Biogenic Diamines Research Articles

Modeling Nonlinear Dynamics of Functionalization Layers: Enhancing Gas Sensor Sensitivity for Piezoelectrically Driven Microcantilever.

This article presents a parametrized response model that enhances the limit of detection (LOD) of piezoelectrically driven microcantilever (PD-MC) based gas sensors by accounting for the adsorption-induced variations in elastic properties of the functionalization layer (binder) and the nonlinear motional dynamics of the PD-MC. The developed model is demonstrated for quantifying cadaverine, a volatile biogenic diamine whose concentration is used to assess the freshness of meat. At low concentrations of cadaverine, an increase in the resonance frequency is observed, contrary to the expected reduction due to mass added by adsorption. The study explores the variations in the elastic modulus vis-à-vis the adsorbed mass of cadaverine and derives the resonance frequency to the adsorbed mass response function. We advance a blended technique involving the analysis of atomic force microscopy (AFM) force-distance (f-d) curves and fitting of the quartz crystal microbalance (QCM) impedance response spectrum to deduce the adsorption-induced changes in the viscoelastic properties of the functionalization layer. The findings obtained are subsequently employed in modeling the response function for a structurally nonhomogenous PD-MC, highlighting the significance of the functionalization layer to the global elastic properties. The structural composition of the PD-MC beam adopted herein features a trapezoidal base hosting the actuating piezoelectric stratum and a rectangular free end with a functionalization layer. The Euler-Bernoulli beam theory coupled with Hamilton's principle is used to develop the equation of motion, which is subsequently discretized into a set of nonlinear ordinary differential equations via Galerkin expansion, and the solutions to the first fundamental mode of vibration are determined using the method of multiple scales. The obtained solutions provide a basis for deducing the nonlinear response function model to the adsorbed mass. The derived model is validated by recorded resonance frequency changes resulting from exposure to known concentrations of cadaverine. We demonstrate that the increase in resonance frequency for low concentrations of cadaverine is due to the dominance of the variation of the elastic modulus of the functionalization layer originating from the initial binder-analyte interactions over damping due to added mass. It is concluded that the developed nonlinear response function model can reliably be used to quantify the cadaverine concentration at low concentrations with an elevated Limit of Detection.

Biogenic Diamines and Their Amide Derivatives Are Present in the Forest Atmosphere and May Play a Role in Particle Formation

Diamines, such as 1,3-diaminopropane (Dap), 1,4-diaminobutane (putrescine, or Put), and 1,5-diaminopentane (cadaverine), are essential organic bases for plants. Such “biogenic diamines” are abundantly present in oak tree flowers and are emitted into the atmosphere. We sampled atmospheric diamines in a typical broadleaf tree forest and chestnut grove during blossom season and carried out a chromatography-mass spectrometry analysis. Amide derivatives of Dap and Put, 3-aminopropanamide and 4-aminobutanamide, respectively, were found in higher atmospheric concentrations than their source diamine. Because their concentrations in oak tree flowers were very low, we deduced that these aminoamides were produced after Dap and Put, respectively, were released into the atmosphere. Time series of biogenic diamine and aminoamide concentrations showed evidence of diurnal variations. Concentrations were lower during daytime in sunny conditions, suggesting relatively fast photochemical decomposition. Biogenic diamines and aminoamides bond more easily than monoamines with water vapor and sulfuric acid in the atmosphere. Biogenic diamines and aminoamides may play a role in the formation of new particles and biogenic secondary organic aerosols in the forest atmosphere during spring and early summer.

Solid-Phase Synthesis of Selectively Mono-Fluorobenz(o)ylated Polyamines as a Basis for the Development of 18F-Labeled Radiotracers.

