amino acid histamine have been synthesised and characterized. Crystal structures have been determined for [CuL1(H2O)Br]-NO31(L1= pyridoxylidenehistamine) and [Cu2L22(NO3)2]·6H2O 2(L2= 5′-phosphopyridoxylidenehistaminate). The crystal structure of complex 1[space group P, a= 8.161(2), b= 10.368(2), c= 11.110(2)A, α= 105.18(1), β= 102.12(1), γ= 72.10(1)° and Z= 2; R= 0.072, R′= 0.083] consists of square-pyramidally co-ordinated copper with the tridentate Schiff base in the zwitterionic form, whereas in 2[space group P, a= 8.727(1), b= 10.308(1), c= 12.845(2)A, α= 110.00(1), β= 78.94(1), γ= 114.35(1)° and Z= 1; R= 0.035, R′= 0.034] the copper has the same co-ordination geometry but the tetradentate Schiff-base ligand exists as a monoanion. The conformational parameters deduced from such structures are important for understanding the stereochemical aspects of Vitamin B6-catalysed model reactions involving histidine.