Polyamines are highly attractive vectors for tumor targeting, particularly with regards to the development of radiolabeled probes for imaging by positron emission (PET) and single-photon emission computed tomography (SPECT). However, the synthesis of selectively functionalized derivatives remains challenging due to the presence of multiple amino groups of similar reactivity. In this work, we established a synthetic methodology for the selective mono-fluorobenz(o)ylation of various biogenic diamines and polyamines as lead compounds for the perspective development of substrate-based radiotracers for targeting polyamine-specific membrane transporters and enzymes such as transglutaminases. For this purpose, the polyamine scaffold was constructed by solid-phase synthesis of the corresponding oxopolyamines and subsequent reduction with BH3/THF. Primary and secondary amino groups were selectively protected using Dde and Boc as protecting groups, respectively, in orientation to previously reported procedures, which enabled the selective introduction of the reporter groups. For example, N1-FBz-spermidine, N4-FBz-spermidine, N8-FBz-spermidine, and N1-FBz-spermine and N4-FBz-spermine (FBz = 4-fluorobenzoyl) were obtained in good yields by this approach. The advantages and disadvantages of this synthetic approach are discussed in detail and its suitability for radiolabeling was demonstrated for the solid-phase synthesis of N1-[18F]FBz-cadaverine.

Pyrrolopyrrole aza-BODIPY dyes for ultrasensitive and highly selective biogenic diamine detection

Biogenic diamines (BAs) are important compounds in food chemistry and life science. Because of structural similarity of amines and low concentration of BAs in real samples, it is exceedingly challenging to design and develop highly efficient probes for visual detection of BAs. To address this gap, we report ultrasensitive and highly selective pyrrolopyrrole aza-BODIPY (PPAB) probes for BAs detection. The detection mechanism study revealed first kinetic-control reaction of a B–N bond cleavage by BAs, and following two fast step reactions (transimination and hydrolysis) to yield much smaller conjugated molecules. The first kinetic-control reaction results in high selectivity towards BAs. The following reactions result in direct large conjugation change, leading to high sensitivity for the detection of BAs. Thus, with over 225 nm hypsochromic shift in the absorption maximum and 12-fold fluorescence enhancement process, PPAB probes showed high sensitivity for BAs with limit of detection up to ppb level and response time on the second timescale. Moreover, visual detection of BAs vapors and monitoring fish spoilage were successfully conducted by the low-cost, high-contrasting, quick-responsive fluorescent trademark of PPAB molecules by naked-eyes.

Characterization of a Putrescine Transaminase From Pseudomonas putida and its Application to the Synthesis of Benzylamine Derivatives.

The reductive amination of prochiral ketones using biocatalysts has been of great interest to the pharmaceutical industry in the last decade for integrating novel strategies in the production of chiral building blocks with the intent of minimizing impact on the environment. Amongst the enzymes able to catalyze the direct amination of prochiral ketones, pyridoxal 5′-phosphate (PLP) dependent ω-transaminases have shown great promise as versatile industrial biocatalysts with high selectivity, regioselectivity, and broad substrate scope. Herein the biochemical characterization of a putrescine transaminase from Pseudomonas putida (Pp-SpuC) was performed, which showed an optimum pH and temperature of 8.0 and 60°C, respectively. To gain further structural insight of this enzyme, we crystallized the protein in the apo form and determined the structure to 2.1 Å resolution which revealed a dimer that adopts a class I transaminase fold comparable to other class III transaminases. Furthermore we exploited its dual substrate recognition for biogenic diamines (i.e., cadaverine) and readily available monoamines (i.e., isopropylamine) for the synthesis of benzylamine derivatives with excellent product conversions and extremely broad substrate tolerance.

Identifying human diamine sensors for death related putrescine and cadaverine molecules.

Pungent chemical compounds originating from decaying tissue are strong drivers of animal behavior. Two of the best-characterized death smell components are putrescine (PUT) and cadaverine (CAD), foul-smelling molecules produced by decarboxylation of amino acids during decomposition. These volatile polyamines act as ‘necromones’, triggering avoidance or attractive responses, which are fundamental for the survival of a wide range of species. The few studies that have attempted to identify the cognate receptors for these molecules have suggested the involvement of the seven-helix trace amine-associated receptors (TAARs), localized in the olfactory epithelium. However, very little is known about the precise chemosensory receptors that sense these compounds in the majority of organisms and the molecular basis of their interactions. In this work, we have used computational strategies to characterize the binding between PUT and CAD with the TAAR6 and TAAR8 human receptors. Sequence analysis, homology modeling, docking and molecular dynamics studies suggest a tandem of negatively charged aspartates in the binding pocket of these receptors which are likely to be involved in the recognition of these small biogenic diamines.

Water-soluble naphthalene diimides: synthesis, optical properties, and colorimetric detection of biogenic amines

Biocompatible water-soluble naphthalene diimides (NDIs) were synthesized and a core-dichlorinated NDI was shown to detect primary amines and biogenic diamines.

Turning Supramolecular Receptors into Chemosensors by Nanoparticle-Assisted "NMR Chemosensing".

By exploiting a magnetization transfer between monolayer-protected nanoparticles and interacting analytes, the NMR chemosensing protocol provides a general approach to convert supramolecular receptors into chemosensors via their conjugation with nanoparticles. In this context, the nanoparticles provide the supramolecular receptor not only with the "bulkiness" necessary for the NMR chemosensing approach but also with a different selectivity as compared to the parent receptor. We here demonstrate that gold nanoparticles of 1.8 nm core coated with a monolayer of 18-crown-6 ether derivatives can detect and identify protonated primary amines in methanol and in water, and even discriminate between two biogenic diamines that are selectively detected over monoamines and α-amino acids.

Study of the naphthalene-2,3-dicarboxaldehyde pre-column derivatization of biogenic mono- and diamines in mixture and fluorescence−HPLC determination

A new fluorescence-HPLC method was developed for the simultaneous determination of eight biogenic monoamines (histamine, methylamine, tyramine, ethylamine, propylamine, tryptamine, 2-phenylethylamine, isoamylamine) and two biogenic diamines (putrescine, cadaverine) in the presence of heptylamine as the internal standard. The amines were pre-column derivatized with naphthalene-2,3-dicarboxaldehyde in the presence of cyanide ion as the nucleophile. The effect of the derivatization reaction conditions on the reaction yield was investigated. The derivatives were separated on an Inertsil ODS-3 column (250 × 4mm i.d., 5 μm) using gradient elution and detected fluorimetrically at excitation and emission wavelengths of 424 and 494 nm, respectively. Limits of detection between 0.002 and 0.4 ng, injected on-column (10-μL loop), were achieved. The within- and between-day relative standard deviations ranged between 0.2-3.4% and 0.3-4.8%, respectively. The utility of the method in assaying biogenic mono- and diamine mixtures in Greek cheeses is demonstrated. Ultrasound-assisted liquid-liquid extraction was applied prior to derivatization.

A Simple Biosensor for Biogenic Diamines, Comprising Amine Oxidase—Containing Threads and Oxygen Sensor

A Simple Biosensor for Biogenic Diamines, Comprising Amine Oxidase—Containing Threads and Oxygen Sensor

Solid-supported Zn(ii) porphyrin tweezers as optical sensors for diamines

A melamine-bridged bis-Zn(II) porphyrin dyad covalently attached onto amino-functionalized TentaGel polymer beads or controlled pore glass (CPG) undergoes a reversible and marked colour change from purple to green upon exposure to a biogenic diamine such as cadaverine both in organic and aqueous media.

Self-assembly in lanthanum(III) and calcium(II) complexes of salicylaldimines derived from putrescine

Abstract The one-step template reaction of salicylaldehyde with putrescine, a biogenic diamine, in the presence of lanthanum(III) or calcium(II) ions produces salicylaldimine complexes containing the N,N′-bis(salicylidene)-1,4-butanediamine ligand L as a result of the [2 + 1] Schiff base condensation. The X-ray diffraction studies of the lanthanum complex reveals an infinite [La2L4(NO3)6]∞ polymeric structure based on networks of 10-coordinated La(III) nodes linked by bridging unionized ligands that use exclusively the oxygens as donor atoms with the nitrogen atoms not being involved in coordination.

Determination of putrescine and cadaverine in seafood (finfish and shellfish) by liquid chromatography using pyrene excimer fluorescence

A liquid chromatography (LC) method is described for the easy determination of the biogenic diamines putrescine (PUT) and cadaverine (CAD) in canned tuna, frozen tuna loin, fresh mahimahi fillet, frozen raw shrimp, cooked lump crabmeat, and fresh and cold-smoked salmon. The method is also a useful screen for histamine (HTA). The method involves homogenization of fish tissue, extraction of biogenic amines into borate-trichloroacetic acid solution, centrifugation, and derivatization of supernatant with 1-pyrenebutanoic acid succinimidyl ester. The derivatized diamine species allow for the intramolecular excimer fluorescence of the pyrene moiety at a higher emission wavelength than is possible for the endogenous tissue monoamines, thus providing visual specificity of detection. All seafood species were fortified with 0.5, 1.0, 5.0, 10.0, and 15.0 μg/g (ppm) of PUT and CAD. Determination was based on standard graphs for PUT and CAD using peak areas with standard solutions equivalent to 0.375, 1.0, 5.0, 10.0, and 20.0 ppm in tissue. A set of five matrix controls (unfortified seafood tissue) were also analyzed; endogenous PUT was found in all samples except the canned tuna, and CAD found only in the shrimp, crab, and cold-smoked salmon. The background amines were thus subtracted prior to determining spike recovery. The intra-assay average recoveries ranged from 71 to 94% across species and spike levels.

The Template Synthesis of the New Macrocyclic and Acyclic Metal Ion Complexes Derived from Putrescine

The template reaction of 2,6-diacetylpyridine with biogenic diamine–putrescine in the presence of cadmium(II), mercury(II) or lead(II) ions produces the complexes of 22-membered macrocyclic ligand L1 with an N6 set of donor atoms as a result of [2 + 2] Schiff base cyclocondensation. The lead(II) complex containing Schiff base acyclic ligand L2 terminated by one carbonyl and one amine group as product of the partial [2 + 2] condensation has been also isolated and might be regarded as possible intermediate in the formation of the macrocyclic L1 complex. Analogous reaction involving the uranyl nitrate generates the complex containing the same Schiff base acyclic ligand L2 as a final product of template reaction. The complexes were characterized by spectral data (IR, 1H NMR, FAB-MS), thermogravimetric and elemental analyses. A notable feature of the FAB mass spectrum of the uranyl complex is the appearance of the clusters of the form [(UO2) n O]+(n= 1–7) along with the peak corresponding to molecular ion.

Reduced aldehyde dehydrogenase levels in the brain of patients with Down syndrome.

Aldehyde dehydrogenase (ALDH) is a key enzyme in fructose, acetaldehyde and oxalate metabolism and represents a major detoxification system for reactive carbonyls and aldehydes. In the brain, ALDH exerts a major function in the metabolism of biogenic aldehydes, norepinephrine, dopamine and diamines and gamma-aminobutyric acid. Subtractive hybridization studies in Down Syndrome (DS) fetal brain showed that mRNA for ALDH are downregulated. Here we studied the protein levels in the brain of adult patients. The proteins from five brain regions of 9 aged patients with DS and 9 controls were analyzed by two-dimensional (2-D) gel electrophoresis and identified by matrix-assisted laser desorption ionization mass spectrometry. ALDH levels were reduced in the brain regions of at least half of the patients with Down Syndrome, as compared to controls. The decreased ALDH levels in the DS brain may result in accumulation of aldehydes which can lead to the formation of plaques and tangles reflecting abnormally cross-linked, insoluble and modified proteins, found in aged DS brain. Furthermore, we constructed a 2-Dmap including approximately 120 identified human brain proteins.

Use of Cold On-Column Injection for the Analysis of Putrescine and Cadaverine by Gas Chromatography

Putrescine and cadaverine are biogenic diamines that are produced during fermentation or spoilage of different food products. Therefore, they are used as indicators to determine food quality. Unfortunately, their chemical analysis is not an easy task. The use of cold on-column gas chromatographic (GC) injection together with a new base-deactivated fused silica capillary column is evaluated for the direct GC analysis of putrescine and cadaverine. Multiple injections of standard mixtures containing putrescine, cadaverine, and heptylamine are made in order to determine reproducibility. Standard mixtures at concentrations from 20 to 400 ppm are also injected to determine the linearity of response with both the column and the flame ionization detector. Excellent resolution of the three amines is achieved as well as symmetrical peaks. Multiple injections produce reproducibilities of 1 % for peak areas and 0.03% for retention times. A good linear response is obtained between concentrations of 20 to 400 ppm.

Histaminergic regulation of antibody-dependent cellular cytotoxicity of granulocytes, monocytes, and natural killer cells

We investigated effects of the biogenic diamine histamine on antibody-dependent cellular cytotoxicity (ADCC) against autologous anti-D-coated red blood cells mediated by human granulocytes, monocytes, and natural killer (NK) cells. Effector cells were separated from peripheral blood by countercurrent centrifugal elutriation. ADCC of monocytes and neutrophilic granulocytes was suppressed by histamine. ADCC of enriched CD3-/56+ NK cells was unchanged by histamine. ADCC of NK cells was effectively inhibited by elutriated monocytes or neutrophils. Histamine completely reversed the inhibition of NK cell-mediated ADCC induced by monocytes and partly reversed the inhibition induced by neutrophils; thereby, histamine augmented ADCC of NK cells in the presence of monocytes or neutrophils. The indirect effect of histamine on ADCC of NK cells and the effect of histamine on ADCC of monocytes/neutrophils were completely antagonized by the specific H2 receptor (H2R) blocker ranitidine. We conclude that activation of H2R suppresses ADCC reactivity of monocytes/neutrophils and, concomitantly, promotes ADCC reactivity of NK cells by abrogating a phagocyte-derived, suppressive signal.

Plant tissue biosensors for the determination of biogenic diamines and of their amino acid precursors: effect of carbonic anhydrase

A new class of plant tissue biosensors has been set up and applied to the determination of biogenic diamines. All the biosensors presented in this work are based on the amperometric determination of H 2O 2 produced by the enzymatic oxidation of diamines (putrescine and cadaverine) by the diamine oxidase (DAO) contained in the cotyledon of legumes (pea and lentil). Putrescine and cadaverine were quantitatively determined by means of these plant tissue electrodes in a range of concentrations between 0.5 and 320 μM and between 0.5 and 200 μM, respectively. The same lentil tissue-based sensor was then used, in combination with a lysine decarboxylase (LDC) membrane, for the realization of a hybrid enzyme electrode for the determination of lysine. The performances of the sensor here proposed, tested in lysine standard solutions, were comparable to those of traditional lysine bienzyme electrodes. A similar enzyme electrode was assembled for the determination of ornithine: in this case the lentil tissue diamine oxidase sensor was used in combination with an adequate amount of ornithine decarboxylase (ODC), added directly into the measuring cell. The effect of carbonic anhydrase (CA) on the speed of the LDC- and ODC-catalysed reactions was also evaluated. The synergistic interaction observed between the decarboxylation reaction, operated by either LDC or ODC, and the faciliated transport of CO 2, operated by CA, is discussed both in terms of its analytical relevance and of its broader physiopathologic implications.

Amperometric flow-injection method for determination of biogenic diamines and hypoxanthine by combined use of immobilized enzyme reactors and a peroxidase electrode

A flow-injection system is proposed for the determination of meat freshness, based on the simultaneous determination of polyamines and hypoxanthine. A putrescine oxidase reactor and xanthine oxidase reactor were incorporated at fixed positions in a flow system, which was based on the splitting of the flow after sample injection and subsequent confluence before reaching the peroxidase electrode. Because each channel has a different residence time, two peaks were obtained. The first peak corresponded to the total polyamine concentration (putrescine, cadaverine and spermidine) the second peak to hypoxanthine. The calibration graphs were linear in the range 1 × 10 −6–5 × 10 −4 M. The detection limit was 0.5 × 10 −6 M for polyamines and hypoxanthine. The measurement of polyamines and hypoxanthine contents in porcine loin meat could be performed at a rate of 25 samples per hour with satisfactory precision (<1.5% R.S.D.).

DETECTION OF BIOGENIC AMINES AS MEAT SPOILAGE INDICATORS

ABSTRACTPreparative ion exchange chromatography was performed on beef and pork samples stored at 4–6°C and wrapped in commercial film (Saran). Different peaks obtained for the two species studied, were attributable to the different type of biogenic diamines produced during spoilage. A second set of experiments was performed with pork, beef and rabbit samples. The last served as a control, since no record was available for the time elapsed since slaughtering of the animals of the other two species. Analyses were performed to determine total amine nitrogen produced during storage at chill temperatures in wrapped and unwrapped samples, and the amount of Pseudomonas, total aerobic organisms and lactic acid bacteria. Results suggested that the wrapping material did not produce the microaerophilic conditions to promote the growth of required lactic acid bacteria sufficient to outnumber the other microorganisms present. However, diamine production was slower in wrapped than in unwrapped samples.